The prevalence and mode of persistence of Salmonella on commercial poultry processing equipment was examined in this study. The equipment surfaces of six commercial processing plants were sampled over three-time periods designated as A (after processing), B (after cleaning), and C (after sanitization) and each plant was visited three times. Salmonella prevalence was greater (p<0.0001) at time A than times B and C, while there were no differences (p=0.386) between times B and C. A total of twentyive Salmonella isolates from five distinct serovars were recovered from the processing plants. Further examination of the recovered isolates showed that tolerance to sanitizing agents (chlorine and quaternary ammonium compounds, QAC) and/or biofilm formation was the possible mode of persistence. In addition, all the isolates were resistant to multiple antibiotics in different classes of drugs and more than two genes that are responsible for ⅰ). biofilm formation, ⅱ). resistance to QAC, ⅲ). oxidative stress response, and ⅳ). resistance to antibiotics were detected. Three selected isolates were further characterized based on virulence factors and antimicrobial resistance using whole genome sequencing (WGS) to possibly predict phenotypic characteristics. The WGS data correlates with phenotypic characteristics that were previously observed in the isolates including the ability to produce biofilms and resistance to antibiotics including β-lactams, aminoglycosides, and cephalosporins. WGS predicted the isolates carried resistance genes for antibiotic drug classes that were not observed phenotypically. These include macrolides and fluoroquinolone, which is a concern due to its use in treating foodborne infection. Furthermore, the genome of the three selected isolates were predicted to have over sixty virulence genes that allow Salmonella to invade, attach, and colonize the host cells. The results from this study suggest that the antimicrobials used for sanitization may be insufficient to inactivate Salmonella because of the ability to produce biofilms on processing surfaces. Most importantly, the results suggest the ability of the isolates to cause infection in humans meaning if contamination were to occur, the right antibiotic treatment could be a challenge. Further research is imperative to determine the effective antimicrobial for Salmonella biofilms.

No description available.

No description available.

In this thesis, low-cost free chlorine sensors for monitoring drinking water have been developed. The starting material, pencil lead, was modified using a ammonium carbamate solution. The main emphasis for this technology is the low cost, scalable and environmental friendly process. The resultant materials were highly sensitive to free chlorine. The second discovery was an advanced understanding of the unsteady state mass transfer during the sensing process, using the customly expanded Cottrell equation. This method could qualitatively indicated the absence of free chlorine, for applications where the removal of free chlorine is the goal. This method allowed better interpretation of transient data and simplified setup. The third discovery was the use of pulsed amperometric detection to detect free chlorine at a much higher sensitivity, while reducing the complexity of the setup, further reducing the cost. This method was based on the previous findings plus understanding of the reaction kinetics. The resultant sensors detected free chlorine with a detection of 0.0414 ppm, while the regulations require the free chlorine to be above 0.2 ppm. The response time was less than three seconds. The range of detection was up to around 20 ppm. The cost of materials for one sensor was less than ten dollars. The maintenance was minimal due to the lack of consumables. The operation could be as a meter or as a device in a large instrument. The target use of the sensors include small and distant communities, bottling industries, fruit and vegetable washing industries. The free chlorine sensing techniques can be readily expanded to biology, environment, and big data applications, based on the knowledge gained through the study. / Thesis / Doctor of Philosophy (PhD) / Low-cost sensors were developed to monitor free chlorine in drinking water for end users, especially in small and distant communities. Free chlorine keeps lethal microorganism pathogens from re-growing after disinfection. Re-growth is more likely to happen in these communities due to poor infrastructure and less usage-driven flow. The contributions include: • A low-cost sensing material for free chlorine based on pencil lead • Determination of operating range of the sensor • Study of sensing mechanisms • Efficiency improvement and cost reduction • Research articles, conference presentations, patent applications, and industrial collaboration based on above research The resultant sensor is easy to use, robust in practical conditions and requires low maintenance, suitable for small and distant communities. Future work is the integration with sensing systems and the application of knowledge gained in this thesis for sensing applications in other fields.

Pharmaceuticals and personal care products (PPCPs) include a wide range of chemicals such as prescription and over-the-counter drugs, fragrances, diagnostic agents, and a litany of other compounds commonly added to household products such as sunscreens, soaps, toothpastes, and deodorants. If present in natural waters, PPCPs can come into contact with disinfectants during drinking water treatment processes. PPCPs are already known to form a variety of disinfection byproducts (DBPs) when oxidized by free chlorine, including trihalomethanes (THMs) and haloacetic acids (HAAs), many of which are known carcinogens. Salts, such as iodide, are also often present in natural water systems. Iodide is known to form a much more reactive oxidant, free iodine, when it reacts with free chlorine. Free iodine can react with organic compounds in waters to form iodinated byproducts, many of which have been shown to form in higher yields and to be more toxic than their chlorinated analogues. For this reason, it is necessary to more fully understand the fate of PPCPs during drinking water processes. The overall goals of this study are to 1) elucidate reaction mechanisms and product formation potentials for PPCP oxidation by free chlorine in the presence of iodide and 2) develop a computer model that can act as a predictive tool to aid in the assessment of potential risks resulting from PPCPs in source waters. Through the course of this research, a model was developed that could fit reaction rate parameters and accurately predict solution reactivity for a range of substituted phenols as well as PPCPs including bisphenol-A and triclosan. Past studies utilizing pseudo-first-order rate constants to determine a reaction rate over-simplified the analysis of halogen substitution reactions. Free chlorine reaction rate constant values were updated from the literature since the mechanism for electrophilic substitution was found to be different than stated in currently published literature. The involvement of H₂OCl⁺ was found to be negligible. The mechanism for the electrophilic substitution of phenolic compounds by free iodide was also different from current literature findings. We found that I₂, rather than H₂OI⁺, was an extremely important species for free iodine reactions and must be considered when analyzing the reaction kinetics. Finally, we found that small amounts of iodide can significantly affect product formation pathways thereby causing preferential formation of iodinated products and a potential increase in the total product formation. In general, the reaction kinetics were highly dependent upon the pH, iodide to free chlorine ratio, and the reactivity of the phenolic compound, and our model was able to successfully address changes in each of these variables. An LFER was developed that showed a linear relationship between reaction rates and the pK_a of a phenolic compound. It is believed that the model developed can be used as a predictive tool to estimate reactivity of natural waters for a range of phenolic PPCPs simply by using the compounds pK_a. / Ph. D.

Four commercially available methods used for the analysis of low-level Chlorine Dioxide (ClO2) concentrations in drinking water were evaluated for accuracy and precision and ranked according to cost, efficiency and ease of the methods under several conditions that might be encountered at water treatment plants. The different analytical methods included: 1.The DPD (N, N-diethyl-p-phenylenediamine) method 2.Lissamine Green B (LGB) wet-chemical method 3.Palintest® kit LGB 4.Amperometric titration All these tests were performed with standard 1.0 mg/L ClO2 either alone or in the presence of different chlorine species, including chlorite ion (ClO2-, 0.5 mg/L), chlorate ion (ClO3-, 0.5 mg/L) and chlorine (Cl2, 1.0 mg/L). The tests were performed with four different matrices, with different concentrations of 0.1 mg/L ClO2, 0.5 mg/L ClO2 and 1.0 mg/L ClO2 at a constant temperature of 20oC and at different temperatures of 0oC, 10oC and 20oC at a fixed ClO2 concentration of 1.0 mg/L. None of the four methods produced the desired level of either accuracy or precision. For all four methods, interference to the measured ClO2 concentration from the addition of ClO2-, ClO3-, and Cl2 was minimal when the methods were performed according to specifications. The Palintest® was the best all-round method because it was easy to perform, performed well at all concentrations tested, and its colored product was stable. The HACH® DPD method was also easy to perform and gave the best results when measuring concentrations of 1.0 mg/L ClO2. The DPD method was less accurate than the Palintest® at lower concentrations. The DPD colored product that formed upon reaction of ClO2 and DPD was unstable, making it necessary to measure the intensity of the colored product at exactly 1 minute. The amperometric titration and lissamine green methods were more cumbersome and time-consuming to perform than either the DPD or Palintest® methods; for this reason they are less desirable for routine use. / Master of Science

Triclosan, 5-chloro-2-(2,4 dichlorophenoxy)phenol, is an anti-microbial additive in a plethora of Pharmaceutical and Personal Care Products (PPCPs) including, toothpastes, hand creams and soaps, and acne creams. Because many triclosan containing products are topical solutions that are readily washed down the drain, significant quantities of triclosan can be introduced to wastewater treatment systems and eventually, to surface waters. Consequently, triclosan has become a contaminant of concern. The reactions between triclosan and free chlorine have been examined previously; however, no kinetic data for these reactions have been reported for conditions typical of drinking water treatment. This investigation focused specifically on the kinetics of the triclosan and free available chlorine (FAC) reactions under drinking water treatment conditions. Triclosan readily reacted with free chlorine via a second-order reaction (first order with respect to each species). No significant temperature dependency was observed from 8 to 25 °C. The reaction stoichiometry was determined to be 1:1 (triclosan oxidized per free chlorine reduced and did not vary over the pH range examined (pH 4-12). However, the reaction rate coefficients exhibited a significant pH dependency. A model that incorporates the rate coefficients for the reactions between HOCl and both neutral and anionic forms of triclosan was generated to fit the experimental data. The anionic free chlorine species hypochlorite (OCl-) was determined to play an insignificant role in the overall rate of reaction, and therefore, only the reactions involving HOCl were incorporated into the model. Additionally, a hypothesized reaction mechanism was tentatively shown to fit the collected data and its strong pH dependency. / Master of Science

Laboratory bioassays results suggest that early life stages of freshwater mussels are sensitivity to toxicants. However, toxicological databases for unionids are rather limited because standard test methods are yet developed, and no published studies report endpoints for chronic test that are > 9 days. The primary goals of my thesis research were to assess acute and chronic toxicities of chlorine and mercury to early life stages. Inter- and intra-specific species variability in the tolerances of glochidia was observed during acute laboratory bioassays as endpoints were between 8 - 43 ppb for Hg tests, 1.0 - 2.5 ppm for NaCl tests, and 70 - 260 ppb for chlorine (TRC) tests. Glochidia of several species had equal or greater sensitivities to Hg and NaCl than test organisms commonly used to assess environmental risk (i.e.Ceridaphnia dubia, Daphnia magna, Pimephales promelas), whereas they were far more tolerant to TRC than many species. Twenty-one day chronic test endpoints for juveniles were substantially lower than those calculated during acute bioassays with glochidia. Villosa iris 3-mo old juveniles were found to be quite sensitive to Hg as growth was significantly impaired at 8 ppb Hg. Chronic bioassays with TRC revealed a distinct decrease in susceptibility with increased aged for V. iris (relative sensitivities 3-mo > 6-mo > 12-mo), and that 2-mo old Epioblasma capsaeformis were more sensitive than comparable age classes of V. iris. However, both species were tolerant compared to other aquatic organisms, as the lowest endpoint was 20 ppb TRC. / Master of Science

In order to determine how solvents control the stereochemical course of the hot substitution reactions, the stereochemistry of the energetic ³⁸Cl for Cl was studied in diastereomeric 1,2-dichloro-1,2-difluoroethane and the geometric isomers of 1,2-dichlorohexa-fluorocyclobutane. In each system, the conformer population was determined by NMR and dipole moment techniques. A comparison was made between the changes of the stereochemical course of the substitution reaction and the concentration and nature of the solvent. The results presented in this investigation indicate that the stereochemical course of a hot atom substitution reaction is directly controlled by solvents participating in the de-excitation stabilization of excited compounds or in the relaxation process of intermediate radicals. This work also indicates that the nature of the solvent cage wall can control the progress of the hot reaction. Abstraction reactions of the Cl can occur in the cage with the compounds composing the cage wall. These reactions can effectively change the stereochemical course of the hot substitution reaction. It appears that the liquid phase hot atom substitution reactions observed in this investigation are best explained by the caged radical-radical combination model. Strong solute-solvent interactions reduce the time for relaxation of the radicals in the solvent cage thus preventing the radicals from obtaining planarity and consequently retention products. On the other hand, weak solute-solvent interactions increase the time for relaxation of the intermediate which leads to a racemization of reaction products. / 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