Nitrification is increasingly of concern in US potable water systems, due to changes from chlorine to chloramine as a secondary disinfectant in order to comply with new regulations for disinfectant by-products. The ammonia that is released from the chloramine decay supports nitrification. A comprehensive literature review systematically examined the complex inter-relationships between nitrification, materials corrosion and metals release. That analysis suggested that nitrification could accelerate decay of chloramine, enhance corrosion of water distribution system materials, and increase leaching of lead and copper to potable water under at least some circumstances. Moreover, that certain plumbing materials would inhibit nitrification, but that in other situations the plumbing materials would enhance nitrification. Experiments verified that nitrification could affect the relative efficacy of chlorine versus chloramine in controlling heterotrophic bacteria in premise plumbing. Without nitrification, chloramine was always more persistent and effective than chlorine in controlling biofilms. But with nitrification and in pipe materials that are relatively non-reactive with chlorine, chloramine was much less persistent and less effective than chlorine. In materials that are reactive with chlorine such as iron pipes, the relative efficacy of chloramine versus chlorine depends on the relative rate of corrosion and rate of nitrification. High rates of corrosion and low rates of nitrification favor the use of chloramine versus free chlorine in controlling bacteria. Plumbing materials had profound impacts on the incidence of nitrification in homes. Effects were due to toxicity (i.e., release of Cu⁺²), recycling of nitrate back to ammonia substrate by reaction (zero-valent iron, lead or zinc materials), or release of nutrients that are essential to nitrification by leaching from concrete or other materials. As a general rule it was determined that concrete and iron materials encouraged growth of nitrifiers in certain oligotrophic waters, materials such as lead, PVC/plastic pipe, glass and surfaces of other materials were readily colonized by nitrifiers, and materials such as copper and brass were very toxic and relatively resistant to nitrifier colonization. Dependent on circumstance, nitrification had no effect, increased or decreased aspects of materials corrosion. Nitrification markedly increased lead contamination of low alkalinity potable water by reducing the pH. In some cases nitrification dramatically decreased leaching of zinc to potable water from galvanized iron, because of lowered dissolved oxygen and reduced pH. Nitrification did not affect copper solubility in low alkalinity water, but is expected to increase copper solubility in higher alkalinity waters. Finally, nitrification in homes plumbed with PVC or plastics can drop the pH and increase leaching of lead from downstream brass materials in faucets. This can explain why some modern homes plumbed with PVC can have more lead in water when compared to homes plumbed with copper pipe. Phosphate had profound impacts on the incidence of nitrification and resulting effects on water quality. While phosphate levels below about 5 ppb could strongly inhibit nitrification due to a nutrient limitation, nitrifiers can obtain sufficient phosphate from plastic, concrete, copper and iron pipe materials to meet nutritional needs. High levels of phosphate inhibitor can reduce the concentration of Cu⁺² ions and make nitrification more likely, but phosphate can also sometimes lower the corrosion rate and increase the stability of disinfectant and its efficacy in controlling nitrifiers. Phosphate plays a key role in determining where, when and if problems with nitrification will occur in a given water distribution system. This work provides some new fundamental and practical insights to nitrification issues through a comprehensive literature review, lab experiments, solubility modeling and field studies. The results and practical tools developed can be used by utilities and consumers to predict nitrification events and resulting water quality problems, and to make rational decisions about practices such as inhibitor dosing, plumbing material selection and use of whole house filters. / Ph. D.

This work investigated material corrosion by nuclear reactor coolants, including pressurized water reactor (PWR) coolant, boiling water reactor (BWR) coolant, high-temperature steam, lead-bismuth eutectic (LBE), and molten salt. Novel cladding materials for accident tolerant fuel (ATF) and additive manufacture (AM) Ni-based alloy were studied in water coolants. Similarly, the ATF material and Ni-based alloys were also examined under high-temperature steam to understand the corrosion behavior in beyond design basis accident (BDBA) scenarios. In addition to isothermal corrosion, stress corrosion cracking (SCC) and oxide layer in situ measurements were also conducted. Unlike conventional studies in liquid LBE that focused on Fe-based alloys, the present studies also investigated Ni-based alloys to explore the Ni content effects on the corrosion by LBE at high temperatures under saturated oxygen conditions. In molten salt environments, the corrosion behaviors of both Ni-based and Fe-based alloys were investigated. This study developed a redox potential range for mitigating corrosion by using a redox couple of UF4 /UF3 and a novel approach of potential measurements against F2/ F- potential experimentally. / Doctor of Philosophy / This work focuses on material degradation in harsh and extreme nuclear environments, including light water reactors and advanced reactors such as molten salt and liquid metal coolant reactors. Given the renewed interest in advanced nuclear reactors as a resource of clean energy, advanced material development, including structural, fuel, and coolant materials, has become a significant and trending research area. Based on our past experiences, we have seen the detrimental effects of material failure due to corrosion. Systems are inherently safe in the absence of material degradation. Nevertheless, this is an idealistic thought, as corrosion is inevitable. Therefore, this research focuses on corrosion mitigation, as absolute material preservation is impossible. This work includes corrosion studies in aqueous environments in light water reactors and advanced nuclear reactors under normal operation and extreme conditions such as accident environments. Much of this work provides insights into material corrosion behavior and mitigation that helps nuclear reactor operators ensure safe operations. Commercially available alloys such as SS316, Hast. X and Hast. N were examined in primary water, molten salt, high-temperature steam, and liquid bismuth environment and model Fe-Cr-Si alloys were investigated in water and steam to compare the corrosion mechanisms.

Phosphorus chemistry controls key aspects of eutrophication, microbial nutrition, corrosion and other environmental processes. It is commonly assumed that phosphorus occurs exclusively as phosphate (+5) in nature. In fact, although phosphate is undoubtedly dominant in many systems, phosphorus compounds with lower oxidation states (reduced phosphorus) can also be present in the environment and could be of practical importance in many circumstances. Most reduced phosphorus compounds are likely to originate in steel-making or thermal phosphorus plants. It was determined that reduced phosphorus would not be detected in routine environmental analyses even if they were present. A new method was developed to detect these compounds, and in a preliminary survey reduced phosphorus was proven to be present in water that contacts corroding iron pipes, steel slag samples, phosphorus plant wastewater, phosphite fertilizers, and in sewage treatment plant effluent. However, no evidence could be obtained for massive bio-reduction of phosphates that has been proposed by some researchers. Given that phosphorus is often a limiting nutrient, and phosphorus compounds sometimes inhibit and sometimes catalyze practically important reactions (e.g. iron corrosion), future work should examine reduced phosphorus occurrence and chemistry in greater detail. / Ph. D.

As the existing steel infrastructure inevitably continues to age and deteriorate, engineers are increasingly looking for innovative and effective methods for repairing and maintaining existing structures. Structural steel components can degrade due to the surrounding environmental conditions, and are susceptible to corrosion damage when exposed to aggressive environments and deicing salts. The conventional methods for repairing steel structures can be labor-intensive and time-consuming, and add considerable weight to the existing structure. One alternative is utilizing carbon fiber reinforced polymers (CFRP). Many studies have documented the ability of CFRPs to enhance the strength of existing structures. Furthermore, CFRP offers the benefits of being non-corrosive and having a high strength-to-weight ratio. Most studies on steel strengthening have focused on the bond behavior of CFRP to steels having a smooth surface condition, which are not representative of deteriorated structures in greater need of retrofitting. Further research has examined the durability of CFRP-steel bonds relative to environmental conditions that do not reflect the service life conditions for typical applications. In this work, a comprehensive study is conducted on the effects of the surface condition and environmental exposure on the bond between CFRP and steel. The influence of corrosion and simulated corrosion pitting is evaluated to determine whether structures with non-uniform surfaces are adequate for CFRP retrofits. In addition, the durability of CFRP-steel bonded systems is investigated through laboratory hygrothermal aging and in-situ environmental conditioning to multiple environments in Virginia. The research can be useful in the development of guidelines that will assist engineers determine if a CFRP retrofit solution is applicable in a given environmental setting and appropriate for the level of deterioration of the structure. / Doctor of Philosophy / As steel structures continue to age, engineers are looking for innovative and effective methods for repairing and maintaining the existing steel infrastructure. Steel components in structures can degrade due to the surrounding environmental conditions. The conventional methods for repairing steel structures can be labor-intensive and time-consuming, and add considerable weight to the existing structure. One alternative is utilizing carbon fiber reinforced polymers (CFRP). The ability of CFRPs to enhance the strength of existing structures has been widely documented. Furthermore, CFRP offers the benefits of being non-corrosive and avoids adding considerable weight to the structure. Most studies on steel strengthening have focused on the bond behavior of CFRP to steels having a smooth surface condition, which are not representative of deteriorated structures in greater need of retrofitting. Further research has examined the durability of CFRP-steel bonds relative to environmental conditions that do not reflect the service life conditions for typical applications. In this work, a comprehensive study is conducted on the effects of the surface condition and environmental exposure on the bond between CFRP and steel. The influence of corrosion and simulated corrosion pitting is evaluated to determine whether structures with non-uniform surfaces are adequate for CFRP retrofits. In addition, the durability of CFRP-steel bonds exposed to laboratory and field conditions is investigated. The research can be useful in the development of guidelines that will assist engineers determine if the application of CFRPs retrofit solution is suitable in a given environment and appropriate for the level of deterioration of the structure.

This research is intended to better understand the structural behavior of steel bridge beams that have experienced section loss near the bearings. This type of deterioration is common in rural bridges with leaking expansion joints, which exposes the superstructure to corrosive road deicing solutions. Seventeen beams from 4 decommissioned structures throughout Virginia were tested to induce web shear failure near the bearing locations and measured for load, vertical displacement, and web strain behavior. The strain was measured using a digital image correlation (DIC) system to create a digital strain field at equal loading and beam displacement intervals during testing. The data recorded during these large-scale tests was compared to several existing methods for calculating the shear capacity of the damaged beams. Finally, the most appropriate method of these approaches was identified based on accuracy, conservatism, and ease of implementation for load rating. When using load rating methods to determine a steel beam's capacity, this study also recommends that the effective area of the web used in determining the percentage of remaining thickness should consist of the bottom 3 inches of the web and should extend the length of the bearing plus one beam height excluding any areas without any noticeable section losses. / Master of Science / Older bridge structures typically include a rubber joint near the ends to allow for expansion and contraction of the bridge due to heating and cooling from the weather. In many cases, these joints will get damaged due to impacts from vehicle tires and other environmental disturbances. Damage to these joints allows for water to leak through, which, while not in of itself harmful, also allows melting snow to carry road salts laid in the winter to spread onto the underlying bridge steel. These salts cause aggravated corrosion of the steel beams below the bridge's deck, resulting in damage or collapse of the bridge itself. The goal of this study was to characterize this damage and determine how it affects the remaining capacity of the bridge. This objective was achieved by testing 17 beams from 4 out of service bridges with varying damage levels. A load was applied near the damaged ends to determine their behavior during loading, to locate areas of high strain resulting from corrosion, and find the beam's capacity. Several methods to predict the remaining strength in corroded steel beams were compared and recommendations made based on accuracy and conservatism.

Fretting corrosion is a form of wear which occurs at the interface of two contacting solid materials as the result of small, relative vibratory motion. It is generally identified by the presence of a red oxide, Fe203. Previously, the majority of the investigators studied the fretting corrosion between two flat specimens or between a single ball and a flat plate held in contact by a normal force. There are a number of interrelated influencing factors involved in fretting corrosion including: the vibration frequency and amplitude, the environmental conditions, the characteristics of the material, and the type of lubrication. The present investigation was conducted in order to investigate the effects of frequency and amplitude of axial vibration and the consequent accelerations acting to produce fretting damage within an unlubricated instrument ball bearing. The effect of bearing axial play on the fretting damage was also examined. The reproducibility of the damage resulting from these variables was determined. / Ph. D.

Corrosion of household copper plumbing infrastructure can cause pipe failure and lead to elevated levels of copper in drinking water which can exceed the USEPA health based standard for copper in drinking water of 1.3 mg/L Cu. The purpose of this study was to determine taste thresholds of copper in different types of water, analyze how copper chemistry can affect tasting, determine if common disinfectants influence the taste of copper and evaluate genetic links to copper sensitivity. A one-out-of-five test was used to define thresholds, evaluate disinfectant influences, and examine copper chemistry differences. A difference from control test was used to analyze soluble copper tasting and a one solution test with visual classification was used to discriminate 6-n-propylthiouracil (PROP) taster status. Solutions containing copper sulfate (0.05 – 8 mg/l Cu) were prepared in distilled water, mineral water of varying pH and mineral water with disinfectant added. Geometric mean copper taste thresholds were 0.48 mg Cu/l and 0.41mg Cu/l in distilled and mineral water pH 7.4 respectively. Logistic regression copper taste thresholds were 1.50 mg Cu/l and 1.96 mg Cu/l in distilled and mineral water pH 7.4 respectively. Soluble copper was readily tasted while particulate copper was poorly tasted. Chlorine and chloramines dosed at typical tap water levels had no significant effect on panelists' tasting abilities for water containing 1 mg/l total copper. Geometric mean copper thresholds values did not correlate with (PROP) status so PROP sensitivity would not be a good indicator for copper sensitivity. / Master of Science

Customer complaints of red water problems remain to be a frequent occurrence for water utilities. While material sources may vary, it is generally accepted that iron rust resulting from corrosion of iron based pipes is the predominant cause of red water issues. Recent efforts have lead to the development of a number of models that predict the occurrence of iron release and subsequent red water formation. This paper provides a detailed analysis of recently developed iron corrosion release models. Significant disagreement exists as to the processes and mechanisms leading to the release of iron corrosion materials into the water supply. This lack of consensus is made evident when comparing each of the iron release models. Considerable variation exists as to mechanisms considered and specific modeling goals. While each model may be beneficial for simulating certain aspects of corrosion release, no single model has been developed that provides a comprehensive portrayal of iron corrosion release phenomena. / Master of Science

Potable water can become contaminated with lead and copper due to the corrosion of pipes, faucets, and fixtures. The US Environmental Protection Agency Lead and Copper Rule (LCR) is intended to target sampling at high-risk sites to help protect public health by minimizing lead and copper levels in drinking water. The LCR is currently under revision with a goal of better crafting sampling protocols to protect public health. This study examined an array of factors that determine the location and timing of "high-risk" in the context of sampling site selection and consumer health risks. This was done using field studies and well-controlled laboratory experiments. A pilot-scale simulated distribution system (SDS) was used to examine the complex relationship between disinfectant type (free chlorine and chloramine), water age (0-10.2 days), and pipe main material (PVC, cement, and iron). Redox gradients developed in the distribution system as controlled by water age and pipe material, which affected the microbiology and chemistry of the water delivered to consumer homes. Free chlorine disinfectant was the most stable in the presence of PVC while chloramine was most stable in the presence of cement. At shorter water ages where disinfectant residuals were present, chlorine tended to cause as much as 4 times more iron corrosion when compared to chloramine. However, the worst localized attack on iron materials occurred at high water age in the system with chloramine. It was hypothesized that this was due to denitrification-a phenomenon relatively unexplored in drinking water distribution systems and documented in this study. Cumulative chemical and biological changes, such as those documented in the study described above, can create "high-risk" hotspots for elevated lead and copper, with associated concerns for consumer exposure and regulatory monitoring. In both laboratory and field studies, trends in lead and copper release were site-specific and ultimately determined by the plumbing material, microbiology and chemistry. In many cases, elevated levels of lead and copper did not co-occur suggesting that, in a revised LCR, these contaminants will have to be sampled separately in order to identify worst case conditions. Temperature was also examined as a potentially important factor in lead and copper corrosion. Several studies have attributed higher incidence of childhood lead poisoning during the summer to increased soil and dust exposure; however, drinking water may also be a significant contributing factor. In large-scale pipe rigs, total and dissolved lead release was 3-5 times higher during the summer compared to the winter. However, in bench scale studies, higher temperature could increase, decrease, or have no effect on lead release dependent on material and water chemistry. Similarly, in a distribution system served by a centralized treatment plant, lead release from pure lead service lines increased with temperature in some homes but had no correlation in other homes. It is possible that changes throughout the distribution system such as disinfectant residual, iron, or other factors can create scales on pipes at individual homes, which determines the temperature dependency of lead release. Consumer exposure to lead can also be adversely influenced by the presence of particulate iron. In the case of Providence, RI, a well-intentioned decrease in the finished water pH from 10.3 to 9.7, resulted in an epidemic of red water complaints due to the corrosion of iron mains and a concomitant increase in water lead levels. Complementary bench scale and field studies demonstrated that higher iron in water is sometimes linked to higher lead in water, due to sorption of lead onto the iron particulates. Finally, one of the most significant emerging challenges associated with evaluating corrosion control and consumer exposure, is the variability in lead and copper during sampling due to semi-random detachment of lead particles to water, which can pose an acute health concern. Well-controlled test rigs were used to characterize the variability in lead and copper release and compared to consumer sampling during the LCR. The variability due to semi-random particulate detachment, is equal to the typical variability observed in LCR sampling, suggesting that this inherent variability is much more important than other common sources including customer error, customer failure to follow sampling instructions or long stagnation times. While instructing consumers to collect samples are low flow rates reduces variability, it will fail to detect elevated lead from many hazardous taps. Moreover, collecting a single sample to characterize health risks from a given tap, are not adequately protective to consumers in homes with lead plumbing, in an era when corrosion control has reduced the presence of soluble lead in water. Future EPA monitoring and public education should be changed to address this concern. / Ph. D.

The ultimate goal of this research was to gain a more fundamental understanding of the effects of “active"? alloying elements on the performance of low voltage, aluminum, sacrificial anodes. We have developed an overview of elemental trends and a comparison with literature, in support of a larger program on predicting anode behavior. The broader impact of this work was to enhance the ability to control corrosion and reduce the likelihood of hydrogen embrittlement induced by cathodic protection on ships and marine structures. As compared to high voltage anodes, low voltage, aluminum, sacrificial anodes reduce the likelihood of causing hydrogen embrittlement or stress corrosion cracking when used to protect high strength steels. In this study, open circuit potential, potentiostatic, galvanostatic and Tafel tests were performed on eleven high-purity aluminum-based binary and ternary alloys containing Bi, Ga, In and Zn in an effort to understand the individual effects of each element and the interactions between these elements. The microstructures of the as-cast alloys and the corrosion surfaces after testing were characterized using electron microscopy. Current capacities and current capacity efficiencies were calculated from potentiostatic and galvanostatic data. Galvanic coupling data from Druschitz et al was plotted with average values from potentiostatic and galvanostatic tests on Tafel curves for all alloys. [1] Variance of weight loss, average galvanostatic current, and average potentiostatic potential of the Al-0.57 wt% Zn-0.55 wt% Bi alloy was evaluated. Indium and gallium had the most significant effect on corrosion behavior (per wt% added), followed by zinc and bismuth. Bismuth had only a small effect on the weight loss, galvanostatic current and potentiostatic potential. However during potentiostatic testing Al-Bi alloys showed a steady increase in current with time, indicating that larger effects may be seen at longer periods of time. In Al-Zn alloys preferential dissolution of the zinc-rich interdendritic regions was observed. The Al-5.3 wt% Zn alloy showed high current values, but also exhibited high weight loss and more adherent corrosion products. Interdendritic corrosion also occurred with the Al-5.3 Zn-0.011 In alloy. Also, non-uniform dissolution of the remaining primary aluminum dendrites by the formation of small holes was observed, possibly due to indium precipitates. Grain boundary attack and severe intra-granular pitting was observed in Al-In alloys. Small holes were also evident on the surface of pits, similar to those seen on dendrites with the Al-5.3 Zn-0.011 In alloy. The addition of Indium greatly shifted voltages to more negative values (-0.802 to -0.858 VSCE at 9 A/m²) and significantly increased the observed currents (42-83 A/m² at -0.730 VSCE). High potentiostatic current capacities were exhibited by Al-In alloys, Al-0.1 wt% Ga, Al-5.3 wt% Zn-0.011 wt% In, and Al-0.57 wt% Zn-0.55 wt% Bi. However some calculated current capacity values were actually above the theoretical values, possibly due to corrosion products affecting the weight loss measurements. / Master of Science