BODY FLUID ANALOGUES AND PERSONAL CARE PRODUCTS AS POTENTIAL DBP PRECURSORS by Zhen Wang A thesis submitted in conformity with the requirements for the degree of Master of Applied science Civil Engineering University of Toronto © Copyright by Zhen Wang 2011 Body Fluid Analogues and Personal Care Products as Potential DBP Precursors Zhen Wang Master of Applied Science Department of Civil Engineering University of Toronto 2011 Abstract Disinfection byproducts (DBPs), such as organic chloramines, THMs, HAAs, and nitrosamines, are formed during mandatory disinfection processes in drinking water treatment. Many of these DBPs have been shown to be potentially carcinogenic. Extensive research has been conducted on the occurrence and formation of these DBPs. However, there has been limited research on their relationships with each other, which may be important for the understanding of their formation mechanisms, and the nature of their precursors is still relatively unknown. Ultimately, this information will be key for the development of possible improvements in treatment technologies. Results of this study improve the understanding of DBP formation in swimming pool water. Some BFAs and PCP additives were identified as potential DBP precursors. Influence of BFAs and PCP additives on DBP formation in swimming pool water was also illustrated. Results provided feasible strategies to minimize DBP formation while maintaining the efficiency of disinfection. ii Acknowledgments Sincerely, I would like to thank my supervisor Dr. Susan A. Andrews for her patience, encouragement, effort and advice throughout the last two and half years. I will not be able to succeed this without your help. I would also like to thank my parents, my wife and my sister's family. They have always been supportive during my life. I would like to extend my thanks to pool managers and pool supervisors who have supported in this study with water samples. Finally, I would like to thank the Drinking Water Research Group in the department of Civil Engineering. It is a harmonious family and everyone is ready to help. iii Table of Contents BODY FLUID ANALOGUES AND PERSONAL CARE PRODUCTS AS POTENTIAL DBP PRECURSORS ............................................................................ i Acknowledgments ...................................................................................................... iii Table of Contents ........................................................................................................ iv List of Tables ................................................................................................................. x List of Figures ........................................................................................................... xiii Chapter 1 Introduction ................................................................................................ 1 Introduction .......................................................................................................... 1 1.1 Overview ................................................................................................................. 1 1.2 Objectives ................................................................................................................ 2 1.2.1 Micro-objective ................................................................................................................ 2 1.2.2 Macro-objective ................................................................................................................ 3 1.3 Thesis organization ................................................................................................ 3 Chapter 2 Literature review ....................................................................................... 4 Literature review .................................................................................................. 4 2.1 Disinfection in drinking water .............................................................................. 4 2.1.1 Free chlorine ..................................................................................................................... 5 2.1.2 Monochloramine ............................................................................................................... 6 2.2 Disinfection byproducts in drinking water .......................................................... 9 2.2.1 Organic chloramines ....................................................................................................... 10 2.2.2 Trihalomethanes (THMs) and haloacetic acids (HAAs) ................................................. 11 2.2.3 Nitrosamines ................................................................................................................... 14 iv 2.3 Regulatory standards for drinking water .......................................................... 16 2.4 Swimming pools ................................................................................................... 17 2.5 Disinfection of swimming pools .......................................................................... 18 2.6 Disinfection byproducts in swimming pools ...................................................... 22 2.7 Regulations and methods to minimize DBP formation in swimming pool water ............................................................................................................................... 25 2.8 Possible DBP precursors in swimming pool water ............................................ 26 2.8.1 Body fluid analogues (BFAs) in simulated swimming pools .......................................... 26 2.8.2 Personal care products (PCPs) in simulated swimming pools ........................................ 27 2.9 Summary of research gaps .................................................................................. 29 Chapter 3 Materials and methods ............................................................................ 30 Materials and methods ...................................................................................... 30 3.1 Materials ............................................................................................................... 30 3.1.1 Chemical reagents and Standard materials ..................................................................... 30 3.1.1.1 Routine chemicals ................................................................................................. 30 3.1.1.2 BFAs ..................................................................................................................... 31 3.1.1.3 PCP compounds .................................................................................................... 32 3.1.1.4 Pool stabilizer (cyanuric acid) and humic acid ...................................................... 33 3.1.1.5 Chemical standards ............................................................................................... 33 3.1.2 Glassware ....................................................................................................................... 33 3.2 Methods ................................................................................................................. 34 3.2.1 Experimental methods .................................................................................................... 34 3.2.2 Analytical methods ......................................................................................................... 35 3.2.2.1 Organic chloramine (HPLC) ................................................................................. 35 3.2.2.2 THMs and HAAs (GC) ......................................................................................... 36 v 3.2.2.3 Nitrosamines (GC/MS) ......................................................................................... 37 3.2.2.4 Other methods and instruments ............................................................................. 40 3.2.3 QA/QC protocol ............................................................................................................. 41 Chapter 4 Water characterization and preliminary tests ...................................... 42 Water characterization and preliminary tests ................................................. 42 4.1 Selection of swimming pools ................................................................................ 42 4.1.1 Indoor swimming pools .................................................................................................. 42 4.1.2 Outdoor swimming pools ............................................................................................... 46 4.2 Ambient water quality of swimming pools (Part I) ........................................... 48 4.2.1 Concentrations of DBPs in swimming pool water .......................................................... 48 4.2.2 Discussion of typical results ........................................................................................... 54 4.2.2.1 TOC and SUVA ..................................................................................................... 54 4.2.2.2 Organic chloramine and nitrosamines ................................................................... 56 4.2.2.3 Discussion related to THMs and HAAs ................................................................ 58 4.2.3 Effects of shocking treatment ......................................................................................... 60 4.2.4 Comparison of indoor swimming pools versus outdoor swimming