Chemical disinfection is the cornerstone of safe drinking water. However, the use of chemical disinfection results in the unintentional formation of disinfection by-products (DBPs), an outcome of reactions between the disinfectant and natural organic matter (NOM) present in the native (raw) water. DBPs are suspected carcinogens, and as such, have been regulated by the U.S. Environmental Protection Agency (USEPA) under the Safe Drinking Water Act (SDWA). This document reports the results of a study that investigated the use of chlorine dioxide pre-oxidation for the reduction of DBP precursors, and subsequently, DBP formation potential (FP). To determine the effectiveness of the chlorine dioxide pre-oxidation process, two surface waters were studied: raw water from Lake Claire (Orlando, FL) and raw water from the East Maui Watershed (Makawao, HI). Lake Claire water contains approximately 11-12 mg/L of NOM and 35 mg/L as CaCO3 of alkalinity, while the Maui source water typically ranges between 7-8 mg/L of NOM with 2-10 mg/L as CaCO3 of alkalinity. Two chlorine dioxide doses were investigated (0.75 mg/L and 1.5 mg/L) and compared to a control to quantify the effectiveness of this advanced pre-treatment oxidation process. Water collected at each site was subject to the following treatment process: oxidation, coagulation, flocculation, sedimentation, ultrafiltration, and disinfection with free chlorine. Disinfection by-product formation potential (DBPFP) analysis showed that ClO2 pre-oxidation, in general, increased the 7-day DBPFP of the East Maui water, and decreased the 7-day DBPFP of the Lake Claire source water. For the Lake Claire water at the higher ClO2 dose, total trihalomethanes (TTHM) were decreased by 37 percent and the five regulated haloacetic acids (HAA5) by 23 percent. For the East Maui source water at the higher ClO2 dose, TTHM’s were increased by 53 percent and HAA5’s by 60 percent. Future research should determine the effect of alkalinity on DBPFP, which could be the reason why chlorine dioxide pre-oxidation caused one water source’s DBPFP to decrease and the other to increase.

Raw water samples from nine utilities were received, and water-quality analyses, bench-scale water treatment, and chlorination were performed to determine the effectiveness of enhanced coagulation at removal of dissolved organic carbon (DOC) and organic halide precursors. Bench-scale treatment included: 1) baseline treatment, defined as the coagulant dose and pH at which the specific utility's water treatment plant was operating on the day the samples were collected, and 2) enhanced treatment, which was determined on the basis of bench-scale studies. Enhanced treatment is defined in the proposed Disinfectant/Disinfection By-Products (D/DBP) Rule as the coagulant dose at which a 10 mg/L increase in coagulant dose does not produce greater than a 0.3 mg/L decrease in dissolved organic carbon (DOC) or total organic carbon (TOC) concentration over the previous dose (Federal Register 1994). The treated samples were then chlorinated and analyzed for disinfection by-products (DBPs), including trihalomethanes (THMs) and non-purgeable dissolved organic halides (NPDOX). Specific objectives included: 1) an evaluation of the effectiveness of enhanced coagulation for TOC reduction, 2) determination of the effectiveness of surrogate parameters: such as raw water DOC and specific ultraviolet absorbance (SUVA); for predicting TOC removal by enhanced coagulation, and 3) determination of the relationship between DOC and NPDOX concentration in raw and treated waters. For all of the utilities, enhanced coagulation was effective at meeting the proposed TOC removal requirements contained in the D/DBP Rule, which range from 20 percent to 50 percent removal based on the alkalinity and TOC of the raw water. Raw water SUVA was the best indicator of the expected Toe removal by enhanced coagulation, with raw water SUVA values > 3.0 L/mg-m typically indicating greater TOC removal. Organic content was a good indicator of DBP formation. The average non-purgeable dissolved organic halogen formation potential (NPDOXFP) yields, based on DOC, were 155 μg as Cl⁻/mg DOC for raw water samples and ranged from 110- 138 μg as CI⁻/mg DOC for treated water samples. / Master of Science

As the population in water stressed areas increases, it is critical that wastewater treatment plants (WWTPs) continue to replenish depleted water supplies, and serve as an alternative water source. WWTPs depend on microorganisms in activated sludge to remove pollutants from wastewater and therefore an understanding of how these microorganisms are affected by various conditions and pollutants is needed. Also, as consumer products and industrial processes evolve, so do the pollutants they discharge to wastewater. In order to keep pace with these changes, understanding the effects of emerging contaminants to WWTP processes is essential. The research herein assesses microbial community dynamics of the response of nitrifying microorganisms in activated sludge to variation in ammonia concentration and evaluates the impact of engineered nanoparticles on activated sludge microbial communities and other emerging pollutants, such as antibiotic resistance genes and disinfection by-products. In order to assess microbial community dynamics of the response of nitrifying microorganisms to removal of ammonia in the feed, nitrifying activated sludge reactors were operated at various relevant temperatures and the nitrifying microbial community was characterized using activity assays and bio-molecular techniques. We found that Nitrospira spp. were the dominant nitrifying microorganisms, exhibiting stable relative abundance across multiple trials and over a range of temperatures. These results indicate the possibility of comammox bacteria in the system and highlight the complexity of nitrifying microbial communities in activated sludge relative to past understanding. Both microbial and chemical impacts of engineered nanoparticles on WWTP processes were also investigated. Metagenomic analysis of DNA extracted from activated sludge sequencing batch reactors dosed with gold nanoparticles with varied surface coating and morphology indicated that nanoparticle morphology impacted the microbial community and antibiotic resistance gene content more than surface coating. However, nanoparticle fate was controlled by surface coating more than morphology. Disinfection by-product formation in the presence of nanoparticles during WWTP disinfection was assessed using silver, titanium dioxide, ceria, and zero valent iron nanoparticles. Silver nanoparticles were found to enhance trihalomethane formation, which was attributed to the citrate coating of the nanoparticles. These studies both raise concern over the relationship between engineered nanoparticles and other emerging concerns in WWTPs, and take a step towards informing nanoparticle design in a manner that limits their associated environmental impact. / Ph. D.

To mitigate microbial activity in swimming pools and to assure hygienic safety for bathers, pool systems have a re-circulating water system ensuring continuous water treatment and disinfection by chlorination. A major drawback associated with the use of chlorine as disinfectant is its potential to react with organic matter (OM) present in pool water to form potentially harmful disinfection by-products (DBP). In this thesis, the treatment performance of different combinations of conventional and novel treatment processes was compared using a pilot scale swimming pool model that was operated under reproducible and fully controlled conditions. The quality of the pool water was determined in means of volatile DBPs and the concentration and composition of dissolved organic carbon (DOC). Further, overall apparent reaction rates for the removal of monochloramine (MCA), a DBP found in pool water, in granular activated carbon (GAC) beds were determined using a fixed-bed reactor system operated under conditions typical for swimming pool water treatment. The reaction rates as well as the type of reaction products formed were correlated with physico-chemical properties of the tested GACs.

To mitigate microbial activity in swimming pools and to assure hygienic safety for bathers, pool systems have a re-circulating water system ensuring continuous water treatment and disinfection by chlorination. A major drawback associated with the use of chlorine as disinfectant is its potential to react with organic matter (OM) present in pool water to form potentially harmful disinfection by-products (DBP). In this thesis, the treatment performance of different combinations of conventional and novel treatment processes was compared using a pilot scale swimming pool model that was operated under reproducible and fully controlled conditions. The quality of the pool water was determined in means of volatile DBPs and the concentration and composition of dissolved organic carbon (DOC). Further, overall apparent reaction rates for the removal of monochloramine (MCA), a DBP found in pool water, in granular activated carbon (GAC) beds were determined using a fixed-bed reactor system operated under conditions typical for swimming pool water treatment. The reaction rates as well as the type of reaction products formed were correlated with physico-chemical properties of the tested GACs.

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Contexte. La chloration est le traitement le plus utilisé pour désinfecter l’eau distribuée à la population. Lors du traitement, des sous-produits de chloration (SPCs) se forment par réaction de la matière organique naturelle présente dans l’eau avec le chlore. Les produits les plus présents sont les trihalométhanes (THMs), les acides haloacétiques (HAAs). Des études toxicologiques (animales et in vitro) ont montré la génotoxicité et/ou carcinogénicité et la reprotoxicité de certains SPCs. Nous avons mené deux études évaluant les effets sur la santé humaine de l’exposition aux SPCs, dans le domaine du cancer et de la reproduction. Association entre exposition aux THMs et risque de cancer de la vessie : une analyse poolée de 3 études cas-témoins européennes. Cette analyse a inclus 2381 cas et 3086 témoins issus de 3 études cas-témoins (France, Espagne, Finlande). L’exposition environnementale aux SPCs a été mesurée par la concentration en THMs estimée rétrospectivement dans les réseaux de distribution d’eau au cours des 40 années de la fenêtre d’exposition. Les usages de l’eau connus sont l’ingestion, les douches et les bains, la fréquentation de piscine (étude espagnole seulement). Une relation croissante a été observée entre le niveau environnemental de THMs, la durée d’exposition à une eau de surface chlorée et le risque de cancer de la vessie, chez les hommes uniquement. Aucune association n’a été observée avec l’exposition via l’ingestion d’eau du robinet. L’exposition via les douches, les bains et la piscine est apparue liée au risque de cancer de la vessie. Trois études cas-témoins nord-américaines ont été intégrées dans une méta-régression. Aucune spécificité européenne de la relation dose-réponse n’a été mise en évidence. Une relation dose-réponse globale incluant 4351 cas et 7055 témoins a été estimée. Association entre exposition aux SPCs et risque de prématurité et de retard de croissance intra-utérin (RCIU). Cette étude est issue de la cohorte bretonne Pélagie (3400 femmes enceintes recrutées en début de grossesse entre 2002 et 2006). L’exposition pendant la grossesse a été mesurée à l’aide de 2 indicateurs : la concentration en THMs de l’eau distribuée dans les réseaux et le dosage d’un biomarqueur urinaire (acide trichloroacétique) pour un sous-échantillon de femmes (étude cas-témoins nichée). Les niveaux dans les réseaux proviennent de la base de données réglementaire SISE-Eaux. Les usages de l’eau du robinet par les femmes pendant la grossesse ont été collectés par questionnaire (quantité d’eau du robinet bue, fréquentation de la piscine, fréquence et durée des douches et des bains). Notre étude suggère une association entre l’exposition prénatale aux SPCs et le risque de RCIU. Aucune association n’est observée avec le risque de prématurité. / Background. Chlorine is the most widely used disinfectant for drinking water treatment. During treatment process, the natural organic matter present in water reacts with chlorine to form disinfection by-products (DBPs), such as trihalomethanes (THMs) and haloacetic acids (HAAs), the most occurring ones. Several identified DBPs were recognized carcinogens or fetotoxic in animals. We conducted two epidemiological studies to assess the health effects of human exposure to DBPs regarding cancer and reproduction. Association between THM exposure and the risk of bladder cancer: a pooled analysis of 3 European case-control studies. The study included 2381 cases and 3086 controls from 3 case-control studies (France, Finland, Spain). Environmental exposure to SPCs was measured by THM concentrations in water distribution systems, retrospectively estimated through the 40-year exposure window. Information about water uses (tap water ingestion, showers and baths, swimming-pool attendance) was available. An increased risk of bladder cancer was observed, in men only, with increasing THM concentrations in water systems and duration of exposure to chlorinated surface water. No association was observed with exposure through tap water ingestion. Exposure through showers, baths and swimming in pools (available in Spanish study only) was associated with an increased risk of bladder cancer. Three North-American case-control studies were joined to the three European ones into a meta-regression. No specific dose-response relationship was identified for European studies. A global dose-response relationship was consequently estimated, including 4351 cases and 7055 controls. Association between DBP exposure and the risk of preterm birth and Intra-Uterine Growth Retardation (IUGR). This study was conducted within the PELAGIE cohort (3400 pregnant women included in early pregnancy, in Brittany, France, between 2002 and 2006). Exposure during pregnancy was measured by 2 indicators: THM concentrations in water distribution systems and a biomarker of HAA ingestion, the level of trichloroacetic acid in maternal urine at inclusion (in a nested case-control study). The regulatory database SISE-Eaux was used to estimate THMs concentrations in the water distribution systems. Water uses during pregnancy (ingested tap water, swimming-pool attendance, showers and bath frequencies and duration) were collected with questionnaires. Our results suggest an association between prenatal exposure to DBPs (THMs and HAAs) and the risk of IUGR. No association was found with the risk of preterm birth.

A new technique for sample preparation and trace analysis of organic pollutants in water using mixed-phase thin film (MPTF) devices, combined with direct thermal desorption, cold trapping, gas chromatography-mass spectrometry (GC-MS) is presented for the first time. Two novel analytical devices, Carboxen/polydimethylsiloxane (CAR/PDMS) and polydimethylsiloxane/divinylbenzene (PDMS/DVB) TF samplers were fabricated using spin coating technique and glass wool fabric mesh as substrate. The samplers were easily tailored in size and shape by cutting tools. Good durability and flat-shape stability were observed during extractions and stirring in water. The latter characteristic obviates the need for an extra framed holder for rapid thin film microextraction (TFME) and makes the samplers more robust and user-friendly. The analytical performance of the MPTF devices was satisfactorily illustrated and compared with those of solid phase microextraction (SPME) fibers and PDMS thin film membrane using water samples spiked with seven N–nitrosamines (NAs), known as disinfection by-products (DBPs) in drinking water. Marked enhancement of extraction efficiencies (typically more than one order of magnitude) for the N-nitrosamines, including the hydrophilic ones, was obtained with the MPTF devices under generally pre-equilibrium conditions, compared to the SPME fibers and PDMS thin film membrane. The analytical results obtained in this study, including linearity, repeatability and detection levels at low ng/L for the tested compounds, indicate that the new thin film devices are promising for rapid sampling and sample preparation of trace levels of polar organic pollutants in water with sensitivities higher than SPME fibers and with a wide application range typical of mixed-phase coatings. The user-friendly format and robustness of the novel devices are also advantageous for on-site applications, which is the ultimate use of thin film samplers. Moreover, the thin film fabrication approach developed in this study offers the possibility of making other novel samplers with PDMS or different absorptive polymers such as polyacrylate (PA) and polyethylene glycol (PEG) as particle-free, or as particle-loaded thin films with a variety of adsorptive solid particles. In another development in the course of this research, the performance and accuracy of the SPME fiber approach for sample preparation of selected DBPs were demonstrated and compared with the conventional liquid-liquid extraction (LLE) method by real drinking water samples analysis in collaboration with Health Canada. Four regulated trihalomethanes (THMs) and seven other DBPs known as priority by-products, including four haloacetonitriles, two haloketones and chloropicrin, were analyzed in real samples during two separate comparative studies. In each study, duplicate samples from several water treatment and distribution systems in Canada, collected and stabilized under the same protocol, were analyzed in parallel by two independent labs; in the University of Waterloo by an optimized headspace SPME-GC-MS and in Health Canada by a LLE-GC-ECD (electron capture detection) method equivalent to EPA 551.1. The values for the concentration of the analytes in the samples obtained by the two methods were in good agreement with each other in majority of the cases indicating that SPME affords the promise of a dependable sample preparation technique for rapid DBPs analysis. In particular, it was shown that the SPME fiber approach combined with GC-MS is a fast reliable alternative to the LLE-GC-ECD (EPA 551.1) method for analysis of the regulated THMs in the concentration ranges that are typical and relevant for drinking water samples.

Disinfectants in drinking water can interact with natural organic matter (NOM) to form disinfection by-products (DBPs). Halogenated furanones (including MX and MCA) are a group of emerging DBPs that can account for a significant amount of the total mutagenicity found in drinking water. Source water characteristics and NOM removal capabilities of coagulation can greatly influence the formation of DBPs. This project examines the effects of bench scale coagulation and chlorination tests on NOM removal, DBP formation, and genotoxicity. NOM was characterized using liquid chromatography-organic carbon detection (LC-OCD). Experiments with Ottawa River, Otonabee River, and Lake Simcoe waters show that DBPs decreased with increases in coagulant dosage, due to the removal of NOM during coagulation. DBP formation and speciation was then compared with NOM content to identify specific fractions that contribute to the formation of these DBPs. Genotoxicity was directly linked to MX presence in chlorinated waters.