CHARACTERIZATION OF DISINFECTION BY-PRODUCT PRECURSORS FROM MISSOURI STREAMS ……………………………………………………………………………………………………………………………………………… A Thesis presented to the Faculty of the Graduate School University of Missouri-Columbia ……………………………………………………………………………………………………………………………… In Partial Fulfillment Of the Requirements for the Degree Master of Science ……………………………………………………………………………………………………………………………………………… By ERIC GENTIL MBONIMPA Dr. Tom E. Clevenger, Thesis Supervisor May 2007 The undersigned, appointed by the Dean of the Graduate School, have examined the thesis entitled CHARACTERIZATION OF DISINFECTION BY-PRODUCT PRECURSORS FROM MISSOURI STREAMS Presented by Eric Gentil Mbonimpa A candidate for the degree of Master of Science And hereby certify that in their opinion it is worthy of acceptance Dr. Tom E. Clevenger Dr. Kathleen Trauth Dr. Stephen H. Anderson Acknowledgements I would like to express my sincere thanks to Dr. Tom Clevenger and the Missouri Water Resources Research Center for the financial support that enabled me to realize my master’s degree goals. His guidance and advice throughout my degree and this work is appreciated. I would like also to extend my thanks to my thesis committee, Dr. Kathleen Trauth, and Dr. Stephen H. Anderson. Their guidance, encouragement and enthusiasm meant a lot to me. I also express my gratitude to the staff of the Missouri Water Resources Research Center, Ed Hinderberger and Dan Crosby, for their help in lab work. I am grateful to fellow graduate students and postdoctoral fellows, especially Jing Cheng and Dr. Bin Hua who introduced me to new technologies for my research. Special thanks go to God and my Mum who took care of me, since I was a child until now. ii Table of Contents Page Acknowledgements………………………………………………………………..ii Table of Contents…………………………………………………………………iii List of Tables.……………………………………………………………..……...vii List of Figures...………………………………………………………………….viii Abstract………...………………………………………………………………….xi CHAPTER 1: INTRODUCTION…………………………………………………1 1.1 Background……………………………………………………………………1 1.2 Motivation of the study………………………………………………………..2 1.3 Objectives of the study………………………………………………………...3 CHAPTER 2: LITERATURE REVIEW………………………………………….3 2.1 Natural Organic matter (NOM)………………………………………….…….4 2.1.1 Overview and sources……………………………………………………4 2.1.2 Characterization………………………………………………………….5 2.1.2.1 Bulk characterization: Total organic carbon (TOC) /Dissolved organic carbon (DOC)……………………………...5 2.1.2.2 Elemental Analysis……………………………………………...6 2.1.2.3 Characterization by “Fractionation” and “Isolation” using resins………………………………….…7 2.1.2.4 Characterization using spectroscopy…………………………….8 2.1.2.4.1 Ultraviolet wave absorbance (UVA) ………………….8 2.1.2.4.2 Fluorescence spectroscopy…………………………….9 2.1.2.4.2.1 Fluorescence Regional Integration (FRI)…10 2.1.2.4.2.2 Fluorescence Index (FI)………………...…11 2.1.2.4.2.3 Humification Index………………………..13 2.1.2.4.3 Carbon-13 Nuclear Magnetic Resonance (13C NMR)…13 2.1.2.4.4 Fourier Transform Infrared spectroscopy (FTIR)……...14 iii 2.1.2.5 Characterization using chromatography…………………………15 2.1.2.6 Characterization by physical methods…………………………...16 2.1.2.6.1 Thermal degradation: Pyrolysis Gas Chromatography-Mass Spectrometry (GC/MS)……………16 2.1.2.6.2 Ultra-filtration………………………………………...17 2.1.2.7 Characterization by Disinfection by-products formation potential (DBPFP)…………………………………....18 2.2 Disinfection byproducts ……………………………………………………...18 2.2.1 Types and formation of DBPs………………………………………….18 2.2.1.1 Chlorine chemistry……………………………………………...18 2.2.1.2 Types of DBPs………………………………………………….19 2.2.1.3 Formation mechanisms…………………………………………20 2.2.2 Health Effects…………………………………………………………...24 2.2.3 Regulations……………………………………………………………...25 CHAPTER 3: DESCRIPTION OF WATERSHEDS CONTAING SAMPLING SITES……………………………………………………………………………..27 3.1 Hydrologic units/subwatershed of sampling sites……………………………27 3.1.1 South Fork Salt sub-basin……………………….……………...............27 3.1.2 North Fork Salt sub-basin………………………….................................29 3.1.3 Little Chariton sub-basin………………………………………………..29 3.1.4 Lower Chariton sub-basin………………………………………………30 3.1.5 Lower Grand sub-basin…………………………………………………31 3.1.6 Upper Grand sub-basin………………………………………………….32 3.1.7 One hundred and Two sub-basin………………………………………..32 3.1.8 Platte sub-basin………………………………………………………….33 3.1.9 Moreau sub-basin………………………………………………………..33 CHAPTER 4: MATERIALS AND METHODS…………………………………34 4.1 Sampling……………………………………………………………………...34 4.2 Chlorination…………………………………………………………………..36 iv 4.2.1 Chlorine demand………………………………………………………..36 4.2.2 Reagents and Procedure………………………………………………...36 4.3 Trihalomethanes (THMs) analysis……………………………………………38 4.3.1 Procedure……………………………………………………………….38 4.3.2 Reagents, standards and quality assurance……………………………..39 4.4 Haloacetic acids (HAAs) analysis……………………………………………42 4.4.1 Procedure……………………………………………………………….42 4.4.2 Reagents, standards and quality assurance……………………………..43 4.5 Ultraviolet absorbance (UVA) analysis………………………………………44 4.6 Fluorescence Analysis………………………………………………………..45 CHAPTER 5: RESULTS AND DISCUSSION…………………………………..48 5.1 UV absorbance characteristics of NOM ……………..………………………...48 5.2 Disinfection by-products formation potential of NOM ……………...………...57 5.2.1 THMs formation potential of NOM………………………………………..57 5.2.2 HAAs formation potential of NOM………………………………...……...59 5.3 Relationship between UVA and DBPs formation potentials……………...…….61 5.3.1 Relationship between UVA and THMs formation potentials………..……61 5.3.2 Relationship between UVA and HAAs formation potentials ……….……63 5.4 Speciation of THMs and HAAs .........................................................................65 5.4.1 Trihalomethanes (THMs)…………………………..……….….……….….65 5.4.2 Haloacetic acids (HAAs)………………………………………….………..68 5.5. Fluorescence Signature of natural organic matter and relationship with THMFP,HAAFP, Aromatic and Source……………...71 5.5.1 Visual interpretation of Fluorophore Centers………………………….71 5.5.1.1 Scans for March samples………………………………………73 5.5.1.2 Scans for June samples………………………………………...77 5.5.1.3 Scans for September-October samples………………………...81 5.6 Approximation using Parallel factor analysis (PARAFAC)………………….85 5.6.1 Parallel factor analysis (PARAFAC) components……………………...85 v 5.6.2 Relationship between PARAFAC Components, DBPs Concentration and UVA 254…………………………………..………..89 5.7 Fluorescence Index………………………………………………………………91 5.8 Fluorescence Regional integration (RFI) results……………………………..94 5.8.1 Relationship between fluorescence regions and THMs………………..95 5.8.2 Relationship between fluorescence regions and HAAs………………..98 5.8.3 Relationship between fluorescence regions and UVA254…………...101 5.8.4 Relationship between fluorescence regions and Fluorescence index……………………………………………….104 CHAPTER 6: CONCLUSIONS AND RECOMMENDATIONS………………107 6.1 Conclusions………………………………………………………………..107 6.2 Recommendations…………………………………………………………109 REFERENCES………………………………………………………………….111 APPENDIX………………………………………………...……………………116 LIST OF ABBREVIATIONS AND ACRONYMS……………………………………124 vi List of Tables Page Table 1: Predominant pyrolysis fragments from aquatic NOM……………….…………17 Table 2: Survey of Disinfectant use in US systems 1997……………………………..…19 Table 3: List of DBPs and Disinfectant Residuals ……………………………………....20 Table 4: Status of health information for THMs and Some HAAs……………………...25 Table 5: Sample number and collection sites.…….……………………………………..35 Table 6: Influence of FI on UVA254, THMs, and HAAs……………………………….91 Table 7: Correlation (+/-) and Coefficient of Determination (R2) of the relationship between Fluorescence Regions and TTHMs…………………..97 Table 8: Correlation (+/-) and Coefficient of Determination (R2) of the relationship between Fluorescence Regions and HAAs…………………..100 Table 9: Correlation (+/-) and Coefficient of Determination (R2) of the relationship between Fluorescence Regions and UVA254…………………103 Table 10: Correlation (+/-) and Coefficient of Determination (R2) of the relationship between Fluorescence Regions and FI……………………….106 Appendix A.1: THMs formation potentials for March samples……...……………………………116 A.2: HAAs formation potentials for March samples………...…………………………117 A.3: THMs formation potentials for June samples…….…..…………………………...118 A.4: HAAs formation potentials for June samples……..………………………………119 A.5: THMs formation potentials for September samples……..………………………..120 A.6: HAAs formation potentials for September samples…..…………………………..121 vii List of Figures Page Figure 1: Classification of DOC by fractionation…………………………………………8 Figure 2: Location of EEM peaks and EEM regions used in FRI……………………….11 Figure 3: Differences in carbon-specific fluorescence emission scans (CSF, Ex: 370 nm) between allochthonous and autochthonous DOC………..12 Figure 4: Examples of reaction models for formation of some DBPs species a) Chlorination of 1, 1, 1-Trichloroacetone b) Chlorination of purvate c) Chlorination of beta-diketone structure…………………………………….21 Figure 5: Missouri State Hydrologic Units………………………….……………….27 Figure 6: Graphical representation of a two-component PARAFAC model of the data array X……………………………………………………………………47 Figure 7: Variation of UVA254 during spring…………………………………………….48 Figure 8: Variation of UVA254 during summer ………………………………………….49 Figures 9: Variation of UVA254 during fall….... …………………...……………………49 Figure 10: Precipitation and river flow variations during sampling periods at the watersheds of sampling locations …..……………..51 Figure 11: Location of sampling sites ………………..……………………………….55 Figure 12: Soil type at sampling sites ………………………………………………...56