Chlorine is always used in disinfection process of water treatment plant (WTP) in Kaohsiung, and the major of disinfection by-products (DBPs) is THMs. Reaction of THMs producing were found in relation to lots of factors of water quality. Therefore we used SPSS to analysis the relation between water quality and THMs content for making prediction model of THMs formation in water distribution system in downtown Kaohsiung city. It is expected to estimate the concentration of THMs with a simple method, and to reduce THMs by controlling some items of water quality. While the variance of TOC value is low, we found that concentration of THMs is related to temperature, pH, and residual chlorine by regression method. In these items, residual chlorine had the highest correlation. While the variance of TOC value is high, the correlation between the three items and THMs is weaker than the front one. From this finding, TOC is best one fitting factor in prediction of THMs. In this study, we found that R-square value of Multivariate regression prediction is higher than the value of Univariate regression prediction probably for THMs producing is a complex reaction, so formation model was hard using only one item of water quality.

The main objective of this study was to conduct a systematic investigation of the disinfection by-products (DBPs) formation in low-bromide and low- specific ultraviolet absorbance (SUVA) waters and the control of DBP precursors by nanofiltration (NF) and ultrafiltration (UF) processes in such waters. To this end, firstly, the effect of bromide ion on the formation and speciation of DBPs was investigated. In fractionated Alibeyk&ouml / y source water, increasing bromide concentrations in NOM fractions increased concentrations of trihalomethanes (THMs), haloacetic acids (HAAs) and adsorbable organic halides (AOX) and resulted in a shift toward the formation of brominated species. Secondly, the impacts of SUVA and differential UV spectroscopy (&amp / #916 / UV), which has been shown to correlate well with DBP formation has been elucidated in terms of DBP formation and speciation. Alibeyk&ouml / y and Karaca&ouml / ren waters were fractionated employing various separation methods and it has been shown that SUVA did not correlate well with the formation and speciation of THMs and HAAs in tested low-SUVA waters. Similarly, no correlations were found among THMs/HAAs formations and &amp / #916 / UV. Finally, the NOM rejection performances of NF and UF membranes were investigated. NF and UF membranes (&lt / 2000 dalton) was found to be suitable for the removal NOM from surface waters having low SUVA and low bromide contents. While higher molecular weight (HMW) fraction was successfully rejected (&gt / 90%) by all membrane types, lower molecular weight (LMW) fraction could be removed with ranging efficiencies from 1.5 to 30%. NF membranes provided DOC, UV254 absorbance, THM, and HAA reductions up to 90%.

The quality of drinking water effects not only human health, but also plays a decisive role in daily life. Although the Taiwan water corporation has improved water quality of Kaohsiung in recent years and most of the random testing results of the drinking water done by the EPB could meet the drinking water standards, many people still lack confidence in the tap water. This study (1) select 500 multi-unit residences from 11 districts in Kaohsiung and survey the water quality of the indirect water supply storage devices to understand the tap water quality of indirect water distribution network in Kaohsiung. (2) Aiming at the inhabitants living in multi-unit residences, a questionnaire about the satisfaction with the tap water in Kaohsiung is undergone by random sampling in order to understand the satisfaction with the tap water of the public. (3) The monitoring values of total trihalomethanes (TTHMs) in tap water distributional network in four seasons from December 2006 to September 2007 are used to analysis the seasonal changes, the equal concentration distribution figure, and the ration of all kinds of compounds of the THMs to the total amounts. The results of above analyses can be offered to Taiwan Water Corporation to make improvement and as the references of following studies. The result of the survey of satisfaction shows that 47% people incline to use tap water as drinking water¡F53% people don¡¦t have confidence in tap water and choose to the bottled water from water stations as drinking water source. 49.1% people living in cluster housing in Kaohsiung consider the quality of tap water common¡F15.4% people are satisfied with the tap water quality and 35.7% people are not satisfied with it. The main reason is the old pipelines, and the secondary reason is about the distasteful water. Most people wish to renew old pipelines as soon as possible, and give priority to strictly control the tap water quality. The analysis result of THMs concentrations shows that the average value of THMs in each district is highest in spring and lowest in autumn, especially in Cianjhen, Siaogang, and Cijin districts. The THMs concentration distribution of Cianjhen district is higher in the spring and winter. The proportion of CHCl3 (chloroform) to total amount of THMs is the highest in the water supply network, and it is also the major source of THMs.

published_or_final_version / Civil Engineering / Doctoral / Doctor of Philosophy

Limited studies focused on reactions occurring during disinfection and oxidation processes of seawater. The aim of this work was to investigate disinfection by-products (DBPs) formation from the chlorination and chloramination of seawater algal organic matter and related model compounds. Simulated algal blooms directly growing in Red Sea, red tide samples collected during an algal bloom event and Hymenomonas sp. monoculture were studied as algal organic matter sources. Experiments were conducted in synthetic seawater containing bromide ion. A variety of DBPs was formed from the chlorination and chloramination of algal organic matter. Brominated DBPs (bromoform, DBAA, DBAN and DBAcAm) were the dominant species. Iodinated DBPs (CIAcAm and iodinated THMs) were detected, which are known to be highly toxic compared to their chlorinated or brominated analogues. Algal organic matter was found to incorporate important precursors of nitrogenous DBPs (N-DBPs), which have been reported to be more toxic than regulated THMs and HAAs. Isotopically-labeled monochloramine (15N- NH2Cl) was used in order to investigate the nitrogen source in N-DBPs. High formation of N-DBPs was found from Hymenomonas sp. sample in exponential growth phase, which was enriched in nitrogen-containing organic compounds. High inorganic nitrogen incorporation was found from the algal samples enriched in humic-like compounds. HAcAms formation was studied from chlorination and chloramination of amino acids. Asparagine, aspartic acid and other amino acids with an aromatic structure were found to be important precursors of HAcAms and DCAN. Factors affecting HAcAms formation (Cl2/ amino acid molar ratio and pH) were evaluated. Studies on the formation kinetics of DCAcAm and DCAN from asparagine suggested a rapid formation of DCAcAm from organic nitrogen (amide group) and a slower incorporation of inorganic nitrogen coming from monochloramine to form DCAN. High amounts of DCAN and DCAcAm were detected from the chloramination of aromatic compounds (i.e., phenol and resorcinol) indicating that N-DBPs can also be formed from organic compounds without any organic nitrogen through the incorporation of inorganic nitrogen from monochloramine. Moreover, results from Hymenomonas sp., aromatic amino acids, and phenolic compounds suggested that aromatic compounds are highly reactive with monochloramine and a major fraction of DBP precursors.

Issues of Disinfection By-Product (DBP) formation in response to chlorination in drinking water treatment systems is a common issue encountered by WTP operators. Efforts to minimize DBP formation are complicated by the presence of zebra mussels, which may inhabit the raw water intake of WTPs. While chlorination at the intake to control zebra mussel populations is effective, the formation of DBPs is exacerbated. Methods for reducing DBPs are explored, including adjusting the location for chlorine additions in the treatment sequence. Multivariate models for Total Trihalomethane (TTHM) and Haloacetic Acid (HAA) subspecies are employed to show that in some instances pre-chlorination can be reduced to lower DBP formation, while post-chlorination can be increased. A Regression model (R2 of 0.75) predicts that DBP levels can be lowered by post-chlorination rather than pre-chlorinating raw water for portions of the year except during the combatable life stage to assist in zebra mussel control. A second multivariate regression model for TTHM (R2 = 0.91) which includes bromide, a variable which, due to lack of data, was previously unused, is described and demonstrates that DBP levels can be reduced by lowering pre-chlorination levels. Finally, a Bayesian network is developed using the Webweavr-IV Toolkit, utilizing causal relationships between raw water quality parameters in the form of conditional probabilities. The results show that the average cancer risk can be decreased by while still maintaining zebra mussel control and simultaneously decreasing the incremental cancer risk, which currently fluctuates between 1 in 50,000 to 100,000 in Ontario. / Canada Research Chair Program, Ontario Research Foundation

Natural organic matter (NOM) is present in all surface waters as a result of decaying vegetation, biological activity, and organic soil. Alternative NOM removal processes such as anion exchange resins (AERs) have shown NOM removals typically ranging between 50 to 90%, with up to 99% removal achieved in some cases. The first portion of this study evaluated the performance of two AERs; a conventional Type 1 AER and magnetic ion exchange resin (i.e. MIEX®) for NOM removal from surface water quantified by UV254, dissolved organic carbon (DOC), and specific UV absorbance (SUVA). Samples were also characterized for chloride, sulphate, and chloride-to-sulphate mass ratio (CSMR) to provide additional information on water quality characteristics of AER treated waters. Overall, the results showed that both AERS were effective for removing NOM. However, the MIEX® resin provided greater removal of NOM with shorter contact times compared to the conventional resin investigated. Water treated with MIEX® resin showed significantly higher chloride and lower sulphate concentrations than the conventional AER. Higher CSMR values were found with MIEX® treated water compared to conventional AER system, although both resins showed CSMR much greater than 0.5, which can increase galvanic corrosion effects with lead. Bench-scale jar tests were conducted to investigate the impact of temperature on the efficacy of three NOM removal treatment technologies; enhanced coagulation with alum, MIEX® and a combined MIEX® treatment followed by coagulation with a low dose of alum. Higher settled water turbidity was observed during cold water operating conditions for all three processes. At cold-water operating conditions, DOC removal was reduced with combined MIEX® -Alum treatment, and UV254 removal was impacted for both MIEX® and MIEX® -Alum processes. The combined MIEX®-Alum process was found to provide the lowest THMFP and HAAFP at both temperatures to concentrations lower than current regulatory maximum acceptable concentration (MAC) guidelines in Canada. Surface charge analysis experiments were performed at bench-scale using synthetic water containing humic acid to determine the relationship between NOM and the charge of AER-treated waters. Further bench and pilot-scale studies were performed to investigate the use of surface charge measurements to monitor and optimize NOM removal during treatment with AER systems. Strong correlations were observed between UV254 and respective charge measurements (i.e. ZP, SC) of AER-treated synthetic and raw waters. The results of this research has shown that it is possible to use charge to optimize the MIEX® process for NOM removal. Additionally, it was found that SC measurements could be used as an operational tool for AER processes, where deviations in SC from optimum treatment would indicate the requirement for fresh resin addition or resin regeneration.

Dissolved organic carbon (DOM) is one of the largest cycled organic carbon pools on Earth and an important biogeochemical factor in aquatic systems. DOM can act as an energy source for microorganisms, alter the depth of the photic zone for photosynthesis, absorb harmful ultraviolet radiation, as well as alter the transport and toxicity of contaminants. The purpose of this research project was to characterize DOM in the Grand River watershed in Ontario, Canada using a wide range of qualitative and quantitative techniques and determine the impact of anthropogenic activities as well as seasonal and longitudinal changes on DOM processes. To reach the study objectives, historical data was analyzed to determine the seasonal cycle in the Grand River watershed. Intensive longitudinal sampling surveys were undertaken to evaluate the DOM characteristics and processes in the Grand River. Surveys of the less impacted Burnt River watershed were used as a comparison watershed to the Grand River to evaluate allochthonous and autochthonous indicators of DOM source and human impacts on DOM processes. Drinking water surveillance data was used to evaluate the effect of DOM in the Grand River on formation of disinfection by-products (DBPs). Different trends were seen in the Grand River in terms of longitudinal area and season. The headwaters of the river showed more autochthonous DOM in the spring and winter compared to the fall and summer. The lower-central river peaked in autochthonous DOM in the summer and was more allochthonous in the winter. DOM generally became more autochthonous downstream in the Grand River and was most autochthonous below the large sewage treatment plants (STPs) in the central portion. Protein content, measured as protein-like fluorescence normalized to DOC concentration, was strongly related to ??15N of DON; both are associated with autochthonous DOM in the Grand River and show the effects of the major STPs. The increase in autochthonous DOM below the STPs is likely associated with nutrient enrichment stimulating primary production and macrophyte growth. Based on the comparison of the Burnt River with the more impacted Grand River, the effect of lakes and photodegradation can make discrimination of autochthonous and allochthonous DOM more difficult. The ratio of DOC/DON and protein-like fluorescence proved to be robust indicators despite photodegradation. Human impacts on the Grand River watershed result in a greater seasonal cycle, high primary production in the summer and a downstream trend of increasing autochthonous DOM compared to the Burnt River. Based on drinking water surveillance data and literature review, autochthonous DOM caused greater DBPs in the drinking waters fed by the Grand River. This is currently a threat to human health and DBPs in sewage treatment plant effluent may be a threat to ecosystem health.

Source water quality plays a critical role in maintaining the quality and supply of drinking water, yet it can be negatively affected by human activities. In Pennsylvania, coal mining and treatment of conventional oil and gas drilling produced wastewaters have affected source water quality for over 100 years. The recent unconventional natural gas development in the Marcellus Shale formation produces significant volumes of wastewater containing bromide and has the potential to affect source water quality and downstream drinking water quality. Wastewater from coal-fired power plants also contains bromide that may be released into source water. Increasing source water bromide presents a challenge as even small amounts of bromide in source water can lead to carcinogenic disinfection by-products (DBPs) in chlorinated finished drinking water. However, bromide is not regulated in source water and is not removed by conventional drinking water treatment processes. The objective of this work is to evaluate the safe bromide concentration in source water to minimize the cancer risk of trihalomethanes - a group of DBPs - in treated drinking water. By evaluating three years of water sampling data from the Monongahela River in Southwestern Pennsylvania, the present analysis reached three conclusions. First, bromide monitoring for source water quality should be taken at drinking water intake points. Water sample types (river water samples vs drinking water intake samples) can lead to different water quality conclusions and thus affect regulatory compliance decision-making. Second, bromide monitoring at drinking water intake points can serve as a predictor for changes in heavily brominated trihalomethanes concentrations in finished water. Increasing bromide in source water can serve as an early warning sign of increasing formation of heavily brominated trihalomethanes and their associated cancer risks in drinking water. Finally, this work developed a statistical simulation model to evaluate the effect of source water bromide on trihalomethane formation and speciation and to analyze the changing cancer risks in water associated with these changing bromide concentrations in the Monongahela River. The statistical simulation method proposed in this work leads to the conclusion that the bromide concentration in source water must be very low to prevent the adverse health effects associated with brominated trihalomethanes in chlorinated drinking water. This method can be used by water utilities to determine the bromide concentration in their source water that might indicate a need for process changes or by regulatory agencies to evaluate source water bromide issues.

N-nitrosamines are considered as a group of emerging disinfection byproducts (DBPs) with potential carcinogenicity at ng/L level. The presence of nitrosamines in drinking water is most commonly associated with chloramination of amine-based precursors. This research investigates the potential of amine-based pharmaceuticals and personal care products (PPCPs) as nitrosamine precursors under practical drinking water disinfection conditions, as well as some critical factors that may affect the nitrosamine formation via PPCPs. All of the twenty selected PPCPs were able to form the corresponding nitrosamines upon chloramine disinfection, and eight of them rendered molar conversions higher than 1 % under practical disinfection conditions. Ranitidine had the highest N-nitrosodimethylamine (NDMA) molar conversion among the tested PPCPs. A three-parameter kinetic model was proposed to describe and predict the NDMA formation from pharmaceuticals during chloramination in various water matrices. The model accurately reflected all three significant characteristics of the NDMA formation curve, including an initial lag phase, followed by a fast increase in NDMA formation, and eventually reaching a plateau. In lab-grade water, the NDMA formation from pharmaceuticals was affected by the Cl2:NH4-N mass ratio, pH, and prechlorination. The NDMA formation increased with the Cl2:NH4-N mass ratio, indicating an enhancement effect of dichloramine. The pH affected both the ultimate NDMA conversion and the reaction rate. The reaction rate is mainly determined by the level of non-protonated amine species, and it increased consistently with increasing pH. The ultimate NDMA conversion is limited by the level of dichloramine, and the maximum NDMA formation occurred in the pH range of 7 to 8. The application of prechlorination may increase or reduce the NDMA conversion, depending on the chlorine reactivity towards the amine group and its surrounding structures. Water matrix components can slow down the initial NDMA formation from selected pharmaceuticals most likely due to the formation of natural organic matter (NOM)-pharmaceutical complexes, while they had less impact on the ultimate NDMA molar conversion. The application of prechlorination may enhance the initial reaction by destroying the NOM-pharmaceutical complexes, but prolonged prechlorination may further inhibit the NDMA formation due to the binding between pharmaceuticals and NOM breakdown products.