Many Canadian water treatment plants supplied by surface waters of the Canadian Prairie and Shield have elevated concentrations of trihalomethanes (THMs), which exceed the provincial standards. These water sources are characterized by elevated levels of dissolved organic carbon (DOC) and varying levels of calcium hardness, which causes a challenge for the removal of THMs precursors. The objective of this study was to investigate the effect of two treatment methods: chemical coagulation and pre-ozonation-coagulation on the removal of DOC as the main THMs precursor. Surface waters typical for the Canadian Prairie and Canadian Shield were used in the experiments which includes Assiniboine River, Red River, and Rainy River. The effects of different experimental conditions such as coagulant dose, coagulant type, and solution pH as well as ozone dosage on THMs removal were investigated. The structural and chemical characteristics of natural organic matter and isolated humic substances, before and after the reaction with ozone, were studied using spectroscopic techniques. The results illustrated that the quality of source water (DOC characteristics, concentration of water DOC and Calcium) has a significant impact on THMs reduction by chemical coagulation and ozonation. Coagulation results showed that reduction of total DOC does not guarantee THMFP reduction and chemical coagulation should be optimized to remove the hydrophobic acid fraction which forms most THMs. The removal of DOC by aluminum-based coagulants was affected more by the concentration of polymeric and colloidal aluminum speciation. This finding is especially important for plants supplied by high alkalinity waters where pH adjustment is a serious challenge. The effect of pre-ozonation on coagulation varies depending on the concentration of calcium, which has the ability to form complexes with DOC compounds promoting their removal in coagulation. For the surface water with high levels of organic carbon and calcium hardness, ozonation prior to coagulation was beneficial in terms of DOC reduction. However, it showed the opposite effect on water with high levels of DOC accompanied with low level of calcium hardness. Spectroscopic results showed that ozonation of NOM and humic substances cause a significant reduction of aromatic and highly conjugated compounds (constituting primarily the hydrophobic acid fraction). / February 2016

Disinfection is an essential process in the treatment of municipal wastewater before the treated wastewater can be discharged to the environment. Hillsborough County's Northwest Regional Water Reclamation Facility (NWRWRF) in Tampa, Florida, currently uses ultraviolet (UV) light for disinfection. However, this method has proven expensive to implement and maintain, and may not be effective if the light transmission is poor. For these reasons, Hillsborough County is considering switching from UV light to sodium hypochlorite for disinfection. However, hypochlorite (chlorine) disinfection has disadvantages as well, such as the production of disinfection by-products (DBPs) such as trihalomethanes (THM) and haloacetic acids (HAAs), which may have adverse impacts on the quality of surface waters that receive the treated wastewater. Therefore, the objectives of this research are (1) to compare NWRWRF typical operating conditions and water quality to those of two nearby facilities (River Oaks and Dale Mabry Advanced Wastewater Treatment Plants) that currently employ chlorine disinfection, (2) to determine the chlorine demand of treated effluent from NWRWRF, (3) to quantify the DBP formation potential of treated effluent from NWRWRF, and (4) to determine the effects of temperature, reaction time, and chlorine dose on chlorine demand and THM formation. To inform laboratory experiments, the quality of final effluent was monitored at NWRWRF and at two nearby wastewater treatment plants that currently use hypochlorite for disinfection. At these two facilities, pH of 7.0-8.0, chemical oxygen demand (COD) of 12-26 mg/L, alkalinity of 200-250 mg/L as CaCO3, chlorine residual of 1.5-6.0 mg/L, and total trihalomethanes of 100-190 ix μg/L (mostly chloroform) were observed. Conditions at NWRWRF were similar to those at Dale Mabry and River Oaks AWWTP, suggesting that chlorine demand and THM formation at NWRWRF would be similar to those at the two AWWTP, if chlorination is to be used. THM experimental results agreed with this suggestion. Chlorine dose and temperature effects on the free chlorine residual and THMs production in NWRWRF filtered wastewater effluent were determined. Filtered effluent was collected and transported to USF laboratory where it was tested for 3 different chlorine doses (6 mg/L, 9 mg/L and 12 mg/L as Cl2) and 3 different temperatures (16°C, 23°C, and 30°C) at 7 different contact times (15, 30, 45, 60, 75, 90, and 120 min) in duplicate. The total number of batches prepared was: 3 different chlorine doses × 3 different temperatures × 7 different reaction times = 126 reactors. According to Florida Administrative code 62-600.440, total chlorine residual should be at least 1 mg/L after a contact time of at least 15 min at peak hourly flow. Also, according to Florida Administrative code 62-600.440, if effluent wastewater has a concentration of fecal coliforms greater than 10,000 per 100 mL before disinfection, FDEP requires that the product of the chlorine concentration C (in mg/L as Cl2) and the contact time t (in minutes) be at least 120. Results showed that free chlorine residual was always above 1 mg/L in 15 min contact time for all chlorine doses and temperatures tested in this thesis. However, to be conservative, thesis conclusions and recommendations were based on the more stringent regulation: C*t ≥ 120 mg.min/L, assuming that the number of fecal coliform in NWRWRF wastewater effluent exceeds 10,000 per 100 mL prior to disinfection. The analysis showed that free chlorine residual for 6 mg/L was below the FDEP standard at all temperatures. At 16 °C and 23 °C, chlorine doses of 9 and 12 mg/L resulted in an appropriate free chlorine residual above the FDEP standard. However, a chlorine dose of 12 mg/L was resulting in high residual, which means high THM would be expected. Therefore, at 16 x and 23°C, 9 mg/L would be preferable. At 30 °C, only the chlorine dose of 12 mg/L met the standard at all contact times. As expected, free chlorine residual decreased with an increase in temperature from 23°C to 30°C. Surprisingly, the residual at 16°C was lower than residual at 23°C. The production of THMs increased with higher contact time in all the experiments completed. Chlorine dose didn't have an effect on THM formation at 23°C, but it did at 30°C and 16°C, where THM concentrations were generally higher with the increase of chlorine dose. Temperature effect was noticed in most of the experiments, where THM production was usually higher at higher temperatures, except some cases where formation was similar for different temperatures. Chloroform, dichlorobromomethane, dibromochloromethane production ranges were respectively: 20-127 μg/L, 18-59 μg/L, and 3-7 μg/L. Bromoform concentrations were not observed in this experiment at any temperature or chlorine dose. According to Florida Administrative code 62-302.530, Criteria for Surface Water Quality Classifications, the Florida Department for Environmental Protection (FDEP) set the following limits for THM concentrations in wastewater effluent to be as the following; 470 μg/L for chloroform, 22 μg/L for dichlorobromomethane, 34 μg/L for dibromochloromethane, and 360 μg/L for bromoform. Experimental results on NWRWRF filtered effluent showed that only dichlorobromomethane exceeded the limits set by FDEP at about 30 min contact time for all temperatures and chlorine doses tested. However, according to Florida Administrative code 62- 302-400, proposed changes to the code have set higher DCBM limit of 57 μg/L. Chlorination would be recommended at NWRWRF if the DCBM regulated limit increases to 57 μg/L. The recommended chlorine dose would be 9 mg/L for water temperatures around 16-23 °C and 12 mg/L for water temperatures around 30 °C

The main theme of this thesis is the usage of the test investigating the formation potential of trihalogenmethanes (THM FP) and its comparison with conventional indicators of water quality (CODMn, A254 and colours). As for the experimental part of the thesis, rating of the effectiveness of selected technological procedures has been applied (e.g.: coagulation, adsorption and ozonation in the act of treatment of artificially prepared water model with a higher content of humic substances in laboratory conditions). Based on the obtained results, it was found that the common indicators of water quality have very similar attributes and also complete each other. On the contrary, those attributes of indicators may not be sufficient in case of the evaluation of water quality with high content of humic substances. The findings made illustrate that the THM FP test enables the accurate evaluation of water quality, especially in connection with the content of an organic material susceptible to chemical changes. THM formation potential has proved its high value and also has confirmed that it can appropriately complete the other standarts that are being used for assessing the quality of treated water up to nowadays.

Historically, chlorination has been widely utilized as a primary and secondary disinfectant in municipal water supplies. Although chlorine disinfection is effective in inactivating pathogenic microbes, the use of chlorine creates the unintentional formation of regulated chemicals. On January 4, 2006, the United States Environmental Protection Agency (EPA) promulgated the Stage 2 Disinfectants/Disinfection by-product rule (DBPR) that focuses on public health protection by limiting exposure to four trihalomethanes (THM) and five haloacetic acids (HAA5), formed when chlorine is used for microbial pathogen control. This thesis examines post-aeration TTHM formation when employing spray-aeration processes to remove semi-volatile TTHMs from chlorinated potable water supplies. A bench scale air stripping unit was designed, constructed and operated to evaluate spray aeration for the removal of the four regulated trihalomethane (THM) species from potable drinking water including bromodichloromethane, bromoform, dibromochloromethane, chloroform. The study was conducted using finished bulk water samples collected from two different water treatment facilities (WTFs) located in Oviedo and Babson Park, Florida. Both treatment plants treat groundwater; however, Oviedo's Mitchell Hammock WTF (MHWTF) supply wells contain dissolved organic carbon and bromide DBP precursors whereas the Babson Park WTF #2 (BPWTF2) supply well contains dissolved organic carbon DBP precursors but is absent of bromide precursor. Three treatment scenarios were studied to monitor impacts on total trihalomethane (TTHM) removal and post-treatment (post-aeration) TTHM formation potential, including 1) no treatment (non-aerated control samples), 2) spray aeration via specially fabricated GridBee® nozzle for laboratory-scale applications, 3) spray aeration via a commercially available manufactured BETE® nozzle used for full-scale applications. Select water quality parameters, chlorine residual, and total trihalomethane concentrations were monitored throughout the study. The GridBee® spray nozzle resulted in TTHM removals ranging from 45.2 ± 3.3% for the BPWTF2 samples, and 37.7 ± 3.1% for the MHWTF samples. The BETE® spray nozzle removed 54.7±3.9% and 48.1±6.6% of total trihalomethanes for the Babson Park and Mitchell Hammock WTF samples, respectively. The lower percent removals at the MHWTF are attributed to the detectable presence of bromide and subsequent formation of hypobromous acid in the samples. Post spray aeration TTHM formation potentials were monitored and it was found that the MHWTF experienced significantly higher formation potentials, once again due to the presence of hypobromous acid which led to increases in overall TTHM formation over time in comparison with the Babson Park WTF #2 TTHM formation samples. In addition, chlorine residuals were maintained post spray aeration treatment, and initial chlorine residual and trihalomethane concentrations did not significantly impact overall spray nozzle performance. Among other findings, it was concluded that spray nozzle aeration is a feasible option for the Babson Park WTF #2 for TTHM compliance. For Oviedo's Mitchell Hammock WTF spray aeration was successful in removing TTHMs, however it was not effective in maintaining DBP rule compliance due to the excessive nature of DBP formation in the water samples. This study was not intended to serve as an assessment of varying nozzle technologies; rather, the focus was on the application of spray aerators for TTHM removal and post-formation in drinking water systems.