臺灣博碩士論文加值系統

加氯消毒是游泳池水質管理中重要的步驟，其主要目的在消滅水體中的微生物或是降低其活性，以確保泳客不會因為水體中致病微生物而引發水媒疾病疫情。衛生福利部疾病管制署提出游泳池的自由有效餘氯建議值應在百萬分之1到3之間，而臺北市衛生營業管理規則也要求台北市的游泳池自由餘氯濃度應該要維持在百萬分之0.3到0.7之間，以維持良好的殺菌效果。

然而，游泳池中泳客所釋放出的有機質 (例如: 汗液、尿液、皮屑、頭髮、保養品等物質)可能跟消毒劑反應而產生消毒副產物，包括三鹵甲烷 (Trihalomethanes, THMs)、鹵乙酸(Haloacetic acids, HAAs)、鹵乙氰 (Haloacetonitriles, HAN)、鹵酮 (Haloketone, HKs)等物質。雖然目前國內外已有研究針對游泳池做實場採樣調查，但是游泳池池水中所累積的組成物質極為複雜，所以實場採樣的結果較難釐清個別來源內源性有機前質的消毒副產物生成特性，以及它們經過不同處理後的處理效果。

本研究採取實驗室模擬的方法，選用了泳池中最主要的內源性有機質，包括尿液及汗液，以代表持續在游泳池中釋放的有機前質。另外也以臭氧、UV/H2O2、UV/Cl2三種前處理方法評估其對於內源性有機消毒副產物前質的降解效果。其中臭氧為一般游泳池實場常見的消毒方法; 而UV/H2O2相關的研究主要應用在飲用水或汙水相關研究裡，截至目前為此以UV/Cl2及UV/H2O2前處理方法對於游泳池水質改善應用的相關研究仍不充足，所以本研究一併將其納入以比較將其應用於游泳池水的優劣，提供未來游泳池水質控制以及消毒副產物前處理技術的背景資訊。
研究結果顯示，隨著內源性有機前質不斷排放到持續加氯的水體裡，不僅會使水中三鹵甲烷、鹵乙酸、鹵乙氰的濃度不斷累積，也會使得水體需氯量大幅增加而引發不揮發性的消毒除副產物 - 鹵乙酸的生成潛勢上升。另外，臭氧、UV/H2O2、UV/Cl2對於汗液內的三鹵甲烷的生成均有良好的控制效果，但僅有UV/H2O2可以同時降低汗液及尿液的三鹵甲烷及鹵乙酸生成潛能，其對水中總有機碳的礦化效果也較顯著。

Disinfection is one of the main treatment processes for recirculating water in swimming pools. The main purpose of disinfection is to kill or inactive pathogens and to protect the public from waterborne diseases. On the other hand, some disinfectants such as chlorine can provide necessary residuals in treated water and prevent microbial regrowth in treated water. The concentration of free residual chlorine for swimming pools in Taipei City should be between 0.3 ~ 0.7 mg/L according to the current sanitation regulation of Center of Disease Control of Taipei.

However, various organic precursors in water could react with chlorine and produce some disinfection by-product (DBPs) including trihalomethanes (THMs), haloacetic acids (HAAs), haloacetonitriles (HANs), haloketones (HKs), halonitromethanes (HNMs) and so on. Nowadays, there is still unclear concerning how different sources of organic endogenous matter from human affect the DBPs formation; therefore how to promote the treatment efficiencies to reduce the DBPs formation via different treatments have been an issue for management of swimming pool water qualities. This study set up a bench-scale system for assessment of DBPs formation potentials of human endogenous organic matter after ozonation, UV/H2O2 and UV/Cl2 pretreatments. Urine and perspiration were selected to represent the major human endogenous organics in this study, since these organics have been considered as the main organic compositions in swimming pools and spas. Although ozonation is widely used in swimming pools, the studies of UV/H2O2 and UV/Cl2 in swimming pools water are still limited. The three AOP treatments were conducted to elucidate their effects on water quality controls and DBPs reductions in order to provide more background knowledge for the swimming pool managements.

The results of this study showed that, continuous addition of body fluids into reaction chamber would result in more and more productions of THMs, HAAs and HANs in swimming pool water. Moreover, the accumulations of swimmer’s body fluids not only result in increasing of DBPs, but also enhance the chlorine demands and much higher DBPs formations in swimming pool water. In addition, ozonation, UV/Cl2 and UV/H2O2 treatments can degrade the organic precursor of DBPs in perspiration, and make the concentrations of DBPs decreased eventually. The results also showed that only the UV/H2O2 treatment can lower down the DBPs formations for both the perspiration and urine; however, both UV/Cl2 and UV/H2O2 methods need to be operated for a sufficient contact time to prevent the DBPs rise in water in the beginning stage of the oxidation treatments.

中文摘要 I
Abstract III
Contents V
List of Figures VIII
List of Tables X
Chapter 1 Introduction 1
1.1 Background of study 1
1.2 Objectives 2
Chapter 2 Literature Review 3
2.1 Circulation systems of general swimming pools 3
2.2 Organic compositions in swimming pools 4
2.2.1 Main pollutants contributed from swimmers in swimming pools 4
2.2.2 Organic chemical composition of human endogenous precursors 6
2.3 Factors related to DBPs formation in pool water 7
•Organic precursors 7
• Temperature 8
• pH 8
• Pool types 9
• Pool operation and management 9
2.4 Water treatment processes 10
2.4.1 Advanced oxidation processes (AOPs) in swimming pools 10
• The mechanism of ozonation 10
• The mechanism of UV/Chlorine 12
• The mechanism of UV/H2O2 13
2.5 Disinfection by-products in swimming pools 14
2.5.1 Health impact of DBPs in swimming pool 16
2.5.2 THMs, HAAs, and other DBPs in swimming pool 18
Chapter 3 Material and Methods 20
3.1 Study design 20
3.1.1 Research framework 20
3.1.2 Study equipment and experimental processes 26
• Continuous organics accumulation experiments 26
• Ozonation system 28
• UV/Chlorine oxidation system 30
• UV/H2O2 oxidation system 32
3.2 Sample preparation and characteristics 34
3.3 Chemicals analysis 38
3.3.1 DBPs formation tests 38
• 7-day DBPs formation potential tests (DBPFP tests) 38
• DBPs formation dynamics tests 39
3.1.2 Sample analysis 41
• THMs, HANs, HKs, and TCNM analysis 41
• HAAs analysis 44
• Organic carbon analysis 47
• Total nitrogen (TN) analysis 49
• NH4+-N analysis 50
• Nitrates and Nitrites (NO3- -N and NO2- -N) analysis 51
• TON analysis 52
Chapter 4 Results and Discussions 53
4.1 Simulation of continuous organics accumulation in swimming pools 53
4.1.1 Organic matter accumulation and chlorine consumption 53
4.1.2 Disinfection by-products formations in the organic matter accumulation experiments 56
4.2 Comparisons of different AOP treatments of human endogenous organic precursors 59
4.2.1 Effects of AOPs on degradations of organic matters 59
4.2.2 Effects of AOPs on degradations of nitrogen species 62
4.2.3 Effects of AOPs on the UV spectrums of the organic matters 65
4.2.4 Effects of AOPs on the EEM spectrums of the organic matters 67
4.3 Comparing the effects of AOP treatments on DBPs precursors 73
4.3.1 Results of DBPFP tests and chlorine demands 73
4.3.2 Dynamics of DBPs formation and chlorine demands 80
4.4 Comparisons of treatment efficiencies with three different treatments 90
Chapter 5 Conclusions 94
Appendix 96
Reference 98

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