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Effect of biological activated carbon (BAC) filtration on the removal and biodegradation of natural organic.. Black, Kerry Elizabeth 2011

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Effect of Biological Activated Carbon (BAC) Filtration on the Removal and Biodegradation of Natural Organic Matter (NOM) by  Kerry Elizabeth Black B.A.Sc., The University of Toronto, 2007  A THESIS SUBMITTED IN PARTIAL FULFILLMENT OF  THE REQUIREMENTS FOR THE DEGREE OF   MASTER OF APPLIED SCIENCE in The Faculty of Graduate Studies (Civil Engineering)   THE UNIVERSITY OF BRITISH COLUMBIA (Vancouver)  July, 2011   © Kerry Elizabeth Black, 2011ii  ABSTRACT Natural organic matter is a complex mixture of various organics including humic substances, carbohydrates, amino acids and carboxylic acids that exist in natural waters.  Integrated treatment processes that combine oxidation processes and activated carbon biofilters have been shown to be effective at reducing natural organic matter (NOM) levels.  The current research project investigated the effect of ozone and advanced oxidation at various doses on specific parameters including: biodegradability of NOM, formation of disinfection by-products (DBPs), change in apparent molecular weight (AMW) of NOM and dissolved organic carbon content (DOC).   Overall, ozonation of the raw water at 2mg O3/mg DOC resulted in significant reductions in aromatic material, resulting in lowered DBPFP.  In addition, ozonation was successful at transforming NOM from high AMW to low AMW, rendering the organic material more biodegradable and preferentially removed during biofiltration.   While the high-dose oxidants (ozonation at 25mg O3/mg DOC and AOP treatment at 4000mJ/cm2 and 10mg/L H202) were successful at reducing DOC, UVA, AMW and DBPFP, the elevated dose required make these options less realistic.  Ozonation at 2mg O3/mg DOC and AOP treatment at 2000mJ/cm2 and 10mg/L H2O2 provide good reduction of UVA, AMW and DBPFP.   The high dose oxidants are unsuitable as pre-treatment options for biofiltration given that they result in highly oxidized NOM that exhibited very little biodegradation during biofiltration.  The lower dose oxidants are suitable pre-treatment options for biofiltration given the high reductions in UVA, AMW and DBPFP exhibited, and the similar biodegradation kinetics observed.   Pre-oxidation prior to biofiltration is essential for removal of non-biodegradable DOC.  The rate kinetics governing biodegradation were not sensitive to oxidant type or dose.    Overall, this project provided beneficial insight into the operation of integrated treatment processes and the effect of these on several NOM characteristics including biodegradation.      iii  TABLE OF CONTENTS Abstract .................................................................................................................................... ii Table of Contents ................................................................................................................... iii List of Tables ........................................................................................................................ viii List of Figures .......................................................................................................................... x List of Equations ................................................................................................................. xvii List of Abbreviations ......................................................................................................... xviii Acknowledgements .............................................................................................................. xix Dedication .............................................................................................................................. xx 1.0 INTRODUCTION....................................................................................................... 1 1.1 Overview .................................................................................................................... 1 1.2 Research Objectives ................................................................................................... 2 1.3 Contributions .............................................................................................................. 3 2.0 LITERATURE REVIEW .......................................................................................... 5 2.1 Natural Organic Matter (NOM) ................................................................................. 5 2.1.1 Sources and Characteristics ................................................................................ 5 2.1.2 Problems Posed to Drinking Water..................................................................... 5 2.1.2.1 Disinfection By-Products ............................................................................ 6 2.1.2.2 Biological Stability ...................................................................................... 7 2.1.3 Characterization of NOM ................................................................................... 8 2.1.3.1 Total Organic Carbon (TOC) ...................................................................... 8 2.1.3.2 Ultraviolet Absorbance (UVA) ................................................................... 8 2.1.3.3 Polarity......................................................................................................... 9 2.1.3.4 Molecular Weight (MW) ............................................................................. 9 2.1.3.5 Disinfection By-Product Formation Potential (DBPFP) ............................. 9 iv  2.2 Technologies for Removal of NOM......................................................................... 10 2.2.1 Ozonation .......................................................................................................... 10 2.2.1.1 Principles of Ozonation ............................................................................. 10 2.2.1.2 Effect on NOM .......................................................................................... 11 2.2.2 UV/ H2O2 Advanced Oxidation ........................................................................ 13 2.2.2.1 Principles of UV/ H2O2 Oxidation............................................................. 13 2.2.2.2 Effect on NOM .......................................................................................... 14 2.2.3 Oxidation/Biofiltration ...................................................................................... 16 2.2.3.1 Principles of Combined Oxidation/Biofiltration ....................................... 16 2.2.3.2 Effect on NOM .......................................................................................... 17 3.0 MATERIALS AND METHODS ............................................................................. 20 3.1 Part 1: Biofiltration Experiments ............................................................................. 20 3.1.1 Raw Water Preparation ..................................................................................... 20 3.1.2 Feed Water Preparation..................................................................................... 21 3.1.3 Biofiltration System .......................................................................................... 24 3.2 Biodegradation Experiments .................................................................................... 28 3.2.1 Raw water preparation ...................................................................................... 28 3.2.2 Feed Water Preparation..................................................................................... 29 3.2.2.1 Ozonation................................................................................................... 29 3.2.2.2 UV/H2O2 .................................................................................................... 29 3.2.3 Batch Biodegradation Experiments .................................................................. 31 3.2.3.1 Batch System ............................................................................................. 31 3.2.3.2 Biomass Analysis ...................................................................................... 33 3.3 Analytical Methods .................................................................................................. 35 3.3.1 Glassware .......................................................................................................... 35 v  3.3.2 pH ...................................................................................................................... 35 3.3.3 Temperature ...................................................................................................... 35 3.3.4 Alkalinity .......................................................................................................... 35 3.3.5 Hardness ............................................................................................................ 36 3.3.6 Total Organic Carbon (TOC) ............................................................................ 37 3.3.7 Ultraviolet Absorbance (UVA) & Specific Ultraviolet Absorbance (SUVA) .. 37 3.3.8 Molecular Weight Determination by High Performance Size Exclusion Chromatography (HPSEC) .............................................................................................. 38 3.3.8.1 HPSEC Analysis ........................................................................................ 38 3.3.8.2 Resolution of HPSEC Chromatograms ..................................................... 40 3.3.9 Disinfection By-Product Formation Potential (DBPFP) ................................... 43 3.3.10 Trihalomethanes (THMs) .................................................................................. 44 3.3.11 Haloacetic Acids (HAAs) ................................................................................. 46 3.4 Quality Control/Quality Assurance .......................................................................... 49 3.4.1 Sample Collection and Storage ......................................................................... 49 3.4.2 Reagents and Laboratory Blanks ...................................................................... 49 3.4.3 Instrument Reproducibility ............................................................................... 49 4.0 RESULTS AND DISCUSSION ............................................................................... 50 4.1 Part 1 - Biofiltration Experiments ............................................................................ 50 4.1.1 Effect of Biofiltration on Dissolved Organic Carbon (DOC) ........................... 50 4.1.2 Effect of Biofiltration on Specific Ultraviolet Absorbance (SUVA) ................ 52 4.1.3 Effect of Biofiltration on Apparent Molecular Weight (AMW) ....................... 54 4.1.4 Effect of Biofiltration on Disinfection By-Produce Formation Potential (DBPFP) .......................................................................................................................... 56 4.2 Part 2 - Biodegradation Experiments ....................................................................... 60 4.2.1 Feed Water Analysis ......................................................................................... 60 vi  4.2.1.1 Effect of Oxidation on Dissolved Organic Carbon (DOC) ....................... 60 4.2.1.2 Effect of Oxidation on Specific Ultraviolet Absorbance (SUVA) ............ 61 4.2.1.3 Effect of Oxidation on Apparent Molecular Weight (AMW) ................... 63 4.2.1.4 Effect of Oxidation on Disinfection By-Produce Formation Potential (DBPFP)  ................................................................................................................... 67 4.2.2 Batch Biodegradation Experiments .................................................................. 72 4.2.2.1 Effect of Oxidation on Biodegradation Kinetics ....................................... 72 4.2.2.2 Effect of Biodegradation on Ultraviolet Absorbance (UVA) .................... 76 4.2.2.3 Effect of Biodegradation on Apparent Molecular Weight (AMW) .......... 77 5.0 CONCLUSIONS AND RECOMMENDATIONS .................................................. 93 5.1 Biofiltration Column Experiments ........................................................................... 93 5.2 Biodegradation Experiments .................................................................................... 94 5.2.1 Raw Water Oxidation ....................................................................................... 94 5.2.2 Batch Biodegradation Experiments .................................................................. 94 5.3 Engineering Significance and Future Work ............................................................. 96 5.3.1 Significance....................................................................................................... 96 5.3.2 Future work ....................................................................................................... 97 References .............................................................................................................................. 99 Appendix A. Ozonation Calibration Data ..................................................................... 109 Appendix B. UV/H2O2 Treatment data ......................................................................... 111 Appendix C. Biomass Analysis and Volatilization Results .......................................... 112 Appendix D. Biofiltration Results for TOC and UVA ................................................. 115 Appendix E. Oxidation HPSEC Chromatograms ........................................................ 118 Appendix F. Peakfit Analysis of Oxidation HPSEC Chromatograms ....................... 120 Appendix G. HAA Results............................................................................................... 130 vii  Appendix H. THM Results .............................................................................................. 132 Appendix I. Oxidation TOC and UVA Data ................................................................ 134 Appendix J. Biodegradation TOC/UV Results ............................................................ 136 Appendix K. Biodegradation Curves for DOC ............................................................. 144 Appendix L. Biodegradation Test Analysis ResultS for DOC..................................... 156 Appendix M.   Biodegradation Curves for SUVA ............................................................ 159 Appendix N. Biodegradation Test analysis ResultS for SUVA ................................... 170 Appendix O. Biodegradation HPSEC Chromatograms ............................................... 175 Appendix P. Peakfit Analysis for Biodegraded Chromatograms ............................... 181 Appendix Q. Biodegradation Bar Graph Results ......................................................... 197 Appendix R. Biodegradation Percent Removal Results ............................................... 213   viii  LIST OF TABLES Table 2-1 - Summary of reported effects of ozonation on NOM characteristics .................... 12 Table 2-2 - Summary of reported effects of UV/H2O2 on NOM characteristics .................... 15 Table 2-3 - Summary of reported effects of oxidation and biofiltration on NOM characteristics .......................................................................................................................... 18 Table 3-1 - Raw water characteristics ..................................................................................... 21 Table 3-2 - Laboratory apparatus characteristics .................................................................... 25 Table 3-3 - Picabiol® granular activated carbon properties ................................................... 27 Table 3-4 - UV/H2O2 experiment conditions .......................................................................... 31 Table 3-5 - Biodegradation experiment description ............................................................... 32 Table 3-6 - Autofit Peak III deconvolution parameters .......................................................... 41 Table 3-7 - Uniform formation conditions .............................................................................. 43 Table 3-8 - GC-ECD properties for THM analysis ................................................................ 45 Table 3-9 - THM retention times (min) .................................................................................. 46 Table 3-10 - GC-MS properties for HAA analysis ................................................................. 48 Table 3-11 - HAA retention times (min) ................................................................................ 48 Table 4-1 - Summary of percent reduction in AMW fractions throughout biofiltration ........ 55 Table 4-2 - Summary of average percent reduction in AMW fractions for each oxidation condition ................................................................................................................................. 66 Table 4-3 - Biodegradation average curve parameters for BAC Column 1 and BAC Column 2 ................................................................................................................................................. 73 Table A-1 - Ozone calibration data ....................................................................................... 109 Table A-2 - Ozone treatment data ......................................................................................... 110 Table B-1- UV/ H2O2 experiment conditions ....................................................................... 111 Table C-1 - Volatilization of harvested GAC ....................................................................... 114 Table D-1- DOC, UVA data for biofiltration ....................................................................... 115 Table G-1 - HAA data run 1 ................................................................................................. 130 Table H-1 -  THM data run 1 ................................................................................................ 132 Table I-1 - Raw TOC and UVA data for oxidation conditions............................................. 134 Table J-1 - TOC/UV data for biodegradation tests ............................................................... 136 ix  Table L-1 - Biodegradation curve analysis results for DOC ................................................ 156 Table L-2 - Biodegradation analysis of % non-biodegradable for DOC .............................. 158 Table N-1 - Biodegradation curve analysis results for SUVA ............................................. 170 Table N-2 - Biodegradation analysis of % non-biodegradable for SUVA ........................... 172 Table N-3 - Biodegradation average curve parameters for BAC Column 1 and BAC Column 2............................................................................................................................................. 173 x  LIST OF FIGURES Figure 1-1- Research plan ......................................................................................................... 4 Figure 3-1 - Jericho Beach pond park ..................................................................................... 20 Figure 3-2 - Schematic of ozonation apparatus ...................................................................... 21 Figure 3-3 - Ozone concentration versus time ........................................................................ 23 Figure 3-4 - A schematic of the laboratory scale apparatus.................................................... 24 Figure 3-5 - Bench-scale apparatus ......................................................................................... 26 Figure 3-6 - Biofilter effluent DOC versus bed volumes filtered ........................................... 28 Figure 3-7 - Experimental semi-batch UV/H2O2 reactor ........................................................ 29 Figure 3-8 - Quality control biodegradation curves ................................................................ 34 Figure 3-9 - HPSEC calibration curve .................................................................................... 39 Figure 3-10 - Typical HPSEC chromatogram ........................................................................ 40 Figure 3-11 - HPSEC chromatogram resolution. .................................................................... 42 Figure 4-1 - Effect of combined oxidation and biofiltration on DOC. ................................... 50 Figure 4-2 - Average percent reductions in DOC throughout the biofilters ........................... 51 Figure 4-3 - Effect of combined oxidation and biofiltration on SUVA levels throughout the filter ......................................................................................................................................... 52 Figure 4-4 - Average percent reductions in SUVA throughout the biofilters. ........................ 53 Figure 4-5 - Effect of combined oxidation and biofiltration on AMW distribution. .............. 54 Figure 4-6 - Effects of oxidation and biofiltration on AMW.................................................. 55 Figure 4-7 - Reduction in THMFP and HAAFP throughout biofiltration .............................. 57 Figure 4-8 - Reduction of each of the four THMs through biofiltration ................................ 58 Figure 4-9 - Reduction in each of the three HAAs (DCAA, MCAA and TCAA) through biofiltration ............................................................................................................................. 59 Figure 4-10 - Effect of oxidation on DOC (mg/L) ................................................................. 60 Figure 4-11 - Effect of oxidation on UVA and SUVA ........................................................... 62 Figure 4-12 - Effect of oxidation on apparent molecular weight ............................................ 64 Figure 4-13 - Effects of oxidation on AMW. ......................................................................... 65 Figure 4-14 - Effect of oxidation on THMFP and HAAFP .................................................... 67 Figure 4-15 - Effect of oxidation on the formation potential of each of the four THMs ........ 69 xi  Figure 4-16 - Effect of oxidation on the formation potential of each of the three main HAAs (TCAA, MCAA, and DCAA). ................................................................................................ 71 Figure 4-17 - Typical biodegradation curve ........................................................................... 72 Figure 4-18 - Non-biodegradable DOC (DOCnon) for each oxidation scenario for BAC Column 1 and BAC Column 2 ................................................................................................ 74 Figure 4-19 - Parameter c for each oxidation scenario for BAC Column 1 ........................... 75 Figure 4-20 - Typical chromatogram for each phase of biodegradation experiment ............. 77 Figure 4-21 - Typical chromatogram result showing raw water, time 0 (treated), time 1 day and time 7 days. ...................................................................................................................... 78 Figure 4-22 - Deconvolution results for raw water biodegradation. ....................................... 79 Figure 4-23 - Deconvolution results for ozonation at 1mg O3/mg DOC feed water biodegradation......................................................................................................................... 81 Figure 4-24 - Deconvolution results for ozonation at 2mg O3/mg DOC feed water biodegradation......................................................................................................................... 83 Figure 4-25 - Deconvolution results for ozonation at 25mg O3/mg DOC feed water biodegradation......................................................................................................................... 85 Figure 4-26 - Deconvolution results for for 4000mJ/cm2 and 0 mg/L H2O2 feed water biodegradation......................................................................................................................... 87 Figure 4-27 - Deconvolution results for 2000mJ/cm2 and 10 mg/L H2O2 feed water biodegradation......................................................................................................................... 89 Figure 4-28 - Deconvolution results for 4000mJ/cm2 and 10 mg/L H2O2 feed water biodegradation......................................................................................................................... 91 Figure C-1 - Image of stained fluorescing GAC ................................................................... 112 Figure C-2 - Percent additional volatilization of harvested GAC compared to virgin GAC 113 Figure E-1- HPSEC chromatogram results ........................................................................... 118 Figure E-2- HPSEC chromatogram results ........................................................................... 119 Figure F-1 - Peakfit analysis results for each of the raw water (ID 1-9) HPSEC chromatograms. ..................................................................................................................... 120 Figure F-2 - Peakfit analysis results for each of the raw water (ID 10 -17) HPSEC chromatograms. ..................................................................................................................... 121 xii  Figure F-3 - Peakfit analysis results for each of the influent BAC column ozonated at 2mgO3/mgDOC (ID 1 to 7) water HPSEC chromatograms. ................................................ 122 Figure F-4 - Peakfit analysis results for each of the influent BAC Column 1 effluent  (ID 1 to 9) water HPSEC chromatograms. ......................................................................................... 123 Figure F-5 - Peakfit analysis results for each of the influent BAC Column 1 effluent  (ID 10 to 16) water HPSEC chromatograms. ................................................................................... 124 Figure F-6 -Peakfit analysis results for each of the influent BAC Column 2 effluent  (ID 1 to 9) water HPSEC chromatograms. ......................................................................................... 125 Figure F-7 -Peakfit analysis results for each of the influent BAC Column 2 effluent  (ID 10 to 17) water HPSEC chromatograms. ....................................................................................... 126 Figure F-8 - Peakfit analysis results for each of the Ozonated at 1mgO3/mgDOC water (ID 1- 7) and extended dose (ID 1 to 2) HPSEC chromatograms. .................................................. 127 Figure F-9 - Peakfit analysis results for each of the UV 4000mJ/cm2 and 0 mg/L H2O2 (ID 1 to 3) and 10mg/L H202treated (ID 1 to 6) HPSEC chromatograms. ..................................... 128 Figure F-10 -Peakfit analysis results for each of the UV 2000mJ/cm2 and 10 mg/L H2O2 (ID 1 to 7) HPSEC chromatograms. ............................................................................................ 129 Figure K-1 - Biodegradation test results for 1mgO3/mg DOC ............................................. 144 Figure K-2 - Biodegradation test results for 1mgO3/mg DOC ............................................. 145 Figure K-3 - Biodegradation test results for 2mgO3/mg DOC ............................................. 146 Figure K-4 - Biodegradation test results for 2mgO3/mg DOC ............................................. 147 Figure K-5 - Biodegradation test results for extended ozonation ......................................... 148 Figure K-6 - Biodegradation test results for 4000mJ/cm2 and 0 mg/L H2O2 ....................... 149 Figure K-7 - Biodegradation test results for 2000mJ/cm2 and 10 mg/L H2O2 ..................... 150 Figure K-8 - Biodegradation test results for 2000mJ/cm2 and 10 mg/L H2O2 ..................... 151 Figure K-9 - Biodegradation test results for 4000mJ/cm2 and 10 mg/L H2O2 ..................... 152 Figure K-10 - Biodegradation test results for 4000mJ/cm2 and 10 mg/L H2O2 ................... 153 Figure K-11 - Biodegradation test results for raw water samples ........................................ 154 Figure K-12 - Biodegradation test results for raw water samples ........................................ 155 Figure M-1 - Biodegradation test results for 1mgO3/mg DOC............................................. 159 Figure M-2 - Biodegradation test results for 1mgO3/mg DOC............................................. 160 Figure M-3 - Biodegradation test results for 2mgO3/mg DOC............................................. 161 xiii  Figure M-4 - Biodegradation test results for 2mgO3/mg DOC............................................. 162 Figure M-5 - Biodegradation test results for 4000mJ/cm2 and 0mg/L H2O2 ........................ 163 Figure M-6 - Biodegradation test results for 2000mJ/cm2 and 10mg/L H2O2 ...................... 164 Figure M-7 - Biodegradation test results for 2000mJ/cm2 and 10mg/L H2O2 ...................... 165 Figure M-8 - Biodegradation test results for 4000mJ/cm2 and 10mg/L H2O2 ...................... 166 Figure M-9 - Biodegradation test results for 4000mJ/cm2 and 10mg/L H2O2 ...................... 167 Figure M-10 - Biodegradation test results for raw water samples ........................................ 168 Figure M-11 - Biodegradation test results for raw water samples ........................................ 169 Figure N-1 - Parameter a for each oxidation scenario for BAC Column 1 and 2 ................ 173 Figure N-2 - Parameter c for each oxidation scenario for BAC Column 1 .......................... 174 Figure O-1 - HPSEC chromatogram results for each of the biodegraded raw water samples. ............................................................................................................................................... 175 Figure O-2 - HPSEC chromatogram results for each of the biodegraded ozonated (at 2mgO3/mg DOC)  water samples. ........................................................................................ 176 Figure O-3 - HPSEC chromatogram results for each of the biodegraded ozonated (at 1mgO3/mg DOC)  water samples. ........................................................................................ 177 Figure O-4 - HPSEC chromatogram results for each of the biodegraded ozonated (at the extended dose) and each of the UV4000 mJ/cm2 and 0 mg/L H2O2 water samples. ............ 178 Figure O-5 - HPSEC chromatogram results for each of the UV2000 mJ/cm2 and 10 mg/L H2O2 water samples. ............................................................................................................. 179 Figure O-6 - HPSEC chromatogram results for each of the UV4000 mJ/cm2 and 10 mg/L H2O2 water samples. ............................................................................................................. 180 Figure P-1 - Peakfit analysis results for each of the raw water biodegraded HPSEC chromatograms. ..................................................................................................................... 181 Figure P-2 - Peakfit analysis results for each of the raw water biodegraded HPSEC chromatograms. ..................................................................................................................... 182 Figure P-3 - Peakfit analysis results for each of the raw water biodegraded HPSEC chromatograms. ..................................................................................................................... 183 Figure P-4 - Peakfit analysis results for each of the ozonated at 2mgO3/mg DOC and biodegraded HPSEC chromatograms. .................................................................................. 184 xiv  Figure P-5 - Peakfit analysis results for each of the ozonated at 2mgO3/mg DOC and biodegraded HPSEC chromatograms. .................................................................................. 185 Figure P-6 - Peakfit analysis results for each of the ozonated at 1mgO3/mg DOC and biodegraded HPSEC chromatograms. .................................................................................. 186 Figure P-7 - Peakfit analysis results for each of the ozonated at 1mgO3/mg DOC and biodegraded HPSEC chromatograms. .................................................................................. 187 Figure P-8 - Peakfit analysis results for each of the ozonated at the extended dose and biodegraded HPSEC chromatograms. .................................................................................. 188 Figure P-9 - Peakfit analysis results for each of the ozonated at the extended dose and biodegraded HPSEC chromatograms. .................................................................................. 189 Figure P-10 - Peakfit analysis results for each of UV4000mJ/cm2 and 0mg/L H2O2 and biodegraded HPSEC chromatograms. .................................................................................. 190 Figure P-11 - Peakfit analysis results for each of UV4000mJ/cm2 and 0mg/L H2O2 and biodegraded HPSEC chromatograms. .................................................................................. 191 Figure P-12 - Peakfit analysis results for each of UV2000mJ/cm2 and 10mg/L H2O2 and biodegraded HPSEC chromatograms. .................................................................................. 192 Figure P-13 - Peakfit analysis results for each of UV2000mJ/cm2 and 10mg/L H2O2 and biodegraded HPSEC chromatograms. .................................................................................. 193 Figure P-14 - Peakfit analysis results for each of UV2000mJ/cm2 and 10mg/L H2O2 and biodegraded HPSEC chromatograms. .................................................................................. 194 Figure P-15 - Peakfit analysis results for each of UV4000mJ/cm2 and 10mg/L H2O2 and biodegraded HPSEC chromatograms. .................................................................................. 195 Figure P-16 - Peakfit analysis results for each of UV4000mJ/cm2 and 10mg/L H2O2 and biodegraded HPSEC chromatograms. .................................................................................. 196 Figure Q-1 - Bar graph results for each of the raw water Peakfit analyzed HPSEC chromatograms. ..................................................................................................................... 197 Figure Q-2 - Bar graph results for each of the raw water Peakfit analyzed HPSEC chromatograms. ..................................................................................................................... 198 Figure Q-3 - Bar graph results for each of the raw water Peakfit analyzed HPSEC chromatograms. ..................................................................................................................... 199 xv  Figure Q-4 - Bar graph results for each of the ozonated 2 mgO3/mg DOC Peakfit analyzed HPSEC chromatograms. ....................................................................................................... 200 Figure Q-5 - Bar graph results for each of the ozonated 2 mgO3/mg DOC Peakfit analyzed HPSEC chromatograms. ....................................................................................................... 201 Figure Q-6  - Bar graph results for each of the ozonated 1 mgO3/mg DOC Peakfit analyzed HPSEC chromatograms. ....................................................................................................... 202 Figure Q-7 - Bar graph results for each of the ozonated 1 mgO3/mg DOC Peakfit analyzed HPSEC chromatograms. ....................................................................................................... 203 Figure Q-8 - Bar graph results for each of the extended ozonated 25 mgO3/mg DOC Peakfit analyzed HPSEC chromatograms. ........................................................................................ 204 Figure Q-9- Bar graph results for each of the extended ozonated 25 mgO3/mg DOC Peakfit analyzed HPSEC chromatograms. ........................................................................................ 205 Figure Q-10 - Bar graph results for each of the UV4000mJ/cm2 and 0mg/L H2O2 Peakfit analyzed HPSEC chromatograms. ........................................................................................ 206 Figure Q-11 - Bar graph results for each of the UV4000mJ/cm2 and 0mg/L H2O2 Peakfit analyzed HPSEC chromatograms. ........................................................................................ 207 Figure Q-12 - Bar graph results for each of the UV2000mJ/cm2 and 10mg/L H2O2 Peakfit analyzed HPSEC chromatograms. ........................................................................................ 208 Figure Q-13 - Bar graph results for each of the UV2000mJ/cm2 and 10mg/L H2O2 Peakfit analyzed HPSEC chromatograms. ........................................................................................ 209 Figure Q-14 - Bar graph results for each of the UV2000mJ/cm2 and 10mg/L H2O2 Peakfit analyzed HPSEC chromatograms. ........................................................................................ 210 Figure Q-15 - Bar graph results for each of the UV4000mJ/cm2 and 10mg/L H2O2 Peakfit analyzed HPSEC chromatograms. ........................................................................................ 211 Figure Q-16 - Bar graph results for each of the UV4000mJ/cm2 and 10mg/L H2O2 Peakfit analyzed HPSEC chromatograms. ........................................................................................ 212 Figure R-1 - Percent removal results for each of the Peakfit analysed HPSEC chromatograms raw water samples. ................................................................................................................ 213 Figure R-2 - Percent removal results for each of the Peakfit analysed HPSEC chromatograms ozonated 1 mgO3/mg DOC water samples. .......................................................................... 214 xvi  Figure R-3 - Percent removal results for each of the Peakfit analysed HPSEC chromatograms ozonated 2 mgO3/mg DOC water samples. .......................................................................... 215 Figure R-4 - Percent removal results for each of the Peakfit analysed HPSEC chromatograms ozonated 25 mgO3/mg DOC water samples. ........................................................................ 216 Figure R-5 - Percent removal results for each of the Peakfit analysed HPSEC chromatograms UV4000mJ/cm2  and 0mg/L H2O2 water samples. ............................................................... 217 Figure R-6 - Percent removal results for each of the Peakfit analysed HPSEC chromatograms UV2000mJ/cm2  and 10mg/L H2O2 water samples. ............................................................. 218 Figure R-7 - Percent removal results for each of the Peakfit analysed HPSEC chromatograms UV2000mJ/cm2  and 10mg/L H2O2 water samples. ............................................................. 219      xvii  LIST OF EQUATIONS Equation 2-1 •→⋅+ OHvhOH 222  ..................................................................................... 14 Equation 3-1  samplemL NBAOLmg ⋅ ××± =⋅ 000,24)(/ 3  ......................................................... 22 Equation 3-2  21 ⋅⋅⋅⋅ −−= TrapKI gaseous TrapKI gaseous sample aqueous sample produced V M V M V M V M  ......................................... 23 Equation 3-3   21 ⋅⋅⋅⋅ −−= TrapKI gaseous TrapKI gaseous sample produced sample consumed V M V M V M V M  .......................................... 24 Equation 3-4   min60 1(min) swfJV V DIT UVr w ×× ××=⋅  ............................................. 30 Equation 3-5  )10ln( 101 ×× − = ×− AbsP wf L AbsPL  .......................................................................... 30 Equation 3-6  )*7776.0(10)(][22 SDAAppmOH o ×××−=  ........................................... 30 Equation 3-7  hrhrs V Q V V Column Column sample harvest min6024 1 1 × ×         = ⋅ ⋅  ....................................... 31 Equation 3-8    )exp( cxbay −+=  ............................................................................... 33 Equation 3-9  sample titred V NV LmgCaCO 000,50/3 ×× =  .................................................... 36 Equation 3-10  sample titred V V LmgCaCO 1000/3 × =  ................................................................. 36 Equation 3-11  [ ]mmgL DOC UVSUVA ⋅×= /100254  ............................................................. 37    xviii  LIST OF ABBREVIATIONS A254  Ultraviolet absorbance at 254nm wavelength   AMW  Apparent Molecular Weight      AOC  Assimilable Organic Carbon      AOP  Advanced Oxidation Process BAC  Biologically Activated Carbon BDOC  Biodegradable Dissolved Organic Carbon BOM  Biodegradable Organic Matter DBP  Disinfection By-Product DBPFP Disinfection By-Product Formation Potential DOC  Dissolved Organic Carbon EBCT  Empty Bed Contact Time GAC  Granular Activated Carbon H2O2  Hydrogen Peroxide HAA  Haloacetic Acids HAA5 Combined total of monochloroacetic acid, dichloroacetic acid, trichloroacetic acid, monobromoacetic acid, and dibromoacetic acid.  HPB  Hydrophobic Fraction HPL  Hydrophilic Fraction HPSEC High Performance Size Exclusion Chromatography HS  Humic Substances MW  Molecular Weight NOM  Natural Organic Matter SUVA  Specific Ultraviolet Absorbance THM  Trihalomethanes TTHM  Total Trihalomethanes USEPA United States Environmental Protection Agency UV  Ultraviolet UV/H2O2 Advanced Oxidation Process Using Ultraviolet and Hydrogen Peroxide UVA  Ultraviolet Absorbance UV254  Ultraviolet Absorbance at 254 nm   xix  ACKNOWLEDGEMENTS  There are many people that I am thankful to for their assistance throughout this project.  I would first and foremost like to express my sincerest thanks to my supervisor, Dr. Pierre Bérubé, for his knowledge, guidance and patience throughout the course of this work.  I would especially like to thank Dr. Bérubé for encouraging me to continue on in my academic studies, and for his continued mentorship. I would like to thank Paula Parkinson, Susan Harper and Timothy Ma for their advice, assistance and wealth of expertise with the challenges faced in the laboratory.  Special thanks to Paula Parkinson for her continued encouragement throughout the past year.   Special thanks to Dr. Madjid Mohseni, Gustavo Imoberdorf and Mehdi Bazri for use of their laboratory and for sharing their knowledge with me.  To PICA Carbon for providing Picabiol activated carbon, which provided an excellent filter bed material from which my experiments were completed. To my research colleagues for their companionship in the lab; especially Isabel, for her continued friendship and encouragement, and our many late nights together in the lab.    I thank my family and friends for their endless support and patience.  Most importantly, I would like to thank my parents for providing unconditional support and guidance throughout my graduate studies (and beyond!).   Finally, I’d like to thank my partner, Adam Robertson, who encouraged me to pursue graduate work and provided many hours of support, assistance and enduring patience.     xx  DEDICATION   To my friends and waterkeepers in Kep, Cambodia -  who serve as a source of constant inspiration  and motivation in my life.                   1  1.0 INTRODUCTION 1.1 Overview Conventional water treatment processes combine coagulation, flocculation, filtration and chlorination as the key steps towards the creation of safe and good quality drinking water.  However, these processes face extensive limitations as drinking water guidelines become more stringent.  While chlorination represents an inexpensive and widely accepted form of disinfection, it may potentially lead to the formation of disinfection by-products (DBPs) which are currently regulated in both Canada and the United States.  In Canada specifically, the Guidelines for Drinking Water Quality suggest maximum acceptable concentrations of 0.1 mg/L for trihalomethanes (THMs) and 0.08 mg/L for haloaceticacids (HAAs) (Health Canada, 2010). Water utilities are faced with the challenge of finding suitable and economical treatment processes that are able to meet these new rigorous guidelines.      Natural Organic Matter (NOM) is a complex mixture of organic materials found in most drinking water sources.  There is no known direct negative health effects associated with the presence of NOM in drinking water.  However, water quality and water treatment objectives may be significantly impacted by the presence of NOM, since it can lead to the formation of DBPs as well as the potential of biological regrowth within the distribution system (Hozalski et al., 1999).  Many water treatment technologies are currently being developed to reduce levels of NOM in drinking water.  Ozonation and advanced oxidation processes such as UV/H2O2 have gained considerable attention as viable alternatives to the conventional treatment methods.  In recent years, integrated treatment processes that combine the power of oxidation processes with subsequent treatment steps such as biological filtration have gained popularity as they can effectively reduce NOM levels in drinking water (van der Kooij et al., 1989; Hozalski et al., 1999; Toor and Mohseni, 2007).  However, oxidation increases biodegradability of NOM, potentially enhancing biological growth within the distribution system (Hozalski et al., 1999; Sarathy and Mohseni, 2009).  Therefore, biofiltration is necessary in order to remove biodegradable dissolved organic content (BDOC) matter prior to distribution.   2  This present research project investigated the effect of ozonation and advanced oxidation (UV/H2O2) on the characteristics of NOM, and its removal in an activated carbon biofilter.   Of particular interest were the rate and extent of BDOC removal in activated carbon biofilters, and the effect of different oxidation doses on these rates.   Initially, biodegradation of BDOC occurs rapidly in activated carbon biofilters (Yavich et al., 2004).   However, a residual amount of BDOC typically remains in the effluent of the biofilter.  This residual BDOC can result in microbial growth in water distribution systems.  Very little is known regarding the effect of different types of oxidants and oxidant doses on the rate of change of biodegradable dissolved organic carbon (BDOC) with time in a biofilter.   1.2 Research Objectives The principle aim of the present research project was to investigate the extent and rate of removal of BDOC in a biofilter over time for different oxidation processes and doses.   The overall objectives of this project were twofold: Part 1 - Biofiltration Experiments: To assess the removal of NOM through biological activated carbon filtration. Part 2 - Biodegradation Experiments: To assess the effect of oxidation on the rate of biodegradation.   The sub-objectives that contributed towards the aims of this project were: Part 1:  • To assess the impact of ozonation and biofiltration on source water quality including TOC, UVA, SUVA, AMW and DBPFP.   • To acclimatize biomass in order to perform the biodegradation experiments in Part 2.   Part 2: • To establish the effect of ozonation or UV/ H2O2 in combination with biological activated carbon filtration on the rate of biodegradation of organic matter and source water quality parameters including TOC, UVA, SUVA, AMW and DBPFP.    3  • To develop a technique to evaluate biodegradation within activated carbon biofilters by determining the rate kinetics governing the removal of DOC over time.     A detailed schema of this research plan is illustrated in Figure 1-1.   1.3 Contributions This project was designed to evaluate the overall efficiency of integrated treatment processes that combine oxidation processes with biological filtration.  Specifically, this project sheds light on operational advantages and limitations of ozonation, advanced oxidation and biofiltration.  The results of this study will allow for a more in-depth understanding of the removal of biological organic matter (BOM) within a biofilter and the degradation of NOM throughout this treatment process.  This study also provides insight from a water utility perspective on the viability of these new innovative treatment processes within the water sector.   4   Figure 1-1- Research plan   5  2.0 LITERATURE REVIEW 2.1 Natural Organic Matter (NOM) 2.1.1 Sources and Characteristics Natural Organic Matter (NOM) is a complex mixture of organic materials found in most water sources.   NOM can contain carbohydrates, lipids, amino acids, proteins, polysaccharides, and biopolymers.  NOM can comprise organic materials from many different sources, including human activities.  It can be classified into humic or non-humic substances.  Sources are typically dominated by humic substances generated from biological activity within and surrounding a water source (Croue et al., 1999).  Humic fractions can represent anywhere from 40 - 60% of the total dissolved organic carbon (DOC).  Humic substances can be further subdivided into humic acids or fulvic acids (HA or FA).  Humic acids contain many functional groups such as hydroxyl-, carbonyl-, methoxyl, phenolic and carboxyl groups (Wang and Hsieh, 2001).  Furthermore, humic acids are typically hydrophobic, while non-humic acids are typically transphilic or hydrophilic (Juhna et al., 2006).   The non-humic fractions are typically present as amino acids, sugars and polysaccharides, though sugars and amino acids are less abundant due to their high biodegradation rates (Croue, 1999).  The non-humic fractions are typically more biodegradable (Yavich, 1998).  Non-humic substances are typically referred to as biodegradable organic matter (BOM).  .   2.1.2 Problems Posed to Drinking Water Due to the complexity of NOM, water quality and water treatment objectives can be significantly impacted by its presence in source waters.  There is currently no known direct negative health effects associated with NOM in drinking water (Hozalski et al., 1999).   However, NOM is a concern in drinking water treatment because it can potentially lead to other consequences including: taste and odour properties, disinfection by-products, high disinfection demand, membrane fouling, biological instability and other performance 6  difficulties within treatment systems.  Reduction in NOM levels before disinfection and distribution is vital for production of safe, high-quality drinking water (Hozalski et al., 1999).  In terms of treatment in North America, NOM is typically removed through chemical coagulation, anion exchange, nanomembrane filtration and/or granular activated carbon (GAC) filtration (Juhna et al., 2006).   2.1.2.1 Disinfection By-Products Chlorine has been cited as one of the greatest public health advances of the 21st century (Okun, 2003).   Chlorine is a simple and effective disinfectant for the inactivation of pathogens, as well as acting as valuable protection against further contamination within the distribution system by providing disinfection residual.  Although chlorine is the most common disinfectant, ozone, chlorine dioxide, chloramines and UV radiation are also in use (USEPA, 2006).   As was mentioned in the previous Section, chlorine can react with NOM to form disinfection by-products (DBPs).  DBPs have been a concern since the early 1970s because of their potential adverse health effects (Wang and Hsieh, 2001; Komulainen, 2004; USEPA, 2006).  NOM is a precursor to most common DBPs such as trihalomethanes (THMs), haloacetic acids (HAAs), chlorinated ketones and haloacetonitriles, which are formed from the reaction of chlorine with naturally occurring organic precursors such as high molecular weight substances, humic and fulvic acids and aromatic structures (Rook, 1977; Reckhow et al., 1990; Singer, 1994; Croue et al., 1999;  Kleiser and Frimmel, 2000; Wang and Hsieh, 2001; Nikolaou and Lekkas, 2001; Chin and Bérubé, 2005; Krasner et al., 2006; WHO, 2008; Sarathy and Mohseni, 2009).   In recent years, the USEPA has imposed maximum allowable concentrations for chloroform to 0.07mg/l, trichloroacetic acid (TCAA) at 0.02mg/L , and monochloroacetic acid (MCAA) at 0.07mg/L.  The limits for total THMs (TTHM) is 0.08mg/L, and five of the nine known HAAs, HAA5 is 0.06mg/L (USEPA, 2006).  These values are based on its Stage 2 Disinfectant and DBP Rule.  Health Canada regulates THMs at 0.1mg/L and HAAs at 0.08mg/L (2010).  THMS and HAAs are a concern to human health because of their potential carcinogenic properties and suspected effects on reproductive and developmental health (Singer 1994; Toledano et al., 2005; USEPA, 2006, WHO 2008).    7  The formation of DBPs can be reduced by using non-chlorinated primary disinfectants, or by removing NOM prior to chlorination.  A large portion of research has been devoted to the latter.  Different treatment strategies alter NOM characteristics in various ways, thereby subsequently affecting its reactivity with chlorine.  Although non-chlorinated primary disinfectants can be used, chlorine is always used for secondary disinfection, as it is long-lasting, and therefore present throughout the distribution system, preventing the growth of pathogens from source to tap.  The WHO warns that disinfection should not be compromised in attempting to control DBPs as the health implications associated with inadequate disinfection are potentially far worse than the threat imposed by DBPs (WHO, 2008).   2.1.2.2 Biological Stability The creation of biologically stable drinking water is vital to the delivery of safe, high quality drinking water.  Biologically stable drinking water can be defined as water in which the microbial quality does not change from treatment system to tap.  Presence of microbial growth within the distribution system supports the reproduction of coliforms and bacteria, and leads to delivery of unsafe drinking water to the consumer.  As was discussed previously, chlorine is applied as a secondary disinfectant to inhibit biological growth in the distribution system.   NOM is a precursor for biogrowth in water treatment and distribution systems (LeChevalier et al., 1996; Croue et al., 1999; Gottschalk et al., 2000; Sarathy and Mohseni, 2007).   As discussed previously, the non-humic fraction of NOM is typically more biodegradable than the humic fractions, and therefore is typically the leading cause for bacterial regrowth within the distribution system (Yavich, 1998).   Reduction in NOM prior to distribution reduces the potential for microbial growth.   The USEPA regulates chlorine residuals at a minimum of 0.2mg/L (2006).  Health Canada however suggests an acceptable range of free chlorine, not to exceed 5mg/L (2010).  In Canada, each drinking water authority stipulates a specific free chlorine residual requirement in its jurisdiction. Treatment processes that target the reduction of NOM, prior to distribution, lead to the formation of biologically stable drinking water.    8  2.1.3 Characterization of NOM 2.1.3.1 Total Organic Carbon (TOC) NOM is typically measured as total organic carbon (TOC) in aquatic sources.  TOC is composed of dissolved organic carbon (DOC) and particulate organic carbon (POC).  DOC is defined as the organic carbon that passes through a 0.45µm filter.  Typically, NOM is present at low concentrations in water sources, between 2 to 10 mg/L DOC (Croue et al., 1999).   Another term important in this discussion is biodegradable dissolved organic carbon (BDOC).  BDOC is the fraction of DOC that can be utilized as substrate by microorganisms (Allgiers et al., 1996).  It typically represents between 10 to 20% of DOC (Servais et al., 1987).  Similarly, assimilable organic carbon (AOC) refers to a fraction of the total organic carbon (TOC), which can be utilized by specific strains or defined mixtures of bacteria, resulting in an increase in biomass concentration that is quantifiable. AOC typically comprises just a small fraction (i.e. 0.1 to 9.0%) of the TOC (van der kooij et al., 1989).   2.1.3.2 Ultraviolet Absorbance (UVA) UV absorbance, measured at 254nm (UV254), in drinking water treatment analyses can provide insight into the composition of NOM in the source water.  Light passes through a body of water and is absorbed by organic compounds leading to a reduction in transmitted light, the amount of which is proportional to the concentration of organic compounds in the solution.   UV254 radiation is typically absorbed by aromatic rings and conjugated double bonds; therefore a reduction UV254 indicates a loss of aromatic and double-bonded structures.  UV254 has been shown to correlate well with the content of aromatic material and DBP formation potential (Najm et al., 1994; Owen et al., 1995; Li et al., 2000; Kitis et al., 2001; Nikolaou and Lekkas, 2001).  The value of the UV254 depends strongly on the concentration of humic acids in the water; when these are low, the UV254 is not accurate (Wang and Hsieh, 2001).   Specific UV absorbance (SUVA) is the ratio of UV254 absorbance to DOC.  SUVA provides insight into the aromaticity and hydrophobicity of NOM (Krasner et al., 1993; Croue et al., 1999).   A higher SUVA can be indicative of NOM with high aromaticity or 9  other unsaturated configurations, which is typically indicative of NOM that is poorly biodegradable (Goel et al., 1995).   2.1.3.3 Polarity Measurement of polarity allows for determination of the hydrophobic and hydrophilic fractions of NOM present in the source water.  Hydrophobic fraction typically represents 30 - 50% of the DOC in natural waters (Kim et al., 2006).   2.1.3.4 Molecular Weight (MW) NOM molecular weight can vary from 100 to 10000 Da and is very diverse in nature (Pelekani et al., 1999.  Apparent molecular weight (AMW) is an important property in drinking water treatment as changes can effect DBPFP and biological stability of the distribution system (Speitel et al., 2000; Thomson et al., 2002a; Parkinson et al., 2003; Buchanan et al., 2004; Buchanan et al., 2005; Wang et al., 2006).   Higher AMW substances tend to be more aromatic in nature so may have a larger number of reaction sites (Westerhoff et al., 1999).    The molecular weight of NOM is an important concept when discussing biodegradability.  Lower molecular weight compounds tend to be more easily transported across cell membranes, attacked by metabolic enzymes and biodegraded (Leisinger et al., 1981).  Kennedy et al., (2005) reported that NOM could be classified into different categories based on its AMW.  According to this work, lower molecular weight organics would be on the order of less than 350Da, building blocks at 300-500Da, humic fractions at around 1000Da and biopolymers at greater than 20kDa.   2.1.3.5 Disinfection By-Product Formation Potential (DBPFP) As discussed previously, DBPs are an important element to consider in drinking water treatment.  It can be difficult to characterize NOM and its tendency to form DBPs (Wang and Hsieh, 2001).  The disinfection by-product formation potential (DBPFP) is a determination of the potential for formation of DBPs including THMs and HAAs.  Factors affecting DBP formation include pH, temperature, chlorine concentration, bromide concentration, DOC, and chlorine reaction time (Ko et al., 2000).   10  Depending on the characteristics of NOM, DBPFP reduction can vary significantly.  Chowdhury et al., (2008), observed that different NOM characteristics such as AMW and polarity are greatly impacted the DBPFP.  2.2 Technologies for Removal of NOM 2.2.1 Ozonation 2.2.1.1 Principles of Ozonation Ozone has been used in water treatment for over 100 years beginning in Nice France in 1906.  Since then, it has seen widespread use across the world (Rakness, 1996; von Gunten 2003a).  Ozone has been traditionally used as a disinfectant or oxidant. When used as an oxidant, ozone can help to reduce taste and odour compounds, colours and oxidize NOM.  Recently it has been shown to be effective at the removal of micropollutants such as some antibiotics/antibacterials (Dodd et al., 2009).    Ozone is unstable in water.  Ozone reacts with organic material by electrophillic addition to double bonds, producing carboxylic acids, alcohols and/or aldehydes.  Ozone reaction kinetics are governed by a rapid first phase, commonly referred to as the instantaneous ozone demand (IOD),  followed by a slower second phase that follows a first order rate (Cho et al., 2003; von Gunten, 2003a).   The ozone reaction rates for both phases are dependent on water quality, pH, DOC and alkalinity (Cho et al., 2003).   Ozonation can occur via two pathways, direct or indirect.  The direct pathway favours reactions primarily with unsaturated double bonds and aromatic compounds, though reaction with amines or sulphides is common (Gottschalk et al., 2000; von Gunten 2003a).  The direct pathway is limited by the availability of dissolved molecular ozone in the water phase (Amirsadari et al., 2001).   Alkalinity plays an important role in the direct pathway; at higher alkalinity, the direct pathway is favoured.     With the indirect pathway, hydroxyl radicals are formed and react with NOM. Hydroxyl radicals are strong, unselective oxidants.   At higher pHs, the indirect pathway is favoured (Hoigne and Bader, 1975).  There are many different ways for these OH radicals to react, a detailed description is provided elsewhere (Glaze et al., 1982).  Alkalinity plays an important role in the indirect pathway.  Carbonates are considered scavengers of hydroxyl 11  radicals and as alkalinity increases, less hydroxyl radicals are available (AWWARF 1999).  Depending on the alkalinity, production of OH radicals is typically much less than what is seen with advanced oxidation processes (AOPs) which is discussed in subsequent Sections.    If the goal of ozonation is disinfection, only enough ozone should be added to inactivate the microorganisms and the formation of BOM is undesirable.   BOM can cause significant bacterial regrowth in the distribution system if it is not removed in subsequent treatment steps (Van der Kooij, 1989; Huang et al., 2004).  If the goal of ozonation is to eliminate/reduce DBPS, then the production of BDOC should be maximized, so that it can be removed by subsequent degradation within a biofilter.   Disadvantages to the use of ozone are the formation of ozone-by-products (OBPs) such as aldehydes (formaldehyde, acetaldehyde, glyoxal, methyl glyoxal, etc.), ketoacids and carboxylic acids (Singer, 1999; von Gunten 2003a; von Gunten 2003b; Huang et al, 2004, Karnik et al., 2005a and Hammes et al, 2006).    One of the main concerns is bromate formed during oxidation of bromide.  (von Gunten, 2003b; WHO, 2008).   Most of the ozonation by- products are highly biodegradable and can be removed through biofiltration prior to releasing the water into the distribution system (Krasner et al., 1993; Swietlik et al., 2004).   2.2.1.2 Effect on NOM During ozonation, NOM is oxidized and transformed into intermediates still present as DOC (Fahmi and Okada, 2003; Bérubé et al., 2004).  Therefore, very little reduction in DOC is observed during low-dose ozonation.  The reaction of ozone with the aromatic structures and double bonds of NOM results in a significant decrease in UV254 (Kim et al., 1997; Kleiser and Frimmel, 2000).     Ozonation greatly impacts the molecular weight of NOM.  Ozone reacts with NOM resulting in fragmentation of organic material, and transformation from high to low AMW (Kaastrup and Halmo, 1987; Owen et al., 1995).   Ozone has been shown to be effective at removing certain DBP precursors naturally present in drinking water sources (Hu et al., 1999; Singer, 1999:  Galapate et al., 2001; Chin and Bérubé, 2005).  Some work has shown that ozonation typically reduces the DCAA, TCAA and THM formation potentials (Glaze et al., 1982; Owen et al., 1995; Kim et al., 1997; Chowdhury et al., 2008).  However, other work has shown that ozonation can also 12  increase DBPFP (Langlais et al., 1991; Siddiqui et al., 1997; Goslan et al., 2007; Toor and Mohseni, 2007).   Ozonation has also been shown to lead to the formation of bromoform, MBAA and DBAA (Huang et al., 2004; WHO, 2008).   The oxidation of NOM by ozone can enhance its biodegradability by reducing the size of NOM molecules, reducing aromaticity and increasing carboxylic acid functionality (Kaastrup and Halmo, 1987; Langlais et al., 1991; Westerhoff et al., 1999).  In previous work, BDOC and AOC contents tended to increase after ozonation (Owen et al., 1995; (Rittman and Huck, 1989, Kim et al., 1997; Sarathy and Mohseni, 2009).   Some work has shown that doses from 1 to 2 mg/mg TOC were optimal for enhancing biodegradation of NOM (Werner and Hambsh, 1986; Murphy, 1993; Siddiqui et al., 1997; Hozalski et al., 1999; AWWARF, 1999; Uhl, 2000; Kim et al., 2006; Melin et al., 2006).  A summary of the reported effects of ozonation on NOM characteristics is presented in Table 2-1. Table 2-1 - Summary of reported effects of ozonation on NOM characteristics Parameter Reported Effect TOC Negligible effect (Kleiser and Frimmel, 2000; Ko et al, 2000; Chin and Bérubé, 2005; Chowdhury et al, 2008; Gunten et al., 2009) 2-10% reduction (Westerhoff et al 1999) 4% reduction (Amirsadari et al., 2001) 10-30% reduction for ozone doses of 1 - 5mg/gmg DOC (Cipparone et al., 1997) 12% reduction of DOC at 1 mg O3/mg TOC (Kim et al., 2006). 20% reduction in DOC following ozonation (Kim et al., 1997) 16-33% TOC reduction (Hozalski et al., 1999) for 2-4 mg O3/mg TOC 0-20% reduction in TOC (AWWARF 1999) 6.4% reduction in DOC following ozonation (up to 1.5mg O3/mg DOC  (Galapate et al, 2001) UVA/SUVA Reduction in UV and SUVA (Ko et al, 2000; Chin and Bérubé, 2005; Gunten et al., 2009) 54% reduction in UVA260 (Galapate et al., 2001) 45% reduction (Kaastrup and Halmo, 1989) 50 - 75% reduction for doses of 0.5 - 1.5 mg O3/mg DOC(Kleiser and Frimmel, 2000)  35-70% reduction (Chowdhury et al., 2008) 28% reduction (Amirsadari et al., 2001) 50% reduction at 1mg O3/mg DOC (Kim et al., 2006) 50% reduction  (Kim et al., 1997) 56% reduction up to 1mg O3/mg DOC (Owen et al. 19950  Polarity Decreased hydrophobicity, increased hydrophilicity (Westerhoff et al, 1999; Galapate et al 200;, Chowdhury et al 2008) 13   Parameter Reported Effect Polarity Decrease in hydrophobic fraction from 54% to 5% following ozonation (Swietlik et al., 2004).  MW  Shift from higher MW to lower MW (von Gunten at al. 2003b) Higher MW oxidised preferentially, resultin in overall lowered MW (Swietlik et al., 2004) 88% increase in compounds less than 500Da, large shift from HMW to LMW. (Hozalski et al., 1999) No effect (Kim et al., 1997) HAAFP  5% increase in HAAFP following ozonation (Siddiqui et al., 1997) Roughly 50% decreased in HAAFP and Chloroform formation potential (Chin and Bérubé, 2005) Observed increases in DCAA following ozonation, however this could be the result of the formation of diketones and oxidation to aldehydes which has been shown to increase DCAA amounts (Reckhow and Singer, 1994).  63% reduction in TCAA values at a dose of 3.5mg/L (Ko et al., 2000) 34% reduction in HAAFP (Hu et al., 1999) 10 - 60% reduction observed for ozone doses from 1 - 5 mg O3/mg DOC (Cipparone et al., 1997) -117% to 38% reduction of HAAFP, mostly due to reduction in DCAA and TCAA formation potentials of the hydrophilic NOM (Chowdhury et al., 2008) THMFP 18-32% reduction observed (Kleiser and Frimmel 2000) 8% reduction at low doses, higher removal of 43% at dose of 3 mg O3/mg DOC(Galapate et al., 2001) -21% to 47% reduction observed (Chowdhury et al., 2008) 20-50% reduction in THMFP for 3.5mg/L preozonation (Ko et al., 2000) 27% reduction (Hu et al., 1999) 5-80% reduction for ozone doses of 1 -5 mg O3/mg DOC (Cipparone et al., 1997) 5% increase in THMFP following ozonation (Siddiqui et al., 1997) 50% reduction of chloroform (Bérubé et al., 2004) 5-20% reduction in THMFP for 0.4 - 1.2 mg O3/mg DOC Biodegradability  Increased BDOC and AOC content (Owen et al., 1995)  Increased in BDOC by 5 - 50% (Hozalski et al., 1999; Cipparone et al., 1997; Digiano et al., 2001) NOM with a higher percentage of high molecular weight compounds experienced the greatest enhancement in biodegradability by ozonation (Hozalski et al., 1999).    2.2.2 UV/ H2O2 Advanced Oxidation 2.2.2.1 Principles of UV/ H2O2 Oxidation Processes that use OH radicals as the main oxidant are called advanced oxidation processes (AOPs).  These hydroxyl radicals are very short lived and extremely strong 14  oxidizing agents.  They react with double bonds, or H-atom abstraction to form carbon centred radicals.   UV/ H2O2 can be used to generate OH radicals, as presented in Equation 2-1.   In this process, OH radicals are formed from cleavage of the hydrogen peroxide molecule.     Equation 2-1 •→⋅+ OHvhOH 222         The units of UV are represented as mJ/cm2.  Most important wavelengths for UV when discussing water treatment are in the range of 200 - 280nm.   The rate of photolysis of H2O2 is dependent on the pH, and increases in more alkaline conditions (Legrini et al., 1993).  In addition, the rate of reaction is highly dependent on the concentration of H2O2 and the UV light intensity, in addition to the chemical structure of the material being oxidized (Sundstrom et al., 1986).    UV light tends to react with H2O2 making less light photons available for the target pollutants at high H2O2 doses (Wang et al., 2006).   As a result, there exists an optimum H2O2 dose, after which hydroxyl radicals become less available (Kleiser and Frimmel 2000; Litter, 2005; Wang et al., 2006; Sarathy 2009).  Wang et al., reported that the formation of OH radicals was optimal at an H2O2 dose of 1% (2000).   While UV/ H2O2 is not typically used for drinking water treatment, UV doses up to 1500mJ/cm2 and H2O2 doses up to 20mg/L have been suggested (Sarathy and Mohseni, 2009).   2.2.2.2 Effect on NOM At high doses, UV/ H2O2 can mineralize NOM and decrease the TOC concentration (Sundstrom et al., 1986; Langlais et al., 1991; Beltran et al., 1993; Gottschalk et al., 2000; Kleiser and Frimmel, 2000; Speitel et al., 2000; Thomson et al., 2004; Wang et al., 2006; Toor and Mohseni, 2007).   However, the high amount of energy required to mineralize NOM makes this option economically unfeasible.   At lower, more economically feasible doses, UV/ H2O2 does not mineralize NOM.  Lower removal rates of DOC are observed at these doses given that NOM is partially oxidized and transformed into intermediates still present as DOC (Fahmi and Okada, 2003; Bérubé et al., 2004).   At the lower, more economically feasible doses,  NOM is oxidized into intermediate compounds that are less aromatic and have been shown to lower the tendency to form DBPs 15  (Thomson et al., 2002b;  Oppenlander, 2003; Thomson et al., 2004; Tuhkanen, 2004; Chin and Bérubé, 2005; Sarathy and Mohseni, 2007).  High removal rates for UV254 have been observed (Goslan et al., 2006; Bond et al., 2009).  Some work has shown that UV/ H2O2 is not efficient at removing DBPs and can lead to increased formation of DBPs (Toor & Mohseni, 2007).   Transformations from high AMW to low AMW have been observed (Thomson et al., 2004; Sarathy, 2009) AOPs can also lead to an increase in biodegradable organics  (Speitel et al., 2000, Liu et al., 2002; Thomson et al., 2004; Toor and Mohseni, 2007)    The lower dose treatments have been shown to increase the biodegradability of NOM (Liu et al., 2002; Toor and Mohseni, 2007).  A summary of the reported effects of UV/ H2O2 on NOM characteristics is presented in Table 2-2.   Table 2-2 - Summary of reported effects of UV/H2O2 on NOM characteristics Parameter Reported Effect TOC 14.5 % reduction at 1500mJ/cm2 and 20 mg/L H2O2.  Higher Reduction of 27% observed for a water with lower initial TOC concentration and absence of high molecular weight compounds (Sarathy and Mohseni, 2009) Up to 78% reduction  for UV/H2O2 (Goslan et al, 2006) Up to 91% reduction for UV/H2O2 for 4700-4800 mJ/cm2 and 78% reduction for 2100mJ/cm2 (Bond et al., 2009).  UVA 55% reduction mostly due to the loss of aromatic and double bonded compounds (Sarathy and Mohseni, 2009) Up to 94% reduction (Goslan et al 2006). Decrease in UV254 after AOP, especially at high UV doses (Toor and Mohseni, 2007) MW Higher MW oxidised preferentially, resulting in overall lowered MW (Sarathy, 2009; Thomson et al., 2004) Milder AOP conditions led to degradation of NOM and formation of smaller species, overall reduction in MW (Sarathy and Mohseni, 2007)  At H2O2 of 5mg/L, and 1350UV reduction of 65, 53 & 29% for 850-1100, 1100-1400 and greater than 1400mJ/cm2.  Greatest impact was achieved using 850 - 1400 mJ/cm2.  (Sarathy and Mohseni, 2009) Polarity 25 % hydrophobic compounds converted to hydrophilic compounds (Sarathy, 2009) Significant reduction in hydrophobic compounds following UV irradiaiton (Buchanan et al., 2005) AOPs are non selective oxidizers that don't necessarily preferentially remove hydrophobic compounds (Crittenden et al., 2005 & Bond et al., 2009).  HAAFP 70(Chin Bérubé 2005) for Ozone UV No effect (Sarathy, 2009) Observed increases in DCAA following AOP treatment could be the result of the formation of diketones and oxidation to aldehydes which has been shown to increase DCAA amounts (Reckhow and Singer, 1994).  Upwards of 1000mJ/cm2 and 100mg/L H2O2 required to reduce DBPs (Liu et al, 2002).   16  Parameter Reported Effect THMFP THMFP Increase of THMFP by 40% (Kleiser and Frimmel 2000) 80% reduction for Ozone/UV (Chin and Bérubé 2005) UV fluence greater than 1500 required for THMFP reduction (Toor and Mohseni, 2007) woth H2O2 of 23 No effect (Toor and Mohseni, 2007; Sarathy, 2009) Upwards of 1000mJ/cm2 and 100mg/L H2O2 required to reduce DBPs (Liu et a.l, 2002).   Upwards of 1500mJ/cm2 and 23mg H2O2 required for reduction in THMFP (Toor and Mohseni, 2007) Limited reduction in chloroform potential (Bérubé et al., 2004) Biodegradability  Increased in BDOC and biodgradability of NOM (Speitel et al., 2000; Liu et al., 2002; Toor and Mohseni, 2007) 2.2.3 Oxidation/Biofiltration 2.2.3.1 Principles of Combined Oxidation/Biofiltration Conventional treatment processes may not necessarily meet current and future water quality requirements.  Oxidation treatment processes alone may not necessarily be practical due to high energy demands, partial oxidation of NOM, insufficient reduction in DBPs and formation of biodegradable oxidation byproducts.  Integrated treatment processes that combine oxidation processes and activated carbon biofilters have been shown to be very effective at reducing natural organic matter (NOM) levels by oxidising NOM in to more biodegradable DOC, which is subsequently removed by biofiltration (Owen et al., 1995).   The use of BAC following oxidation treatment processes has the advantage of preferentially removing biodegradable material formed during oxidation.  Biological activated carbon (BAC) is a filtration system where granular activated carbon (GAC) is used as a growth medium, rather than for adsorption (AWWARF, 1994).  GAC supports more dense populations than sand or anthracite (i.e. 4 to 8 times more biomass per gram of media), likely due to many factors including porosity, surface area, surface roughness, surface charge and adsorption capacity (Speitel 2000; Wang et al., 2006).    GAC filtration has been shown to be effective at reducing DBP precursors, lowering nutrient availability for bacterial regrowth, and producing more biologically stable water (USEPA, 2006).  It’s also extremely good at reducing DOC levels and high AMW and humic fractions (Owen et al., 1995).    According to research, combined oxidation and biofiltration systems have the potential of resulting in the production of biological stable water, the minimization of the potential for bacterial regrowth within the distribution system; the removal of biodegradable 17  organic matter (BOM) and disinfection by-product precursors; the reduction in chlorine demand; and the potential removal/control of oxidation by-products (Cipparone et al., 1997; Wu et al., 2003; Fahmi and Okada, 2003).   Empty bed contact time (EBCT) is one of the single most important parameters for removal of BOM in biofilters.  Many previous studies have found that removal of NOM was directly proportional to EBCT.   (Lechevalier et al., 1992; Huck et al., 1994; Hozalski et al., 1995; Carlson and Amy, 1998) .  However, some research has shown that the EBCT has no effect on TOC removal (Hozalski et al., 1995).  Typical EBCT can vary however, EBCTs of 15 - 20 minutes have been reported (Yavich et al., 2004; Wang et al., 1995).  Another important parameter to consider with biofiltration is acclimation.  Acclimation of biofilters ensures the filters are operating at steady-state conditions, which allow filters to maximize the amount of BOM removed during filtration.  Typical acclimation periods required to reach steady-state can vary widely and depend largely on source water characteristics and temperature.  Acclimation periods in the range of 4 - 6 months have been reported (Wang et al., 1995; Yavich et al., 2004).   2.2.3.2 Effect on NOM The use of oxidation processes requires biofiltration since these processes increase the amount of BOM ((Speitel et al., 2000, Liu et al., 2002 and Thomson et al., 2004; Toor and Mohseni, 2007).    Biologically-active filtration is an approach for removing NOM from water to limit both concerns of DBP formation and microbial regrowth (Hozalski et al., 1999; Thomson et al., 2002a; Buchanan et al., 2004).     Biologically active filtration has been shown to reduce the concentration of DOC (Krasner et al., 1993; Fonseca and Summers, 2003).   Hozalski et al., (1999), found that removal of organic carbon by biodegradation was directly proportional to the percentage of low molecular weight compounds, and inversely proportional to SUVA.    BAC alone does not provide significant reduction in DCAA, TCAA or THM formation potentials (Toor and Mohseni, 2007).  Standalone AOP or oxidation systems are generally not viable given that they results in partial oxidation of NOM, insufficient reduction in DBPs and formation of biodegradable oxidation byproducts.  UV /H2O2 followed by biofiltration has been shown to have a significant impact on removal of THMs 18  (Speitel et al., 2000; Xie and Zhou, 2002). However some research has shown that biological treatment can also increase HAAFP (Bond et al., 2009).   According to several researchers, there is presence of a rapidly biodegradable fraction of NOM that can be substantially removed in the biofiltration process (BDOCr), and a slowly biodegradable fraction that is largely released to the distribution system (BDOCs) (Prévost et al., 1992; Servais et al., 1994; Wang and Summers, 1994; Carlson et al., 1996, Carlson and Amy, 1997).  BDOCr provides an indication of the DOC that can be removed during biofiltration and therefore its formation is desired.  BDOCr can also potentially lead to the formation of DBPs when chlorinated.  BDOCs gives an estimate of the NOM that is not significantly removed during biofiltration but can contribute to the biological instability of the treated water.   In previous work, the fraction of initial DOC that was converted to BDOCr during ozonation was reported not to be sensitive to DOC concentration for doses ranging from 0.2 - 1.4mgO3/mgDOC (Carlson and Amy, 1997).    On the other hand, the formation of BDOCs was almost always a function of source water composition rather than ozone dose (Carlson and Amy, 1997).  BDOCs increased with source water DOC for ozone doses between 1 and 2 mgO3/mg DOC (Carlson and Amy, 1997).      With respect to the biodegradation kinetics, according to Huck et al. (1998), a first order relationship was found for BDOC removal through a full-scale GAC contactor.  Yavich et al. (2001), found that biodegradation rates increased with increasing ozone dose (2004).  Carlson and Amy found that there was some maximal value of ozone dosing, above which BDOCr rate of biodegradation was not increasing.  A summary of the reported effects of combined oxidation and biofiltration on NOM characteristics is provided in Table 2-3.    Table 2-3 - Summary of reported effects of oxidation and biofiltration on NOM characteristics Parameter Reported Effect     TOC     NOM with higher % of high MW had substantial improvement of TOC removal followed by biodegradation (Goel et al., 1995).   30% reduction in DOC for ozone doses of 1.5 mgO3/mg DOC and subsequent biofiltration (Fonseca and Summers, 2003). 21-29% reduction (Wang et al., 1995) 52% reduction (Toor and Mohseni, 2007) 19  Parameter Reported Effect TOC  15-40% reduction for ozone doses 1 - 5 mgO3/mg DOC with biofiltration (Cipparone et al., 1997) 14-15% (Servais et al., 1994) 14-23% reduction (Klevens et al., 1996) 20-40% reduction by biodegradation (with starting TOC of 4mg/L) (Hozalski et al., 1999) UVA Further Decrease in UV254 after AOP and biofiltration - 59% reduction after 500Mj and 20mg/L in comparison to 22% reduction with BAC alone. (Toor and Mohseni, 2007) 59% reduction (Toor and Mohseni 2007) 60-80% reduction in SUVA (Hozalski et al., 1999) Polarity 20% decrease in hydrophobicity (Fahmi et al., 2002) MW 15-50% reduction in MW (Hozalski et al., 1999) HAAFP 37% reduction in DCAA to 50% reduction in TCAA for 500 mJ/cm2 and 20mg/L H2O2 with BAC as compared to 0 and 7% with BAC alone (Toor and Mohseni, 2007). Observed increases in DCAA following AOP treatment (or ozonation) could be the result of the formation of diketones and oxidation to aldehydes which has been shown to increase DCAA amounts but this would be reducd by subsequent biofiltration (Reckhow and Singer, 1994).  Reduction in TCAA by 69%, and DCAA by 74% for 3000 mJ/cm2 and 10-20mg/L H2O2 (Toor and Mohseni, 2007).  38% of HAAFP following ozonation and biofiltration (Joslyn and Summers, 1992) DBPFP was the lowest for biofilters treating ozonated wate, as compared to ozonation alone (Fonseca and Summers, 2003) No significant additional reduction over biotreatment alone (Wang et al., 1995) 47% reduction of HAAFP (Siddiqui et al., 1997) Near complete removal of 5 HAAs with BAC (Xie and Zhou,  2001)   46% reduction of HAAFP following ozonation and biofiltration (Joslyn and Summers, 1992) Additional 15% to almost 100% with ozone doses of 1 - 5 mgO3/mg DOC (Cipparone et al., 1997) THMFP 42% reduction for 500mJ/cm2 and 20mg/L H2O2 with BAC as compared to 11% with BAC alone (Toor and Mohseni, 2007). 69% for high dose of 3000mJ/cm2 and 10-20mg/L H2O2 (Toor and Mohseni, 2007) Significant Reduction in THMs (Speitel et al., 2000)  Reduction in THMFP of 45% as compared to 25% with conventional treatment (AWWARF, 1994).   50% removal (Wang et al., 1995 ) 40-80% for ozone doses of 1 -5 mgO3/mg DOC (Cipparone et al., 1997) DBPFP was the lowest for biofilters treating ozonated water, as compared to ozonation alone (Fonseca and Summers, 2003) 46% removal of THMFP (Siddiqui et al., 1997) 40-59% removal of THMFP (Shukiary et al., 1992) Biodegradability Substantial reduction in BDOCr during oxidation and biofiltration (Carlson et al., 1996; Carlson and Amy, 1997).   BDOCr formed during ozonation was sensitive to DOC concentration while BDOC s was not (Carlson and Amy, 1997)   20  3.0 MATERIALS AND METHODS 3.1 Part 1: Biofiltration Experiments  3.1.1 Raw Water Preparation The raw water used for the study consisted of a mixture of pond water and tap water.  The pond water was obtained from Jericho Beach Park, Vancouver, British Columbia (Figure 3-1).    Figure 3-1 - Jericho Beach pond park Pond water was collected every 2 months throughout the duration of the project.  The collected pond water was stored at 4°C for at least 1 week to allow for large particles to settle, and then filtered through binder-free borosilicate glass filters (Whatman Binder-Free Glass Microfiber Filters Type GF/D, Fisher Scientific).  Tap water was added to the filtered pond water to achieve a DOC concentration of approximately 5mg/L.  The resulting raw water had the characteristics outlined in Table 3-1.     21  Table 3-1 - Raw water characteristics Parameter Value DOC (mg/L) 5 ± 0.2 pH 7 ± 0.3 Temperature (°C) 21 ± 1 Hardness (mg/L as CaCO3) 50 ± 10 Alkalinity (mg/L as CaCO3) 50 ± 10  3.1.2 Feed Water Preparation Feed water for the biofiltration system (Section 3.1.3) consisted of raw water treated with ozone to a dose of 2mg O3/mg DOC.  Ozone was generated by coronal discharge through compressed air.  The O3 was bubbled using a stainless steel diffuser through a 2.5L amber bottle which was tightly fitted with a rubber fitting to limit off-gas release into the atmosphere.  Exactly 2L of raw water was placed in the contactor for treatment.  All tubing consisted of PTFE Teflon® tubing.  Figure 3-2 illustrates a schematic of the ozonation system.    COMPRESSED AIR OZONE  GENERATOR      2.5L REACTOR 200mL KI Trap O3 200mL KI Trap FLOW METER PRESSURE GAUGE Figure 3-2 - Schematic of ozonation apparatus 22   To determine the ozone flow rate an initial calibration of the apparatus was necessary.  The following procedure was used to calibrate the ozonation apparatus: 1. A 2L potassium iodide (KI) calibration solution was prepared based on Standard Method 423.A (APHA, 1989).  Exactly 40g of potassium iodide (Fisher Scientific) was dissolved in 2L of ultra-pure water.  The Iodometric method for ozone concentration determination has also been used in previous studies (Galapate et al., 2001).   2. Two secondary 200mL KI trap were prepared by dissolving 4g of potassium iodide in 200mL of ultra-pure water.   3. The 2L solution was placed in a 2.5L amber bottle contactor (the same vessel used for subsequent raw water treatment).  A secure rubber stop was placed at the top of the vessel.  Ozone off-gas was directed from the headspace to the secondary KI traps using PTFE Teflon® tubing.   4. The 2L solution was ozonated for a specific time period and purged for a minimum of 5 minutes at a flow rate of 0.2 - 1L/min to ensure that all ozone was swept from the sample.   5. Ozone production is calculated based on the volume obtained from subsequent titration with sodium thiosulfate (Fisher Scientific).  A 0.01N solution of sodium thiosulfate was prepared daily.  Exactly 100ml of KI solution was placed in a 400ml beaker on a stir plate.  5ml of sulphuric acid (Pure, Fisher Scientific) was placed in the beaker with the sample.  The sample was titrated with sodium thiosulfate until the yellow colour was almost discharged.  1ml of starch indicator solution was then added to impart a blue colour.  The sample was then quickly titrated until the blue colour was discharged.  Equation 3-1  was used to determine the ozone concentration.    Equation 3-1  samplemL NBAOLmg ⋅ ××± =⋅ 000,24)(/ 3      where A = mL titration for sample, B = mL titration for blank and N is the normality of Na2S2O3  23  6. The final ozone production amount was determined as using Equation 3-2.   Equation 3-2  21 ⋅⋅⋅⋅ −−= TrapKI gaseous TrapKI gaseous sample aqueous sample produced V M V M V M V M   where Maqueous and Mgaseous are determined based on the KI method described above.     7. Calibration was repeated for several treatment times to determine the ozone production rate.   Figure 3-3 illustrates the calibration curve for ozonation concentration versus time.  A full summary of raw data is provided in Appendix A.    Figure 3-3 - Ozone concentration versus time Ozone consumption was then determined by treating a 2L raw water sample for a given time.  Captured ozone in the secondary KI traps was subtracted from total ozone production to determine the final O3 dose as described in Equation 3-3.  y = 15.367x + 1.9025 R² = 0.9995 0 50 100 150 200 250 0 2 4 6 8 10 12 14 16 C o n ce n tr a tio n  (m g O 3/ L) Treatment Time (min) Ozone Production (mg/L) Trendline: Ozone Production (mg/L) 24  Equation 3-3   21 ⋅⋅⋅⋅ −−= TrapKI gaseous TrapKI gaseous sample produced sample consumed V M V M V M V M    where Mproduced is determined during calibration (as described above) and Maqueous and Mgaseous are determined based on the KI method described above.  Ozone consumption was highly dependent on the raw water matrix and varied substantially for a given dissolved organic carbon content.  For this reason, it was necessary to calibrate and calculate the final ozone dose prior to each analysis.    3.1.3 Biofiltration System A laboratory scale filtration apparatus was assembled in the Environmental Engineering Laboratory at the University of British Columbia.  A schematic of the system is presented in Figure 3-4, and details of the system operation and geometry are summarized in Table 3-2.    Figure 3-4 - A schematic of the laboratory scale apparatus.  25  Feed water (Section 3.1.2) was fed to the first column using a 1-100 RPM Masterflex L/S variable apeed console drive and multi-channel 8-cartridge pump head (Cole Parmer).  Filtered water from Column 1 was then collected from effluent tank 1 for sampling and the remaining water was pumped to the second column using a 1-100 RPM Ismatec 4-channel compact pump (Cole Parmer).  Filtered water from Column 2 was then collected for sampling.   Table 3-2 - Laboratory apparatus characteristics Parameter Setting Temperature (°C) 21 ± 1 Co lu m n 1  Volume (mL) 22 ± 1 Diameter (cm) 1 Flow Rate (ml//min) 1.1 EBCT 20 min Co lu m n 2  Volume (mL) 1000 Diameter (cm) 6.5 Flow Rate (ml//min) 0.2 EBCT 3 Days  For quality control and assurance, a total of 4 separate filtration apparatuses were constructed and operated in parallel.   The filtration apparatus was constructed using the following materials/  • 4 - 1 cm diameter glass Pyrex® columns, 30 cm long • 4 - 1000mL plastic Nalgene® graduated cylinders • 4 - 2L amber bottles for feed water • 8 - 1L amber bottles for filtered water collection • ⅛ʺ and  ¼ʺ PTFE Teflon® tubing for water circulation • 4 - 3-stop Tygon® red/red/red tubing (1.14mm ID) • 4 - 3-stop Tygon® yellow/blue/yellow tubing (1.5mm ID) • 8 - stainless steel Swagelok® fittings (½ʺ to ⅛ʺ diameter) • 8 - ½ʺ PTFE Teflon® ferrules   • 8 - ⅛ʺ PTFE Teflon® ferrules • 6- ⅛ʺ stainless steel compression fittings, union tees (Cole Parmer) 26  Amber bottles were used for feed and effluent tanks to minimize potential effects of exposure to light.  In addition, all tubing, columns walls and openings were covered using aluminum foil.  Feed water was replenished daily.  An image of the bench-scale apparatus is shown in Figure 3-5.    Figure 3-5 - Bench-scale apparatus Each column contained wood-base Picabiol® granular activated carbon (PICA Carbon).   Table 3-3 identifies the properties of the GAC used in this project.     Feed Tank BAC Column 1 BAC Column 2 Effluent Tank 1 Effluent Tank 2 27  Table 3-3 - Picabiol® granular activated carbon properties Properties Specification Actual Apparent Density (dry, g/mL) 0.18 - 0.26 0.22 Moisture (as packed, %) 5 Max 3.3 Ash (wt. %) 5% Max 3.4% Iodine No. (mg I2/g GAC) 900 min 1125 Uniformity Coefficient < 1.5 1.41 Effective Size 0.85 - 1.1 mm 1.04 Particle Size Distribution On 10 mesh 3.2% 10x12 mesh 16.7% 12x14 mesh 27.6% 14x16 mesh 27.2% 16x18 mesh 18.5% 18x20 mesh 5.4% Through 20 mesh 1.4%  The empty bed contact time (EBCT) of 20 minutes for Column 1 was selected based on the previous work of Allgeier et al. (1996), Carlson and Amy (1997) and Yavich et al. (2004) to remove the rapidly biodegradable fractions of NOM (BDOCr).  An EBCT of 20 minutes is also representative of EBCTs at full-scale BAC treatment plants.  The EBCT for Column 2 was selected to approximate the extent of biodegradation that occurs in distribution systems.  .  The maximum average residence time in a distribution system was assumed to be approximately 3 days.  In order to ensure consistency and ensure reproducible results, the EBCT was carefully monitored for each column.  Equally important was biofilter acclimatization which can impact DOC removal rates.  It was important to operate the biofilter process as close to steady-state as possible to achieve optimum results (Carlson and Amy, 1996; Prévost et al.,1997; Urfer et al., 1997).  Filter acclimatization can be roughly estimated by monitoring the removal efficiency of DOC, or the number of bed volumes filtered.  Figure 3-6 illustrates the removal of DOC through the filter as a function of time to indicate when filter acclimatization was achieved.  Figure 3-6 also illustrates the approximate number of bed volumes filtered prior to acclimatization.   28   Figure 3-6 - Biofilter effluent DOC versus bed volumes filtered Acclimatization or assurance that the filter was operating at steady-state was essential in order to begin any analysis.  An excess of 4 months and approximately 10,000 bed volumes was necessary in order to ensure acclimatization of the filter.   As evidenced in other research, it was important to closely monitor and manage water temperature, NOM source and ozone dose in order to ensure constant biodegradation in the system (Hozalski et al., 1999).  Though the NOM source remained consistent, seasonal changes may have affected the performance of the biofilters.   3.2 Biodegradation Experiments 3.2.1 Raw water preparation Please refer to Section 3.1.1 for relevant discussion regarding raw water preparation.   0 5000 10000 15000 20000 25000 0 1 2 3 4 5 6 Aug, 2009 Nov, 2009 Feb, 2010 May, 2010 Aug, 2010 Bed Volumes Filtered D iss o lv ed  O rg an ic  Ca rb o n  (m g/ L) Column 2 Column 1 Experimentation Period 29  3.2.2 Feed Water Preparation 3.2.2.1 Ozonation A description of the apparatus used for ozonation of the raw water is presented in Section 3.1.2.  For the batch biodegradation experiments, the target ozone doses for the feed water were 1 mgO3/mg DOC, 2mg O3/mg DOC and an extended ozone dose.  The extended ozone dose in this case was in the order of 25mg O3/mg DOC.   3.2.2.2 UV/H2O2 The UV/H2O2 oxidation apparatus consisted of a semi-batch reactor comprising a storage tank, UV light source, recirculation line and heat exchanger illustrated in Figure 3-7.   The low-pressure mercury lamp (Light Sources Inc., G10T5 ½L) was capable of an output of 5.7W at 254nm.  The lamp was enclosed in a glass sleeve giving a net volume capacity of 85mL.    Raw water was re-circulated through the reactor at a constant flow rate.     UV fluence was calculated using potassium ferrioxalate actinometry as described elsewhere (Murov, 1993).  Based on the desired UV dose and the characteristics of the source water,   Pump Storage  Tank     Photoreactor    Heat Exchanger UV Lamp Figure 3-7 - Experimental semi-batch UV/H2O2 reactor 30  irradiation times were calculated based on Equation 3-4 and Equation 3-5 as described in Bolten and Linden (2003).  Equation 3-4   min60 1(min) swfJV V DIT UVr w ×× ××=⋅    Equation 3-5  )10ln( 101 ×× − = ×− AbsP wf L AbsPL       where D is the desired UV dose, Vw is the volume of water treated, Vr is the volume of the reactor, JUV is the output of the lamp (mw/cm2), wf is the water factor, PL is the path length (0.5cm) and Abs is the absorbance of the sample at 254nm.   The storage tank contained a 1L solution of raw water to which an H2O2 solution (30%, Fisher Scientific) was added to achieve a final concentration of approximately 10mg/L.  H2O2 concentration was calculated using Equation 3-6 as described in Klassen et al. (1994). Equation 3-6  )*7776.0(10)(][22 SDAAppmOH o ×××−=   where A is the absorbance of the prepared sample at 351nm, Ao is the absorbance of the blank at 351nm, D is the additional dilution (1 if none), and S is the sample volume (0.5mL). Following UV/H2O2 treatment of the raw water samples, H2O2 was quenched using 0.2mg/L bovine liver catalase (lyophilized powder, ≥ 10,000 units/mg protein, Sigma Aldrich Canada) as recommended by Liu et al. (2003).  There was no observable increase in the DOC following the addition of 0.2mg/L of catalase.   For the batch biodegradation experiments, the target UV/ H2O2 doses for the feed water are summarized in.  A full summary of raw data is provided in Appendix B.       31  Table 3-4 - UV/H2O2 experiment conditions Desired Dose, D (mJ/cm2) H2O2 Concentration (mg/L) Volume of Water Treated (mL) Irradiation Time , IT (min) 4000 0 1000 65.5 2000 10 1500 49.1 4000 10 1500 99.0 3.2.3 Batch Biodegradation Experiments 3.2.3.1 Batch System The biodegradation experiments were completed based on similar work by Allgeier et al. (1996), Carlson and Amy (1997) and Yavich et al. (2004) and is described as follows. 1. GAC is first harvested from the acclimated filter bed.  In order to ensure a representative sample of biomass was selected, the entire contents of the column were removed and mixed prior to harvesting.  The amount harvested was selected to achieve a specific biomass load in the batch biodegradation test over a 24 hour period that was similar to that in BAC Column 1.  Equation 3-7 describes this relationship: Equation 3-7  hrhrs V Q V V Column Column sample harvest min6024 1 1 × ×         = ⋅ ⋅   where Vharvest is the amount of GAC to be harvested (in mL), Vsample is the amount of sample used in the biodegradation experiment (50mL), QColumn1 is the flow rate of Column 1 (1.1mL/min) and VColumn1 is the volume of GAC in Column 1.   Approximately 0.7mL of GAC was harvested for each batch biodegradation experiment.  The same amount was used for biodegradation experiments performed on Column 2.   2. The harvested GAC was placed in a 150mL Erlenmeyer flask.  Prior to analysis, the flasks were meticulously cleaned with detergent and rinsed at least three times with tap water, distilled water and ultra-pure water (Millipore Aqua-Q Ultra-Pure Water System) and baked in a muffle oven at 450°C for a minimum of 4 hours.  Prior to use, 32  the muffled flasks were stored in a clean container with aluminum foil covering the openings.   3. Exactly 50mL of feed water was added to each Erlenmeyer flask.  Table 3-5 describes the type of sample water that was considered for each biodegradation experiment.  4. Batch reactors were then placed in an incubated shaker (NBS 4230, GMI Inc.) at 100 RPM and temperature controlled at 21°C for  each of the following times: 4, 8, 12, 18 hours and 1, 2, 3, 4, 5, 6 and 7 days.  The temperature was selected to be consistent with the temperature observied during biofiltration (Section 3.1.3).  A summary of each of the different scenarios is presented in Table 3-5.     Table 3-5 - Biodegradation experiment description Source of Biomass Oxidant Dose  Reaction Times Separate experiments performed using both BAC Column 1 & 2 None  -  4, 8, 12, 18 hrs; 1, 2, 3, 4, 5, 6, 7 days Ozone  1 mg/ mg DOC  Ozone   2 mg/ mg DOC  Ozone   Extended Dose  (≈25 mg/mg DOC) AOP  2000 mJ/cm2 & 10 mg/L H2O2  AOP  4000 mJ/cm2 & 10 mg/L H2O2  AOP  4000 mJ/cm2 & 0 mg/L H2O2  5. Once the reaction time was complete, the samples were removed and immediately filtered through 0.45µm filter paper (Millipore, Fisher Scientific) and stored at 4°C for subsequent analysis of DOC, UVA and molecular weight by HPSEC.   All batch biodegradation tests were fully randomized so as to minimize potential human and experimental error.  For each of the conditions described in Table 3-5 a minimum of three replicates was performed.      A simple decay curve was used to analyze all data obtained from biodegradation experiments.  Equation 3-8 was used for analysis of biodegradation curves.     33   Equation 3-8    )exp( cxbay −+=    where, a represents the Concentration of non-biodegradable DOC (DOCnon), b represents the initial Concentration of DOC, less the DOCnon (DOCi), c represents the kinetic rate constant for the biodegradation reaction (kinetic rate constant, kDOC) For each of the biodegradation curves obtained, the values of a, b and c were averaged for each scenario.  This allowed for comparison of each of these values to determine whether any trends existed with respect to biodegradation.  The most important parameter was of course the kinetic rate constant which was indicative of the rate at which DOC was biodegraded by the available biomass.   3.2.3.2 Biomass Analysis As a secondary confirmation of acclimatization, it was necessary to confirm the presence of biomass within the filter and to confirm that the removal of DOC was due to biodegradation and not adsorption to GAC.  The biomass was qualitatively examined using acridine orange staining similar to the technique described in Hobbie et al. (1977).  Samples of activated carbon from each of the columns were collected and stained with 0.01% acridine orange prepared with ultra-pure laboratory water and preserved with 2% formaldehyde.  Samples were rinsed with ultra-pure water prior to analysis by fluorescing microscope.  Because of the shape, size and contour of the granular activated carbon particles it was necessary to use a laser scanning confocal microscope capable of examining fluorescent emissions.  A Zeiss Laser Scanning Microscope 510 DuoScan equipped with an LSM 5 Pascal Exciter and Zeiss AxioCam High Resolution camera was used.  Results are provided in Appendix C.   In addition to analysis by microscopy, total volatile solids were also determined in accordance with Standard Methods 2540 (APHA, 2005) as an indicator of biomass growth.  Biomass growth was also confirmed through visual inspection of the filtration apparatus.  Results are provided in Appendix C.   Sample blanks were completed by repeating the biodegradation test with the harvested GAC using distilled and deionized ultrapure water (MilliQ water).  In addition, sodium azide was used to kill the existing biomass so that any uptake by adsorption could be 34  accounted for.   A solution of 0.1N Sodium Azide was required.  No significant amount of DOC loss or gain can be attributed to the biomass and, therefore, it is expected that the biodegradation curves obtained in this study reflect the biodegradation potential of the harvested biomass.  Results are illustrated in Figure 3-8.    Figure 3-8 - Quality control biodegradation curves In addition, a secondary quality control method was employed.  At random, double biomass or half of the biomass used in the original biodegradation experiment was used and these results were compared to the rest of the biodegradation test results.  When double the amount of biomass was placed in the reactor, it was expected that it would removed the same amount of DOC, but in half the time.  When half of the biomass was placed in the reactor, it was expected that it would take twice the time to remove the same amount of DOC.  Results achieved during this process were as expected and repeated at random, to ensure good behaviour during the biodegradation test. 0 0.5 1 1.5 2 2.5 3 3.5 4 4.5 5 0 1 2 3 4 5 6 7 D O C  (m g/ L) Time (Days) 0.1 Sodium Azide 0.01 Sodium Azide 0.05 Sodium Azide Blank 1 Blank 235  3.3 Analytical Methods 3.3.1 Glassware Due to low concentrations of each of the various parameters examined in both the raw, feed, biofiltered and biodegraded water matrix, glassware was meticulously cleaned prior to use in order to minimize any potential contamination.  All glassware, lids, Teflon- lined septa, lids and sampling vials were washed with detergent and rinsed at least three times with tap water, distilled water and ultrapure water (Millipore Aqua-Q Ultra-Pure Water System).  In addition, all non-volumetric glassware and sampling vials were then baked in a muffle oven at 450°C for a minimum of 4 hours.  Volumetric glassware was baked at 105°C in an oven for a minimum of 1 hour.  After cleaning and baking, all glassware was stored in a clean, dry place with aluminum foil covering all openings.   3.3.2 pH  Throughout the duration of the experiments, pH was measured using an Accumet pH Meter 50 (Fisher Scientific).  Prior to analysis, the pH meter was calibrated using three standard buffer solutions of pH 4.0, 7.0 and 10.0.  The target pH of the prepared raw water was 7.0.   3.3.3 Temperature Temperature was measured using a Fisherbrand* general purpose thermometer (Fisher Scientific).  Measurements were recorded to the nearest degree.   3.3.4 Alkalinity  Alkalinity was measured in accordance with Standard Methods 2320 (APHA, 2005) described below.   • 100ml of water sample was measured and place in Erlenmeyer flask.  1 drop of 0.1N sodium thiosulfate was then added to the sample. • The sample was placed on stir plate with stir bar and one aliquot of phenolphthalein indicator was added.   36  • The sample was then titrated with standard acid solution until the red colour was almost discharged.  • One aliquot of bromcresol green was then added and the water sample was titrated until the colour changed from blue to yellow.   Alkalinity was calculated using Equation 3-9.   Equation 3-9  sample titred V NV LmgCaCO 000,50/3 ×× =    where Vtitred is the volume of titrant used, N is the normality of the standard acid and Vsample is the volume of sample used (100mL).  The target alkalinity of the prepared raw water was 50mg/L as CaCO3.   3.3.5 Hardness Total hardness was measured in accordance with Standard Methods 2340 C. EDTA Titrimetric Method (APHA, 2005) described below: • 25mls of sample was diluted to 50ml with distilled water and placed in a 250ml Erlenmeyer flask.  The flask was then placed on a stir plate with a stir bar.  • 1-2ml of buffer solution and one aliquot of Total Hardness Indicator were added to the sample. • The sample was then titrated with EDTA until the reddish tinge was discharged and a pure blue colour remained.  The entire titration was completed within 5 minutes to minimize CaCO3 precipitation.   Total hardness was calculated using Equation 3-10.   Equation 3-10  sample titred V V LmgCaCO 1000/3 × =     where Vtitred is the volume of titrant used, and Vsample is the volume of sample used (25mL).  37  The target total hardness of the prepared raw water was 50mg/L as CaCO3.   3.3.6 Total Organic Carbon (TOC) For the raw, feed, biofiltered and biodegraded water analyzed in this experiment, nearly all (90%) of the TOC was present as DOC.   DOC concentrations were measured in accordance with the Persulfate-Ultraviolet Oxidation Method in Standard Methods 5310C (APHA, 2005).  A Dohrman Pheonix 8000 UV-Persulfate Analyzer was used with a calculated method detection limit (MDL) of 0.1mg/L (Standard Methods 1030C, APHA 2005).  Samples were filtered through 0.45µm filter paper (Millipore, Fisher Scientific) prior to analysis.  Due to the low concentrations of DOC present in the waters analyzed, the lowest analytical range of the instrument was employed (0.1 - 20mg/L).  Three replicates of each sample were collected and each one was analyzed three times.  A 5mg/L standard was analyzed for each instrument run.  Blanks were prepared using ultra-pure laboratory water.   3.3.7 Ultraviolet Absorbance (UVA) & Specific Ultraviolet Absorbance (SUVA) Ultraviolet absorbance (UVA) was measured at 254nm (UV254) in accordance with Standard Methods 5910B (APHA, 2005).  A UV 300 UV-Visible spectrometer (Spectronic Unicam) with a 1cm pathlength quartz cuvette was used.  Samples were filtered through 0.45µm filter paper (Millipore, Fisher Scientific) prior to analysis.  Three replicates of each sample were collected and each one was analyzed three times.  A 5mg/L standard was analyzed for each instrument run.  Blanks were prepared using ultra-pure laboratory water.   Specific UV was calculated based on the UV254 and DOC values using Equation 3-11.  SUVA values were multiplied by 100 given that measurements were done with a 1cm UV cell (Xie, 2004).   Equation 3-11  [ ]mmgL DOC UVSUVA ⋅×= /100254     where UV254 is the absorbance at 254nm (cm-1) and DOC is the dissolved organic carbon content (mg/L).    38  3.3.8 Molecular Weight Determination by High Performance Size Exclusion Chromatography (HPSEC) 3.3.8.1 HPSEC Analysis HPSEC analysis was performed using a Waters 2695 Separation Module HPLC system equipped with a Waters 2998 Photodiode Array Detector, set to detection at 260nm.  The carrier solvent consisted of 0.02 M phosphate buffer (Laboratory grade, Fisher Scientific), at pH 6.8, adjusted with sodium chloride (Certified A.C.S, Fisher Scientific) to 0.1M ionic strength and the column flowrate was 0.7 mL/min.  Results from the HPSEC provided the detector response for a given retention time.  AMW was correlated to the retention time by performing a calibration with Polystyrene Sulfonate Standards (American Polymer Standards Corporation) with defined molecular weights of 1100, 4000, 5000 and 7000 Da.  A calibration curve with a coefficient of determination of 0.9975 is illustrated in Figure 3-9.  Molecular weights of the standards did not cover the complete range of molecular weights considered in the present study; therefore the calibration curve was extrapolated using the equation displayed in Figure 3-9 for analysis.   39   Figure 3-9 - HPSEC calibration curve Each HPSEC run included standards that were verified against the original calibration curve to ensure consistency and are also shown in Figure 3-9.   A typical HPSEC chromatogram for the sample water is shown in Figure 3-10.  The different NOM fractions are depicted in Figure 3-10, as described previously.  The molecular weight estimates of these fractions were used for subsequent analysis.   y = -0.3752x + 6.2864 R² = 0.9975 2.00 2.20 2.40 2.60 2.80 3.00 3.20 3.40 3.60 3.80 4.00 5.5 6 6.5 7 7.5 8 8.5 9 Log ( M W  [D a] ) Retention Time (min) Calibration Data Standard Run Checks40   Figure 3-10 - Typical HPSEC chromatogram It is important to note that baselines varied between runs, resulting in small shifts in chromatogram results.  Baselines were therefore adjusted to normalise the data and allow for proper peak resolution.  Baselines were adjusted using Systat’s Peakfit version 4.12 “Baseline Fit and Subtract” function.  To ensure reproducibility, results were confirmed through the analysis of replicates.   3.3.8.2 Resolution of HPSEC Chromatograms Although the chromatograms provide insight into the characteristics of the NOM, it is difficult to quantitatively compare the chromatograms from different analyses.  To overcome this limitation, the chromatograms were deconvoluted into a series of Gaussian peaks (Thomson et al., 2004; Sarathy and Mohseni, 2007).  Using Systat’s Peakfit software version 4.12, the “Autofit Peak III Deconvolution” function was applied with the parameters outlined in Table 3-6 .  41  Table 3-6 - Autofit Peak III deconvolution parameters Parameter Setting Peak Type Extreme Value 4 Parameter Tailed (Amplitude) Response Width 20s Response Width Defined at Full Width at Half-Maximum Frequency Domain Filter 60% Amplitude Rejection Threshold 4% Minimum R2 Value  > 0.99  The above settings were selected based on the minimum R2 of the fit and yielded a minimum R2 of 0.99 for all fitted chromatograms.  These settings resulted in a 14-peak chromatogram that was used to fit all HPSEC data, presented in Figure 3-11.  The summation of the 14 peaks corresponds to the original HPSEC chromatogram (Figure 3-11).    42   Figure 3-11 - HPSEC chromatogram resolution.  Showing the actual response, and the generated response from summation of the 14 peaks fitted.  Peaks were categorized based on molecular weight (Da): >1350 (F1), 1050 - 1350 (F2), 750-1050 (F3), 500-750 (F4), 300-500 (F5), <300 (F6)). The resolved peaks were categorized based on molecular weight and placed into apparent molecular weight (AMW) fractions based on their retention times using the calibration procedure discussed in Section 3.3.8.1.  The largest fraction represented molecular weights greater than 1350Da and corresponded to the leading edge of the chromatogram (F1).  The remaining peaks were resolved into the following fractions:  1050 - 1350 (F2), 750-1050 (F3), 500-750 (F4), 300-500 (F5), <300 (F6).  The fractions F1, F2, F3, and F4 roughly corresponded to the humic substances, F5, to the building blocks and F6, to the lower molecular weight organics and neutrals, as depicted in Figure 3-10 (Kennedy et al., 2005).  The areas of each individual peak were quantified to determine the area corresponding to each fraction.   43  3.3.9 Disinfection By-Product Formation Potential (DBPFP) To quantify the disinfection by-product formation potential (DBPFP) of raw, treated and biodegraded waters the Uniform Formation Conditions (UFC) Method was performed (Summers et al., 1996).  This method was chosen over the traditional seven-day formation potential test outlined in Standard Methods 5710 (APHA, 2005) as the traditional method applies high chlorine doses over long incubation time, which may lead to higher concentrations of DBPs, and higher chlorine-based over bromine-based DBPs (Symons et al., 1993; Symons et al., 1996; Shukairy and Summers, 1995).  The UFC procedure targets conditions outlined in Table 3-7 .   Table 3-7 - Uniform formation conditions Uniform Formation Conditions pH 8.0 ± 0.2 Temperature 20.0 ± 1.0 Incubation Time 24 ± 1 hr Chlorine Residual (as Free Chlorine after 24 hrs) 1.0 ± 0.4 mg/L  The UFC procedure used was as follows: 1. Samples were removed from storage at 4°C and allowed to equilibrate to room temperature (approximately 1 hour).   2. 2mL/L of pH 8 borate buffer (described in Summers et al., 1996)  was added to the water sample and the pH was adjusted to 8.0 using sulphuric acid (Fisher Scientific) 3. An aliquot of the sample was placed into pre-cleaned 43mL amber glass vials until three quarters full. 4. Dosing of the aliquot was then done using the combined hypochlorite-buffer solution (described in Summers et al., 1996), and inverted twice using a Teflon-lined screw cap.   5. Vials were then filled with remaining sample and capped headspace free.  The vials were inverted a minimum of ten times.  44  6. Vials were incubated for 24 hours at 20.0°C.  Following incubation, test vials were opened to measure the chlorine residual and pH, and quenched for subsequent analysis.   In order to determine the correct dosing amount, trial and error at various Cl2:TOC ratios was used to determine the required dose to allow for a 1.0 ± 4mg/L chlorine residual after 24 hours of incubation.   Prior to trihalomethane analysis, the aliquots of sample were quenched with 5g/50mL sodium thiosulfate (Fisher Scientific).  Prior to haloacetic acid analysis, the aliquots of sample were quenched with 2.5g/50mL ammonium chloride (Fisher Scientific).   3.3.10 Trihalomethanes (THMs) Trihalomethane (THM) concentrations were measured based on the Liquid-Liquid Extraction Gas Chromatography Method described in Standard Methods 6232B (APHA, 2005).  Pentane was used as the extraction solvent.  Pentane was cleaned in accordance with the method developed at the UBC Environmental Engineering Laboratory which has been shown to produce pentane which is below the MDL for chloroform concentration (Bush, 2008).  The following procedure was used to clean pentane: 1. A gas chromatograph column was packed with basic alumina and placed in a Hewlett-Packard 5880A Series GC and heated to 220°C while passing helium carrier gas through the column.  To ensure negligible concentrations of chloroforms, the column was heated for minimum of 24 hours.      2. Pentane was then passed through the alumina-packed column with the help of a 100cc glass syringe (Benton Dickinson Luer-Lock Reusable Syringe, Fisher Scientific).  Clean pentane was collected in a pre-cleaned amber bottle. To minimize re-contamination of the pentane, cleaned pentane was used within 2 days, or it was necessary to repeat this procedure.   The following procedure was then used for trihalomethane extraction and analysis: 1. Pre-quenched samples were removed from storage at 4°C and allowed to equilibrate to room temperature (approximately 1 hour).  2. Clean pentane was spiked with 1,2 dibromopropane as the internal standard to achieve a final concentration of 60µg/L.   45  3. Calibration standards were prepared from commercially available THM calibration mixes (approximately 99% purity) in methanol (Supelco Analytical).  A minimum of 5 standards covering the expected range of results were prepared.   4. Calibration standards and blanks were made using a commercially available brand of ozonated spring water (Safeway Select Refreshe, Canada Safeway Ltd) to reduce the potential for contamination from chloroform.   5. Exactly 5mL of sample was removed and discarded. 6. Exactly 4mL of clean pentane was added to each sample vial.  Each vial was then shaken vigorously for 5 minutes.  Phases were allowed to separate for at least 2 minutes.   7. The upper layer was then removed from each vial and placed in a pre-cleaned GC vial using disposable Pasteur pipettes (Fisher Scientific).  8. Extracts were analyzed immediately or stored in the freezer at ≤ 10°C.    Extracts were analyzed for chloroform, bromoform, dibromochloromethane and bromodichloromethane using a Hewlett Packard 6890 Series GC with a Ni63 electron capture detector (ECD) affixed with a Hewlett Packard 7672A autosampler.  Helium was used as the carrier gas.  One microliter (µL) of extract was injected in the GC column for each analysis.  The GC-ECD properties for the THM analysis are outlined in Table 3-8.   Table 3-8 - GC-ECD properties for THM analysis Parameter Setting Injector   Type Splitless Temperature 90°C Detector  Type ECD Temperature 260°C Oven  Initial Temperature 30°C, hold for 2 minutes Ramp 6°C/min  Final Temperature 120°C  Retention times for each of the compounds are summarized in Table 3-9.    46  Table 3-9 - THM retention times (min)  Compound Retention Time (min) Chloroform 6.552 Bromodichloromethane 9.876 Dibromochloromethane 13.553 IS (1,2 DBP) 15.6 Bromoform 17.307  The sum of each of the above compounds (excluding the internal standard), were used to determine the total THM (THM4) concentration in the source water.   3.3.11 Haloacetic Acids (HAAs) Haloacetic acids (HAAs) were measured based on the Liquid-Liquid Microextraction Gas Chromatography Method described in USEPA 552.3 (USEPA, 2003).   The following procedure was used for haloacetic acid extraction and analysis: 1. Pre-quenched samples were removed from storage at 4°C and allowed to equilibrate to room temperature (approximately 1 hour).  2. 30mL of sample was measured in a pre-cleaned graduate cylinder.  The remaining sample was discarded and exactly 30mL of sample was placed back in the vial.  The graduate cylinder was rinsed with ultra-pure laboratory water between samples.  3. Calibration standards were prepared from commercially available HAA calibration mixes (approximately 99% purity) in methanol (Supelco Analytical).  A minimum of 5 standards covering the expected range of results were prepared.   4. Calibration standards and blanks were made using a commercially available brand of ozonated spring water (Safeway Select Refreshe, Canada Safeway Ltd) to reduce the potential for contamination.   5. An 80µg/L surrogate solution of 2,3 dibromopropionic acid was prepared in methyl tert butyl ether (MTBE).  Exactly 80µL of surrogate standard was added to the water sample using a disposable-tip pipette.  The tip was placed below the surface of the water and the vial was capped and inverted a minimum of 3 times.   6. The pH was adjusted through the addition of 2mL of concentrated sulphuric acid.   47  7. Approximately 14g of sodium sulphate (muffled at 400°C for 4 hours and cooled) was added immediately after addition of sulphuric acid.  The vial was capped and shaken using a Burrell Wrist-Action Shaker (Burrell Scientific) for approximately 1 minute.  8. A 1µg/mL internal standard solution was prepared using 1,2,3 trichloropropane.  Exactly 4mL of internal standard was added to the sample and shaken using a Burrell Wrist-Action Shaker for approximately 3 minutes.   9. Phases were allowed to separate for 5 minutes.  The upper layer was transferred to a pre-cleaned COD vial using a disposable Pasteur pipette.   10. 3mL of 10% sulphuric acid in methanol was added to each COD vial using a disposable-tip pipette.  Vials were capped and inverted.  11. Vials were placed capped in an uncovered water bath at a temperature of 50°C for 2 hours.  The water level was carefully monitored so as not to exceed half the depth of the COD vial.  If the tube walls are heated, the tubes can evaporate some of the measured compounds, leading to higher variability in analytical results (EPA, 2003). 12. Vials were removed and allowed to cool.   13. 5mL of 150g/L sodium sulphate solution was added to each COD vial and vortexed using a vortex mixer (Fisher Scientific) for 5 seconds.     14. Phases were allowed to separate for no more than 2 minutes to limit loss of HAA- esters.   15. The upper layer was then transferred to a second pre-cleaned COD vial.   16. 1mL of saturated sodium bicarbonate solution was added to the vial using a pipette.  Each vial was then vortexted four times for five seconds each time.  Phases were allowed to separate for 1 minute.  17. The upper layer was then removed from each vial and placed in a pre-cleaned GC vial using disposable Pasteur pipettes.  18. Extracts were analyzed immediately or stored in the freezer at ≤ 10°C.   Extracts were analyzed for all 9 HAAs including bromoacetic acid (MBAA), bromochloroacetic acid (BCAA), bromodichloroacetic acid (BDCAA), chloroacetic acid (MCAA), chlorodibromoacetic acid (CDBAA), dibromoacetic acid (DBAA), dichloroacetic acid (DCAA), tribromoacetic acid (TBAA), and trichloroacetic acid (TCAA).  Analysis was 48  performed using a Hewlett Packard 6890 Series GC affixed with a Hewlett Packard 5973 Mass Selective (MS) detector and Hewlett Packard 6890 Series autosampler.  Helium was used as the carrier gas.  One microliter (µL) of extract was injected in the GC column for each analysis.  The GC-MS properties for the HAA analysis are outlined in Table 3-10.   Table 3-10 - GC-MS properties for HAA analysis Parameter Setting Injector   Type Splitless Temperature 200°C Detector  Type MS Oven  Initial Temperature 30°C, hold for 8 minutes Ramp 5°C/min for 16 minutes Final Temperature 110°C  Retention times for each of the compounds are summarized in Table 3-11. Table 3-11 - HAA retention times (min) Compound Quantification Ion Secondary Ions Retention Time (min) MCAA 105 64, 77 9.124 MBAA 152 93, 121 12.218 DCAA 83 87, 85 12.81 TCAA 117 119, 141 16.002 BCAA 127 129, 131 16.264 IS (1,2,3 TCP) 75 110, 112 16.481 DBAA 173 171, 175 19.27 BDCAA 163 141, 161 19.468 CDBAA 205 207, 209 22.658 Surrogate (2,3 DBPA) 165 167 22.72 TBAA 251 253, 231 25.65  The sum of each of the above compounds (excluding the internal standard and surrogate), were used to determine the total HAA (HAA9) concentration in the source water.   49  3.4 Quality Control/Quality Assurance 3.4.1 Sample Collection and Storage QA/QC measures were implemented to verify integrity of the samples during collection and storage.  All samples collected throughout the duration of the project were collected in amber glass vials and bottles to minimize any potential effects from exposure to light.  All bottles were meticulously cleaned with detergent, tap water, distilled water, Millipore Aqua-Q Ultrapure water and baked at 400°C for a minimum of 1 hour prior to use.  All samples were immediately stored at 4°C and analysed within one week of collection.    3.4.2 Reagents and Laboratory Blanks All reagents used were laboratory quality unless otherwise stated.  Storage blanks and laboratory blanks were used to determine if there was any contamination of the samples during sampling, storage or analysis.  All blanks were made using Millipore Aqua-Q Ultrapure Water.   3.4.3 Instrument Reproducibility  Instrument reproducibility was determined through the analysis of known standards for each of the analysis performed.  The reproducibility of each of the analyses was validated by conducting recovery tests where an amount of known standard is spiked into one of the samples being analyzed.  Recovery is expressed as the percentage (%) recovered from the initial spiked samples. Method detection limits were also performed according to Standard Methods 1030C (APHA, 2005).        50  4.0 RESULTS AND DISCUSSION 4.1 Part 1 - Biofiltration Experiments 4.1.1 Effect of Biofiltration on Dissolved Organic Carbon (DOC) The effect of oxidation and subsequent biofiltration on DOC was determined throughout the course of this research project.  Figure 4-1 illustrates the effect of oxidation and subsequent biofiltration on each of the four BAC Column 1 filters and the four BAC Column 2 filters.  A full of summary of results obtained can be found in Appendix C.  Note that the DOC reduction achieved by each of the replicates from BAC Column 1 and BAC Column 2 were similar.    Figure 4-1 - Effect of combined oxidation and biofiltration on DOC. (Error bars represent the 90% confidence intervals) Figure 4-2 illustrates the average percent reductions in DOC throughout the biofiltration process.   0 1 2 3 4 5 6 Raw Water Feed Water (2mg/mg DOC) Effluent from BAC Column 1.1 Effluent from BAC Column 1.2 Effluent from BAC Column 1.3 Effluent from BAC Column 1.4 Effluent from BAC Column 2.1 Effluent from BAC Column 2.2 Effluent from BAC Column 2.3 Effluent from BAC Column 2.4 D iss o lv ed  O rg an ic  Ca rbon  (m g/ L)51   Figure 4-2 - Average percent reductions in DOC throughout the biofilters  (Error bars represent the 90% confidence intervals of the average of each replicate experiment, and data labels represent the average percent reductions) Ozonation at 2 mgO3/mg DOC did not result in a significant reduction in DOC.  These results are consistent with those from other research (Westerhoff et al., 1999; Amirsadari et al., 2001; AWWARF, 1999; Galapate et al., 2001).   Biofiltration through BAC Column 1 resulted in significant removal of DOC of 48%.  These results are consistent with those from other studies (Hozalski et al., 1999; Fonseca and Summers, 2003; Toor and Mohseni, 2007).    The reduction in DOC observed is, however, 20% to 30% higher than that reported in other studies (Wang et al., 1995; Klevens et al., 1996; Cipparone et al., 1997).  However, it is difficult to compare different studies that use different raw waters, EBCT, temperatures, etc.  An additional 26% removal of DOC was observed following biofiltration through BAC Column 2.   0 -5 -53 -76 0 1 2 3 4 5 6 Raw Water Feed Water (2mg O3/mg DOC) Effluent from BAC Column 1 Effluent from BAC Column 2 D iss o lv ed  O rg an ic  Ca rbon  (m g/ L)52  These results suggest that ozonation at the doses considered is not successful at reducing overall DOC levels, while biofiltration significantly reduces the DOC levels of the raw water.   4.1.2 Effect of Biofiltration on Specific Ultraviolet Absorbance (SUVA) The effect of oxidation and subsequent biofiltration on SUVA was determined throughout the course of this research project.  Figure 4-3 illustrates the effect of oxidation and subsequent biofiltration on SUVA on each of the four BAC Column 1 filters and the four BAC Column 2 filters.  A full of summary of results obtained can be found in Appendix C.  Figure 4-3 - Effect of combined oxidation and biofiltration on SUVA levels throughout the filter  (Error bars represent the 90% confidence intervals) Figure 4-4 illustrates the average percent reductions in DOC throughout the biofiltration process.   0 1 1 2 2 3 3 4 4 Raw Water Feed Water (2mg/mg DOC) Effluent from BAC Column 1.1 Effluent from BAC Column 1.2 Effluent from BAC Column 1.3 Effluent from BAC Column 1.4 Effluent from BAC Column 2.1 Effluent from BAC Column 2.2 Effluent from BAC Column 2.3 Effluent from BAC Column 2.4 Sp ec ifi c U V  A bs o rb an ce  (S U V A )53   Figure 4-4 - Average percent reductions in SUVA throughout the biofilters.   Solid lines represent the SUVA, and the dashed line represents the UVA.   (Error bars represent the 90% confidence intervals of the average of each replicate experiment, and data labels represent the average percent reductions) Ozonation at 2mgO3/mg DOC resulted in a significant reduction in SUVA of 30%.   This result is consistent with those from previous work (Amirsadari et al., 2001; Gunten et al., 2009; Ko et al., 2000).  Biofiltration through BAC Column 1 resulted in no significant additional reduction in SUVA, but an additional 35% reduction in UVA.  These results are consistent with those from previous work (Hozalski et al., 1999; Toor and Mohseni, 2007).    An additional 21% removal of SUVA and 23% removal in UVA was observed following biofiltration through BAC Column 2.   These results suggest that, while ozonation did not successfully reduce DOC levels (Section 4.1.1), it did significantly transform the NOM into less aromatic material.  Although biofiltration in BAC Column 1 did not substantially change the fraction of the organic 0 -26 -29 -50 0 -30 -65 -88 0.000 0.020 0.040 0.060 0.080 0.100 0.120 0.140 0.160 0.180 0 1 1 2 2 3 3 4 4 Raw Water Feed Water (2mg O3/mg DOC) Effluent from BAC Column 1 Effluent from BAC Column 2 U V  A bs o rb an ce  (U V A ) Sp ec ifi c U V  A bs o rb an ce  (S U V A )54  material that was aromatic, it did significantly reduce the amount of aromatic material present in the feed water, given the high reduction in DOC observed in Section 4.1.1.   4.1.3 Effect of Biofiltration on Apparent Molecular Weight (AMW) The effect of oxidation and biofiltration on the apparent molecular weight (AMW) was determined and is presented in Figure 4-5.  The results are presented as averages of all replicate samples analyzed.  Results from each of the replicate samples are presented in Appendix E.     Figure 4-5 - Effect of combined oxidation and biofiltration on AMW distribution. Ozonation at 2mgO3/mg DOC resulted in moderate reductions in the amount of NOM of most AMW.  Further reduction in the amount of NOM of most AMW was observed following biofiltration through BAC Column 1 and BAC Column 2.   As discussed previously, although AMW chromatograms provide insight into the characteristics of NOM, it is difficult to quantitatively compare results from different analyses.  For this reason, the AMW chromatograms were deconvoluted as discussed in Section 3.3.8.2.  The area below each of the peaks provided a quantitative estimate of the 0.00E+00 1.00E-03 2.00E-03 3.00E-03 4.00E-03 5.00E-03 6.00E-03 7.00E-03 8.00E-03 9.00E-03 0.01 0.1 1 10 100 R es po n se  (A bs o rb an ce  @  26 0n m ) MW [kDa] Raw Water Feed Water (2mg O3/mg DOC) Effluent from BAC Column 1 Effluent from BAC Column 255  amount of organic material in that particular AMW range.  The results from the deconvolution of AMW chromatograms are presented in Figure 4-6 and Table 4-1.  Detailed results for each analysis is presented in Appendix F.      Figure 4-6 - Effects of oxidation and biofiltration on AMW   (Error Bars represent the 90% confidence interval of the average of each of the replicate samples, data labels correspond to average percent reductions from raw water samples.) Table 4-1 - Summary of percent reduction in AMW fractions throughout biofiltration  (90% confidence intervals of the average of each of the replicates samples are shown in parentheses) Source > 1350                                                             (F1) 1050 - 1350           (F2) 750 - 1050                                 (F3) 500 - 750                                                     (F4) 300 - 500                             (F5) < 300                                               (F6) Raw Water 0 (15) 0 (7) 0 (7) 0 (11) 0 (13) 0 (11) 2 mgO3/mg DOC -47 (39) -52 (20) -52 (4) -35 (14) -23 (17) -2 (18) BAC Column 1 -55 (21) -64 (8) -68 (7) -70 (10) -69 (6) -68 (6) BAC Column 2 -91 (26) -90 (17) -89 (18) -89 (21) -88 (17) -86 (16)  Ozonation at 2mgO3/mg DOC resulted in significant reductions in the amount of organic material for most of the AMW ranges, particularly the higher AMW NOM.  0 0 0 0 0 0-47 -52 -52 -35 -23 -2 -55 -64 -68 -70 -69 -68 -91 -90 -89 -89 -88 -86 0 0.05 0.1 0.15 0.2 0.25 > 1350                                                             (F1) 1050 - 1350                                                    (F2) 750 - 1050                           (F3) 500 - 750                                                   (F4) 300 - 500                             (F5) < 300                                                 (F6) A re a  C o u n t Apparent Molecular Weight (Da) Raw Water Feed Water (2 mgO3/mg DOC) Effluent from BAC Column 1 Effluent from BAC Column 256  Biofiltration through BAC Column 1 resulted in overall reductions in the amount of organic material, in excess of 55%.  A higher reduction in lower AMW content was observed.  These results are consistent with previous work (Hozalski et al., 1999).   A 19% to 36% reduction of organic material was observed following biofiltration through BAC Column 2.  In contrast to BAC Column 1, larger reductions in the amount of AMW were observed for the larger AMW ranges for BAC Column 2.      These results suggest that BAC Column 1 preferentially biodegraded the smaller molecular weight NOM.  Lower molecular weight compounds tend to be more biodegradable, therefore BAC Column 1 preferentially removed the lower AMW, more biodegradable organic compounds (Leisinger et al., 1981).  The effluent of BAC Column 1 contained larger NOM that was less biodegradable (i.e. material that was not preferentially biodegraded in BAC Column 1).  Although not readily biodegradable the greater amount of larger molecular weight NOM in the BAC Column 1 effluent, resulted in higher removal of this fraction in BAC Column 2, compared to the removal of lower molecular NOM.    It should be noted that the approach used to measure the molecular weight distribution of the NOM can only detect chromophoric NOM and ignored NOM that does not adsorb light at 200nm (such as biopolymers).   4.1.4 Effect of Biofiltration on Disinfection By-Produce Formation Potential (DBPFP) The effect of oxidation and biofiltration on the disinfection by-product formation potential was determined and is presented in Figure 4-7.  A full of summary of the raw data obtained can be found in Appendix G and Appendix H.  THM4 formation potential corresponds to the formation potential of all four THMs; similarly, HAA9 formation potential corresponds to the formation potential of all nine known HAAs.   57   Figure 4-7 - Reduction in THMFP and HAAFP throughout biofiltration  (Each point represents an average of at least 6 replicates, each chlorinated, incubated and analyzed separately. Data labels indicate the percent reduction based on average values.  Error bars represent the 90% confidence interval for the average of the replicates analyzed.) Ozonation at 2mgO3/mg DOC resulted in significant reductions in THMFP and HAAFP of 44% and 45% respectively.  These results are consisted with those presented in other studies (Chin and Bérubé, 2004; Chowdhury et al., 2008).  Biofiltration through BAC Column 1 resulted in additional reduction in THMFP and HAAFP of 23% and 15%, respectively.  These results are consisted with previous work (Shukiary et al. .1992; Cipparone et al., 1997).  However, these results are between 10% to 30% higher than previous work (Joslyn and Summer, 1992; Wang et al., 1995; Siddiqui et al., 1997).   An additional 20% removal of HAAFP and THMFP was observed following biofiltration through BAC Column 2.  Given the very high DBPFP in the raw water, only subsequent treatment by BAC Column 2 was able to lower the DBPFP under the Guidelines for Canadian Drinking Water Quality limits of 0.1(THMs) and 0.08 mg/L (HAAs).   0 -44 -67 -87 0 -45 -60 -80 0 50 100 150 200 250 300 350 400 450 Raw Water Feed Water                                     (2mg O3/mg DOC) Effluent from BAC Column 1 Effluent from BAC Column 2 Con ce n tr at ion   (ug /L ) THM4 FP HAA9 FP Health Canada THM Guideline (2010) Health Canada HAA Guideline (2010) 58  These results suggest that ozonation caused a transformation in NOM, resulting in less aromatic compound (as discussed in Section 4.1.2) and therefore, ultimately significantly reduced the DBPFP.  Similarly, BAC Column 1 and BAC Column 2 resulted in additional decreases IN DBPFP due to the reduction in aromatic compounds (as discussed in Section 4.1.2).      Further work was completed in order to determine the effect of oxidation and biofiltration on each of the DBPs.  Figure 4-8 illustrates the removal efficiency of oxidation and biofiltration on the four known THMs.    Figure 4-8 - Reduction of each of the four THMs through biofiltration  (Each point represents an average of at least 6 replicates, each chlorinated, incubated and analyzed separately. Data labels indicate the percent reduction based on average values.  Error bars represent the 90% confidence interval for the average of the replicates analyzed.) Ozonation at 2mgO3/mg DOC resulted in significant reductions in THMFP.  Biofiltration through BAC Column 1 resulted in significant additional reductions in chloroform, bromodichloroform formation potential.   An additional 25% removal of chloroform formation potential was observed following biofiltration through BAC Column 2.  These results suggest that ozonation is successful at reducing THMFP; however, the overall 0 -52 -67 -92 0 -36 -73 -88 0 -20 -54 -66 0 -16 -37 101 0 50 100 150 200 250 Raw Water Feed Water                                     (2mg O3/mg DOC) Effluent from BAC Column 1 Effluent from BAC Column 2 Con ce n tr at ion  (ug /L ) Chloroform (ug/L) Bromodichloroform (ug/L) Dibromochloroform (ug/L) Bromoform (ug/L) Health Canada THM Guideline (2010) 59  reduction was not significant enough to meet current Guidelines for Canadian Drinking Water Quality limits.  Subsequent biofiltration is necessary to lower the THMFP below guideline levels.   Figure 4-9  illustrates the removal efficiency of each oxidation condition on the three main HAAs; TCAA, MCAA and DCAA.  Bromoacetic acids were not present in significant quantities, and have therefore been omitted from this discussion.      Figure 4-9 - Reduction in each of the three HAAs (DCAA, MCAA and TCAA) through biofiltration  (Each point represents an average of at least 6 replicates, each chlorinated, incubated and analyzed separately. Data labels indicate the percent reduction based on average values.  Errors bars represent the 90% confidence interval for the average of the replicates analyzed.) Ozonation at 2mgO3/mg DOC resulted in significant reductions in HAAFP.  A significant additional reduction of 33% was observed for TCAAFP levels following biofiltration through BAC Column 1.  An additional 27% reduction of DCAAFP was 0 -50 -61 -88 0 -27 -64 -73 0 -70 -59 -97 0 50 100 150 200 250 300 Raw Ozonated                       (2mg O3/mg DOC) BAC Column 1 BAC Column 2 Con ce n tr at ion  (ug /L ) DCAA (ug/L) TCAA (ug/L) MCAA (ug/L) Health Canada HAA Guideline (2010) Water 60  observed following biofiltration through BAC Column 2.  No significant additional reduction of DCAAFP was observed following BAC Column 1.     These results suggest that ozonation was successful at reducing HAAFP; however, the overall reduction was not significant enough to meet current Health Canada guidelines.  Subsequent biofiltration is necessary to lower the HAAFP below guideline levels.   4.2 Part 2 - Biodegradation Experiments 4.2.1 Feed Water Analysis 4.2.1.1 Effect of Oxidation on Dissolved Organic Carbon (DOC) The effect of oxidation on the dissolved organic carbon content was determined for the six conditions described previously and are presented in Figure 4-10.  Raw data is provided in Appendix J.     Figure 4-10 - Effect of oxidation on DOC (mg/L)  (Bars represent the average of all samples analyzed.  Errors bars represent the 90% confidence interval and the data labels represent the average percent reduction.) 0 -3% -3% -38% -13% -44% -60% 0 1 2 3 4 5 6 Raw Ozonated                                                  1mg/mg DOC Ozonated                                                  2mg/mg DOC Ozonated                                                                               Extended Dose UV 4000mJ/cm2 & 0mg/L H2O2 UV 2000mJ/cm2 & 10mg/L H2O2 UV 4000mJ/cm2 & 10mg/L H2O2 D O C  (m g/ L) Water 61  As expected, ozonation at 1 and 2 mgO3/mg DOC did not result in a significant reduction in DOC.  These results are consistent with those from other research (Westerhoff et al., 1999; Amirsadari et al., 2001; AWWARF, 1999; Galapate et al., 2001).   Ozonation at an extended dose of 25mgO3/mg DOC achieved a high removal of DOC, reducing the raw water DOC concentration by 38%.  Compared to oxidation using ozone, oxidation using UV/H2O2 resulted in greater reduction in DOC for the doses considered.  UV/H2O2 treatment at of 2000 and 4000 mJ/cm2 and 10 mg/L H2O2, resulted in significant reductions in DOC of 44% and 60% respectively.  These results are consistent with those from other research (Goslan et al., 2006; Bond et al., 2009).  UV/H2O2 treatment at 4000mJ/cm2 and 0mg/L H2O2 resulted in a DOC reduction of 13%.  This result was not expected, and the present study was unable to further determine the cause for this elevated DOC removal rate.   These results suggest that significant reduction in DOC is only observed following excessive oxidation of raw water, therefore at oxidation doses that are not economically feasible.  In addition, high dose UV/H2O2 was more successful at reducing the DOC levels of raw water than O3, at the doses considered.   4.2.1.2 Effect of Oxidation on Specific Ultraviolet Absorbance (SUVA) The effect of oxidation on the specific UV absorbance was determined for the six conditions described previously and are presented in Figure 4-11.  A full of summary of results obtained can be found in Appendix J.  For further comparison, a graph depicting UVA and SUVA removal resulting from oxidation is illustrated in Figure 4-11.   62   Figure 4-11 - Effect of oxidation on UVA and SUVA  (Data points represent the average of all samples analyzed.  Errors bars represent the 90% confidence interval and the data labels represent the average percent reduction.)  Ozonation at 1 and 2 mgO3/mg DOC achieved overall UVA reductions of 18% and 30% respectively.  These results are consistent with those from other research (Amirsadari et al., 2001; Gunten et al., 2009; Ko et al., 2000) as well as the results obtained in the biofiltration experiments (Section 4.1.2).  However, these results are not consistent with those from some previous research, where UVA reductions in excess of 50% were achieved (Kim et al., 2006; Kim et al., 1997; Owen et al., 1995; Kaastrup and Halmo, 1989; Kleiser and Frimmel, 2000; Galapate et al., 2001).  However, it is difficult to compare different studies that use different raw waters, EBCT, temperatures, etc.  Ozonation at an extended dose of 25mgO3/mg DOC achieved an overall UVA reduction of 79%.     Compared to oxidation using ozone, oxidation using UV/H2O2 resulted in greater reduction in UVA at the doses considered.  UV/H2O2 treatment at of 2000 and 4000 mJ/cm2 and 10 mg/L H2O2, resulted in reductions of UVA in excess of 70% and 81%, respectively.   0 -15% -28% -65% -7% -45% -51% 0 -18% -30% -79% -19% -70% -81% 0 0.02 0.04 0.06 0.08 0.1 0.12 0.14 0.16 0.18 0 0.5 1 1.5 2 2.5 3 3.5 Raw Ozonated                                                  1mg/mg DOC Ozonated                                                  2mg/mg DOC Ozonated                                                                           Extended Dose UV 4000mJ/cm2 & 0mg/L H2O2 UV 2000mJ/cm2 & 10mg/L H2O2 UV 4000mJ/cm2 & 10mg/L H2O2 U V  A bs o rb a n ce  (U V A ) Sp ec ifi c U V  A bs o rb a n ce  (S U V A ) SUVA UVA Water 63  These results are consistent with those from other research (Sarathy and Mohseni, 2009; Goslan et al., 2006; Toor and Mohseni, 2007).  UV/H2O2 treatment at 4000mJ/cm2 and  0mg/L H2O2 resulted in a UVA reduction of 19% .   These results suggest that, while ozonation did not successfully reduce DOC levels (Section 4.2.1), it did significantly transform the NOM into less aromatic material.  High dose ozonation, as well as AOPs, were successful at significantly lowering the fraction of the organic material that was aromatic, and the amount of aromatic material present in the feed water.   4.2.1.3 Effect of Oxidation on Apparent Molecular Weight (AMW) The effect of oxidation on the apparent molecular weight (AMW) was determined for the six conditions described previously by HPSEC.  Graphical results are shown in Figure 4-12.  The results are presented as averages of all replicate samples analyzed.  Results from each of the replicate samples are presented in Appendix E.   64   Figure 4-12 - Effect of oxidation on apparent molecular weight  Ozonation at 1 and 2mgO3/mg DOC resulted in moderate reductions in the amount of NOM of most AMW as observed in Figure 4-12.  UV/H2O2 treatment at of 2000 and 4000 mJ/cm2 and 10 mg/L H2O2, resulted in large reductions in the amount of NOM of most AMW.  As expected, the 4000mJ/cm2 and 0 mg/L H2O2 resulted in what visually appeared to be the least impact on raw water levels.    As discussed previously, although AMW chromatograms provide insight into the characteristics of NOM, it is difficult to quantitatively compare results from different analyses.  For this reason, the AMW chromatograms were deconvoluted, as discussed in Section 3.3.8.2.  The area below each of the peaks provided a quantitative estimate of the amount of organic material in that particular AMW range.  The results from the deconvolution of AMW chromatograms are presented in Figure 4-13 and Table 4-2.  Detailed results for each analysis are presented in Appendix F.   65   Figure 4-13 - Effects of oxidation on AMW.   Peaks were categorized based on molecular weight (Da): >1350 (F1), 1050 - 1350 (F2), 750-1050 (F3), 500-750 (F4), 300-500 (F5), <300 (F6)).  Error Bars represent the 90% confidence interval, data labels correspond to average percent reductions. 0 0 0 0 0 0-45 -24 -11 -8 -7 10 -81 -80 -70 -61 -67 -50 -95 -94 -90 -85 -86 -78 -55 -37 -22 -8 4 19 -47 -52 -52 -35 -23 -2 -92 -98 -100 -99 -97 -96 0 0.05 0.1 0.15 0.2 0.25 > 1350                                                             (F1) 1050 - 1350                                                    (F2) 750 - 1050                                 (F3) 500 - 750                                                     (F4) 300 - 500                             (F5) < 300                                                     (F6) A r e a  C o u n t Molecular Weight (Da) Raw Water 4000 mJ/cm2 & 0mg/L H2O2 2000 mJ/cm2 & 10mg/L H2O2 4000 mJ/cm2 & 10mg/L H2O2 1 mgO3/mg DOC 2 mgO3/mg DOC Extended Ozonation66  Table 4-2 - Summary of average percent reduction in AMW fractions for each oxidation condition  (90% confidence intervals of reported reductions shown in parentheses) Oxidation Scenario > 1350                                                             (F1) 1050 - 1350                                                    (F2) 750 - 1050                                 (F3) 500 - 750                                         (F4) 300 - 500                             (F5) < 300                                                     (F6) Raw Water 0 (15) 0 (7) 0 (7) 0 (11) 0 (13) 0 (11) 1 mgO3/mg DOC -55 (13) -37 (19) -22 (19) -8 (9) 4 (5) 19 (9) 2 mgO3/mg DOC -47 (39) -52 (20) -52 (4) -35 (14) -23 (17) -2 (18) 2000 mJ/cm2 & 10mg/L H2O2 -80 (28) -80 (13) -70 (7) -61 (7) -67 (6) -50 (6) 4000 mJ/cm2 & 10mg/L H2O2 -95 (13) -94 (34) -90 (16) -85 (8) -86 (20) -78 (19) 4000 mJ/cm2 & 0mg/L H2O2 -45 (21) -24 (10) -11 (2) -8 (3) -7 (15) 10 (18) Extended Ozonation -92 (0) -98 (0) -100 (0) -99 (0) -97 (0) -96 (0)  Ozonation at 1 mgO3/mg DOC resulted in a shift from high molecular weight to low molecular weight NOM.  Ozonation at 1mg resulted in a significant decrease in compounds greater than 750Da, while an increase in the smaller fractions was observed.  However, this effect was not as noticeable at the higher dose of 2mgO3/mg DOC.  This is most likely explained by the fact that the smaller organic material formed during oxidation was also oxidized at this higher dose.  These results are consistent with those from other research (von Gunten et al., 2003b; Swietlik et al., 2004).  Ozonation at an extended dose of 25 mgO3/mg DOC did not result in an apparent shift from high molecular weight to low molecular weight compounds, due to the high oxidation of NOM.  UV/H2O2 treatment at a dose of 2000mJ/cm2 and 10 mg/L H2O2 resulted in a shift from high molecular weight to low molecular weight.  These results are consistent with those from other research (Thomson et al., 2004; Sarathy, 2009)    However, this effect was not as noticeable at the higher dose of 4000mJ/cm2 and 10 mg/L H2O2, and is most likely explained by the fact that the smaller material formed during oxidation was also oxidized at this higher dose.  The results for average percent removals are somewhat higher than previous research (Sarathy and Mohseni, 2007; Sarathy, 2009).  It should be noted that the approach used to measure the molecular weight distribution of the NOM can only detect chromophoric NOM and ignores NOM that does not absorb light at 200nm (such as biopolymers).   67  4.2.1.4 Effect of Oxidation on Disinfection By-Produce Formation Potential (DBPFP) The effect of oxidation on the disinfection by-product formation potential was determined for the six conditions described previously and are shown in Figure 4-14.  A full of summary of results obtained can be found in Appendix G and Appendix H.  THM4 formation potential corresponds to the formation potential of all four THMs; similarly, HAA9 formation potential corresponds to the formation potential of all nine known HAAs.    Figure 4-14 - Effect of oxidation on THMFP and HAAFP  (Each bar represents an average of at least 3 replicates (in some cases, over 10 replicates were performed), each chlorinated, incubated and analyzed separately. Data labels indicate the percent reduction based on average values.  Errors bars represent the 90% confidence interval). Ozonation at 1 mgO3/mgDOC resulted in no statistically significant reduction in either HAAFP or THMFP.  This result is consistent with those from previous work that found either no effect or slight increases in both THM and HAA formation potential 0 -5 -16 -45 -6 -44 -64 0 22 -28 -50 -5 -45 -92 0 100 200 300 400 500 600 Raw 4000 mJ/cm2 & 0 mg/L H2O2 2000 mJ/cm2 & 10 mg/L H2O2 4000 mJ/cm2 & 10 mg/L H2O2 Ozonated                                                 (1mg O3/mg DOC) Ozonated                                    (2mg O3/mg DOC) Extended Ozonation                                    (25mg O3/mg DOC) Con ce n tr at ion  (ug /L ) THM4 FP HAA9 FP Health Canada HAA Guideline (2010) Health Canada THM Guideline (2010) Water 68  following low-dose ozonation (Sidiqui et al., 1997; Galapate et al., 2001; Cipparone et al., 1997; Chowdhury et al., 2008).   Ozonation at 2 mgO3/mgDOC resulted in an overall reduction of 45% for both THM and HAA formation potentials.  These results are consistent with previous work that achieved between 30 - 60% removals at similar doses (Kleiser and Frimmel, 2000; Chin and Bérubé, 2005; Hu et al., 1999; Cipparone et al., 1997; Chowdhury et al., 2008; Ko et al., 2000). Ozonation at the extended dose of 25mgO3/mg DOC resulted in extremely high reductions in THMFP and HAAFP, achieving 64% and 92% removals, respectively.   UV/ H2O2 treatment at a dose of 2000mJ/cm2 and 10 mg/L H2O2 did not result in a significant reduction in DBPFP.  However, UV/ H2O2 treatment at a dose of 4000 mJ/cm2 and 10 mg/L H2O2 resulted in significant reductions in excess of 44% for both HAAFP and THMFP.  UV/ H2O2 treatment at a dose of 4000mJ/cm2 and 0 mg/L H2O2 resulted in an increased in HAAFP, which was consistent with findings with those from previous work where HAAFP increased at low dose applications (Chowdhury et al., 2008).   Previous studies have reported quite varied results in terms of the effect of AOP on both HAAFP and THMFP, and therefore, further research is needed in order to confirm these findings.  Total HAA and THM formation potentials were well above the Health Canada standards of 0.1mg/L for THMs and 0.08 mg/L for HAAs, with only the extended ozonation dose of 25mg/mg DOC resulting in concentrations of THMs and HAAs that met the current Guidelines for Canadian Drinking Water Quality limits for HAAs.   Further work was completed in order to determine the effect of oxidation on each of the DBPs.  Figure 4-15 illustrates the removal efficiency of each oxidation condition on the four known THMs.   69   Figure 4-15 - Effect of oxidation on the formation potential of each of the four THMs  (Each point represents an average of at least 6 replicates, each chlorinated, incubated and analyzed separately. Data labels indicate the percent reduction based on average values.  Errors bars represent the 90% confidence interval for the average of the replicates analyzed.) Ozonation at the lower dose of 1mgO3/mg DOC resulted in increases in all THMs with the exception of chloroform.  Slight increases in all brominated THMs were observed, but results remain inconclusive.  In contrast, ozonation at the higher dose of 2mgO3/mg DOC resulted in significant decreases for all four THMFPs.   These results are consistent with those from previous work (Cipparone et al., 1997; Kleiser and Frimmel, 2000; Galapate et al., 2001; Bérubé et al., 2004).  Ozonation at 25 mgO3/mg DOC resulted in significant decreases in bromodichloroform and chloroform formation potentials, but a substantial increase in bromoform formation potential levels was observed following ozonation.  Compared to oxidation using ozone, oxidation using UV/ H2O2 resulted in similar reductions in THMFP for all doses considered.  UV/H2O2 treatment at the lower dose of 2000mJ/cm2 0 -14 -41 -40 -27 -52 -88 0 -2 3 -54 13 -36 -60 0 43 81 -52 75 -20 32 0 125 349 -54 163 -16 646 0 50 100 150 200 250 300 Raw Water 4000 mJ/cm2 & 0 mg/L H2O2 2000 mJ/cm2 & 10 mg/L H2O2 4000 mJ/cm2 & 10 mg/L H2O2 Ozonated                                                 (1mg O3/mg DOC) Ozonated                                   (2mg O3/mg DOC) Extended Ozonation                                    (25 mgO3/mg DOC) Con ce n tr at ion  (ug /L ) Chloroform (ug/L) Bromodichloroform (ug/L) Dibromochloroform (ug/L) Bromoform (ug/L) Health Canada THM Guideline (2010) 70  and 10 mg/L H2O2 resulted in no significant reduction in THMFP   In contrast, UV/ H2O2 treatment at the higher dose of 4000mJ/cm2 and 10 mg/L H2O2 resulted in significant decreases in all four THMs with reductions in excess of 40%.  These results are consistent with previous work (Toor and Mohseni, 2007).  However, these results do not achieve similar reduction in THMFP as those from previous studies (Liu et al., 2002; Bérubé et al., 2004; Sarathy, 2009).  UV/ H2O2 treatment at 4000mJ/cm2 and 0mg/L H2O2 did not result in any significant reductions in THMFP.  Oxidation appeared to increase the brominated THMFP at the lower dose applications for ozonation and UV/ H2O2 treatment.  However, the THMFP substantially decreased at the higher oxidation doses for ozonation and UV/ H2O2 treatment.  Therefore, high-dose treatment is required in order to reduce THMFP levels to meet water quality guidelines.   Figure 4-16 illustrates the removal efficiency of each oxidation condition on the three main HAAs present; TCAA, MCAA, and DCAA.  Bromoacetic acids were not present in significant quantities, and have therefore been omitted from this discussion.     71   Figure 4-16 - Effect of oxidation on the formation potential of each of the three main HAAs (TCAA, MCAA, and DCAA).  (Each point represents an average of at least 6 replicates, each chlorinated, incubated and analyzed separately. Data labels indicate the percent reduction based on average values.  Errors bars represent the 90% confidence interval for the average of the replicates analyzed.). Ozonation at the lower dose of 1mgO3/mg DOC did not result in any significant reduction in HAAFP.  An increase of 8% in DCAAFP levels was observed.  These results are consistent with previous work (Siddiqui et al., 1997; Reckhow and Singer, 1994).  In contrast, ozonation at the higher dose of 2mgO3/mg DOC resulted in significant decreases in DCAAFP levels.   These results are consistent with previous work (Hu et al., 1999; Chin and Bérubé, 2004; Chowdhuyry et al., 2008).  Ozonation at 25 mgO3/mg DOC resulted in significant decreases in all three HAAs.  Compared to oxidation using ozone, oxidation using UV/ H2O2 resulted in higher reductions in HAAFP.  UV/H2O2 treatment at the lower dose of 2000mJ/cm2 and 10 mg/L H2O2 resulted in decreases in DCAAFP and TCAAFP of 27% and 0 37 -27 -33 8 -50 -94 0 10 -37 -74 -16 -27 -88 0 53 2 -88 -5 -70 -100 0 50 100 150 200 250 300 350 Raw Water 4000 mJ/cm2 & 0 mg/L H2O2 2000 mJ/cm2 & 10 mg/L H2O2 4000 mJ/cm2 & 10 mg/L H2O2 Ozonated                                                 (1mg O3/mg DOC) Ozonated                                    (2mg O3/mg DOC) Extended Ozonation                                    (25 mg O3/mg DOC) Con ce n tr at ion (ug /L ) DCAA (ug/L) TCAA (ug/L) MCAA (ug/L) Health Canada HAA Guideline (2010) 72  37% respectively.  UV/ H2O2treatment at the higher dose of 4000mJ/cm2 and 10 mg/L H2O2 resulted in significant decreases in the FP of all three HAAs, with reductions of 33% to 88%.  These results achieve much higher reductions than some reported in previous studies (Liu et al., 2002; Sarathy, 2009).  UV/ H2O2 treatment at 4000mJ/cm2 and 0mg/L H2O2 resulted in increases in FP for each of the HAAs.   4.2.2 Batch Biodegradation Experiments 4.2.2.1 Effect of Oxidation on Biodegradation Kinetics The effect of oxidation on biofiltration kinetics was examined for each of the oxidation scenarios outlined previously.  Note that for all conditions investigated, the coefficient of correlation (R2) obtained by fitting Equation 3-8 (see Section 3.2.3.1) using Systat software Table Curve 2D to the biodegradation data was 0.97.  Typical results from the biodegradation experiments are presented in Figure 4-17.  A full summary of results is provided in Appendix K.    Figure 4-17 - Typical biodegradation curve  (Showing 90% confidence interval of fitted curve) 0 0.5 1 1.5 2 2.5 0 1 2 3 4 5 6 7 8 D O C (m g/ L) Time (Days) Generated Curve Fit 90% Confidence Interval Actual Data73  The average values of a,b and c (see Section 3.2.3.1) for both BAC columns are summarized in Table 4-3, Figure 4-18 and Figure 4-19.  Appendix L provides a full summary of the analysis of results. Table 4-3 - Biodegradation average curve parameters for BAC Column 1 and BAC Column 2  (Error shown in parentheses corresponds to the 90% interval for the average of all replicates analyzed). Oxidation Average DOCnon (a) DOCi (b) kDOC(c) Biomass from BAC Column 1 Raw Water 2.546 (±0.182) 2.069 (±0.857) 1.857 (±0.505) 4000 mJ/cm2 & 0 mg/L H2O2 2.464 (±0.248) 1.760 (±0.169) 1.751 (±0.834) 2000 mJ/cm2 & 10 mg/L H2O2 1.288 (±0.227) 1.425 (±0.605) 2.300 (±0.668) 4000 mJ/cm2 & 10 mg/L H2O2 0.878 (±0.136) 1.070 (±0.301) 2.604 (±0.389) Ozonated  (1mg O3/mg DOC) 2.942 (±0.320) 2.102 (±0.692) 1.632 (±0.686) Ozonated (2mg O3/mg DOC) 2.816 (±0.105) 1.807 (±0.219) 1.632 (±0.462) Extended Ozonation (25mg O3/mg DOC) 0.8467 (±0.018) 1.947 (±0.240) 0.626 (±0.062) Biomass from BAC Column 2 Raw Water 2.383  (±0.250) 2.680 (±0.280) 2.223 (±0.907) 4000 mJ/cm2 & 0 mg/L H2O2 2.030  (±0.300) 2.087 (±0.076) 1.687 (±1.149) 2000 mJ/cm2 & 10 mg/L H2O2 1.255  (±0.653) 1.302  (±0.419) 1.780 (±0.527) 4000 mJ/cm2 & 10 mg/L H2O2 0.962  (±0.010) 0.863 (±0.417) 1.490 (±0.589) Ozonated  (1mg O3/mg DOC) 2.570  (±0.153) 2.509 (±0.563) 1.916 (±1.180) Ozonated (2mg O3/mg DOC) 2.429  (±0.176) 2.127 (±0.101) 1.614 (±0.940) Extended Ozonation (25mg O3/mg DOC) 0.650  (±0.250) 1.842 (±0.294) 0.449 (±0.096)  Figure 4-18 illustrates the amount of non-biodegradable DOC remaining following biodegradation for each of the oxidation scenarios.   74   Figure 4-18 - Non-biodegradable DOC (DOCnon) for each oxidation scenario for BAC Column 1 and BAC Column 2  (Bars represent the average of all replicates analyzed, error bars shown correspond to the 90% interval for the average of all replicates analyzed.  Data labels indicate the average percent reduction). Ozonation at 1mgO3/mg DOC and 2 mgO3/mg DOC did not result in a significant effect on the DOCnon of the raw water.  Extended ozonation at 25 mgO3/mg DOC did result in a 67% decrease in DOCnon.  Compared to oxidation using ozone, oxidation using UV/H2O2 resulted in significant reductions in DOCnon.  UV/ H2O2 treatment at 2000 mJ/cm2 and 4000 mJ/cm2 with 10mg/L H2O2 resulted in 49% and 66% reductions in DOCnon, respectively.   Similar results were obtained for BAC Column 2.  Therefore, it can be concluded that the ability of the biomass present in both Column 1 and Column 2 biodegradable NOM was not significantly different despite the fact that they were each acclimated to different feed waters (as discussed in Section 3.1.3).  Recall that the feed water fed to BAC Column 2 contained primarily the larger AMW, slow biodegradable material as discussed in Section 4.1.3.  Therefore, the biomass acclimatized to the feed water containing the slowly 0 -3 -49 -66 16 11 -67 0 -15 -47 -60 8 2 -73 0.000 0.500 1.000 1.500 2.000 2.500 3.000 3.500 Raw Water 4000 mJ/cm2 & 0 mg/L H2O2 2000 mJ/cm2 & 10 mg/L H2O2 4000 mJ/cm2 & 10 mg/L H2O2 Ozonated                                                 (1mg O3/mg DOC) Ozonated                                                            (2mg O3/mg DOC) Extended Ozonation                                    (25mg O3/mg DOC) D O Cnon  (m g/ L) BAC Column 1 BAC Column 275  biodegradable organic matter (BAC Column 2) was no better at biodegrading the non- biodegradable material (DOCnon) than the biomass in BAC Column 1.   Overall, the extended ozonation dose, and the AOPs that combined 10 mg/L H2O2 and both the 2000 and 4000 mJ/cm2 UV doses were successful at sufficiently altering the NOM such that the removal of biodegradable organic matter was maximized during biodegradation, (i.e. the DOCnon levels were lowest).  These results are consistent with those presented in Section 4.2.1, whereby it was concluded that these oxidation scenarios were superior at reducing DOC levels, reducing both the fraction and amount of aromatic content of the NOM, and decreasing the overall AMW of the NOM in the raw water.  These results suggest that the non-biodegradable DOC, (DOCnon), is a function of the type and dose of oxidation used.  However, it is not a function of acclimation conditions of the biomass.   Figure 4-19 illustrates the kinetic rate constant for biodegradation for each of the oxidation scenarios.    Figure 4-19 - Parameter c for each oxidation scenario for BAC Column 1  (Bars represent the average of all replicates analyzed, error bars shown correspond to the 90% interval for the average of all replicates analyzed.  Data labels indicate the average percent reduction). 0 -6 24 40 -12 -12 -66 0 -24 -20 -33 -14 -27 -80 0.000 0.500 1.000 1.500 2.000 2.500 3.000 3.500 Raw Water 4000 mJ/cm2 & 0 mg/L H2O2 2000 mJ/cm2 & 10 mg/L H2O2 4000 mJ/cm2 & 10 mg/L H2O2 Ozonated                                                 (1mg O3/mg DOC) Ozonated                                  (2mg O3/mg DOC) Extended Ozonation                                    (25mg O3/mg DOC) Parameter c - Kinetic Rate Constant (k) BAC Column 1 BAC Column 276  With the exception of the ozonation at 25 mgO3/mg DOC, the different oxidation types and doses did not have a significant effect on the rate of DOC biodegradation.  Similar results were obtained for BAC Column 2.  The low kdoc value obtained for ozonation at 25 mgO3/mg DOC may be due to the fact that most of the DOC is oxidised during extensive ozonation and only very slowly biodegradable DOC remained.   These results indicate that rate of biodegradation, or kDOC, is not a function of the type and dose of oxidation, or to the acclimation conditions of the biomass.    4.2.2.2 Effect of Biodegradation on Ultraviolet Absorbance (UVA) The effect of oxidation on biofiltration kinetics for UVA was examined for each of the oxidation scenarios outlined previously.  The results obtained mirror those for DOC presented in Section 4.2.2.1.  Full results are provided in Appendix M and Appendix N.  Similar results were obtained for both BAC Column 1 and BAC Column 2.   These results provided further certainty that the ability of the biomass present in both BAC Column 1 and BAC Column 2 to biodegrade NOM, was not significantly different despite the fact that each were acclimated to different feed water as discussed in Section 3.1.3.  Recall that the feed water fed to BAC Column 2 contained primarily the larger AMW, less aromatic, slowly biodegradable material (as discussed in Section 4.1.2 and 4.1.3).  Therefore the biomass acclimatized to the feed water containing the less aromatic material (BAC Column 2) was no better at biodegrading the organic material than BAC Column 1.   Overall, the high ozonation dose and the AOPs that combined 10mg/L H2O2 and both the 2000 and 4000 mJ/cm2 UV doses were successful at significantly lowering the aromaticity of the raw water (thereby increasing its biodegradability) such that removal of biodegradable organic material was maximized during biodegradation.  These results are consistent with those presented in Section 4.2.2, whereby it was concluded that these particular oxidation scenarios were superior at lowering DOC, reducing both the fraction and amount of aromatic content of NOM, and decreasing the overall AMW of the NOM in the raw water.  These results suggest that the amount of remaining UVA (present in NOM as DOCnon) is sensitive to the type and dose of oxidation used.   With the exception of the ozonation at 25mg O3/mg DOC, the different oxidation types and doses did not have a significant effect on the rate of UVA biodegradation.  These 77  results indicate that the rate of biodegradation of UVA, or kUVA, is not a function of the type and dose of oxidation or to the acclimation conditions of the biomass.   4.2.2.3 Effect of Biodegradation on Apparent Molecular Weight (AMW) The effect of each oxidation and biodegradation was evaluated for each of the oxidation scenarios considered.  Apparent Molecular Weight (AMW) was determined for each of the biodegradation samples.  Figure 4-20 illustrates the HPSEC chromatograms that were obtained for each of the biodegradation experiments considered.      Figure 4-20 - Typical chromatogram for each phase of biodegradation experiment For the analysis that follows, results are presented for times of 0, 1 and 7 days.  As discussed in Section 3.2.3.1, a batch test duration of 1 day is equivalent to an EBCT of approximately 15 minutes in a BAC Column (i.e. similar to BAC Column 1).  Raw results for the batch biodegradation tests for each duration analyzed are presented in Appendix O.  A typical chromatogram showing these three points is illustrated in Figure 4-21.   -1.00E-03 0.00E+00 1.00E-03 2.00E-03 3.00E-03 4.00E-03 5.00E-03 6.00E-03 7.00E-03 8.00E-03 0.01 0.1 1 10 100 R es po n se MW [kDa] Raw Treated 4 hours 8 hours 12 hours 18 hours 1 Day 2 Days 3 Days 4 Days 5 Days 6 Days 7 Days78   Figure 4-21 - Typical chromatogram result showing raw water, time 0 (treated), time 1 day and time 7 days.   As discussed previously, although AMW chromatograms provide insight into the characteristics of NOM, it is difficult to quantitatively compare results from different analyses. For this reason, the AMW chromatograms were deconvoluted as discussed in Section 3.3.8.2. The area below each of the peaks provided a quantitative estimate of the amount of organic material in that particular AMW range. The results from the deconvolution of AMW chromatograms are presented below.  Detailed results for each analysis is presented in Appendix P, Appendix Q and Appendix R.   In the case of raw water samples (no treatment applied prior to biodegradation) results are presented in Figure 4-22.        0.00E+00 2.00E-03 4.00E-03 6.00E-03 8.00E-03 1.00E-02 0.01 0.1 1 10 100 R es po n se MW [kDa] Raw Treated Time 1 day Time 7 day79   Figure 4-22 - Deconvolution results for raw water biodegradation.   (Error bars represent the 90% confidence intervals.  Data labels represent the percent reductions at time 1 day and time 7day.) 0 0 0 0 0 0 -37 -34 -36 -48 -26 -39 -70 -60 -60 -62 -52 -65 0 0 0 0 0 0 -51 -52 -50 -57 -50 -64 -74 -75 -70 -72 -63 -66 0 0.05 0.1 0.15 0.2 0.25 0.3 0.35 > 1350                                                             (F1) 1050 - 1350                                 (F2) 750 - 1050                  (F3) 500 - 750                                                     (F4) 300 - 500              (F5) < 300                                                     (F6) A r e a  C o u n t Molecular Weight (Da) Feed Water - BAC Column 1 1 Day Biodegradation - BAC Column 1 7 Day Biodegradation - BAC Column 1 Feed Water - BAC Column 2 1 Day Biodegradation - BAC Column 2 7 Day Biodegradation - BAC Column 280  For each of the molecular weight ranges shown in Figure 4-22, significant reduction in the amount of NOM present in each AMW range was observed following both 1 day and 7 day biodegradation.  High removal percentages were observed for the smaller molecular weight ranges during the 1 day biodegradation (also corresponding to BAC Column 1).  Significant additional reduction in AMW was observed following the 7 day biodegradation, including biodegradation of the larger AMW material.   These results suggest that insufficient removal of biodegradable compounds occurred during the 1 day biodegradation (corresponding to an EBCT of 15minutes) and therefore there exists a significant amount of residual biodegradable organic matter present following 1 day biodegradation.   This residual organic matter, as discussed in Section 2.2.3, can lead to the formation of DBPs during chlorination and potential regrowth with the distribution system.  The results for the raw water biodegradation provide a basis for comparison for the feed water biodegradation experiments with oxidized feed water.   For ozonation at 1 mg O3/mg DOC, results are presented in Figure 4-23.    81   Figure 4-23 - Deconvolution results for ozonation at 1mg O3/mg DOC feed water biodegradation.   (Error bars represent the 90% confidence intervals.  Data labels represent the percent reductions at time 1 day and time 7day.) 0 0 0 0 0 0 -33 -54 -58 -49 -42 -33 -55 -65 -68 -60 -55 -50 0 0 0 0 0 0 -45 -65 -69 -66 -62 -54 -49 -67 -72 -65 -60 -54 0 0.02 0.04 0.06 0.08 0.1 0.12 0.14 0.16 > 1350                                                             (F1) 1050 - 1350                                 (F2) 750 - 1050                  (F3) 500 - 750                                                     (F4) 300 - 500              (F5) < 300                                                     (F6) A r e a  C o u n t Molecular Weight (Da) Feed Water - BAC Column 1 1 Day Biodegradation - BAC Column 1 7 Day Biodegradation - BAC Column 1 Feed Water - BAC Column 2 1 Day Biodegradation - BAC Column 2 7 Day Biodegradation - BAC Column 282  For each of the molecular weight ranges shown on Figure 4-23, significant reduction in the amount of NOM in each AMW range was observed following 1day biodegradation.  In contrast to the raw water biodegradation experiments, in most cases, no significant additional reduction in AMW was observed following the 7 day biodegradation. These results suggest that ozonation at 1mg O3/mg DOC successfully transformed the NOM present in the raw water (Section 4.2.1.2), such that this material was preferentially biodegraded within 1 day.  For ozonation at 2 mg O3/mg DOC, results are presented in Figure 4-24.                         83   Figure 4-24 - Deconvolution results for ozonation at 2mg O3/mg DOC feed water biodegradation.   (Error bars represent the 90% confidence intervals.  Data labels represent the percent reductions at time 1 day and time 7day.) 0 0 0 0 0 0 -33 -29 -23 -25 -25 -32-52 -58 -48 -46 -43 -50 0 0 0 0 0 0 -52 -46 -35 -39 -39 -39 -59 -59 -50 -47 -45 -51 0 0.02 0.04 0.06 0.08 0.1 0.12 0.14 0.16 > 1350                                                             (F1) 1050 - 1350                                 (F2) 750 - 1050                  (F3) 500 - 750                                                     (F4) 300 - 500              (F5) < 300                                                     (F6) A r e a  C o u n t Molecular Weight (Da) Feed Water - BAC Column 1 1 Day Biodegradation - BAC Column 1 7 Day Biodegradation - BAC Column 1 Feed Water - BAC Column 2 1 Day Biodegradation - BAC Column 2 7 Day Biodegradation - BAC Column 284  For each of the molecular weight ranges shown in Figure 4-24, significant reduction in the amount of NOM in each AMW range was observed following both 1day and 7 day biodegradation.  In most cases, no significant additional reduction in AMW was observed following the 7 day biodegradation. These results suggest that ozonation at 2mg O3/mg DOC successfully transformed the NOM present in the raw water (Section 4.2.1.3), such that this material was preferentially biodegraded within 1 day.  In contrast to the 1mg O3/mg DOC, lower removal percentages (in the order of 20% less removal) were observed following 1 day biodegradation for most fractions investigated (F2 - F5).  These results suggest that the rapid phase biodegradation (BDOCr) is a function of the oxidant dose.   For ozonation at the extended dose of 25 mg O3/mg DOC, results are presented in Figure 4-25.    85   Figure 4-25 - Deconvolution results for ozonation at 25mg O3/mg DOC feed water biodegradation.   (Error Bars represent the 90% confidence intervals.  Data labels represent the percent reductions at time 1 day and time 7day.) 0 0 0 0 0 0 22 34 24 -1 -30 -7 -44 37 48 -22 -42 -16 0 0 0 0 0 0 -94 -63 -7 -45 -34 -12 -89 -56 1 -48 -41 -14 0 0.01 0.02 0.03 0.04 0.05 0.06 0.07 > 1350                                                             (F1) 1050 - 1350                                 (F2) 750 - 1050                  (F3) 500 - 750                                                     (F4) 300 - 500              (F5) < 300                                                     (F6) A r e a  C o u n t Molecular Weight (Da) Feed Water - BAC Column 1 1 Day Biodegradation - BAC Column 1 7 Day Biodegradation - BAC Column 1 Feed Water - BAC Column 2 1 Day Biodegradation - BAC Column 2 7 Day Biodegradation - BAC Column 286  For each of the molecular weight ranges shown in Figure 4-25, no significant reduction in the amount of NOM in each AMW range was observed following both 1 day and 7 day biodegradation.  These results suggest that very little biodegradable organic matter remains prior to the start of biodegradation, and therefore no additional biodegradation is able to occur.  These results are consistent with those presented in 4.2.1 whereby it was shown that the extended ozonation resulted in significant removal of DOC, UVA, SUVA and AMW.   For AOP oxidation using 4000mJ/cm2 and 0 mg/L H2O2, results are presented in Figure 4-26.   87   Figure 4-26 - Deconvolution results for for 4000mJ/cm2 and 0 mg/L H2O2 feed water biodegradation.   (Error Bars represent the 90% confidence intervals.  Data labels represent the percent reductions at time 1 day and time 7day.) 0 0 0 0 0 015 -44 -58 -61 -58 -60 -16 -59 -73 -79 -78 -81 0 0 0 0 0 0 24 -52 -68 -76 -73 -76 -39 -71 -82 -83 -85 -89 0 0.02 0.04 0.06 0.08 0.1 0.12 0.14 0.16 > 1350                                                             (F1) 1050 - 1350                                 (F2) 750 - 1050                  (F3) 500 - 750                                                     (F4) 300 - 500              (F5) < 300                                                     (F6) A r e a  C o u n t Molecular Weight (Da) Feed Water - BAC Column 1 1 Day Biodegradation - BAC Column 1 7 Day Biodegradation - BAC Column 1 Feed Water - BAC Column 2 1 Day Biodegradation - BAC Column 2 7 Day Biodegradation - BAC Column 288  For each of the molecular weight ranges shown in Figure 4-26, significant reduction in the amount of NOM in each AMW range was observed following both 1day and 7 day biodegradation.  Higher removal percentages were observed for the smaller molecular weight ranges during the 1 day biodegradation (also corresponding to BAC Column 1) indicating that smaller AMW material is more easily biodegraded during the initial rapid phase of biodegradation.  Significant additional reduction in AMW was observed following the 7 day biodegradation, including biodegradation of the larger AMW material.   These results suggest that the smaller molecular weight material is more easily degraded during the initial biodegradation.    These results correspond well with those obtained during biofiltration, as presented in Section 4.1.3.   For AOP oxidation using 2000mJ/cm2 and 10 mg/L H2O2, results are presented in Figure 4-27.  89   Figure 4-27 - Deconvolution results for 2000mJ/cm2 and 10 mg/L H2O2 feed water biodegradation.   (Error bars represent the 90% confidence intervals.  Data labels represent the percent reductions at time 1 day and time 7day.) 0 0 0 0 0 0 -62 -45 -49 -50 -45 -56-54 -21 -33 -52 -32 -49 0 0 0 0 0 0 -50 -54 -57 -58 -60 -68 -56 -52 -57 -65 -60 -62 0 0.01 0.02 0.03 0.04 0.05 0.06 0.07 > 1350                                                             (F1) 1050 - 1350                                 (F2) 750 - 1050                  (F3) 500 - 750                                                     (F4) 300 - 500              (F5) < 300                                                     (F6) A r e a  C o u n t Molecular Weight (Da) Feed Water - BAC Column 1 1 Day Biodegradation - BAC Column 1 7 Day Biodegradation - BAC Column 1 Feed Water - BAC Column 2 1 Day Biodegradation - BAC Column 2 7 Day Biodegradation - BAC Column 290  For each of the molecular weight ranges shown in Figure 4-27, significant reduction in the amount of NOM in each AMW range was observed following 1 day biodegradation.  These results suggest that the oxidant used reduced the AMW of the NOM present in the raw water (Section 4.2.1.3), such that this material was preferentially removed during rapid biodegradation.  The material present following 1 day biodegradation (BAC Column 1) was therefore less aromatic and biodegradable and was not preferentially removed during biodegradation.  These results are not consistent with those obtained during biofiltration whereby BAC Column 2 removed the larger AMW substances during biofiltration (Section 4.1.3).   For AOP oxidation using 4000mJ/cm2 and 10 mg/L H2O2, results are presented in Figure 4-28.     91   Figure 4-28 - Deconvolution results for 4000mJ/cm2 and 10 mg/L H2O2 feed water biodegradation.   (Error bars represent the 90% confidence intervals.  Data labels represent the percent reductions at time 1 day and time 7day.) 0 0 0 0 0 0 54 2 -11 -18 -19 -31 30 65 29 8 -2 -24 0 0 0 0 0 0 61 9 -9 -18 -28 -41 20 54 19 1 -11 -35 0 0.005 0.01 0.015 0.02 0.025 0.03 0.035 > 1350                                                             (F1) 1050 - 1350                                                    (F2) 750 - 1050                                 (F3) 500 - 750                                                     (F4) 300 - 500                             (F5) < 300                                                     (F6) A r e a  C o u n t Molecular Weight (Da) Feed Water - BAC Column 1 1 Day Biodegradation - BAC Column 1 7 Day Biodegradation - BAC Column 1 Feed Water - BAC Column 2 1 Day Biodegradation - BAC Column 2 7 Day Biodegradation - BAC Column 292  For each of the molecular weight ranges shown in Figure 4-25, no significant reduction in the amount of NOM in each AMW range was observed following both 1 day and 7 day biodegradation.  These results suggest that very little biodegradable organic matter remains prior to the start of biodegradation, and therefore no additional biodegradation is able to occur.  These results are consistent with those presented in 4.2.1 whereby it was shown that the high dose AOP resulted in significant removal of DOC, UVA, SUVA and AMW.  These results are similar to those of presented for the extended ozonation biodegradation experiment.    Overall these results suggest that the rapid phase biodegradation (1 Day biodegradation) is a function of the oxidant type and dose.     93  5.0 CONCLUSIONS AND RECOMMENDATIONS 5.1 Biofiltration Column Experiments The objective of Part 1 of this project was to assess the removal of NOM through biological activated carbon filtration.  Major conclusions from this work are presented below.  1. Ozonation at 2 mg O3/mg DOC did not result in a significant reduction in DOC from the raw water.  However, based on UVA and SUVA analysis, ozonation did successfully reduce the amount and fraction of the organic material that was aromatic.  Ozonation also successfully reduced the AMW of the NOM present in the raw water.  DBPFP was significantly reduced following ozonation; this was attributed to the decrease in aromatic material during ozonation.  However, overall ozonation was unable to lower DBPFP below the Canadian Drinking Water Guideline values.   2. Subsequent biofiltration resulted in significant reduction in DOC levels.  Biofiltration through BAC Column 1 did not result in a change in the fraction of organic material that was aromatic, but it significantly reduced the amount of aromatic material present.  BAC Column 1 preferentially biodegraded the smaller molecular weight NOM that was more biodegradable.  Effluent from BAC Column 1 contained higher AMW that was less biodegradable.  The effluent of BAC Column 1 served as the feed water for BAC Column 2, and during biofiltration the larger AMW was successfully removed in BAC Column 2.  Given the high reductions in aromatic content observed during biofiltration, a significant reduction in DBPFP was observed.  However, only BAC Column 2 was able to lower the DBPFP and generate THM and HAA concentrations that were below the Health Canada Canadian Drinking Water Guideline values.   Overall, ozonation of the raw water at 2mg O3/mg DOC resulted in significant reductions in aromatic material, resulting in lowered DBPFP.  In addition, ozonation was successful at transforming NOM from high AMW to low AMW, rendering the organic material more biodegradable and preferentially removed during biofiltration.    94  5.2 Biodegradation Experiments 5.2.1 Raw Water Oxidation The objective of Part 2 of this project was to assess the effect of oxidation on the rate of biodegradation.  The first sub-objective was to determine the effect of different oxidation doses and types of oxidants on the removal of NOM.  Major conclusions from this work are presented below. 1. High dose oxidation is required to lower DOC levels significantly.  In addition, treatment of raw water using UV/H2O2 resulted in higher removal of DOC compared to ozonation at the doses considered.  While ozonation did not significantly reduce DOC levels, it resulted in a decrease in aromatic material.  High dose ozonation as well as UV/H2O2 was successful at significantly lowering the fraction and amount of aromatic material present in feed water.   2. Ozonation at 2mg O3/mg DOC and UV/H2O2 treatment at 2000mJ/cm2 and 10 mg/L resulted in a shift from high AMW to low AMW NOM.  This effect was not as noticeable for the higher ozonation and AOP doses which was likely due to the fact that the smaller AMW organics formed during oxidation were also oxidized at the higher doses.   3. While significant reduction in DBPFP was observed for each of the scenarios investigated, only the extended ozonation dose of 25 mgO3/mg DOC was able to meet the Canadian Drinking Water Guideline limits for THMs and HAAs.   Overall, while the high-dose oxidants (ozonation at 25mg O3/mg DOC and AOP treatment at 4000mJ/cm2 and 10mg/L H202) were successful at reducing DOC, UVA, AMW and DBPFP, the elevated dose required make these options less practically and economically feasible.  Ozonation at 2mg O3/mg DOC and AOP treatment at 2000mJ/cm2 and 10mg/L H2O2 provide good removal of UVA and AMW and a reduction of the DBPFP.   5.2.2 Batch Biodegradation Experiments The second sub-objective was to assess the effect of oxidation on the rate of biodegradation.  Major conclusions from this work are presented below. 95  1. Ozonation at 1 and 2 mg O3/mg DOC was not successful at reducing the amount of residual DOC (or non-biodegradable DOC) remaining following biodegradation.  Extended ozonation and high dose AOPs at 2000 and 4000 mJ/cm2 with 10mg/L H2O2 were successful at lowering the amount of non-biodegradable DOC present following biodegradation. These results suggest that the amount of non-biodegradable DOC is a function of the type and dose of oxidant used.  Reduction of non- biodegradable DOC can, therefore, be maximized by using the appropriate pre- oxidation treatment or dose.   2. With the exception of the ozonation at 25mgO3/mg DOC, the different oxidation doses and types of oxidants used did not have a significant effect on the rate of DOC biodegradation.  Therefore, kDOC is not a function of the type or dose of oxidant used.   3. Ozonation at 1 and 2mg O3/mg DOC, and AOP treatment using 2000 mJ/cm2 and 10mg/L H2O2, was successful at reducing UVA and AMW of the NOM, rendering it more biodegradable, such that this material was preferentially removed during the rapid phase biodegradation (1 day biodegradation).  This result suggests that potentials for DBPFP and regrowth within the distribution system are minimized, given the high reduction in biodegradable organic content.   4. Extended ozonation at 25 mgO3/mg DOC and AOP treatment using 4000 mJ/cm2 and 10mg/L H2O2, oxidized most of the NOM, significantly reducing the DOC, UVA, AMW and DBPFP.  However, very littler biodegradation occurred given the high oxidation of NOM, making oxidation at these doses unsuitable as pre-treatment for biofiltration systems.   5. Results from both the raw water biodegradation experiment and the biodegradation experiment using only 4000mJ/cm2 of UV light suggest that lower AMW NOM is preferentially biodegraded during biofiltration.   6. Biomass from BAC Column 1 and BAC Column 2 resulted in similar biodegradation kinetics and therefore both biomasses (regardless of the extended EBCT for BAC Column 2 and the different feed water) exhibited similar biodegradation rates.  Therefore, this may indicate that the acclimation of biomass to highly biodegradable or slowly biodegradable NOM in the feed water would achieve similar biodegradation results.   96  Overall, the high dose oxidants (ozonation at 25mg O3/mg DOC and AOP treatment at 4000mJ/cm2 and 10mg/L H2O2) are unsuitable as pre-treatment options for biofiltration given that they result in highly oxidized NOM that exhibits very little biodegradation during biofiltration.  The lower dose oxidants are suitable pre-treatment options for biofiltration, given the high reductions in UVA, AMW and DBPFP exhibited, and the similar biodegradation kinetics observed.   However, ozonation resulted in the lowest removals of non-biodegradable DOC and, therefore, the AOP dose of 2000mJ/cm2 and 10mg/L H2O2 would maximize removal of non-biodegradable DOC, while also ensuring sufficient biodegradation of NOM during subsequent biofiltration.    5.3 Engineering Significance and Future Work 5.3.1 Significance  This work is useful to water utilities in evaluating the effect of oxidation on the biodegradability of NOM.   Since sources of NOM vary widely in their chemical composition, and the degree to which they are able to be biodegraded will vary, it is important that water utilities considering biological treatment (or BAC treatment) perform batch biodegradation experiments, to obtain a preliminary estimate of the biodegradation potential of the NOM particular to their area.  As an alternative, the SUVA may be a good indicator of the biodegradation potential, which is consistent with findings from Goel et al., (1995).   Because of the variability in NOM, it’s also important that water utilities determine the optimum ozone dose or AOP dose to achieve maximum biodegradability by BAC, as demonstrated by this research.  Pre-oxidation prior to biofiltration provides an opportunity to maximize the removal of the non-biodegradable fraction of NOM while biofiltration does not appear to affect the amount of non-biodegradable DOC.  In addition, regardless of the pre- oxidant used, the rate kinetics appear to be constant when operating a steady-state biofiltration system.  For small water utilities, the complexity and cost of ozone based systems makes UV irradiation a more attractive alternative (AWWARF 1999).  Given the results obtained in this 97  study, it may be more advantageous from a water quality perspective to employ advanced oxidation processes using UV.  However, significant financial assessments would be required for any of the integrated treatment processes discussed in this report, given the potential for high capital and operating costs.    Despite the complexities involved in treating source water, BAC is simple and easy to operate and is a viable alternative for small and rural communities looking to achieved high water quality objectives with minimal operational requirements.  Additional investigation into the feasibility of ozonation and AOPs in small and remote communities should be investigated.   5.3.2 Future work 1. Investigation into the effect of different water sources with various types of NOM and AMW footprints on biodegradation kinetics is necessary as this study only used on type of raw water.   2. Investigation of ozonation by-products removal efficiency within BAC would be beneficial, given that water quality standards may become more stringent with respect to these compounds.   3. Future work should explore other alternative integrated treatment processes.  Exploring the feasibility of combined catalytic ozonation, or vaccum UV in combination with biofiltration biofiltration to determine whether this integrated treatment process is advantageous (see work by Chen et al., 2009).   4. It would be beneficial to explore more ozone dose ranges - research has shown that the differences between ozone doses of 1 and 2 mg/mgDOC may not be significant enough to observe any differences (Cipparone et al., 1997; Buchanan et al., 2004).  5. Future work should explore the effect of backwashing on BAC filter performance , even though some research with sand/glass beads has shown minimal effect on continuous flow biofilters after backwashing (Hozalski et al., 1999).   6. It would be advantageous to better articulate the degradation of ozone and hydrogen peroxide in BAC filters.   98  7. Future work should investigate the effect of these treatment processes on membrane fouling.  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OZONATION CALIBRATION DATA Table A-1 - Ozone calibration data ID Date Time (min) N                  Sodium Thiosulfate Titration 1 Titration 2 Blank Titration Primary KI Trap Titration Calculated O3 Produced (mg/L) Calculated O3 Produced in 2L (mg) mg O3 (200ml Trap 1) Total O3 Produced (mg) Total O3 Produced (mg/L) C a l i b r a t i o n  July 19th, 2010 3.00 0.01 20.8 21 0 0.2 50.16 100.32 0.096 100.224 50.112 July 19th, 2010 6.00 0.01 38.7 39.7 0 0.3 94.08 188.16 0.144 188.016 94.008 July 20th, 2010 2.50 0.01 16.1 16.5 0 0.2 39.12 78.24 0.096 78.144 39.072 July 20th, 2010 5.00 0.01 31.7 33.5 0 0.3 78.24 156.48 0.144 156.336 78.168 July 21st, 2010 2.50 0.01 16.5 16.4 0 0.2 39.48 78.96 0.096 78.864 39.432 July 21st, 2010 1.00 0.01 8.5 8.6 0 0.1 20.52 41.04 0.048 40.992 20.496 July 21st, 2010 0.50 0.01 3.8 3.7 0 0.1 9 18 0.048 17.952 8.976 July 21st, 2010 0.25 0.01 1.9 2 0 0 4.68 9.36 0 9.36 4.68 July 21st, 2010 0.50 0.01 3.8 3.6 0 0.1 8.88 17.76 0.048 17.712 8.856 July 22nd, 2010 0.50 0.01 3.7 3.6 0 0.1 8.76 17.52 0.048 17.472 8.736 July 22nd, 2010 0.75 0.01 5.4 5.6 0 0.1 13.2 26.4 0.048 26.352 13.176 July 23rd, 2010 0.75 0.01 5.6 5.8 0 0.1 13.68 27.36 0.048 27.312 13.656 July 25th, 2010 0.67 0.01 5 4.8 0 0.1 11.76 23.52 0.048 23.472 11.736 July 25th, 2010 0.50 0.01 3.8 3.8 0 0.1 9.12 18.24 0.048 18.192 9.096 July 31st, 2010 15.00 0.01 96.4 96.7 0 0.1 231.72 463.44 0.048 463.392 231.696 August 8th, 2010 5.00 0.01 33.7 33.9 0 0.1 81.12 162.24 0.048 162.192 81.096 110  Table A-2 - Ozone treatment data ID Date Time (min) N                  Sodium Thiosulfate Primary KI Trap Titration Secondary Trap KI  Titration mg O3 (200ml Trap 1) mg O3 (200ml Trap 2) Total O3 Produced (mg) Total O3 Produce d (mg/L) DOC Raw Water (mg/L) Total O3 Produced (mg O3/mg DOC ) T r e a t m e n t  703 1.1 July 3rd, 2010 0.75 0.01 1.9 0.1 0.888 0.048 20.1456 10.0728 4.8763 2.0657 704 1.1 July 4th, 2010 0.75 0.01 1.7 0.1 0.792 0.048 20.2416 10.1208 5.1247 1.9749 705 1.1 July 5th, 2010 0.75 0.01 1.4 0.1 0.648 0.048 20.3856 10.1928 4.9957 2.0403 706 1.1 July 6th, 2010 0.75 0.01 1.9 0.1 0.888 0.048 20.1456 10.0728 4.9875 2.0196 710 1.1 July 10th, 2010 0.75 0.01 2.3 0.1 1.08 0.048 19.9536 9.9768 5.3112 1.8784 714 1.1 July 14th, 2010 0.75 0.01 3 0.1 1.416 0.048 19.6176 9.8088 4.8865 2.0073 715 1.1 July 15th, 2010 0.75 0.01 2.6 0.1 1.224 0.048 19.8096 9.9048 4.9876 1.9859 718 1.1 July 18th, 2010 0.75 0.01 3.2 0.1 1.512 0.048 20.1936 10.0968 4.8995 2.0608 719 1.4 July 19th, 2010 0.5 0.01 19 0.1 9.12 0.048 9.024 4.512 5.164 0.8737 720 1.1 June 20th, 2010 0.75 0.01 2.8 0.1 1.32 0.048 19.7136 9.8568 5.0134 1.9661 721 1.1 July 21st, 2010 2.5 0.01 65 0.1 31.32 0.048 47.496 23.748 5.2443 4.5283 721 2.1 July 21st, 2010 0.5 0.01 13.7 0.1 6.624 0.048 11.52 5.76 5.2853 1.0898 721 2.2 July 21st, 2010 0.5 0.01 4.3 0.1 2.088 0.048 16.056 8.028 4.8346 1.6605 721 2.3 July 21st, 2010 0.5 0.01 0.9 0.1 0.408 0.048 17.736 8.868 4.7217 1.8781 721 2.4 July 21st, 2010 0.5 0.01 3.1 0.1 1.488 0.048 16.656 8.328 4.596 1.8120 723 1.1 July 23rd, 2010 0.75 0.01 2.8 0.1 1.32 0.048 22.39344 11.19672 5.0646 2.2108 723 1.1 July 23rd, 2010 0.75 0.01 3.4 0.1 1.608 0.048 19.4256 9.7128 4.9876 1.9474 723 1.2 July 23rd, 2010 0.75 0.01 3.8 0.1 1.872 0.048 25.392 12.696 5.1337 2.4731 724 1.1 July 24th, 2010 0.75 0.01 2.8 0.1 1.32 0.048 19.7136 9.8568 5.0646 1.9462 725 1.1 July 25th, 2010 0.75 0.01 25.1 0.1 12.096 0.048 11.328 5.664 4.7393 1.1951 725 1.2 July 25th, 2010 0.75 0.01 23.9 0.1 11.424 0.048 12 6 4.6721 1.2842 730 1.1 June 30th, 2010 0.75 0.01 2.5 0.1 1.176 0.048 19.8576 9.9288 5.2347 1.8967 731 1.1 July 31st, 2010 15 0.01 46.2 0.8 22.728 0.384 440.28 220.14 4.4398 49.5833 731 1.2 July 31st, 2010 0.75 0.01 3.4 0.1 1.608 0.048 25.656 12.828 4.8264 2.6579 731 1.3 July 31st, 2010 30 0.01 220 80 106.56 38.4 781.824 309.576 4.0277 76.8617 801 1.1 August 1st, 2010 45 0.01 305 105 147.6 50.4 1192.176 434.568 5.7945 74.9966 803 1.1 August 2nd, 2010 0.5 0.01 3.6 0.1 1.752 0.048 16.392 8.196 4.8913 1.6756 808 1.1 August 8th, 2010 5 0.01 230 0.8 110.88 0.384 50.928 25.464 4.9583 5.1356 815 1.1 August 25th, 2010 0.75 0.01 1.8 0.1 0.84 0 20.1936 10.0968 4.8995 2.0608 825 1.1 August 25th, 2010 2.5 0.01 74 75 35.76 0.24 42.864 21.432 5.1225 4.1839 825 1.2 August 25th, 2010 5 0.01 236 234 112.8 0.288 49.104 24.552 4.6883 5.2369 111  APPENDIX B. UV/H2O2 TREATMENT DATA Table B-1- UV/ H2O2 experiment conditions ID UVA254 (cm-1) wf UV Dose (mJ/cm2) Volume (mL) Irradiation Time, IT (min) H2O2 Dose Bovine Liver Stock Concentration (mg/L) Bovine Liver Dosing (mL) Jphh 06/23 1.1 0.155 0.91585 2000 1000 32.7 0 mg/L 500 0.4 Jphh 06/23 1.2 0.157 0.91483 2000 1000 32.7 0 mg/L 500 0.4 Jphh 06/23 1.3 0.157 0.91483 4000 1000 65.4 0 mg/L 500 0.4 Jphh 06/23 1.4 0.159 0.91381 4000 1000 65.5 0 mg/L 500 0.4 Jphh 06/23 2.1 0.151 0.9179 2000 1000 32.6 10 mg/L 500 0.4 Jphh 06/23 2.2 0.155 0.91585 2000 1000 32.7 10 mg/L 500 0.4 Jphh 06/23 2.3 0.157 0.91483 4000 1000 65.4 10 mg/L 500 0.4 Jphh 06/23 2.4 0.152 0.91739 4000 1000 65.3 10 mg/L 500 0.4 Jphh 06/26 1.1 0.154 0.91637 2000 900 29.4 10 mg/L 500 0.36 Jphh 06/26 1.2 0.153 0.91688 2000 900 29.4 10 mg/L 500 0.36 Jphh 06/26 1.3 0.142 0.92254 4000 900 58.4 10 mg/L 500 0.36 Jphh 06/26 1.4 0.149 0.91893 4000 900 58.6 10 mg/L 500 0.36 Jphh 06/26 2.1 0.172 0.90721 2000 1500 49.5 10 mg/L 500 0.6 Jphh 06/26 2.2 0.169 0.90873 4000 1500 98.8 10 mg/L 500 0.6 Jphh 06/26 2.3 0.148 0.91944 4000 1500 97.7 0 mg/L 500 0 Jphh 06/26 2.4 0.157 0.91483 4000 1500 98.2 0 mg/L 500 0 Jphh 06/26 3.1 0.156 0.91534 2000 1500 49.1 0 mg/L 500 0 Jphh 06/26 3.2 0.156 0.91534 4000 1500 98.1 0 mg/L 500 0 Jphh 06/27 1.1 0.175 0.9057 4000 1500 99.2 10 mg/L 500 0.6 Jphh 06/27 1.2 0.172 0.90721 4000 1500 99.0 10 mg/L 500 0.6 Jphh 06/27 1.3 0.158 0.91432 2000 1500 49.1 10 mg/L 500 0.6 Jphh 06/27 1.4 0.157 0.91483 2000 1500 49.1 10 mg/L 500 0.6 112  APPENDIX C. BIOMASS ANALYSIS AND VOLATILIZATION RESULTS The three biomass analysis techniques were described in the previous Section.  The first was through the use of a modified acridine orange staining method.  Results are illustrated in Figure C-1 - Image of stained fluorescing GAC.   a)  b)  Figure C-1 - Image of stained fluorescing GAC  (a is GAC from BAC Column 1, b is GAC from BAC Column 2) Given the constraints of the microscope and the complexity of the surface of GAC particles, it was difficult to observe the presence of rod-shaped (bacteria) fluorescing elements.  The virgin GAC did not respond similarly to this treatment, and produced no fluorescence under the microscope.  Given that both particles underwent similar procedures, this provides a qualitative confirmation of the presence of biomass on the GAC particles.  The second analysis involved the determination of volatile solids on the granular activated carbon extracted from the columns.  This analysis proved difficult given the medium used.  It was necessary to perform a volatile solids test on both virgin GAC and GAC extracted from the columns.  Results are presented in Figure C-2 and Table C-1.   113   Figure C-2 - Percent additional volatilization of harvested GAC compared to virgin GAC The value of percent additional volatization provides a semi-quantitative confirmation that biomass was present on the filter media.  Given the complexity in analyzing results from this test, it is important that secondary tests be performed in order to confirm presence of biomass within filters.   The tests performed provided confirmation of presence of biomass growth within biofilters.   0 1 2 3 4 5 6 7 A dd iti o n al  V o la til iz at io n  (% ) Slow Fast114  Table C-1 - Volatilization of harvested GAC Virgin GAC Volatilization ID Dish Weight Dish + GAC After 40°C After 105°C After 550°C Weight of Dry GAC Weight of GAC after 105°C Weight of GAC after 550°C % Virgin GAC Volatilized Average Virgin GAC 1.1080 3.6082 3.2279 3.2440 1.4803 2.1199 2.1360 0.3723 82.5702 86.2936 Virgin GAC 1.0791 2.7499 2.4750 2.5583 1.3025 1.3959 1.4792 0.2234 84.8972 Virgin GAC 1.1087 2.1020 1.8805 1.8140 1.1887 0.7718 0.7053 0.0800 88.6573 Virgin GAC 1.0804 1.8907 1.7017 1.7644 1.1553 0.6213 0.6840 0.0749 89.0497 Filter GAC Volatilization ID Dish Weight Dish + GAC After 40°C After 105°C After 550°C Weight of Dry GAC Weight of GAC after 105°C Weight of GAC after 550°C Remaining weight if Virgin GAC only Additional amount volatilized Additional % volatilized Average  Slow 1.1018 5.4954 3.9964 2.0057 1.1784 2.8946 0.9039 0.0766 0.1239 0.0766 5.2320 5.6976 Slow 1.0904 4.9891 3.5212 1.9736 1.1632 2.4308 0.8832 0.0728 0.1211 0.0728 5.4636 Slow 1.0962 4.6407 3.1389 1.8791 1.1611 2.0427 0.7829 0.0649 0.1073 0.0649 5.4167 Slow 1.0760 4.9307 3.2027 1.9158 1.1466 2.1267 0.8398 0.0706 0.1151 0.0706 5.2996 Slow 1.0753 2.1236 1.5761 1.3323 1.0946 0.5008 0.2570 0.0193 0.0352 0.0193 6.1830 Slow 1.1074 2.0499 1.5153 1.3559 1.1268 0.4079 0.2485 0.0194 0.0341 0.0194 5.9166 Slow 1.0786 2.2287 1.5821 1.3652 1.1019 0.5035 0.2866 0.0233 0.0393 0.0233 5.5639 Slow 1.1014 5.7544 4.1847 2.2448 1.1926 3.0833 1.1434 0.0912 0.1567 0.0912 5.7302 Slow 1.0900 4.8918 3.4525 1.9876 1.1604 2.3625 0.8976 0.0704 0.1230 0.0704 5.8632 Slow 1.0957 3.5090 2.3734 1.6688 1.1397 1.2777 0.5731 0.0440 0.0786 0.0440 6.0288 Slow 1.0758 4.5127 2.9312 1.9011 1.1396 1.8554 0.8253 0.0638 0.1131 0.0638 5.9759 Fast 1.1008 1.8131 1.3852 1.2878 1.1177 0.2844 0.1870 0.0169 0.0256 0.0169 4.6929 4.4597 Fast 1.0895 2.1716 1.6189 1.3245 1.1115 0.5294 0.2350 0.0220 0.0322 0.0220 4.3273 Fast 1.0952 2.4319 1.8488 1.3813 1.1219 0.7536 0.2861 0.0267 0.0392 0.0267 4.3588 115  APPENDIX D. BIOFILTRATION RESULTS FOR TOC AND UVA Table D-1- DOC, UVA data for biofiltration Raw Water Treated Water (2mg/mg DOC) ID DOC (Std Dev) UVA SUVA ID DOC (Std Dev) UVA SUVA 7/03 1.1 4.8763 0.062566 0.173 3.548 7/03 1.1 4.632485 0.077607 0.112 2.417709 7/04 1.1 5.1247 0.075093 0.156 3.038 7/04 1.1 4.868465 0.072941 0.116 2.382681 7/05 1.1 4.9957 0.073391 0.125 2.493 7/05 1.1 4.745915 0.034136 0.112 2.359924 7/06 1.1 4.9875 0.059522 0.162 3.247 7/06 1.1 4.738125 0.064205 0.117 2.469331 7/07 1.1 5.1104 0.0673 0.194 3.802 7/07 1.1 4.85488 0.030808 0.11 2.265761 7/07 1.2 4.9583 0.0489 0.136 2.743 7/07 1.2 4.710385 0.080567 0.12 2.547562 7/10 1.1 5.3112 0.068035 0.190 3.585 7/10 1.1 5.04564 0.09385 0.1 1.981909 7/14 1.1 4.8865 0.08278 0.163 3.334 7/14 1.1 4.642175 0.08996 0.118 2.541912 7/15 1.1 4.9876 0.034424 0.130 2.598 7/15 1.1 4.73822 0.065116 0.104 2.194917 7/18 1.1 4.8995 0.061799 0.166 3.396 7/18 1.1 4.654525 0.055671 0.112 2.406261 7/19 1.1 5.0896 0.1007 0.173 3.399 7/19 1.1 4.7845 0.0555 0.109 2.27819 7/19 1.4 5.6839 0.0821 0.176 3.096 7/19 1.4 4.837635 0.048563 0.103 2.12914 7/20 1.1 5.0134 0.0827 0.127 2.527 7/20 1.1 4.7154 0.1029 0.115 2.438817 7/21 1.1 5.2853 0.0576 0.181 3.425 7/21 1.1 5.021035 0.003186 0.111 2.2107 7/21 2.1 4.91 0.0704 0.162 3.299 7/21 2.1 4.6411 0.0346 0.108 2.327035 7/21 2.2 4.8346 0.1403 0.128 2.648 7/21 2.2 4.7154 0.1029 0.115 2.438817 7/21 2.3 4.7217 0.132 0.163 3.452 7/21 2.3 4.391181 0.014173 0.106 2.413929 7/21 2.4 4.596 0.0673 0.160 3.481 7/21 2.4 4.45812 0.062726 0.117 2.624425 7/23 1.1 5.0646 0.0543 0.158 3.120 7/23 1.1 4.8959 0.0523 0.119 2.430605 7/23 1.2 5.1337 0.0446 0.160 3.117 7/23 1.2 5.0439 0.0918 0.118 2.33946 7/24 1.1 5.0646 0.000525 0.203 4.004 7/24 1.1 4.834086 0.062503 0.116 2.399626 7/25 1.1 4.7393 0.1165 0.163 3.439 7/25 1.1 4.765542 0.099263 0.105 2.203317 7/25 1.2 4.6721 0.0547 0.169 3.617 7/25 1.2 4.578658 0.017186 0.105 2.293248 7/30 1.1 5.2347 0.070709 0.153 2.923 7/30 1.1 5.339394 0.029089 0.108 2.022701 7/31 1.1 4.4398 0.006 0.141 3.176 7/31 1.1 4.7633 0.077378 0.119 2.498268 7/31 1.2 4.8264 0.0809 0.174 3.605 7/31 1.2 4.8694 0.0209 0.12 2.464369 7/31 1.3 4.0277 0.1319 0.150 3.724 7/31 1.3 3.62493 0.036364 0.111 3.062128 8/01 1.1 5.7945 0.1627 0.193 3.331 8/01 1.1 5.21505 0.000985 0.11 2.10928 8/03 1.1 4.8913 0.1422 0.159 3.251 8/03 1.1 4.40217 0.076535 0.125 2.839509 803 1.1 4.9223 0.056908 0.152 3.088 803 1.1 4.43007 0.065962 0.122 2.753907 825 1.1 4.8995 0.007096 0.153 3.123 825 1.1 4.40955 0.077968 0.121 2.744044   116  Column 1.1 Column 1.2 ID DOC (Std Dev) UVA SUVA ID DOC (Std Dev) UVA SUVA c1.1 2.5585 0.056 0.052 2.032 c1.2 1.4105 0.0082 0.028 1.985 c1.1 2.845 0.0896 0.071 2.496 c1.2 2.1604 0.0059 0.04 1.852 c1.1 2.915 0.0307 0.069 2.367 c1.2 2.7963 0.0471 0.063 2.253 c1.1 2.8739 0.0222 0.066 2.297 c1.2 1.3516 0.0234 0.025 1.850 c1.1 2.7396 0.0102 0.069 2.519 c1.2 1.8969 0.0357 0.035 1.845 c1.1 2.6032 0.0278 0.07 2.689 c1.2 1.8712 0.0295 0.041 2.191 c1.1 2.9943 0.1883 0.07 2.338 c1.2 2.1581 0.0174 0.053 2.456 c1.1 2.8505 0.0563 0.033 1.158 c1.2 1.7933 0.0033 0.052 2.900 c1.1 1.8807 0.0353 0.037 1.967 c1.2 1.3208 0.0513 0.023 1.741 c1.1 2.0768 0.0375 0.034 1.637 c1.2 2.6759 0.0305 0.069 2.579 c1.1 2.567 0.0038 0.058 2.259 c1.2 2.8325 0.0286 0.065 2.295 c1.1 2.8731 0.0387 0.066 2.297 c1.2 2.8851 0.0411 0.067 2.322 c1.1 1.6374 0.0251 0.031 1.893 c1.2 2.0382 0.0394 0.056 2.748 c1.1 1.868 0.0265 0.032 1.713 c1.2 1.81 0.0349 0.05 2.762 c1.1 1.858 0.0146 0.036 1.938 c1.2 3.0689 0.1246 0.074 2.411 c1.1 2.4749 0.0263 0.058 2.344 c1.2 3.1687 0.0044 0.074 2.335 c1.1 1.8673 0.0086 0.051 2.731 c1.2 2.7536 0.0616 0.057 2.070 c1.1 1.6415 0.0202 0.046 2.802 c1.2 2.8848 0.2498 0.078 2.704 c1.1  2.1401 0.0658 0.054 2.523 c1.2 2.7341 0.0464 0.073 2.670 c1.1  1.9782 0.0106 0.054 2.730 Column 1.4 c1.1  3.0086 0.1572 0.075 2.493 ID DOC (Std Dev) UVA SUVA Column 1.3 c1.4 2.5487 0.0096 0.062 2.433 ID DOC (Std Dev) UVA SUVA c1.4 2.0699 0.035 0.051 2.464 c1.3 2.4422 0.0174 0.058 2.375 c1.4 2.7137 0.0279 0.072 2.653 c1.3 2.8445 0.0388 0.078 2.742 c1.4 1.7791 0.0495 0.039 2.192 c1.3 2.8857 0.0093 0.072 2.495 c1.4 1.863 0.0088 0.066 3.543 c1.3 2.7753 0.0197 0.07 2.522 c1.4 2.0976 0.0214 0.038 1.812 c1.3 2.6879 0.0721 0.068 2.530 c1.4 2.4814 0.0263 0.051 2.055 c1.3 2.658 0.0341 0.067 2.521 c1.4 3.0319 0.0246 0.07 2.309 c1.4 2.8797 0.0748 0.07 2.431 c1.4 2.1572 0.021 0.034 1.576 c1.4 2.0717 0.0316 0.04 1.931 c1.4 2.2008 0.0137 0.052 2.363 c1.4 1.9851 0.0209 0.053 2.670 c1.4 2.0756 0.0087 0.045 2.168 c1.4 2.1134 0.0218 0.041 1.940 c1.4 1.873 0.0237 0.032 1.708  117  Column 2.1 Column 2.2 ID DOC (Std Dev) UVA SUVA ID DOC (Std Dev) UVA SUVA c2.1 1.7927 0.0046 0.026 1.450 c2.2 1.4958 0.0031 0.021 1.404 c2.1 0.6786 0.0407 0.011 1.621 c2.2 0.5745 0.0109 0.01 1.741 c2.1 0.9522 0.031 0.014 1.470 c2.2 0.7179 0.0148 0.011 1.532 c2.1 1.497 0.0367 0.029 1.937 c2.2 0.937 0.0271 0.016 1.708 c2.1 1.3036 0.0107 0.019 1.458 c2.2 1.5214 0.0223 0.022 1.446 c2.1 1.4422 0.0196 0.023 1.595 c2.2 1.4938 0.0285 0.022 1.473 c2.1 1.1268 0.0636 0.018 1.597 c2.2 1.1601 0.057 0.02 1.724 c2.1 0.9713 0.0345 0.016 1.647 c2.2 1.779 0.0416 0.029 1.630 c2.1 0.9121 0.0203 0.014 1.535 c2.2 1.1613 0.0299 0.022 1.894 c2.1 0.7126 0.0224 0.011 1.544 c2.2 1.2679 0.0282 0.023 1.814 c2.1 1.3294 0.0223 0.024 1.805 c2.2 0.8409 0.0185 0.013 1.546 c2.1 1.3034 0.012 0.022 1.688 c2.2 1.0364 0.0258 0.016 1.544 c2.1 1.099 0.0109 0.02 1.820 c2.2 1.0935 0.0421 0.011 1.006 c2.1 1.8723 0.0323 0.035 1.869 c2.2 1.0643 0.0085 0.019 1.785 c2.1 0.8101 0.057 0.01 1.234 c2.2 1.6923 0.0628 0.031 1.832 c2.1 0.7984 0.0025 0.012 1.503 c2.2 0.9251 0.0362 0.013 1.405 c2.1 1.1518 0.0102 0.018 1.563 c2.2 0.8752 0.0384 0.014 1.600 c2.1 1.2449 0.0154 0.021 1.687 c2.2 1.4174 0.0087 0.026 1.834 c2.1 1.1038 0.0333 0.017 1.540 Column 2.4 Column 2.3 ID DOC (Std Dev) UVA SUVA ID DOC (Std Dev) UVA SUVA c2.4 1.2809 0.0024 0.017 1.327 c2.3 1.3626 0.0099 0.019 1.394 c2.4 0.9609 0.01 0.02 2.081 c2.3 0.9923 0.0105 0.012 1.209 c2.4 1.7212 0.0101 0.037 2.150 c2.3 0.4287 0.0196 0.006 1.400 c2.4 1.2298 0.0261 0.013 1.057 c2.3 0.6108 0.0096 0.011 1.801 c2.4 0.9502 0.018 0.012 1.263 c2.4 0.8915 0.0127 0.015 1.683 c2.4 0.975 0.0321 0.015 1.538 c2.4 2.142 0.0279 0.051 2.381 c2.4 0.9851 0.0103 0.014 1.421 c2.4 1.5226 0.0089 0.023 1.511 c2.4 1.9644 0.0018 0.037 1.884 c2.4 2.3996 0.045 0.048 2.000     118  APPENDIX E. OXIDATION HPSEC CHROMATOGRAMS     Figure E-1- HPSEC chromatogram results  1. Raw Water; 2. Influent Water (Ozonated); 3. BAC Column 1; 4. BAC Column 2; 5. Ozonated 1mg; 6. Ozonated 2mg; 7. Extended Ozonation; 8. 4000mJ/cm2, 0mg/L H2O2; 9. 2000mJ/cm2, 10mg/L H2O2 1 2 3 4 5 6 9 8 7 119   Figure E-2- HPSEC chromatogram results  1. 4000mJ/cm2, 10mg/L H2O2 1 120  APPENDIX F. PEAKFIT ANALYSIS OF OXIDATION HPSEC CHROMATOGRAMS  Figure F-1 - Peakfit analysis results for each of the raw water (ID 1-9) HPSEC chromatograms.   Using Systat Peakfit v4.12,  Autofit Peak III Deconvolution. 121   Figure F-2 - Peakfit analysis results for each of the raw water (ID 10 -17) HPSEC chromatograms.   Using Systat Peakfit v4.12,  Autofit Peak III Deconvolution.  122   Figure F-3 - Peakfit analysis results for each of the influent BAC column ozonated at 2mgO3/mgDOC (ID 1 to 7) water HPSEC chromatograms.   Using Systat Peakfit v4.12,  Autofit Peak III Deconvolution. 123   Figure F-4 - Peakfit analysis results for each of the influent BAC Column 1 effluent  (ID 1 to 9) water HPSEC chromatograms.   Using Systat Peakfit v4.12,  Autofit Peak III Deconvolution. 124   Figure F-5 - Peakfit analysis results for each of the influent BAC Column 1 effluent  (ID 10 to 16) water HPSEC chromatograms.   Using Systat Peakfit v4.12,  Autofit Peak III Deconvolution.  125    Figure F-6 -Peakfit analysis results for each of the influent BAC Column 2 effluent  (ID 1 to 9) water HPSEC chromatograms.   Using Systat Peakfit v4.12,  Autofit Peak III Deconvolution. 126   Figure F-7 -Peakfit analysis results for each of the influent BAC Column 2 effluent  (ID 10 to 17) water HPSEC chromatograms.   Using Systat Peakfit v4.12,  Autofit Peak III Deconvolution. 127   Figure F-8 - Peakfit analysis results for each of the Ozonated at 1mgO3/mgDOC water (ID 1-7) and extended dose (ID 1 to 2) HPSEC chromatograms.   Using Systat Peakfit v4.12,  Autofit Peak III Deconvolution. 128    Figure F-9 - Peakfit analysis results for each of the UV 4000mJ/cm2 and 0 mg/L H2O2 (ID 1 to 3) and 10mg/L H202treated (ID 1 to 6) HPSEC chromatograms.   Systat Peakfit v4.12 using Autofit Peak III Deconvolution. 129    Figure F-10 -Peakfit analysis results for each of the UV 2000mJ/cm2 and 10 mg/L H2O2 (ID 1 to 7) HPSEC chromatograms.   Systat Peakfit v4.12 using Autofit Peak III Deconvolution. 130  APPENDIX G. HAA RESULTS Table G-1 - HAA data run 1  Description Sample ID TBAA (ug/L) CDBAA (ug/L) BDCAA (ug/L) DBAA (ug/L) BCAA (ug/L) TCAA (ug/L) MCAA (ug/L) DCAA (ug/L) MBAA (ug/L) HAA9 (ug/L) 4000,10 626 1.4 1 0.000 0.000 0.000 0.000 13.218 20.706 0.191 156.429 0.000 190.545 4000,10 626 1.3 3 0.000 0.000 0.000 0.000 12.630 21.419 1.780 159.922 0.000 195.751 Extended 805 1.1 4 0.000 0.000 0.000 0.000 1.681 14.225 0.000 9.441 0.000 25.347 c2.1 705 5 23.673 0.000 0.000 6.238 1.651 16.900 0.091 11.707 17.810 78.069 Extended 805 1.3 6 0.000 0.000 0.000 0.000 1.743 14.551 0.000 10.321 0.000 26.614 Extended 805 1.4 7 0.000 0.000 0.000 0.000 1.511 16.615 0.000 11.789 0.000 29.915 Extended 805 1.2 8 0.000 0.000 1.040 0.152 1.591 21.269 0.000 15.571 0.000 39.622 c1.2 707 9 0.000 0.000 1.606 0.000 1.907 63.269 0.000 62.623 0.000 129.405 2mg 715 11 0.000 0.000 2.956 0.000 2.746 98.658 0.000 93.285 0.000 197.645 2mg 713 12 0.000 0.000 1.937 0.000 2.665 98.687 0.000 100.573 0.000 203.862 c1.2 710 13 0.000 0.000 1.197 0.000 2.154 49.044 4.318 64.708 0.000 121.422 4000,10 627 1.1 14 32.074 0.000 0.000 0.463 3.659 67.848 0.000 80.288 0.000 184.331 4000,10 627 1.2 14 DUP 0.000 0.000 0.000 0.000 13.072 18.071 2.106 152.449 0.000 185.698 1mg 718 15 0.000 0.000 3.597 0.346 11.659 119.225 0.000 229.185 0.000 364.012 2000,10 626 2.1 16 0.000 0.000 2.608 0.227 7.605 73.330 12.357 152.103 0.000 248.230 c1.1 707 17 0.000 0.000 2.457 0.477 31.605 39.841 0.000 115.856 0.000 190.237 4000,10 627 1.2 18 0.000 0.000 0.000 0.450 31.712 45.784 0.000 128.032 0.000 205.978 4000,10 623 1.3 19 0.000 0.000 3.072 0.331 3.479 34.942 0.000 155.932 0.000 197.756 Raw 721 2.1 20 0.000 0.000 21.567 7.238 59.843 123.438 0.000 223.440 3.484 439.010 Raw 723 1.2 21 0.000 0.000 4.902 0.281 6.998 144.009 11.926 210.777 0.000 378.893 Raw 719 1.4 22 0.000 0.000 0.000 0.416 15.614 115.425 14.919 233.696 0.000 380.070 Raw 719 1.4 22 DUP 0.000 0.000 3.988 0.000 14.540 105.479 14.964 208.757 0.000 347.728 1mg 713 24 0.000 0.000 2.596 0.000 11.372 122.908 13.069 238.396 0.000 388.341 1mg 712 25 0.000 0.000 0.000 0.000 9.448 106.585 16.637 214.176 0.000 346.846 15 Spike (60) 576.828 314.808 102.60429 73.17381 145.35918 197.51118 180.516 374.00598 113.8041   15 Recover (%) 98 104 88 121 110 110 98 92 93   60 STD 588.6 302.7 112.59 60.18 120 59.79 184.2 178.98 122.37    131  Description Sample ID TBAA (ug/L) CDBAA (ug/L) BDCAA (ug/L) DBAA (ug/L) BCAA (ug/L) TCAA (ug/L) MCAA (ug/L) DCAA (ug/L) MBAA (ug/L) HAA9 (ug/L) c2.2 801 26 0.000 0.000 3.038 0.000 4.074 40.979 0.000 27.590 0.000 75.681 c2.2 804 27 0.000 0.000 3.317 0.429 3.660 42.650 0.000 23.293 0.000 73.349 c2.2 806 28 0.000 0.000 3.259 0.308 3.986 46.280 0.000 31.693 0.000 85.525 c2.1 801 29 0.000 0.000 4.061 0.398 3.919 49.236 0.000 33.139 0.000 90.753 c2.1 803 30 0.000 0.000 3.117 0.234 2.577 27.838 2.012 19.300 0.000 55.079 2000,10 626 1.2 31 0.000 0.000 3.052 0.325 8.823 85.144 11.950 168.803 0.000 278.095 c1.2 806 32 0.000 0.000 1.508 0.000 2.163 74.766 3.953 71.941 0.000 154.330 2mg 801 33 0.000 0.000 2.288 0.314 3.085 119.049 5.575 104.904 0.000 235.214 2mg 802 33 0.000 0.000 2.735 0.000 2.854 103.478 2.345 100.035 0.000 211.447 4000,10 627 34 0.000 0.000 0.000 0.000 1.381 45.084 4.399 145.094 0.000 195.958 2000,10 627 1.3 35 0.000 0.000 1.146 0.256 3.540 144.853 4.600 135.714 0.000 290.108 2mg 803 36 0.000 0.000 0.000 0.000 3.603 91.748 5.425 110.487 0.000 211.263 2mg 804 37 0.000 0.000 1.823 0.239 3.766 96.803 5.475 115.504 0.000 223.610 4000,0 626 2.3 38 0.000 0.000 4.211 0.488 13.087 155.531 17.998 302.787 0.000 494.101 4000,0 626 2.4 39 0.000 0.000 0.000 0.355 12.487 135.827 16.292 270.210 0.000 435.171 c1.1 801 40 0.000 0.000 2.336 0.422 30.549 32.661 8.597 95.381 0.000 169.946 c1.1 804 40 DUP 0.000 0.000 3.2654 0.000 32.465 31.185 8.655 86.789 0 162.359 2000,10 627 1.3 41 0.000 0.000 2.418 0.692 36.720 61.574 11.592 172.901 0.000 285.897 c1.1 801 42 0.000 0.000 4.962 0.246 5.085 61.890 4.594 83.475 0.000 160.252 2000,10 626 1.2 43 0.000 0.000 19.609 4.835 40.771 80.563 8.815 146.367 2.426 303.386 Raw 721 2.1 44 0.000 0.000 5.017 0.408 9.460 203.217 10.511 188.253 0.000 416.866 Raw 721 2.1 45 0.000 0.000 4.037 0.222 6.244 139.430 10.321 195.777 0.000 356.031 4000,0 623 1.1 46 0.000 0.000 0.352 0.426 13.782 167.094 13.650 292.436 0.000 487.740 2000,10 627 1.4 47 0.000 0.000 3.478 0.000 10.425 76.543 14.321 150.478 0.000 255.245 34 Spike (20) 174.618 118.053 35.654 18.656 42.540 59.500 65.361 98.060 39.566   34 Recover (%) 89 117 95 93 103 92 99 48 97   20 STD 196.2 100.9 37.53 20.06 40 19.93 61.4 59.66 40.79    132  APPENDIX H. THM RESULTS  Table H-1 -  THM data run 1  Description Sample ID Chloroform (ug/L) Bromodichloroform (ug/L) Dibromochloroform (ug/L) Bromoform (ug/L) Raw 802 39 250.804535 51.10706977 6.063689458 0 Raw 731 1.2 33 206.9451227 31.63243132 2.778186312 0 Raw 731 1.2 32 204.7230835 27.16993318 2.279237894 0 Raw 731 1.1 31 264.4803594 19.13325392 0 0 Raw 725 1.2 30 157.3051628 72.78095509 25.23699774 0 Raw 725 1.1 27 211.784019 101.553403 35.16377021 2.573537148 Raw 725 1.1 27 DUP 196.9861091 95.54887981 33.31593809 2.461003698 Raw 719 1.4 3 178.574 95.684 35.985 3.121 Raw 719 1.4 3 DUP 167.030 90.174 33.964 2.979 Raw 719 1.2 76 205.498856 117.8887309 65.75337216 8.836802552 Raw 719 1.1 2 271.333 155.969 61.869 5.467 Raw 719 1.1 1 206.043 119.455 44.448 4.047 Raw 707 1.4 9 170.137 95.855 36.794 3.146 Raw 707 1.2 7 208.882 114.091 43.657 3.842 Extended 806 44 DUP 24.00932068 27.38452356 28.38760902 13.27881389 Extended 806 44 21.76928435 24.99147686 27.80790972 12.39275519 Extended 805 46 23.30938468 26.61728637 27.85598276 12.83999739 Extended 804 45 32.37661894 34.88766049 43.09139428 16.15064574 Extended 803 47 28.3646767 35.85088398 40.39216478 21.00848481 Extended 802 48 24.67935672 40.10804452 47.78671664 26.41884547 Extended 801 79 25.66645486 40.43240802 51.56573015 26.9162005 c2.2 806 62 54.45040949 12.3848969 2.961951409 0 c2.2 724 71 10.65838967 12.48548776 16.0913155 10.0547004 c2.2 723 70 9.20241938 10.63496849 14.00835355 8.642110457 c2.2 719 69 11.07243045 12.80789526 15.88505235 9.231351688 c2.2 719 69 DUP 9.639340614 11.06313313 14.28986189 8.821460881 c2.2 717 68 8.559610743 9.910030354 12.95782043 8.035877997 c2.1 806 67 26.19423468 11.90137728 10.56963021 0 c2.1 717 65 12.21923085 4.323988733 0 0 c2.1 708 63 6.566480383 7.037528097 8.953098529 5.623485762 c1.3 721 13 63.941 28.919 9.514 0.000 c1.3 719 40 42.92812524 33.39187239 23.46873248 5.801638462 c1.2 805 61 67.57416301 15.35265811 3.648219675 0 c1.2 803 60 DUP 67.96797626 16.78824546 4.107742649 0 c1.2 803 60 59.55193203 14.3952766 3.529976065 0 c1.2 801 72 17.51249287 20.95193513 26.70045751 12.78411784 c1.2 725 59 78.80912886 19.95684368 4.52851584 0 c1.2 713 58 134.0903971 35.95916834 9.295534404 0 c1.2 713 58 DUP 120.5987487 32.42883821 8.389534854 0 c1.2 707 57 100.2366471 26.20468464 6.749745782 0 c1.1 806 56 78.25103799 19.13770853 4.349084878 0 c1.1 805 55 64.51433342 13.34929493 0 0 c1.1 801 54 89.10700381 21.96673422 0 0 c1.1 801 66 59.24951559 23.39366873 0 0 c1.1 801 66 DUP 42.91749782 18.3151619 8.025130576 0 c1.1 723 53 136.5448694 37.42827607 7.856443882 0 c1.1 718 11 DUP 64.073 37.602 20.474 2.189 c1.1 718 11 58.826 33.977 18.305 2.246 c1.1 715 52 56.7601021 15.7898895 3.527770076 0133                                    Description Sample ID Chloroform (ug/L) Bromodichloroform (ug/L) Dibromochloroform (ug/L) Bromoform (ug/L) c1.1 710 64 9.063877698 9.751668923 111.9087153 6.806400828 c1.1 707 51 82.81542359 19.53688122 0 0 4000,10 6301.4 18 100.097 53.831 19.970 0.000 4000,10 6301.4 16 121.961 54.528 18.432 0.000 4000,10 628 1.2 12 91.088 53.968 29.279 3.665 4000,10 628 1.2 75 93.67730639 54.51220053 28.3604886 4.014777014 4000,10 628 1.2 12 DUP 66.271 38.555 20.862 2.576 4000,10 628 1.1 38 DUP 160.9202888 32.35952543 3.694472598 0 4000,10 628 1.1 38 152.24346 30.24480897 3.441213521 0 4000,10 627 1.3 23 81.67231363 51.95056201 28.16341428 4.102771205 4000,10 627 1.3 23 DUP 73.65376382 47.16427986 25.64689683 3.731376557 4000,10 626 1.4 37 150.2098969 16.9799564 0 0 4000,10 626 1.4 36 175.4308497 10.76951614 0 0 4000,10 626 1.3 81 198.3206802 14.15201661 0 0 4000,10 626 1.3 26 101.5351401 46.2841196 15.54093654 0 4000,0 731 1.2 35 234.06108 51.14474629 11.40636839 0 4000,0 723 1.2 22 156.5054694 99.52207248 60.46156947 9.014687415 4000,0 723 1.2 21 152.837 94.684 56.779 8.428 2mg 803 6 DUP 124.295 67.713 25.265 2.029 2mg 803 6 114.457 61.110 22.808 0.000 2mg 801 80 61.336 79.147 29.897 2.462 2mg 731 1.2 78 114.3666571 36.61431523 11.48246322 0 2mg 731 1.2 34 116.0322474 24.51691957 5.260213764 0 2mg 723 1.2 20 116.520 72.016 42.792 6.477 2mg 723 1.1 24 117.8779411 70.5704658 41.12016985 5.695010945 2mg 723 1.1 25 75.83086314 44.69755575 25.6838767 3.417264377 2mg 713 17 94.709 42.827 14.493 0.000 2mg 712 14 111.095 48.608 16.276 0.000 2mg 703 28 90.59996746 53.14386964 30.45344812 3.717114248 2mg 703 28 DUP 62.59834194 35.85652179 20.5421347 2.59409317 2000,10 627 1.4 8 DUP 135.786 71.283 26.571 2.141 2000,10 627 1.4 10 125.994 61.227 22.450 0.000 2000,10 627 1.4 8 131.299 68.275 25.107 2.000 2000,10 627 1.3 15 132.575 61.402 21.516 0.000 2000,10 628 1.4 50 142.4026778 114.4578269 79.80530419 17.57563913 2000,10 626 1.2 43 120.4717811 97.41789612 73.71977376 18.83953007 2000,10 626 1.2 42 DUP 108.5744702 90.39805444 68.53048874 17.95469006 2000,10 626 1.2 42 95.08601854 77.10942042 58.19514044 15.05775365 2000,10 626 1.1 41 142.5217178 117.7229605 85.33129985 21.38335835 1mg 725 1.1 77 158.7835577 91.30627225 50.63579869 6.823898321 1mg 725 1.1 29 153.6594333 90.94253809 53.25132562 6.49110536 1mg 721 2.1 73 176.5813409 101.8294673 53.99799587 6.72268539 1mg 721 2.1 74 121.6692871 69.24695982 36.6252595 4.668102388 1mg 719 1.1 5 170.342 115.781 65.386 8.725 1mg 719 1.1 4 144.161 96.347 54.614 7.315 15 mg 802 81 94.30235287 56.45637264 24.67210191 4.556008756 15 mg 803 82 72.03931998 51.40218912 25.17019917 2.733811501 15 mg 804 83 75.76708134 44.1113371 14.05863986 0 65 Spike (20) 33.062 21.912 19.879 21.859 65 Recover (%) 107 95 106 121 20 STD 18.54884 18.85581 18.75349 18.06512134  APPENDIX I. OXIDATION TOC AND UVA DATA Table I-1 - Raw TOC and UVA data for oxidation conditions  Treatment ID DOC Std. Dev. UVA JP 7/25 1.1 4.7393 0.1165 0.163 JP 7/25 1.1 TREATED 4.6681 0.0655 0.134 JP 7/25 1.2 4.6721 0.0547 0.169 JP 7/25 1.2 TREATED 4.4361 0.01514 0.11 JP 7/21 2.3 4.7217 0.132 0.163 JP 7/21 2.3 TREATED 4.6922 0.0386 0.152 JP 7/21 2.4 4.596 0.0673 0.16 JP 7/21 2.4 TREATED 4.5131 0.0039 0.11 JP 7/21 2.1 4.91 0.0704 0.162 JP 7/21 2.1 TREATED 4.3941 0.0417 0.159 JP 7/21 2.2 4.8346 0.1403 0.128 JP 7/21 2.2 TREATED 4.6293 0.0814 0.127 JP 7/19 1.4 5.6839 0.0821 0.176  JP 7/19 1.4 TREATED 5.683 0.0943 0.124 JP 7/19 1.4 5.6839 0.0821 0.176 JP 7/19 1.4 TREATED 5.683 0.0943 0.124 JP 7/21 2.1 4.91 0.0704 0.162 JP 7/21 2.1 TREATED 5.0749 0.101 0.1298 JP 7/25 1.2 4.6721 0.0547 0.169 JP 7/25 1.2 TREATED 4.4361 0.01514 0.11 JP 7/25 1.1 4.7393 0.1165 0.163 JP 7/25 1.1 TREATED 4.7028 0.0612 0.132 JP 7/25 1.1 4.7393 0.1165 0.163  JP 7/25 1.1 4.7854 0.0436 0.131 JP 7/19 1.4 5.6839 0.0821 0.176 JP 7/19 1.4 TREATED 5.4763 0.0399 0.149 JP 7/21 2.1 4.91 0.0704 0.162 JP 7/21 2.1 TREATED 4.3941 0.0417 0.159 JP 7/25 1.1 4.7393 0.1165 0.163 JP 7/25 1.1 TREATED 4.6681 0.0655 0.134 JP 7/23 1.1 5.0646 0.0543 0.158 JP 7/23 1.1 TREATED 4.8959 0.0523 0.109 JP 7/23 1.2 5.1337 0.0446 0.16 JP 7/23 1.2 TREATED 5.0439 0.0918 0.107 JP 7/23 1.1 5.0646 0.0543 0.158 19.0 JP 7/23 1.1 TREATED 4.7154 0.1029 0.115 JP 7/23 1.1 5.0646 0.0543 0.158 20.0 JP 7/23 1.1 TREATED 4.7154 0.1029 0.115 JP 7/23 1.2 5.1337 0.0446 0.16 21.0 JP 7/23 1.2 TREATED 4.7845 0.0555 0.109 JP 7/23 1.2 5.1337 0.0446 0.16 22.0 JP 7/23 1.2 TREATED 4.6411 0.0346 0.108 JP 731 1.2 RAW 4.8264 0.0809 0.174 36.0 JP 731 1.2 TREATED 4.8694 0.0209 0.12 JP 731 1.2 RAW 4.8264 0.0809 0.174 JP 731 1.2 TREATED 4.7633 0.0609 0.119 O zo n e 1m g O 3/m g D O C O zo n e 2m g O 3/m g D O C135    Treatment ID DOC (mg/L) Std. Dev. UVA JP 6/26 2.3  4.8775 0.0948 0.148 JP 6/26 2.3 TREATED 4.2048 0.1682 0.123 JP 6/26 2.4 5.1373 0.0341 0.157 JP 6/26 2.4 TREATED 4.4845 0.0303 0.134 JP 6/26 2.3 4.9335 0.0955 0.156 JP 6/26 2.3 TREATED 4.3566 0.0561 0.133 JP 6/26 2.3 2 4.8775 0.0948 0.148 JP 6/26 2.3 TREATED 2 4.112 0.0304 0.129 JP 6/26 2.4 2 4.9288 0.0442 0.156 JP 6/26 2.4 TREATED 2 4.269 0.0249 0.136 JP 6/26 1.1 4.7135 0.029 0.142 JP 6/26 1.1 TREATED 3.6977 0.0314 0.053 JP 6/27 1.3 5.0687 0.0143 0.158 JP 6/27 1.3 TREATED 2.9073 0.0316 0.065 JP 6/27 1.4 4.8559 0.0493 0.157 JP 6/27 1.4 TREATED 2.2997 0.0536 0.047 JP 6/26 2.1 4.8595 0.1124 0.172 JP 6/26 2.1 TREATED 1.9949 0.0391 0.033 JP 6/26 2.1 4.8595 0.1124 0.172 JP 6/26 2.1 TREATED 1.9763 0.012 0.034 JP 6/27 1.3 2 5.0687 0.0143 0.158 JP 6/27 1.3 TREATED 2 3.2331 0.0133 0.059 JP 6/27 1.4 2 4.8559 0.0493 0.157 JP 6/27 1.4 TREATED 2 2.6893 0.0061 0.053 JP 6/26 1.2 4.9293 0.0779 0.153 JP 6/26 1.2 TREATED 3.4552 0.0154 0.048 JP 6/26 1.3 4.7135 0.029 0.142 JP 6/26 1.3 TREATED 2.1466 0.0326 0.027 JP 6/27 1.2 5.0434 0.091 0.172 JP 6/27 1.2 TREATED 1.778 0.0307 0.031 JP 6/26 1.4 4.7874 0.0311 0.149 JP 6/26 1.4 TREATED 2.7439 0.0061 0.029 JP 6/27 1.1 5.0602 0.0852 0.175 JP 6/27 1.1 TREATED 1.9613 0.012 0.034 JP 731 1.3 RAW 4.0277 0.1319 0.15 JP 731 1.3 T(extended) 2.6255 0.0315 0.028 JP 801 1.1 RAW 5.7945 0.1627 0.193 JP 801 1.1 T(45 min) 3.6678 0.0121 0.031 JP 803 1.1 RAW 4.8913 0.1422 0.159 JP 803 1.1 T(2 hours) 2.9117 0.0321 0.045 E x te n de d O zo n e D o se 40 00  m J/ cm 2  &                  0 m g/ L  H 2 O 2 20 00  m J/ cm 2  &  10  m g/ L  H 2 O 2 40 00  m J/ cm 2  &                               10  m g/ L  H 2 O 2136  APPENDIX J. BIODEGRADATION TOC/UV RESULTS Table J-1 - TOC/UV data for biodegradation tests  ID DOC Average TOC standard deviation UV254 ID DOC Average TOC standard deviation UV254 ID DOC Average TOC standard deviation UV254 1.1 1.7211 0.0086 0.019 3.1 2.7633 0.0262 0.037 5.1 1.6276 0.0125 0.029 1.10 1.221 0.0068 0.026 3.10 1.645 0.0111 0.029 5.10 1.3584 0.0287 0.02 1.11 1.2351 0.0099 0.024 3.11 1.4202 0.0027 0.033 5.11 0.9495 0.0104 0.014 1.2 1.4859 0.0102 0.018 3.2 2.4929 0,0198 0.035 5.2 1.5137 0.0066 0.026 1.3 1.2606 0.0109 0.017 3.3 2.2112 0.0289 0.031 5.3 1.4139 0.0097 0.024 1.4 1.1053 0.011 0.017 3.4 1.1844 0.0164 0.031 5.4 1.2717 0.0028 0.022 1.5 0.9156 0.0126 0.016 3.5 1.651 0.0139 0.025 5.5 1.1454 0.0082 0.021 1.6 0.7993 0.0247 0.016 3.6 1.281 0.0166 0.022 5.6 1.3972 0.1682 0.017 1.7 0.7692 0.0105 0.017 3.7 1.3545 0.0089 0.024 5.7 1.2346 0.044 0.014 1.8 1.1608 0.0136 3.8 1.5377 0.0133 0.024 5.8 1.1352 0.0075 0.017 1.9 1.057 0.097 0.015 3.9 1.8212 0.0056 0.026 5.9 1.1861 0.0159 0.016 2.1 1.6282 0.0153 0.018 4.1 2.0119 0.0029 0.026 6.1 1.5288 0.0085 0.019 2.10 1.0065 0.0024 0.014 4.10 1.0989 0.001 0.017 6.10 0.9266 0.171 0.015 2.11 1.0853 0.0157 0.016 4.11 1.1266 0.0073 0.016 6.11 1.0185 0.0151 0.016 2.12 1.0705 0.0089 0.014 4.2 1.7643 0.0063 0.024 6.12 1.1932 0.0081 0.015 2.2 1.1039 0.02 0.016 4.3 1.5557 0.0083 0.022 6.2 1.3434 0.0176 0.02 2.3 1.2059 0.0148 0.016 4.4 1.384 0.0216 0.023 6.3 1.2189 0.0047 0.016 2.4 1.1896 0.0059 0.018 4.5 1.1572 0.0081 0.018 6.4 1.1277 0.0091 0.014 2.5 1.0814 0.0078 0.015 4.6 1.0305 0.011 0.019 6.5 0.9405 0.0086 0.012 2.6 0.9359 0.0046 0.016 4.7 0.9172 0.0082 0.015 6.6 0.9073 0.062 0.014 2.7 0.7839 0.0072 0.013 4.8 1.1822 0.0098 0.014 6.7 1.0143 0.008 0.016 2.8 1.0864 0.0076 0.014 4.9 1.1714 0.0154 0.014 6.9 0.7799 0.0212 0.013 2.9 1.1875 0.0114 0.015137    ID DOC Average TOC standard deviation UV254 ID DOC Average TOC standard deviation UV254 ID DOC Average TOC standard deviation UV254 7.1 1.6137 0.0019 0.016 9.1 2.3005 0.0098 0.037 11.10 0.9819 0.0368 0.019 7.10 0.8666 0.0329 0.011 9.10 1.3997 0.0485 0.019 11.1 1.2846 0.0167 0.017 7.11 0.9981 0.0236 9.11 1.3304 0.0196 0.019 11.11 0.9114 0.0113 0.014 7.12 1.3962 0.0079 0.014 9.12 1.2377 0.0556 0.011 11.12 0.7586 0.0128 0.011 7.2 1.5228 0.0174 0.017 9.2 2.1872 0.0092 0.036 11.2 1.2921 0.0061 0.016 7.3 1.4156 0.0026 0.015 9.3 1.9324 0.0076 0.03 11.3 1.1752 0.0186 0.016 7.4 1.337 0.0057 0.013 9.4 1.8218 0.0045 0.028 11.4 0.85 0.0082 0.012 7.5 1.2029 0.0103 0.011 9.5 1.7725 0.0056 0.026 11.5 0.8496 0.1034 0.011 7.6 1.0057 0.0038 0.012 9.7 1.3011 0.0101 0.018 11.6 0.791 0.0136 0.01 7.7 1.1195 0.0148 0.015 9.8 1.4311 0.0377 0.019 11.7 0.756 0.0209 0.014 7.9 0.8956 0.0119 0.013 9.9 1.355 0.0122 0.026 11.8 0.7962 0.0266 0.016 8.1 2.4882 0.0074 0.042 10.10 1.1613 0.0344 0.016 11.9 0.8273 0.0159 0.017 8.10 1.3585 0.0425 0.025 10.1 1.5574 0.0058 0.018 12.10 1.412 0.053 0.026 8.11 1.4505 0.0545 0.026 10.11 1.0343 0.0138 0.012 12.1 2.0747 0.0087 0.039 8.12 1.3751 0.0166 0.021 10.2 1.3533 0.1151 0.015 12.11 1.3804 0.0226 0.021 8.2 2.4184 0.0076 0.044 10.3 1.3843 0.0203 0.014 12.2 1.9219 0.0241 0.031 8.3 1.9468 0.0066 0.033 10.4 1.2426 0.0138 0.013 12.3 1.5975 0.0383 0.026 8.4 1.7156 0.0068 0.031 10.5 1.118 0.0251 0.012 12.4 1.5917 0.0183 0.026 8.5 1.6777 0.027 0.029 10.6 0.9766 0.0096 0.012 12.5 1.4865 0.007 0.023 8.7 1.4379 0.0588 0.025 10.7 0.8365 0.0293 0.011 12.6 1.3521 0.0247 0.017 8.8 1.1641 0.0162 0.018 10.8 0.9852 0.0538 0.015 12.7 1.2762 0.0087 0.021 8.9 1.2958 0.0069 0.024 10.9 0.9891 0.0694 0.016 12.8 1.3958 0.0068 0.025 12.9 1.2938 0.0204 0.024138     ID DOC Average TOC standard deviation UV254 ID DOC Average TOC standard deviation UV254 ID DOC Average TOC standard deviation UV254 13.10 1.0863 0.0716 0.01 15.10 2.945 0.0298 0.064 17.1 4.3308 0.059 0.074 13.1 1.4699 0.0253 0.018 15.1 4.5976 0.0124 0.125 17.10 2.5984 0.0418 0.054 13.11 1.154 0.0143 0.023 15.11 2.9911 0.0057 0.062 17.2 3.9203 0.0674 0.06 13.2 1.4235 0.0163 0.014 15.2 4.1334 0.0754 0.113 17.3 3.5959 0.0188 0.074 13.3 1.1877 0.0134 0.016 15.3 4.0656 0.1076 0.105 17.4 3.4498 0.0277 0.068 13.4 1.0841 0.0406 0.011 15.4 3.638 0.024 0.092 17.5 3.222 0.0692 0.062 13.5 0.8675 0.022 0.013 15.5 3.6558 0.0451 0.093 17.6 2.7184 0.0273 0.055 13.6 1.0622 0.0641 0.016 15.6 3.6121 0.0595 0.077 17.7 2.7288 0.0247 0.059 13.7 0.896 0.0207 0.015 15.7 3.468 0.0294 0.073 17.8 2.8023 0.0988 0.065 13.8 1.2024 0.0358 0.014 15.8 3.1172 0.1046 0.067 17.9 2.8324 0.0318 0.052 13.9 1.2493 0.0137 0.016 15.9 2.9474 0.0508 0.067 18.1 4.5944 0.0059 14.10 0.8251 0.0316 0.011 16.10 2.4517 0.0283 0.056 18.10 2.507 0.0088 0.036 14.1 1.4756 0.0078 0.014 16.1 4.2561 0.066 0.111 18.11 2.5418 0.0015 0.049 14.11 0.8524 0.0418 0.012 16.11 2.5174 0.0162 0.046 18.2 4.0905 0.1866 0.092 14.2 1.363 0.0098 0.009 16.2 3.7525 0.1157 0.095 18.3 3.7093 0.0357 0.083 14.3 1.2497 0.0341 0.011 16.3 3.4011 0.0571 0.084 18.4 3.5722 0.0423 0.075 14.4 1.0894 0.068 0.009 16.4 3.3019 0.0288 0.089 18.5 3.6135 0.0708 0.081 14.5 0.9978 0.0142 0.008 16.5 3.0653 0.0099 0.068 18.6 2.7099 0.062 0.06 14.6 0.8421 0.0225 0.01 16.6 2.764 0.0327 0.054 18.7 2.6921 0.0326 0.062 14.7 0.7335 0.0388 0.01 16.7 2.7639 0.0093 0.062 18.8 2.5523 0.0549 0.055 14.8 0.985 0.0021 0.009 16.8 2.6266 0.1351 0.06 18.9 2.7944 0.0552 0.054 14.9 1.0045 0.0125 0.009 16.9 2.4932 0.0173 0.058139    ID DOC Average TOC standard deviation UV254 ID DOC Average TOC standard deviation UV254 ID DOC Average TOC standard deviation UV254 19.10 2.8091 0.0638 0.062 21.10 2.5881 0.0617 0.052 23.10 3.0524 0.0202 0.074 19.1 3.9903 0.0341 0.094 21.1 3.9295 0.081 0.088 23.1 4.2801 0.0847 0.113 19.11 2.6918 0.2917 0.056 21.11 2.6384 0.0195 0.056 23.11 3.0381 0.0452 0.075 19.2 3.7961 0.0202 0.091 21.2 3.6171 0.0284 0.081 23.2 3.9105 0.11 0.102 19.3 3.4684 0.0506 0.082 21.3 3.45 0.0456 0.079 23.3 3.9433 0.0615 0.1 19.4 3.3863 0.0141 0.07 21.4 3.5809 0.0813 0.074 23.4 3.733 0.0139 0.095 19.5 3.4979 0.0858 0.069 21.5 3.5027 0.0313 0.078 23.5 3.5321 0.0276 0.09 19.6 3.083 0.0311 0.069 21.6 2.9661 0.033 0.068 23.6 3.2662 0.0472 0.055 19.7 2.9624 0.062 0.065 21.7 2.8455 0.0242 0.065 23.7 2.6045 0.0293 0.071 19.8 3.2581 0.0094 0.063 21.8 2.9546 0.0153 0.058 23.8 2.931 0.0512 0.072 19.9 2.8207 0.0275 0.065 21.9 2.6175 0.0312 0.055 23.9 2.798 0.0267 0.06 20.10 2.3525 0.0904 0.043 22.10 2.4007 0.0152 0.038 24.10 2.2729 0.0428 0.045 20.1 3.8379 0.0687 0.088 22.1 4.0184 0.0537 0.085 24.1 4.0677 0.0427 0.104 20.11 2.1587 0.0589 0.042 22.11 2.3551 0.1722 0.043 24.11 2.4317 0.0386 0.049 20.2 3.4167 0.0292 0.078 22.2 3.8281 0.1229 0.079 24.2 3.4376 0.0294 0.088 20.3 3.1835 0.0468 0.073 22.3 3.3906 0.0364 0.07 24.3 3.3787 0.0301 0.085 20.4 3.0144 0.0784 0.068 22.4 3.1962 0.0702 0.063 24.4 3.1355 0.0294 0.077 20.5 3.0861 0.0329 0.067 22.5 3.3918 0.0122 0.066 24.6 2.6308 0.0091 0.061 20.6 2.6976 0.0327 0.056 22.6 2.7616 0.049 0.057 24.7 2.5192 0.0162 0.054 20.7 2.4808 0.0148 0.05 22.7 2.5125 0.0669 0.049 24.8 2.6205 0.0383 0.052 20.8 2.6255 0.0065 0.047 22.8 2.4396 0.0688 0.048 24.9 2.3591 0.0989 0.048 20.9 2.18 0.068 0.043 22.9 2.3514 0.0121 0.049140    ID DOC Average TOC standard deviation UV254 ID DOC Average TOC standard deviation UV254 ID DOC Average TOC standard deviation UV254 25.10 2.43 0.0407 0.058 27.10 2.6334 0.0098 0.059 31.10 2.3971 0.0323 0.049 25.1 4.0642 0.0861 0.133 27.1 4.3956 0.0676 0.142 31.1 3.7289 0.0834 0.084 25.11 1.8741 0.0928 27.11 2.4792 0.0306 31.11 2.3745 0.04 0.049 25.2 4.1683 0.0413 0.127 27.2 4.3513 0.039 0.134 31.2 3.3778 0.0288 0.092 25.3 3.7683 0.0532 0.104 27.3 4.1297 0.024 0.114 31.3 3.2189 0.0306 0.084 25.4 3.4682 0.0221 0.097 27.4 4.0908 0.0298 0.157 31.4 3.0494 0.0327 0.078 25.5 3.1568 0.0175 0.095 27.5 3.5716 0.04 0.1 31.6 2.5456 0.0205 0.061 25.6 2.9713 0.0154 0.083 27.6 3.5124 0.0416 0.07 31.7 2.58 0.041 0.056 25.7 2.8446 0.0312 0.077 27.7 3.1599 0.0094 0.068 31.8 2.7371 0.0307 0.051 25.8 2.8201 0.0706 0.061 27.8 2.8396 0.0123 0.066 31.9 2.4094 0.1142 0.051 25.9 2.4995 0.0321 0.058 27.9 2.6344 0.0088 0.059 32.1 3.5608 0.0439 0.096 26.10 2.4048 0.0644 0.059 28.10 1.8863 0.0435 0.039 32.10 1.9789 0.0495 0.011 26.1 4.0836 0.0362 0.095 28.1 4.0397 0.0363 0.127 32.11 1.8688 0.0245 0.034 26.11 2.2964 0.0255 0.053 28.11 1.8793 0.0234 32.2 3.1568 0.0343 0.083 26.2 3.7604 0.0608 0.12 28.2 3.5867 0.0199 0.104 32.3 2.9731 0.0327 0.078 26.3 3.6107 0.0407 0.105 28.3 3.6126 0.0561 0.099 32.4 3.1864 0.0426 0.073 26.4 3.3684 0.0111 0.095 28.4 3.2752 0.0228 0.109 32.5 2.5287 0.0731 0.065 26.5 3.18 0.0404 0.092 28.5 2.8356 0.0353 0.071 32.6 0.029 26.6 2.7132 0.0447 0.074 28.6 2.0176 0.0517 0.061 32.7 1.969 0.2038 0.036 26.7 2.6367 0.0289 0.073 28.7 2.3916 0.023 32.8 2.0413 0.037 0.038 26.8 2.571 0.0068 0.062 28.8 2.081 0.0269 0.078 32.9 2.0517 0.0054 0.036 26.9 2.5422 0.0351 0.06 28.9 2.0254 0.0519 0.041141     ID DOC Average TOC standard deviation UV254 ID DOC Average TOC standard deviation UV254 ID DOC Average TOC standard deviation UV254 33.1 3.7655 0.0572 0.106 35.10 2.5557 0.042 0.068 37.1 4.207 0.0842 0.103 33.10 2.3261 0.0445 0.026 35.1 3.8837 0.0838 0.112 37.10 2.7472 0.0167 0.056 33.11 2.055 0.006 0.043 35.11 2.4554 0.0935 0.064 37.11 2.6708 0.0171 0.057 33.2 3.4 0.076 0.094 35.3 3.6077 0.0659 0.111 37.2 3.7943 0.0475 0.098 33.3 3.2089 0.0464 0.087 35.4 3.4793 0.045 0.078 37.3 3.6244 0.0468 0.09 33.4 3.3497 0.0388 0.079 35.5 3.3378 0.0565 0.092 37.4 3.4318 0.0748 0.087 33.5 3.0381 0.0416 0.076 35.6 3.0293 0.0201 0.086 37.5 3.1491 0.0628 0.063 33.6 2.8636 0.0292 0.057 35.7 2.8223 0.0691 0.076 37.6 3.0506 0.0394 0.069 33.7 2.5918 0.1329 0.055 35.8 2.8172 0.0918 0.035 37.7 2.895 0.0599 0.065 33.8 2.3829 0.0311 0.049 35.9 2.5355 0.0105 0.07 37.8 3.0334 0.0579 0.067 33.9 2.401 0.0328 0.051 36.1 3.8298 0.0697 0.085 37.9 2.658 0.1279 0.061 34.10 1.9434 0.0395 0.035 36.10 2.4859 0.0158 0.044 38.1 3.9209 0.0791 0.13 34.1 3.4642 0.0374 0.092 36.11 2.4142 0.0099 0.043 38.10 2.4143 0.005 0.054 34.11 1.8268 0.0523 0.033 36.2 3.4169 0.0256 0.077 38.11 2.1325 0.044 34.3 2.8847 0.0368 0.07 36.3 3.3375 0.0608 0.059 38.2 3.2038 0.045 0.103 34.4 2.6919 0.1416 0.06 36.4 3.1394 0.0125 0.071 38.3 3.1053 0.0318 0.109 34.5 2.4311 0.0569 0.056 36.5 2.8951 0.1197 0.051 38.4 3.1344 0.0253 0.101 34.6 2.1687 0.0317 0.045 36.6 2.655 0.035 0.055 38.5 2.7083 0.0906 0.07 34.7 2.1447 0.024 0.04 36.7 2.4744 0.0452 0.05 38.6 2.6764 0.0186 0.076 34.8 2.2618 0.1773 0.035 36.8 2.7024 0.1745 0.051 38.7 2.4735 0.0262 0.067 34.9 1.8985 0.0223 0.035 36.9 2.4162 0.0685 0.048 38.8 2.617 0.0665 0.047 38.9 2.3019 0.0466 0.056142   ID DOC Average TOC standard deviation UV254 ID DOC Average TOC standard deviation UV254 ID DOC Average TOC standard deviation UV254 39.1 3.9402 0.0697 0.136 42.2 1.9468 0.0353 0.018 14.12 (half 12 hr) 1.4117 0.0227 0.012 39.10 2.467 0.0161 0.055 42.3 2.0398 0.0395 0.019 15.0 JP 7/19 1.4 T 5.683 0.0943 0.124 39.11 2.3382 0.0046 0.052 42.4 2.0164 0.0223 0.017 15.12 (half 4 hr) 4.8306 0.0724 0.134 39.2 3.4349 0.0329 0.114 42.6 2.3904 0.021 16.0 JP 7/19 1.4 T 5.683 0.0943 0.124 39.3 3.2178 0.0488 0.111 42.7 1.3878 0.054 0.016 16.12 (half 4hr) 4.5109 0.0775 0.139 39.4 3.2159 0.0466 0.106 42.8 0.8671 0.0087 0.021 17.0 JP 7/21 2.1 T 5.0749 0.101 0.1298 39.5 2.685 0.0968 0.074 42.9 0.8011 0.0143 0.014 17.12 (Double 12 hr) 3.116 0.0232 0.062 39.7 2.4261 0.0154 0.064 43.1 2.2747 0.0406 0.026 18.0 JP 7/21 2.1 T 5.0749 0.101 0.1298 39.8 2.5873 0.0707 0.064 43.2 2.0469 0.0215 0.019 18.12 (Double 12 hr) 3.2784 0.0304 0.067 39.9 2.4742 0.0838 0.063 43.3 1.9509 0.0124 0.018 19.0 JP 7/23 1.1 T 4.7154 0.1029 0.115 40.1 2.487 0.1102 0.033 43.4 2.0319 0.0109 0.019 19.12 (half 24 hr) 3.7066 0.0827 0.088 40.2 2.278 0.0257 0.028 43.6 1.5804 0.007 0.019 2.0 JP 6.26 1.4 2.7439 0.0061 0.029 40.3 2.2552 0.0328 0.028 43.7 1.1366 0.0346 0.015 20.0 JP 7/23 1.1 T 4.7154 0.1029 0.115 40.4 2.3193 0.0091 0.028 43.8 0.895 0.04 0.015 20.12 (half 24 hr) 3.3969 0.1189 0.081 40.6 1.2257 0.0214 0.034 43.9 0.8029 0.0212 0.014 21.0 JP 7/23 1.2 T 4.7845 0.0555 0.109 40.8 1.0203 0.0033 0.022 1.0 JP 6/26 1.3 2.1466 0.0326 0.027 21.12 (half 8hr) 3.8569 0.2011 0.091 40.9 0.9703 0.0104 0.021 1.12 (Dup 24hr) 0.9597 0.0023 0.016 22.0 JP 7/23 1.2 T 4.6411 0.0346 0.108 41.1 2.4898 0.0925 0.034 10.0 JP 6/27 1.2 1.778 0.0307 0.031 22.12 (Half 8 hour) 4.0394 0.0865 0.078 41.2 2.641 0.0317 0.031 10.12 (half, 10.7) 0.784 0.0111 0.011 23.0 JP 7/25 1.1 T 4.7028 0.0612 0.132 41.4 2.189 0.0304 0.027 11.0 JP 6/27 1.2 1.778 0.0307 0.031 23.12 (Dup 4 hr) 4.2439 0.0516 0.123 41.6 1.2314 0.0211 0.026 12.0 JP 6/27 1.4 2.2997 0.0536 0.047 34.0 JP 626 2.4 4.4845 0.0303 0.134 41.7 1.1726 0.0411 0.022 12.12 (Double 24hr) 1.1783 0.0425 0.019 24.0 JP 7/25 1.1 4.7854 0.0436 0.131 41.8 0.9857 0.0208 0.013 13.0 JP 6/26 2.1 1.9949 0.0391 0.033 24.12 (Dup 4 hr) 4.0437 0.0258 0.105 41.9 0.9917 0.0413 0.021 13.12 (half 12 hr) 1.3599 0.0298 0.016 25.0 JP 7/7 1.1 5.1719 0.0814 0.177 42.1 2.2532 0.0227 0.025 14.0 JP 6/26 2.1 1.9763 0.012 0.034 25.12 (half 24 hr) 3.676 0.0669 0.111 4.12 (Dup 24hr) 1.2618 0.0091 0.021143   ID DOC Average TOC standard deviation UV254 ID DOC Average TOC standard deviation UV254 ID DOC Average TOC standard deviation UV254 20.12 (half 24 hr) 3.3969 0.1189 0.081 35.0 JP 728 1.1 RAW 3.9812 0.0165 0.161 22.0 JP 7/23 1.2 T 4.6411 0.0346 0.108 21.0 JP 7/23 1.2 TREATED (2.4) 4.7845 0.0555 0.109 36.0 JP 731 1.2 T 4.8694 0.0209 0.12 22.12 (Half 8 hour) 4.0394 0.0865 0.078 21.12 (half 8hr) 3.8569 0.2011 0.091 37.0 JP 731 1.2 T 4.8694 0.0209 0.12 23.0 JP 7/25 1.1 T 4.7028 0.0612 0.132 22.0 JP 7/23 1.2 TREATED (2.4) 4.6411 0.0346 0.108 38.0 JP 801 1.1 RAW 5.2779 0.1281 0.175 23.12 (Dup 4 hr) 4.2439 0.0516 0.123 22.12 (Half 8 hour) 4.0394 0.0865 0.078 39.0 JP 801 1.1 RAW 5.2779 0.1281 0.175 34.0 JP 626 2.4 4.4845 0.0303 0.134 23.0 JP 7/25 1.1 TREATED (1.17) 4.7028 0.0612 0.132 4.0 JP 6.26 1.2 3.4552 0.0154 0.048 24.0 JP 7/25 1.1 4.7854 0.0436 0.131 23.12 (Dup 4 hr) 4.2439 0.0516 0.123 4.12 (Dup 24hr) 1.2618 0.0091 0.021 24.12 (Dup 4 hr) 4.0437 0.0258 0.105 34.0 JP 626 2.4 4.4845 0.0303 0.134 40.0 JP 805 T 2.7905 0.0348 0.036 25.0 JP 7/7 1.1 5.1719 0.0814 0.177 24.0 JP 7/25 1.1 4.7854 0.0436 0.131 41.0 JP 805 T 2.7905 0.0348 0.036 25.12 (half 24 hr) 3.676 0.0669 0.111 24.12 (Dup 4 hr) 4.0437 0.0258 0.105 42.0 JP 805 T 2.7905 0.0348 0.036 26.0JP 7/7 1.2 5.1375 0.0462 0.176 25.0 JP 7/7 1.1 5.1719 0.0814 0.177 6.0 JP 6/27 1.1 1.9613 0.012 0.034 26.12 (Double 12 hr) 3.1102 0.0717 0.084 25.12 (half 24 hr) 3.676 0.0669 0.111 7.0 JP 6/27 1.1 1.9613 0.012 0.034 27.0 JP 7/7 1.3 5.0133 0.0591 0.169 43.0 JP 805 T 2.7905 0.0348 0.036 8.0 JP 6/27 1.3 2.9073 0.0316 0.065 27.0 JP 7/7 1.3 5.0414 0.0128 0.176 5.0 JP 6/27 1.3 3.2331 0.0133 0.059 9.0 JP 6/27 1.4 2.6893 0.0061 0.053 27.12 (Double 24 hr) 2.8886 0.0387 0.079 5.12 (Dup 24hr) 0.9605 0.0019 0.017 14.12 (half 12 hr) 1.4117 0.0227 0.012 28.0 JP 7/7 1.4 5.3385 0.0569 0.181 26.0JP 7/7 1.2 5.1375 0.0462 0.176 15.0 JP 7/19 1.4 T 5.683 0.0943 0.124 28.0 JP 7/7 1.4 5.3562 0.0339 0.187 26.12 (Double 12 hr) 3.1102 0.0717 0.084 15.12 (half 4 hr) 4.8306 0.0724 0.134 28.12 (Half 12 hr) 3.8895 0.0137 0.11 27.0 JP 7/7 1.3 5.0133 0.0591 0.169 16.0 JP 7/19 1.4 T 5.683 0.0943 0.124 3.0 JP 6.26 1.1 3.6977 0.0314 0.053 27.0 JP 7/7 1.3 5.0414 0.0128 0.176 16.12 (half 4hr) 4.5109 0.0775 0.139 3.12 (Dup 3.7) 1.1505 0.0122 0.02 27.12 (Double 24 hr) 2.8886 0.0387 0.079 17.0 JP 7/21 2.1 T 5.0749 0.101 0.1298 31.0 JP 626 2.3 4.3566 0.0561 0.0133 28.0 JP 7/7 1.4 5.3385 0.0569 0.181 17.12 (Double 12 hr) 3.116 0.0232 0.062 31.12 (Half 48 hr) 2.9457 0.0457 0.075 28.0 JP 7/7 1.4 5.3562 0.0339 0.187 18.0 JP 7/21 2.1 T 5.0749 0.101 0.1298 32.0 JP 626 2.3 4.112 0.0304 0.129 28.12 (Half 12 hr) 3.8895 0.0137 0.11 18.12 (Double 12 hr) 3.2784 0.0304 0.067 32.12 (Half 48hr) 1.8698 0.0158 0.03 3.0 JP 6.26 1.1 3.6977 0.0314 0.053 19.0 JP 7/23 1.1 T 4.7154 0.1029 0.115 33.0 JP 626 2.4 4.269 0.0249 0.136 3.12 (Dup 3.7) 1.1505 0.0122 0.02 19.12 (half 24 hr) 3.7066 0.0827 0.088 35.0 JP 728 1.1 RAW 3.9812 0.0165 0.161 31.0 JP 626 2.3 4.3566 0.0561 0.0133 2.0 JP 6.26 1.4 2.7439 0.0061 0.029 36.0 JP 731 1.2 T 4.8694 0.0209 0.12 31.12 (Half 48 hr) 2.9457 0.0457 0.075 20.0 JP 7/23 1.1 T 4.7154 0.1029 0.115 37.0 JP 731 1.2 T 4.8694 0.0209 0.12 32.0 JP 626 2.3 4.112 0.0304 0.129 20.12 (half 24 hr) 3.3969 0.1189 0.081 38.0 JP 801 1.1 5.2779 0.1281 0.175 32.12 (Half 48hr) 1.8698 0.0158 0.03 21.0 JP 7/23 1.2 T 4.7845 0.0555 0.109 39.0 JP 801 1.1 5.2779 0.1281 0.175 33.0 JP 626 2.4 4.269 0.0249 0.136 21.12 (half 8hr) 3.8569 0.2011 0.091 4.0 JP 6.26 1.2 3.4552 0.0154 0.048 42.0 JP 805 T 2.7905 0.0348 0.036 40.0 JP 805 T 2.7905 0.0348 0.036 41.0 JP 805 T 2.7905 0.0348 0.036144  APPENDIX K. BIODEGRADATION CURVES FOR DOC  Figure K-1 - Biodegradation test results for 1mgO3/mg DOC   0 1 2 3 4 5 6 7 0 1 2 3 4 5 6 7 D O C  ( m g / L ) Time (Days) Curve 15.0 BAC Column 1 Generated Curve Fit 90% Confidence Interval 90% Confidence Interval Actual Data 0 1 2 3 4 5 6 0 1 2 3 4 5 6 7 D O C  ( m g / L ) Time (Days) Curve 17.0 BAC Column 1 Generated Curve Fit 90% Confidence Interval 90% Confidence Interval Actual Data 0 1 2 3 4 5 6 0 1 2 3 4 5 6 7 D O C  ( m g / L ) Time (Days) Curve 23.0 BAC Column 1 Generated Curve Fit 90% Confidence Interval 90% Confidence Interval Actual Data 0 1 2 3 4 5 6 7 0 1 2 3 4 5 6 7 D O C  ( m g / L ) Time (Days) Curve 16.0 BAC Column 2 Generated Curve Fit 90% Confidence Interval 90% Confidence Interval Actual Data145   Figure K-2 - Biodegradation test results for 1mgO3/mg DOC          0 1 2 3 4 5 6 0 1 2 3 4 5 6 7 D O C  ( m g / L ) Time (Days) Curve 18.0 BAC Column 2 Generated Curve Fit 90% Confidence Interval 90% Confidence Interval Actual Data 0 1 2 3 4 5 6 0 1 2 3 4 5 6 7 D O C  ( m g / L ) Time (Days) Curve 24.0 BAC Column 2 Generated Curve Fit 90% Confidence Interval 90% Confidence Interval Actual Data146   Figure K-3 - Biodegradation test results for 2mgO3/mg DOC    0 1 2 3 4 5 6 0 1 2 3 4 5 6 7 D O C  ( m g / L ) Time (Days) Curve 19.0 BAC Column 1 Generated Curve Fit 90% Confidence Interval 90% Confidence Interval Actual Data 0 1 2 3 4 5 6 0 1 2 3 4 5 6 7 D O C  ( m g / L ) Time (Days) Curve 21.0 BAC Column 1 Generated Curve Fit 90% Confidence Interval 90% Confidence Interval Actual Data 0 1 2 3 4 5 6 0 1 2 3 4 5 6 7 D O C  ( m g / L ) Time (Days) Curve 37.0 BAC Column 1 Generated Curve Fit 90% Confidence Interval 90% Confidence Interval Actual Data 0 1 2 3 4 5 6 0 1 2 3 4 5 6 7 D O C  ( m g / L ) Time (Days) Curve 20.0 BAC Column 2 Generated Curve Fit 90% Confidence Interval 90% Confidence Interval Actual Data147   Figure K-4 - Biodegradation test results for 2mgO3/mg DOC          0 0.5 1 1.5 2 2.5 3 3.5 4 4.5 5 0 1 2 3 4 5 6 7 D O C  ( m g / L ) Time (Days) Curve 22.0 BAC Column 2 Generated Curve Fit 90% Confidence Interval 90% Confidence Interval Actual Data 0 1 2 3 4 5 6 0 1 2 3 4 5 6 7 D O C  ( m g / L ) Time (Days) Curve 36.0 BAC Column 2 Generated Curve Fit 90% Confidence Interval 90% Confidence Interval Actual Data148    Figure K-5 - Biodegradation test results for extended ozonation    0 0.5 1 1.5 2 2.5 3 3.5 0 1 2 3 4 5 6 7 D O C  ( m g / L ) Time (Days) Curve 40.0 BAC Column 1 Generated Curve Fit 90% Confidence Interval 90% Confidence Interval Actual Data 0 0.5 1 1.5 2 2.5 3 3.5 0 1 2 3 4 5 6 7 D O C  ( m g / L ) Time (Days) Curve 41.0 BAC Column 1 Generated Curve Fit 90% Confidence Interval 90% Confidence Interval Actual Data 0 0.5 1 1.5 2 2.5 3 0 1 2 3 4 5 6 7 D O C  ( m g / L ) Time (Days) Curve 42.0 BAC Column 2 Generated Curve Fit 90% Confidence Interval 90% Confidence Interval Actual Data 0 0.5 1 1.5 2 2.5 3 0 1 2 3 4 5 6 7 D O C  ( m g / L ) Time (Days) Curve 43.0 BAC Column 2 Generated Curve Fit 90% Confidence Interval 90% Confidence Interval Actual Data149     Figure K-6 - Biodegradation test results for 4000mJ/cm2 and 0 mg/L H2O2 0 0.5 1 1.5 2 2.5 3 3.5 4 4.5 5 0 1 2 3 4 5 6 7 D O C  ( m g / L ) Time (Days) Curve 31.0 BAC Column 1 Generated Curve Fit 90% Confidence Interval 90% Confidence Interval Actual Data 0 0.5 1 1.5 2 2.5 3 3.5 4 4.5 5 0 1 2 3 4 5 6 7 D O C  ( m g / L ) Time (Days) Curve 33.0 BAC Column 1 Generated Curve Fit 90% Confidence Interval 90% Confidence Interval Actual Data 0 0.5 1 1.5 2 2.5 3 3.5 4 4.5 0 1 2 3 4 5 6 7 D O C  ( m g / L ) Time (Days) Curve 32.0 BAC Column 2 Generated Curve Fit 90% Confidence Interval 90% Confidence Interval Actual Data 0 0.5 1 1.5 2 2.5 3 3.5 4 4.5 5 0 1 2 3 4 5 6 7 D O C  ( m g / L ) Time (Days) Curve 34.0 BAC Column 2 Generated Curve Fit 90% Confidence Interval 90% Confidence Interval Actual Data150    Figure K-7 - Biodegradation test results for 2000mJ/cm2 and 10 mg/L H2O2 0 0.5 1 1.5 2 2.5 3 3.5 4 4.5 0 1 2 3 4 5 6 7 D O C  ( m g / L ) Time (Days) Curve 3.0 BAC Column 1 Generated Curve Fit 90% Confidence Interval 90% Confidence Interval Actual Data 0 0.5 1 1.5 2 2.5 3 3.5 0 1 2 3 4 5 6 7 D O C  ( m g / L ) Time (Days) Curve 8.0 BAC Column 1 Generated Curve Fit 90% Confidence Interval 90% Confidence Interval Actual Data 0 0.5 1 1.5 2 2.5 3 0 1 2 3 4 5 6 7 D O C  ( m g / L ) Time (Days) Curve 12.0 BAC Column 1 Generated Curve Fit 90% Confidence Interval 90% Confidence Interval Actual Data 0 0.5 1 1.5 2 2.5 0 1 2 3 4 5 6 7 D O C  ( m g / L ) Time (Days) Curve 13.0 BAC Column 1 Generated Curve Fit 90% Confidence Interval 90% Confidence Interval Actual Data151   Figure K-8 - Biodegradation test results for 2000mJ/cm2 and 10 mg/L H2O2 0 0.5 1 1.5 2 2.5 3 3.5 0 1 2 3 4 5 6 7 D O C  ( m g / L ) Time (Days) Curve 5.0 BAC Column 2 Generated Curve Fit 90% Confidence Interval 90% Confidence Interval Actual Data 0 0.5 1 1.5 2 2.5 3 0 1 2 3 4 5 6 7 D O C  ( m g / L ) Time (Days) Curve 9.0 BAC Column 2 Generated Curve Fit 90% Confidence Interval 90% Confidence Interval Actual Data 0 0.5 1 1.5 2 2.5 0 1 2 3 4 5 6 7 D O C  ( m g / L ) Time (Days) Curve 14.0 BAC Column 2 Generated Curve Fit 90% Confidence Interval 90% Confidence Interval Actual Data152   Figure K-9 - Biodegradation test results for 4000mJ/cm2 and 10 mg/L H2O2 0 0.5 1 1.5 2 2.5 0 1 2 3 4 5 6 7 D O C  ( m g / L ) Time (Days) Curve 1.0 BAC Column 1 Generated Curve Fit 90% Confidence Interval 90% Confidence Interval Actual Data 0 0.5 1 1.5 2 2.5 0 1 2 3 4 5 6 7 D O C  ( m g / L ) Time (Days) Curve 6.0 BAC Column 1 Generated Curve Fit 90% Confidence Interval 90% Confidence Interval Actual Data 0 0.2 0.4 0.6 0.8 1 1.2 1.4 1.6 1.8 2 0 1 2 3 4 5 6 7 D O C  ( m g / L ) Time (Days) Curve 11.0 BAC Column 1 Generated Curve Fit 90% Confidence Interval 90% Confidence Interval Actual Data 0 0.2 0.4 0.6 0.8 1 1.2 1.4 1.6 1.8 2 0 1 2 3 4 5 6 7 D O C  ( m g / L ) Time (Days) Curve 7.0 BAC Column 2 Generated Curve Fit 90% Confidence Interval 90% Confidence Interval Actual Data153   Figure K-10 - Biodegradation test results for 4000mJ/cm2 and 10 mg/L H2O2       0 0.5 1 1.5 2 2.5 0 1 2 3 4 5 6 7 D O C  ( m g / L ) Time (Days) Curve 10.0 BAC Column 2 Generated Curve Fit 90% Confidence Interval 90% Confidence Interval Actual Data154   Figure K-11 - Biodegradation test results for raw water samples 0 1 2 3 4 5 6 0 1 2 3 4 5 6 7 D O C  ( m g / L ) Time (Days) Curve 25.0 BAC Column 1 Generated Curve Fit 90% Confidence Interval 90% Confidence Interval Actual Data 0 1 2 3 4 5 6 0 1 2 3 4 5 6 7 D O C  ( m g / L ) Time (Days) Curve 27.0 BAC Column 1 Generated Curve Fit 90% Confidence Interval 90% Confidence Interval Actual Data 0 0.5 1 1.5 2 2.5 3 3.5 4 4.5 0 1 2 3 4 5 6 7 D O C  ( m g / L ) Time (Days) Curve 35.0 BAC Column 1 Generated Curve Fit 90% Confidence Interval 90% Confidence Interval Actual Data 0 1 2 3 4 5 6 0 1 2 3 4 5 6 7 D O C  ( m g / L ) Time (Days) Curve 26.0 BAC Column 2 Generated Curve Fit 90% Confidence Interval 90% Confidence Interval Actual Data155   Figure K-12 - Biodegradation test results for raw water samples 0 1 2 3 4 5 6 0 1 2 3 4 5 6 7 D O C  ( m g / L ) Time (Days) Curve 28.0 BAC Column 2 Generated Curve Fit 90% Confidence Interval 90% Confidence Interval Actual Data 0 1 2 3 4 5 6 0 1 2 3 4 5 6 7 D O C  ( m g / L ) Time (Days) Curve 38.0 BAC Column 2 Generated Curve Fit 90% Confidence Interval 90% Confidence Interval Actual Data 0 1 2 3 4 5 6 0 1 2 3 4 5 6 7 D O C  ( m g / L ) Time (Days) Curve 39.0 BAC Column 2 Generated Curve Fit 90% Confidence Interval 90% Confidence Interval Actual Data156  APPENDIX L. BIODEGRADATION TEST ANALYSIS RESULTS FOR DOC Table L-1 - Biodegradation curve analysis results for DOC   # of t test a b c a b c a stdev b stdev c stdev n t 1mg, Column 1 15 3.114 2.412 1.942 3 2.92 1mg, Column 1 17 2.738 2.257 1.782 3 2.92 1mg, Column 1 23 2.973 1.637 1.171 3 2.92 1mg, Column 2 16 2.642 2.884 2.612 3 2.92 1mg, Column 2 18 2.599 2.402 1.213 3 2.92 1mg, Column 2 24 2.468 2.243 1.924 3 2.92 2mg, Column 1 19 2.870 1.716 1.772 3 2.92 2mg, Column 1 21 2.747 1.748 1.316 3 2.92 2mg, Column 1 37 2.832 1.956 1.808 3 2.92 2mg, Column 2 20 2.336 2.155 1.567 3 2.92 2mg, Column 2 22 2.409 2.058 1.081 3 2.92 2mg, Column 2 36 2.542 2.168 2.193 3 2.92 Extended, Column 1 40 0.84394 1.90845 0.61641 2 6.314 Extended, Column 1 41 0.84951 1.98462 0.63608 2 6.314 Extended, Column 2 42 0.68948 1.79511 0.46431 2 6.314 Extended, Column 2 43 0.61014 1.88826 0.43379 2 6.314 4000,0 Column 1 31 2.50299 1.78627 1.88347 2 6.314 4000,0 Column 1 33 2.42443 1.73288 1.6194 2 6.314 4000,0 Column 2 32 1.98264 2.07546 1.50524 2 6.314 4000,0 Column 2 34 2.0776 2.09951 1.86904 2 6.314 4000,10 Column 1 1 0.88089 1.27537 2.44539 3 2.92 4000,10 Column 1 6 0.95692 0.98943 2.8685 3 2.92 4000,10 Column 1 11 0.79569 0.94663 2.4986 3 2.92 Oxidation ID Variables Average 2.942 2.102 1.632 2.429 2.127 1.614 0.847 1.947 0.626 2.570 2.509 1.916 2.816 1.807 1.632 2.030 2.087 1.687 0.878 1.070 2.604 0.650 1.842 0.449 2.464 1.760 1.751 0.179 0.230 Error (a) 0.6862 0.1530 0.274 0.104 0.060 0.557 0.004 0.054 0.014 Standard Deviation 0.190 0.410 0.407 0.091 0.334 0.700 0.063 0.130 0.3201 0.5627 1.1798 0.2193 0.4623 0.1014 0.9397 Error (b) Error (c) 0.6915 0.1054 0.1760 0.3885 1.1485 0.83370.1686 0.0759 0.3013 0.06210.2404 0.09630.29410.2505 0.1360 0.2998 0.2480 0.056 0.066 0.022 0.0176 0.056 0.038 0.187 0.067 0.017 0.257 0.081157    # of Sampl t test a b c a b c a stdev b stdev c stdev n t 4000,10 Column 2 7 0.96049 0.79719 1.58339 2 6.314 4000,10 Column 2 10 0.96361 0.92925 1.39666 2 6.314 2000,10 Column 1 3 1.49012 2.15492 2.47212 4 2.132 2000,10 Column 1 8 1.32546 1.59285 1.63663 4 2.132 2000,10 Column 1 12 1.34841 0.97498 2.00203 4 2.132 2000,10 Column 1 13 0.98829 0.9759 3.08819 4 2.132 2000,10 Column 2 5 1.55115 1.57668 1.89486 3 2.92 2000,10 Column 2 9 1.39649 1.2366 1.42665 3 2.92 2000,10 Column 2 14 0.81642 1.09256 2.0191 3 2.92 Raw, Column 1 25 2.66683 2.48096 1.51736 3 2.92 Raw, Column 1 27 2.51378 2.22517 0.50666 3 2.92 Raw, Column 1 35 2.45825 1.50135 0.48051 3 2.92 Raw, Column 2 26 2.51434 2.38034 1.54561 4 2.132 Raw, Column 2 28 2.03146 3.02042 1.46405 4 2.132 Raw, Column 2 38 2.4875 2.68266 3.16743 4 2.132 Raw, Column 2 39 2.49896 2.63664 2.71658 4 2.132 Oxidation ID Variables Average Standard Deviation Error (a) 0.4169 0.6046 0.4191 0.8566 0.2804 Error (b) Error (c) 0.9067 0.9967 0.5267 0.6685 0.5895 0.1821 0.2502 0.6530 0.2267 0.0098 0.213 0.567 0.627 0.002 0.093 0.132 0.108 0.508 0.591 0.235 0.263 0.851 0.387 0.249 0.312 2.383 2.680 2.223 1.255 1.302 1.780 2.546 2.069 0.835 0.962 0.863 1.490 1.288 1.425 2.300158  Table L-2 - Biodegradation analysis of % non-biodegradable for DOC  a b c 1mg, Column 1 15 3.114 2.412 1.942 56% 1mg, Column 1 17 2.738 2.257 1.782 55% 1mg, Column 1 23 2.973 1.637 1.171 64% 1mg, Column 2 16 2.642 2.884 2.612 48% 1mg, Column 2 18 2.599 2.402 1.213 52% 1mg, Column 2 24 2.468 2.243 1.924 52% 2mg, Column 1 19 2.870 1.716 1.772 63% 2mg, Column 1 21 2.747 1.748 1.316 61% 2mg, Column 1 37 2.832 1.956 1.808 59% 2mg, Column 2 20 2.336 2.155 1.567 52% 2mg, Column 2 22 2.409 2.058 1.081 54% 2mg, Column 2 36 2.542 2.168 2.193 54% Extended, Column 1 40 0.84394 1.90845 0.61641 31% Extended, Column 1 41 0.84951 1.98462 0.63608 30% Extended, Column 2 42 0.68948 1.79511 0.46431 28% Extended, Column 2 43 0.61014 1.88826 0.43379 24% 4000,0 Column 1 31 2.50299 1.78627 1.88347 58% 4000,0 Column 1 33 2.42443 1.73288 1.6194 58% 4000,0 Column 2 32 1.98264 2.07546 1.50524 49% 4000,0 Column 2 34 2.0776 2.09951 1.86904 50% 4000,10 Column 1 1 0.88089 1.27537 2.44539 41% 4000,10 Column 1 6 0.95692 0.98943 2.8685 49% 4000,10 Column 1 11 0.79569 0.94663 2.4986 46% 4000,10 Column 2 7 0.96049 0.79719 1.58339 55% 4000,10 Column 2 10 0.96361 0.92925 1.39666 51% 2000,10 Column 1 3 1.49012 2.15492 2.47212 41% 2000,10 Column 1 8 1.32546 1.59285 1.63663 45% 2000,10 Column 1 12 1.34841 0.97498 2.00203 58% 2000,10 Column 1 13 0.98829 0.9759 3.08819 50% 2000,10 Column 2 5 1.55115 1.57668 1.89486 50% 2000,10 Column 2 9 1.39649 1.2366 1.42665 53% 2000,10 Column 2 14 0.81642 1.09256 2.0191 43% Raw, Column 1 25 2.66683 2.48096 1.51736 52% Raw, Column 1 27 2.51378 2.22517 0.50666 53% Raw, Column 1 35 2.45825 1.50135 0.48051 62% Raw, Column 2 26 2.51434 2.38034 1.54561 51% Raw, Column 2 28 2.03146 3.02042 1.46405 40% Raw, Column 2 38 2.4875 2.68266 3.16743 48% Raw, Column 2 39 2.49896 2.63664 2.71658 49% 9% 5% 12% 8% 3% 7% 11% 0% 2% 2% 9% 3 3%3 2.92 Error 61% 53% 30% 26% 58% 49% Oxidation ID Variables %  non- biodegra dable Std DevAverage 3 2.92 4 2.132 45% 53% 49% 48% 56% 47% 4% 3% 7% 5% 6% 5% 2% 1% 0% 2% 0% 1% TN 2 6.314 4 2.132 3 2.92 2 6.314 2 6.314 3 2.92 2.92 2.92 2 6.314 2 6.314 59% 5% 9%3 2.92 51% 3% 4%3159  APPENDIX M. BIODEGRADATION CURVES FOR SUVA  Figure M-1 - Biodegradation test results for 1mgO3/mg DOC   0 0.02 0.04 0.06 0.08 0.1 0.12 0.14 0 1 2 3 4 5 6 7 S U V A Time (Days) Curve 15.0 BAC Column 1 Generated Curve Fit 90% Confidence Interval 90% Confidence Interval Actual Data 0 0.02 0.04 0.06 0.08 0.1 0.12 0.14 0.16 0 1 2 3 4 5 6 7 S U V A Time (Days) Curve 17.0 BAC Column 1 Generated Curve Fit 90% Confidence Interval 90% Confidence Interval Actual Data 0 0.02 0.04 0.06 0.08 0.1 0.12 0.14 0.16 0 1 2 3 4 5 6 7 S U V A Time (Days) Curve 23.0 BAC Column 1 Generated Curve Fit 90% Confidence Interval 90% Confidence Interval Actual Data 0 0.02 0.04 0.06 0.08 0.1 0.12 0.14 0 1 2 3 4 5 6 7 S U V A Time (Days) Curve 16.0 BAC Column 2 Generated Curve Fit 90% Confidence Interval 90% Confidence Interval Actual Data160    Figure M-2 - Biodegradation test results for 1mgO3/mg DOC         0 0.02 0.04 0.06 0.08 0.1 0.12 0.14 0.16 0 1 2 3 4 5 6 7 S U V A Time (Days) Curve 18.0 BAC Column 2 Generated Curve Fit 90% Confidence Interval 90% Confidence Interval Actual Data 0 0.02 0.04 0.06 0.08 0.1 0.12 0.14 0.16 0 1 2 3 4 5 6 7 S U V A Time (Days) Curve 24.0 BAC Column 2 Generated Curve Fit 90% Confidence Interval 90% Confidence Interval Actual Data161    Figure M-3 - Biodegradation test results for 2mgO3/mg DOC    0 0.02 0.04 0.06 0.08 0.1 0.12 0.14 0 1 2 3 4 5 6 7 S U V A Time (Days) Curve 19.0 BAC Column 1 Generated Curve Fit 90% Confidence Interval 90% Confidence Interval Actual Data 0 0.02 0.04 0.06 0.08 0.1 0.12 0 1 2 3 4 5 6 7 S U V A Time (Days) Curve 21.0 BAC Column 1 Generated Curve Fit 90% Confidence Interval 90% Confidence Interval Actual Data 0 0.02 0.04 0.06 0.08 0.1 0.12 0.14 0 1 2 3 4 5 6 7 S U V A Time (Days) Curve 37.0 BAC Column 1 Generated Curve Fit 90% Confidence Interval 90% Confidence Interval Actual Data 0 0.02 0.04 0.06 0.08 0.1 0.12 0.14 0 1 2 3 4 5 6 7 S U V A Time (Days) Curve 20.0 BAC Column 2 Generated Curve Fit 90% Confidence Interval 90% Confidence Interval Actual Data162   Figure M-4 - Biodegradation test results for 2mgO3/mg DOC          0 0.02 0.04 0.06 0.08 0.1 0.12 0 1 2 3 4 5 6 7 S U V A Time (Days) Curve 22.0 BAC Column 2 Generated Curve Fit 90% Confidence Interval 90% Confidence Interval Actual Data 0 0.02 0.04 0.06 0.08 0.1 0.12 0.14 0 1 2 3 4 5 6 7 S U V A Time (Days) Curve 36.0 BAC Column 2 Generated Curve Fit 90% Confidence Interval 90% Confidence Interval Actual Data163   Figure M-5 - Biodegradation test results for 4000mJ/cm2 and 0mg/L H2O2    0 0.02 0.04 0.06 0.08 0.1 0.12 0.14 0.16 0 1 2 3 4 5 6 7 S U V A Time (Days) Curve 31.0 BAC Column 1 Generated Curve Fit 90% Confidence Interval 90% Confidence Interval Actual Data 0 0.02 0.04 0.06 0.08 0.1 0.12 0.14 0.16 0 1 2 3 4 5 6 7 S U V A Time (Days) Curve 33.0 BAC Column 1 Generated Curve Fit 90% Confidence Interval 90% Confidence Interval Actual Data 0 0.02 0.04 0.06 0.08 0.1 0.12 0.14 0.16 0 1 2 3 4 5 6 7 S U V A Time (Days) Curve 32.0 BAC Column 2 Generated Curve Fit 90% Confidence Interval 90% Confidence Interval Actual Data 0 0.02 0.04 0.06 0.08 0.1 0.12 0.14 0.16 0 1 2 3 4 5 6 7 S U V A Time (Days) Curve 34.0 BAC Column 2 Generated Curve Fit 90% Confidence Interval 90% Confidence Interval Actual Data164   Figure M-6 - Biodegradation test results for 2000mJ/cm2 and 10mg/L H2O2    0 0.01 0.02 0.03 0.04 0.05 0.06 0.07 0 1 2 3 4 5 6 7 S U V A Time (Days) Curve 3.0 BAC Column 1 Generated Curve Fit 90% Confidence Interval 90% Confidence Interval Actual Data 0 0.01 0.02 0.03 0.04 0.05 0.06 0.07 0.08 0 1 2 3 4 5 6 7 S U V A Time (Days) Curve 8.0 BAC Column 1 Generated Curve Fit 90% Confidence Interval 90% Confidence Interval Actual Data 0 0.01 0.02 0.03 0.04 0.05 0.06 0 1 2 3 4 5 6 7 S U V A Time (Days) Curve 12.0 BAC Column 1 Generated Curve Fit 90% Confidence Interval 90% Confidence Interval Actual Data 0 0.005 0.01 0.015 0.02 0.025 0.03 0.035 0.04 0 1 2 3 4 5 6 7 S U V A Time (Days) Curve 13.0 BAC Column 1 Generated Curve Fit 90% Confidence Interval 90% Confidence Interval Actual Data165   Figure M-7 - Biodegradation test results for 2000mJ/cm2 and 10mg/L H2O2    0 0.005 0.01 0.015 0.02 0.025 0.03 0.035 0.04 0 1 2 3 4 5 6 7 S U V A Time (Days) Curve 5.0 BAC Column 2 Generated Curve Fit 90% Confidence Interval 90% Confidence Interval Actual Data 0 0.01 0.02 0.03 0.04 0.05 0.06 0 1 2 3 4 5 6 7 S U V A Time (Days) Curve 9.0 BAC Column 2 Generated Curve Fit 90% Confidence Interval 90% Confidence Interval Actual Data 0 0.005 0.01 0.015 0.02 0.025 0.03 0.035 0.04 0 1 2 3 4 5 6 7 S U V A Time (Days) Curve 14.0 BAC Column 2 Generated Curve Fit 90% Confidence Interval 90% Confidence Interval Actual Data166   Figure M-8 - Biodegradation test results for 4000mJ/cm2 and 10mg/L H2O2    0 0.005 0.01 0.015 0.02 0.025 0.03 0 1 2 3 4 5 6 7 S U V A Time (Days) Curve 1.0 BAC Column 1 Generated Curve Fit 90% Confidence Interval 90% Confidence Interval Actual Data 0 0.005 0.01 0.015 0.02 0.025 0.03 0.035 0.04 0 1 2 3 4 5 6 7 S U V A Time (Days) Curve 6.0 BAC Column 1 Generated Curve Fit 90% Confidence Interval 90% Confidence Interval Actual Data 0 0.005 0.01 0.015 0.02 0.025 0.03 0.035 0.04 0 1 2 3 4 5 6 7 S U V A Time (Days) Curve 11.0 BAC Column 1 Generated Curve Fit 90% Confidence Interval 90% Confidence Interval Actual Data 0 0.005 0.01 0.015 0.02 0.025 0.03 0.035 0.04 0 1 2 3 4 5 6 7 S U V A Time (Days) Curve 7.0 BAC Column 2 Generated Curve Fit 90% Confidence Interval 90% Confidence Interval Actual Data167   Figure M-9 - Biodegradation test results for 4000mJ/cm2 and 10mg/L H2O2          0 0.005 0.01 0.015 0.02 0.025 0.03 0.035 0.04 0 1 2 3 4 5 6 7 S U V A Time (Days) Curve 10.0 BAC Column 2 Generated Curve Fit 90% Confidence Interval 90% Confidence Interval Actual Data168   Figure M-10 - Biodegradation test results for raw water samples    0 0.02 0.04 0.06 0.08 0.1 0.12 0.14 0.16 0.18 0.2 0 1 2 3 4 5 6 7 S U V A Time (Days) Curve 25.0 BAC Column 1 Generated Curve Fit 90% Confidence Interval 90% Confidence Interval Actual Data 0 0.02 0.04 0.06 0.08 0.1 0.12 0.14 0.16 0.18 0.2 0 1 2 3 4 5 6 7 S U V A Time (Days) Curve 27.0 BAC Column 1 Generated Curve Fit 90% Confidence Interval 90% Confidence Interval Actual Data 0 0.02 0.04 0.06 0.08 0.1 0.12 0.14 0.16 0.18 0.2 0 1 2 3 4 5 6 7 S U V A Time (Days) Curve 35.0 BAC Column 1 Generated Curve Fit 90% Confidence Interval 90% Confidence Interval Actual Data 0 0.02 0.04 0.06 0.08 0.1 0.12 0.14 0.16 0.18 0.2 0 1 2 3 4 5 6 7 S U V A Time (Days) Curve 26.0 BAC Column 2 Generated Curve Fit 90% Confidence Interval 90% Confidence Interval Actual Data169     Figure M-11 - Biodegradation test results for raw water samples  0 0.05 0.1 0.15 0.2 0.25 0 1 2 3 4 5 6 7 S U V A Time (Days) Curve 28.0 BAC Column 2 Generated Curve Fit 90% Confidence Interval 90% Confidence Interval Actual Data 0 0.02 0.04 0.06 0.08 0.1 0.12 0.14 0.16 0.18 0.2 0 1 2 3 4 5 6 7 S U V A Time (Days) Curve 38.0 BAC Column 2 Generated Curve Fit 90% Confidence Interval 90% Confidence Interval Actual Data 0 0.02 0.04 0.06 0.08 0.1 0.12 0.14 0.16 0.18 0.2 0 1 2 3 4 5 6 7 S U V A Time (Days) Curve 39.0 BAC Column 2 Generated Curve Fit 90% Confidence Interval 90% Confidence Interval Actual Data170  APPENDIX N. BIODEGRADATION TEST ANALYSIS RESULTS FOR SUVA Table N-1 - Biodegradation curve analysis results for SUVA   # of t test a b c a b c a stdev b stdev c stdev n t 1mg, Column 1 15 0.06455 0.06255 0.83051 2 6.314 1mg, Column 1 17 0.06081 0.06869 9.0581 2 6.314 1mg, Column 1 23 0.07041 0.05706 1.286 2 6.314 1mg, Column 2 16 0.05602 0.06725 1.40967 3 2.92 1mg, Column 2 18 0.05183 0.07232 1.26796 3 2.92 1mg, Column 2 24 0.05085 0.07531 1.64377 3 2.92 2mg, Column 1 19 0.06302 0.05054 2.1454 3 2.92 2mg, Column 1 21 0.05852 0.04584 1.68405 3 2.92 2mg, Column 1 37 0.06123 0.05778 1.4891 3 2.92 2mg, Column 2 20 0.04622 0.06134 1.46622 3 2.92 2mg, Column 2 22 0.04681 0.0579 1.77716 3 2.92 2mg, Column 2 36 0.04922 0.06775 2.88359 3 2.92 4000,0 Column 1 31 0.05271 0.06916 1.78344 2 6.314 4000,0 Column 1 33 0.04459 0.08218 1.16448 2 6.314 4000,0 Column 2 32 0.02958 0.09117 1.20847 2 6.314 4000,0 Column 2 34 0.0367 0.09885 1.8782 2 6.314 4000,10 Column 1 1 0.01626 0.01064 6.93199 3 2.92 4000,10 Column 1 6 0.01494 0.01873 6.73574 3 2.92 4000,10 Column 1 11 0.0127 0.01799 6.66209 3 2.92 4000,10 Column 2 7 0.01319 0.02066 9.54416 2 6.314 4000,10 Column 2 10 0.01294 0.01799 7.1755 2 6.314 0.0061.4740.0760.049 1.675 0.0008 0.0084 7.4779 0.4380.009 0.23520.0075 1.95400.0411 2.11430.0225 0.0242 0.0185 0.0069 0.3200 0.0101 0.5682 0.0084 1.2559 Error (b) Error (c) 0.0173 0.0030 0.0256 0.0038 0.0027 0.005 0.005 0.474 Error (a) 1.4380 0.0046 0.337 0.002 0.005 0.745 Standard Deviation 0.004 0.004 0.322 0.003 0.004 0.190 0.000 0.002 0.002 0.004 0.140 0.002 0.006 0.013 0.019 8.360 0.033 0.095 1.543 0.015 0.016 6.777 0.047 0.062 2.042 0.053 0.072 1.440 0.061 0.051 1.773 Oxidation ID Variables Average 0.067 0.060 1.058171          # of Sampl t test a b c a b c a stdev b stdev c stdev n t 2000,10 Column 1 3 0.02651 0.02553 3.83604 3 2.92 2000,10 Column 1 8 0.02407 0.03834 2.64703 3 2.92 2000,10 Column 1 12 0.02165 0.02586 2.92244 3 2.92 2000,10 Column 1 13 0.0138 0.0192 9.1839 3 2.92 2000,10 Column 2 5 0.01608 0.01408 1.13352 3 2.92 2000,10 Column 2 9 0.01918 0.03117 1.96156 3 2.92 2000,10 Column 2 14 0.00938 0.0246 9.83805 3 2.92 Raw, Column 1 25 0.06637 0.1017 1.61297 3 2.92 Raw, Column 1 27 0.05746 0.10843 0.77662 3 2.92 Raw, Column 1 35 0.07332 0.07971 2.24371 3 2.92 Raw, Column 2 26 0.06282 0.10931 1.64948 4 2.132 Raw, Column 2 28 0.05606 0.12548 2.62282 4 2.132 Raw, Column 2 38 0.05615 0.10883 1.66028 4 2.132 Raw, Column 2 39 0.05957 0.10929 1.63307 4 2.132 0.0041 0.0084 1.0493 8.0996 1.2407 0.5199 Oxidation ID Variables Average Standard Deviation Error (a) 0.0123 0.0145 0.0253 0.0087 Error (b) Error (c) 0.0134 0.0034 0.002 0.007 0.622 0.008 0.015 0.736 0.003 0.008 0.488 0.005 0.009 4.804 0.059 0.113 1.891 0.015 0.023 4.311 0.066 0.097 1.544 0.024 0.030 3.135172  Table N-2 - Biodegradation analysis of % non-biodegradable for SUVA   a b c 1mg, Column 1 15 0.06455 0.06255 0.83051 51% 1mg, Column 1 17 0.06081 0.06869 9.0581 47% 1mg, Column 1 23 0.07041 0.05706 1.286 55% 1mg, Column 2 16 0.05602 0.06725 1.40967 45% 1mg, Column 2 18 0.05183 0.07232 1.26796 42% 1mg, Column 2 24 0.05085 0.07531 1.64377 40% 2mg, Column 1 19 0.06302 0.05054 2.1454 55% 2mg, Column 1 21 0.05852 0.04584 1.68405 56% 2mg, Column 1 37 0.06123 0.05778 1.4891 51% 2mg, Column 2 20 0.04622 0.06134 1.46622 43% 2mg, Column 2 22 0.04681 0.0579 1.77716 45% 2mg, Column 2 36 0.04922 0.06775 2.88359 42% 4000,0 Column 1 31 0.05271 0.06916 1.78344 43% 4000,0 Column 1 33 0.04459 0.08218 1.16448 35% 4000,0 Column 2 32 0.02958 0.09117 1.20847 24% 4000,0 Column 2 34 0.0367 0.09885 1.8782 27% 4000,10 Column 1 1 0.01626 0.01064 6.93199 60% 4000,10 Column 1 6 0.01494 0.01873 6.73574 44% 4000,10 Column 1 11 0.0127 0.01799 6.66209 41% 4000,10 Column 2 7 0.01319 0.02066 9.54416 39% 4000,10 Column 2 10 0.01294 0.01799 7.1755 42% 2000,10 Column 1 3 0.02651 0.02553 3.83604 51% 2000,10 Column 1 8 0.02407 0.03834 2.64703 39% 2000,10 Column 1 12 0.02165 0.02586 2.92244 46% 2000,10 Column 1 13 0.0138 0.0192 9.1839 42% 2000,10 Column 2 5 0.01608 0.01408 1.13352 53% 2000,10 Column 2 9 0.01918 0.03117 1.96156 38% 2000,10 Column 2 14 0.00938 0.0246 9.83805 28% Raw, Column 1 25 0.06637 0.1017 1.61297 39% Raw, Column 1 27 0.05746 0.10843 0.77662 35% Raw, Column 1 35 0.07332 0.07971 2.24371 48% Raw, Column 2 26 0.06282 0.10931 1.64948 36% Raw, Column 2 28 0.05606 0.12548 2.62282 31% Raw, Column 2 38 0.05615 0.10883 1.66028 34% Raw, Column 2 39 0.05957 0.10929 1.63307 35% 2.13242%34% 2%40% 6%2.13245%44% 10%49% 2.9232%26% 2.9236%39% ErrorTN 9%6.3142 2.923 2.923 3 2.92 2.92 2.92 13% 7% 3% 1% 40% 41% 54% 43% 51% 4% 7%3 2.92 43% 3% 4%3 Oxidation ID Variables %  non- biodegra dable Std DevAverage 3% 22% 11% 3% 17% 2% 10% 3 4%3 2.92173  Table N-3 - Biodegradation average curve parameters for BAC Column 1 and BAC Column 2 Oxidation Average DOCnon (a) DOCi (b) kDOC (1/c) Raw, BAC Column 1 0.066 (±0.013) 0.097 (±0.025) 0.784 (±0.749) 4000,0 BAC Column 1 0.049 (±0.026) 0.076 (±0.041) 0.709 (±0.941) 2000,10 BAC Column 1 0.024 (±0.004) 0.030 (±0.012) 0.327 (±0.101) 4000,10 BAC Column 1 0.015 (±0.003) 0.016 (±0.008) 0.147 (±0.005) 1mg, BAC Column 1 0.067 (±0.019) 0.060 (±0.017) 0.991 (±1.34) 2mg, BAC Column 1 0.061 (±0.004) 0.051 (±0.010) 0.577(±0.174) Raw, BAC Column 2 0.059 (±0.003) 0.113 (±0.009) 0.551 (±0.120) 4000,0 BAC Column 2 0.033 (±0.022) 0.095 (±0.024) 0.680 (±0.932) 2000,10 BAC Column 2 0.015 (±0.008) 0.023 (±0.015) 0.498 (±0.658) 4000,10 BAC Column 2 0.013 (±0.003) 0.019 (±0.008) 0.122 (±0.005) 1mg, BAC Column 2 0.053 (±0.005) 0.072 (±0.007) 0.702 (±0.152) 2mg, BAC Column 2 0.047 (±0.003) 0.062 (±0.008) 0.53 (±0.286)    Figure N-1 - Parameter a for each oxidation scenario for BAC Column 1 and 2  0 -26 -63 -78 3 -70 -43 -75 -78 -10 -19 0 0.01 0.02 0.03 0.04 0.05 0.06 0.07 0.08 0.09 0.1 Raw 4000 mJ/cm2 & 0 mg/L H2O2 2000 mJ/cm2 & 10 mg/L H2O2 4000 mJ/cm2 & 10 mg/L H2O2 Ozonated                                                 (1mg O3/mg DOC) Ozonated                                                            (2mg O3/mg DOC) Parameter a - UVAresidual BAC Column 1 BAC Column 2174   Figure N-2 - Parameter c for each oxidation scenario for BAC Column 1 0 -10 -58 -81 26 -260 24 -10 -78 28 -4 -0.5 0 0.5 1 1.5 2 2.5 Raw 4000 mJ/cm2 & 0 mg/L H2O2 2000 mJ/cm2 & 10 mg/L H2O2 4000 mJ/cm2 & 10 mg/L H2O2 Ozonated                                                 (1mg O3/mg DOC) Ozonated                                                            (2mg O3/mg DOC) Parameter k=1/c - Kinetic Rate Constant Series1 Series2175  APPENDIX O. BIODEGRADATION HPSEC CHROMATOGRAMS  Figure O-1 - HPSEC chromatogram results for each of the biodegraded raw water samples.  Measured at time 0, 1 day, 7 days, using biomass from BAC Column 1 and BAC Column 2. 176     Figure O-2 - HPSEC chromatogram results for each of the biodegraded ozonated (at 2mgO3/mg DOC)  water samples.  Measured at time 0, 1 day, 7 days, using biomass from BAC Column 1 and BAC Column 2. 177     Figure O-3 - HPSEC chromatogram results for each of the biodegraded ozonated (at 1mgO3/mg DOC)  water samples.  Measured at time 0, 1 day, 7 days, using biomass from BAC Column 1 and BAC Column 2. 178   Figure O-4 - HPSEC chromatogram results for each of the biodegraded ozonated (at the extended dose) and each of the UV4000 mJ/cm2 and 0 mg/L H2O2 water samples.  Measured at time 0, 1 day, 7 days, using biomass from BAC Column 1 and BAC Column 2. 179   Figure O-5 - HPSEC chromatogram results for each of the UV2000 mJ/cm2 and 10 mg/L H2O2 water samples.  Measured at time 0, 1 day, 7 days, using biomass from BAC Column 1 and BAC Column 2. 180    Figure O-6 - HPSEC chromatogram results for each of the UV4000 mJ/cm2 and 10 mg/L H2O2 water samples.  Measured at time 0, 1 day, 7 days, using biomass from BAC Column 1 and BAC Column 2.    181  APPENDIX P. PEAKFIT ANALYSIS FOR BIODEGRADED CHROMATOGRAMS  Figure P-1 - Peakfit analysis results for each of the raw water biodegraded HPSEC chromatograms.   Showing time 0, 1 day and 7days for both BAC Column 1 and BAC Column 2 using Systat Peakfit v4.12, Autofit Peak III Deconvolution. 182   Figure P-2 - Peakfit analysis results for each of the raw water biodegraded HPSEC chromatograms.   Showing time 0, 1 day and 7days for both BAC Column 1 and BAC Column 2 using Systat Peakfit v4.12, Autofit Peak III Deconvolution. 183   Figure P-3 - Peakfit analysis results for each of the raw water biodegraded HPSEC chromatograms.   Showing time 0, 1 day and 7days for both BAC Column 1 and BAC Column 2 using Systat Peakfit v4.12, Autofit Peak III Deconvolution.   184   Figure P-4 - Peakfit analysis results for each of the ozonated at 2mgO3/mg DOC and biodegraded HPSEC chromatograms.   Showing time 0, 1 day and 7days for both BAC Column 1 and BAC Column 2 using Systat Peakfit v4.12, Autofit Peak III Deconvolution. 185   Figure P-5 - Peakfit analysis results for each of the ozonated at 2mgO3/mg DOC and biodegraded HPSEC chromatograms.   Showing time 0, 1 day and 7days for both BAC Column 1 and BAC Column 2 using Systat Peakfit v4.12, Autofit Peak III Deconvolution. 186   Figure P-6 - Peakfit analysis results for each of the ozonated at 1mgO3/mg DOC and biodegraded HPSEC chromatograms.   Showing time 0, 1 day and 7days for both BAC Column 1 and BAC Column 2 using Systat Peakfit v4.12, Autofit Peak III Deconvolution. 187   Figure P-7 - Peakfit analysis results for each of the ozonated at 1mgO3/mg DOC and biodegraded HPSEC chromatograms.   Showing time 0, 1 day and 7days for both BAC Column 1 and BAC Column 2 using Systat Peakfit v4.12, Autofit Peak III Deconvolution. 188   Figure P-8 - Peakfit analysis results for each of the ozonated at the extended dose and biodegraded HPSEC chromatograms.   Showing time 0, 1 day and 7days for both BAC Column 1 and BAC Column 2 using Systat Peakfit v4.12, Autofit Peak III Deconvolution. 189   Figure P-9 - Peakfit analysis results for each of the ozonated at the extended dose and biodegraded HPSEC chromatograms.   Showing time 0, 1 day and 7days for both BAC Column 1 and BAC Column 2 using Systat Peakfit v4.12, Autofit Peak III Deconvolution.     190   Figure P-10 - Peakfit analysis results for each of UV4000mJ/cm2 and 0mg/L H2O2 and biodegraded HPSEC chromatograms.   Showing time 0, 1 day and 7days for both BAC Column 1 and BAC Column 2 using Systat Peakfit v4.12, Autofit Peak III Deconvolution. 191   Figure P-11 - Peakfit analysis results for each of UV4000mJ/cm2 and 0mg/L H2O2 and biodegraded HPSEC chromatograms.   Showing time 0, 1 day and 7days for both BAC Column 1 and BAC Column 2 using Systat Peakfit v4.12, Autofit Peak III Deconvolution.         192   Figure P-12 - Peakfit analysis results for each of UV2000mJ/cm2 and 10mg/L H2O2 and biodegraded HPSEC chromatograms.   Showing time 0, 1 day and 7days for both BAC Column 1 and BAC Column 2 using Systat Peakfit v4.12, Autofit Peak III Deconvolution. 193   Figure P-13 - Peakfit analysis results for each of UV2000mJ/cm2 and 10mg/L H2O2 and biodegraded HPSEC chromatograms.   Showing time 0, 1 day and 7days for both BAC Column 1 and BAC Column 2 using Systat Peakfit v4.12, Autofit Peak III Deconvolution. 194   Figure P-14 - Peakfit analysis results for each of UV2000mJ/cm2 and 10mg/L H2O2 and biodegraded HPSEC chromatograms.   Showing time 0, 1 day and 7days for both BAC Column 1 and BAC Column 2 using Systat Peakfit v4.12, Autofit Peak III Deconvolution.     195   Figure P-15 - Peakfit analysis results for each of UV4000mJ/cm2 and 10mg/L H2O2 and biodegraded HPSEC chromatograms.   Showing time 0, 1 day and 7days for both BAC Column 1 and BAC Column 2 using Systat Peakfit v4.12, Autofit Peak III Deconvolution. 196   Figure P-16 - Peakfit analysis results for each of UV4000mJ/cm2 and 10mg/L H2O2 and biodegraded HPSEC chromatograms.   Showing time 0, 1 day and 7days for both BAC Column 1 and BAC Column 2 using Systat Peakfit v4.12, Autofit Peak III Deconvolution.  197  APPENDIX Q. BIODEGRADATION BAR GRAPH RESULTS   Figure Q-1 - Bar graph results for each of the raw water Peakfit analyzed HPSEC chromatograms.   Showing time 0, 1 day, 7day for BAC Column 1. 0 0 0 0 0 0-48 -37 -38 -10 -10 -32 -79 -67 -63 -69 -51 -68 0 0.05 0.1 0.15 0.2 0.25 > 1350                                                             (F1) 1050 - 1350                                 (F2) 750 - 1050       (F3) 500 - 750                                         (F4) 300 - 500                        (F5) < 300                                       (F6) A re a  Co u n t Molecular Weight (Da) ID 25 RAW Column 1 Raw 1 day 7 days 0 0 0 0 0 0 -31 -30 -31 -32 -32 -37 -73 -61 -57 -62 -50 -66 0 0.05 0.1 0.15 0.2 0.25 > 1350                                                             (F1) 1050 - 1350                                 (F2) 750 - 1050       (F3) 500 - 750                                         (F4) 300 - 500                        (F5) < 300                                       (F6) A re a  Co u n t Molecular Weight (Da) ID 27 RAW Column 1 Raw 1 day 7 days 0 0 0 0 0 0 -34 -37 -43 -40 -40 -51 -60 -50 -58 -47 -54 -58 0 0.05 0.1 0.15 0.2 0.25 0.3 0.35 > 1350                                                             (F1) 1050 - 1350                                (F2) 750 - 1050       (F3) 500 - 750                                         (F4) 300 - 500                        (F5) < 300                                       (F6) Ar ea  Co u n t Molecular Weight (Da) ID 35 RAW Column 1 Raw 1 day 7 days198    Figure Q-2 - Bar graph results for each of the raw water Peakfit analyzed HPSEC chromatograms.   Showing time 0, 1 day, 7day for BAC Column 2.  0 0 0 0 0 0-48 -39 -37 -23 -10 -48-73 -60 -60 -67 -56 -71 0 0.05 0.1 0.15 0.2 0.25 > 1350                                                             (F1) 1050 - 1350                                  (F2) 750 - 1050       (F3) 500 - 750                                         (F4) 300 - 500                    (F5) < 300                                       (F6) Ar ea  Co u n t Molecular Weight (Da) ID 26 RAW Column 2 Raw 1 day 7 days 0 0 0 0 0 0 -48 -52 -53 -53 -10 -63 -84 -78 -73 -75 -64 -75 0 0.02 0.04 0.06 0.08 0.1 0.12 0.14 0.16 0.18 0.2 > 1350                                                             (F1) 1050 - 1350                                  (F2) 750 - 1050       (F3) 500 - 750                                         (F4) 300 - 500                    (F5) < 300                                       (F6) A re a  Co u n t Molecular Weight (Da) ID 28 RAW Column 2 Raw 1 day 7 days199   Figure Q-3 - Bar graph results for each of the raw water Peakfit analyzed HPSEC chromatograms.   Showing time 0, 1 day, 7day for BAC Column 2.             0 0 0 0 0 0 -52 -58 -58 -64 -10 -76 -73 -82 -80 -75 -70 -55 0 0.05 0.1 0.15 0.2 0.25 0.3 0.35 > 1350                                                             (F1) 1050 - 1350                                  (F2) 750 - 1050       (F3) 500 - 750                                         (F4) 300 - 500                    (F5) < 300                                       (F6) Ar ea  Co u n t Molecular Weight (Da) ID 39 RAW Column 2 Raw 1 day 7 days200    Figure Q-4 - Bar graph results for each of the ozonated 2 mgO3/mg DOC Peakfit analyzed HPSEC chromatograms.   Showing  raw, time 0, 1 day, 7day for BAC Column 1 0 0 0 0 0 0 -41 -44 -45 -42 -42 -33 -52 -53 -55 -53 -51 -46 -76 -73 -74 -72 -71 -71 0 0.02 0.04 0.06 0.08 0.1 0.12 0.14 0.16 0.18 0.2 > 1350                                                             (F1) 1050 - 1350                                (F2) 750 - 1050       (F3) 500 - 750                                         (F4) 300 - 500                        (F5) < 300                                       (F6) Ar ea  Co u n t Molecular Weight (Da) ID 19 Ozone 2mg Column 1 Raw Treated Time 1 Day Time 7 Days 0 0 0 0 0 0 -35 -43 -48 -41 -42 -34 -55 -53 -55 -52 -52 -52 -69 -68 -68 -64 -63 -61 0 0.02 0.04 0.06 0.08 0.1 0.12 0.14 0.16 0.18 0.2 > 1350                                                             (F1) 1050 - 1350                                  (F2) 750 - 1050       (F3) 500 - 750                                         (F4) 300 - 500                    (F5) < 300                                       (F6) Ar ea  Co u n t Molecular Weight (Da) ID 21 Ozone 2mg Column 1 Raw Treated Time 1 Day Time 7 Days 0 0 0 0 0 0 44 -20 -47 -37 -37 -15 -14 -55 -68 -67 -68 -68 -27 -76 -75 -68 -62 -59 0 0.02 0.04 0.06 0.08 0.1 0.12 0.14 0.16 0.18 0.2 > 1350                                                             (F1) 1050 - 1350                                  (F2) 750 - 1050       (F3) 500 - 750                                         (F4) 300 - 500                    (F5) < 300                                       (F6) A re a  Co u n t Molecular Weight (Da) ID 37 Ozone 2mg Column 1 Raw Treated Time 1 Day Time 7 Days201   Figure Q-5 - Bar graph results for each of the ozonated 2 mgO3/mg DOC Peakfit analyzed HPSEC chromatograms.   Showing  raw, time 0, 1 day, 7day for BAC Column 2  0 0 0 0 0 0 -41 -44 -45 -42 -42 -33 -58 -62 -62 -60 -60 -59 -70 -66 -67 -65 -64 -63 0 0.02 0.04 0.06 0.08 0.1 0.12 0.14 0.16 0.18 0.2 > 1350                                                             (F1) 1050 - 1350                                  (F2) 750 - 1050       (F3) 500 - 750                                         (F4) 300 - 500                    (F5) < 300                                       (F6) Ar ea  Co u n t Molecular Weight (Da) ID 20 Ozone 2mg Column 2 Raw Treated Time 1 Day Time 7 Days 0 0 0 0 0 0 -41 -44 -45 -42 -42 -33 -50 -62 -69 -73 -68 -53 -73 -69 -69 -66 -65 -64 0 0.02 0.04 0.06 0.08 0.1 0.12 0.14 0.16 0.18 0.2 > 1350                                                             (F1) 1050 - 1350                                  (F2) 750 - 1050       (F3) 500 - 750                                         (F4) 300 - 500                    (F5) < 300                                       (F6) A re a  Co u n t Molecular Weight (Da) ID 22 Ozone 2mg Column 2 Raw Treated Time 1 Day Time 7 Days 0 0 0 0 0 0 36 -22 -46 -25 -34 -16 -67 -70 -63 -47 -60 -59 -52 -83 -83 -75 -74 -76 0 0.02 0.04 0.06 0.08 0.1 0.12 0.14 0.16 0.18 0.2 > 1350                                                             (F1) 1050 - 1350                                  (F2) 750 - 1050       (F3) 500 - 750                                         (F4) 300 - 500                    (F5) < 300                                       (F6) A re a  Co u n t Molecular Weight (Da) ID 36 Ozone 2mg Column 2 Raw Treated Time 1 Day Time 7 Days202   Figure Q-6  - Bar graph results for each of the ozonated 1 mgO3/mg DOC Peakfit analyzed HPSEC chromatograms.   Showing  raw, time 0, 1 day, 7day for BAC Column 1  0 0 0 0 0 0 -44 -30 -22 -11 -16 -10 -68 -71 -67 -49 -47 -42 -72 -77 -76 -60 -57 -49 0 0.05 0.1 0.15 0.2 0.25 > 1350                                                             (F1) 1050 - 1350                                  (F2) 750 - 1050       (F3) 500 - 750                                         (F4) 300 - 500                    (F5) < 300                                       (F6) Ar ea  Co u n t Molecular Weight (Da) ID 15 Ozone 1mg Column 1 Raw Treated Time 1 Day Time 7 Days 0 0 0 0 0 0 -29 -23 -18 -14 -10 -9 -72 -75 -76 -63 -55 -50 -73 -75 -73 -59 -52 -46 0 0.02 0.04 0.06 0.08 0.1 0.12 0.14 0.16 0.18 > 1350                                                             (F1) 1050 - 1350                                  (F2) 750 - 1050       (F3) 500 - 750                                         (F4) 300 - 500                    (F5) < 300                                       (F6) A re a  Co u n t Molecular Weight (Da) ID 17 Ozone 1mg Column 1 Raw Treated Time 1 Day Time 7 Days 0 0 0 0 0 0 -29 -26 -31 -25 -23 -10 -25 -47 -57 -62 -52 -29 -67 -71 -77 -81 -78 -66 0 0.02 0.04 0.06 0.08 0.1 0.12 0.14 0.16 0.18 > 1350                                                             (F1) 1050 - 1350                                  (F2) 750 - 1050       (F3) 500 - 750                                         (F4) 300 - 500                    (F5) < 300                                       (F6) A re a  Co u n t Molecular Weight (Da) ID 23 Ozone 1mg Column 1 Raw Treated Time 1 Day Time 7 Days203   Figure Q-7 - Bar graph results for each of the ozonated 1 mgO3/mg DOC Peakfit analyzed HPSEC chromatograms.   Showing  raw, time 0, 1 day, 7day for BAC Column 2 0 0 0 0 0 0 -43 -29 -21 -17 -7 -6 -92 -91 -89 -87 -89 -87 -78 -83 -82 -73 -63 -56 0 0.05 0.1 0.15 0.2 0.25 > 1350                                                             (F1) 1050 - 1350                                  (F2) 750 - 1050       (F3) 500 - 750                                         (F4) 300 - 500                    (F5) < 300                                       (F6) Ar ea  Co u n t Molecular Weight (Da) ID 16 Ozone 1mg Column 2 Raw Treated Time 1 Day Time 7 Days 0 0 0 0 0 0 -29 -23 -18 -14 -10 -9 -64 -73 -73 -61 -54 -52 -55 -75 -81 -78 -73 -56 0 0.02 0.04 0.06 0.08 0.1 0.12 0.14 0.16 0.18 > 1350                                                             (F1) 1050 - 1350                                  (F2) 750 - 1050       (F3) 500 - 750                                         (F4) 300 - 500                    (F5) < 300                                       (F6) A re a  Co u n t Molecular Weight (Da) ID 18 Ozone 1mg Column 2 Raw Treated Time 1 Day Time 7 Days 0 0 0 0 0 0 -41 -34 -27 -19 -12 -1 -31 -51 -60 -65 -56 -34 -68 -67 -67 -62 -58 -56 0 0.02 0.04 0.06 0.08 0.1 0.12 0.14 0.16 0.18 > 1350                                                             (F1) 1050 - 1350                                  (F2) 750 - 1050       (F3) 500 - 750                                         (F4) 300 - 500                    (F5) < 300                                       (F6) A re a  Co u n t Molecular Weight (Da) ID 24 Ozone 1mg Column 2 Raw Treated Time 1 Day Time 7 Days204   Figure Q-8 - Bar graph results for each of the extended ozonated 25 mgO3/mg DOC Peakfit analyzed HPSEC chromatograms.   Showing  raw, time 0, 1 day, 7day for BAC Column 1.  0 0 0 0 0 0 -99 -96 -90 -87 -92 -46 -89 -92 -94 -89 -97 -58 -97 -92 -89 -91 -97 -62 0 0.05 0.1 0.15 0.2 0.25 > 1350                                                             (F1) 1050 - 1350                                  (F2) 750 - 1050       (F3) 500 - 750                                         (F4) 300 - 500                    (F5) < 300                                       (F6) Ar ea  Co u n t Molecular Weight (Da) ID 40 Extended O3 Column 1 Raw Treated Time 1 Day Time 7 Days 0 0 0 0 0 0 -80 -91 -95 -85 -94 -61 -93 -90 -89 -83 -92 -57 -94 -90 -90 -87 -94 -60 0 0.02 0.04 0.06 0.08 0.1 0.12 0.14 0.16 0.18 > 1350                                                             (F1) 1050 - 1350                                  (F2) 750 - 1050       (F3) 500 - 750                                         (F4) 300 - 500                    (F5) < 300                                       (F6) A re a  Co u n t Molecular Weight (Da) ID 41 Ozone 1mg Column 1 Raw Treated Time 1 Day Time 7 Days205   Figure Q-9- Bar graph results for each of the extended ozonated 25 mgO3/mg DOC Peakfit analyzed HPSEC chromatograms.   Showing  raw, time 0, 1 day, 7day for BAC Column 2.        0 0 0 0 0 0 -80 -91 -95 -85 -94 -61 -99 -97 -96 -92 -96 -66 -98 -96 -95 -92 -97 -67 0 0.02 0.04 0.06 0.08 0.1 0.12 0.14 0.16 0.18 > 1350                                                             (F1) 1050 - 1350                                  (F2) 750 - 1050       (F3) 500 - 750                                         (F4) 300 - 500                    (F5) < 300                                       (F6) Ar ea  Co u n t Molecular Weight (Da) ID 42 Extended O3 Column 2 Raw Treated Time 1 Day Time 7 Days 0 0 0 0 0 0 -78 -89 -95 -87 -95 -70 -99 -96 -95 -92 -97 -73 -98 -95 -94 -93 -97 -73 0 0.02 0.04 0.06 0.08 0.1 0.12 0.14 0.16 0.18 > 1350                                                             (F1) 1050 - 1350                                  (F2) 750 - 1050       (F3) 500 - 750                                         (F4) 300 - 500                    (F5) < 300                                       (F6) A re a  Co u n t Molecular Weight (Da) ID 43 Extended O3 Column 2 Raw Treated Time 1 Day Time 7 Days206   Figure Q-10 - Bar graph results for each of the UV4000mJ/cm2 and 0mg/L H2O2 Peakfit analyzed HPSEC chromatograms.  Showing  raw, time 0, 1 day, 7day for BAC Column 1. 0 0 0 0 0 0 -31 -21 -12 1 8 31 -42 -60 -63 -55 -50 -47 -32 -66 -75 -80 -74 -74 0 0.02 0.04 0.06 0.08 0.1 0.12 0.14 0.16 0.18 > 1350                                                             (F1) 1050 - 1350                                  (F2) 750 - 1050       (F3) 500 - 750                                         (F4) 300 - 500                    (F5) < 300                                       (F6) Ar ea  Co u n t Molecular Weight (Da) ID 31 UV 4000,0 Column 1 Raw Treated Time 1 Day Time 7 Days 0 0 0 0 0 0 -28 -23 -12 -3 12 26 4 -52 -64 -67 -58 -51-49 -71 -78 -79 -77 -78 0 0.02 0.04 0.06 0.08 0.1 0.12 0.14 0.16 0.18 > 1350                                                             (F1) 1050 - 1350                                  (F2) 750 - 1050       (F3) 500 - 750                                         (F4) 300 - 500                    (F5) < 300                                       (F6) A re a  Co u n t Molecular Weight (Da) ID 33 UV 4000,0 Column 1 Raw Treated Time 1 Day Time 7 Days207   Figure Q-11 - Bar graph results for each of the UV4000mJ/cm2 and 0mg/L H2O2 Peakfit analyzed HPSEC chromatograms.  Showing  raw, time 0, 1 day, 7day for BAC Column 2.        0 0 0 0 0 0 -35 -22 -12 0 10 32 -13 -62 -69 -74 -66 -65-59 -79 -83 -84 -83 -86 0 0.02 0.04 0.06 0.08 0.1 0.12 0.14 0.16 0.18 > 1350                                                             (F1) 1050 - 1350                                  (F2) 750 - 1050       (F3) 500 - 750                                         (F4) 300 - 500                    (F5) < 300                                       (F6) Ar ea  Co u n t Molecular Weight (Da) ID 32 UV 4000,0 Column 2 Raw Treated Time 1 Day Time 7 Days 0 0 0 0 0 0 -28 -23 -12 -3 12 26 -18 -64 -75 -79 -73 -72 -58 -76 -85 -83 -84 -86 0 0.02 0.04 0.06 0.08 0.1 0.12 0.14 0.16 0.18 > 1350                                                             (F1) 1050 - 1350                                  (F2) 750 - 1050       (F3) 500 - 750                                         (F4) 300 - 500                    (F5) < 300                                       (F6) A re a  Co u n t Molecular Weight (Da) ID 34 UV 4000,0 Column 2 Raw Treated Time 1 Day Time 7 Days208   Figure Q-12 - Bar graph results for each of the UV2000mJ/cm2 and 10mg/L H2O2 Peakfit analyzed HPSEC chromatograms.  Showing  raw, time 0, 1 day, 7day for BAC Column 1.  0 0 0 0 0 0 -80 -85 -74 -65 -58 -44 -92 -87 -82 -77 -76 -70 -84 -78 -76 -72 -75 -69 0 0.02 0.04 0.06 0.08 0.1 0.12 0.14 0.16 0.18 0.2 > 1350                                                             (F1) 1050 - 1350                                  (F2) 750 - 1050       (F3) 500 - 750                                         (F4) 300 - 500                    (F5) < 300                                       (F6) Ar ea  Co u n t Molecular Weight (Da) ID 3 UV 2000,10 Column 1 Raw Treated Time 1 Day Time 7 Days 0 0 0 0 0 0 -76 -79 -71 -61 -64 -42 -83 -86 -83 -78 -80 -75 -90 -85 -82 -84 -68 -69 0 0.02 0.04 0.06 0.08 0.1 0.12 0.14 0.16 0.18 0.2 > 1350                                                             (F1) 1050 - 1350                                  (F2) 750 - 1050       (F3) 500 - 750                                         (F4) 300 - 500                    (F5) < 300                                       (F6) A re a  Co u n t Molecular Weight (Da) ID 8 UV 2000,10 Column 1 Raw Treated Time 1 Day Time 7 Days 0 0 0 0 0 0 -74 -81 -73 -62 -66 -49 -89 -88 -84 -77 -79 -73 -91 -86 -81 -78 -73 -72 0 0.02 0.04 0.06 0.08 0.1 0.12 0.14 0.16 0.18 0.2 > 1350                                                             (F1) 1050 - 1350                                  (F2) 750 - 1050       (F3) 500 - 750                                         (F4) 300 - 500                    (F5) < 300                                       (F6) A re a  Co u n t Molecular Weight (Da) ID 12UV 2000,10 Column 1 Raw Treated Time 1 Day Time 7 Days209   Figure Q-13 - Bar graph results for each of the UV2000mJ/cm2 and 10mg/L H2O2 Peakfit analyzed HPSEC chromatograms.  Showing  raw, time 0, 1 day, 7day for both BAC Column 1 and BAC Column 2. 0 0 0 0 0 0-68 -75 -65 -43 -59 -31 -97 -96 -92 -86 -82 -81 -89 -89 -83 -86 -81 -71 0 0.02 0.04 0.06 0.08 0.1 0.12 0.14 0.16 0.18 > 1350                                                             (F1) 1050 - 1350                                  (F2) 750 - 1050       (F3) 500 - 750                                         (F4) 300 - 500                    (F5) < 300                                       (F6) Ar ea  Co u n t Molecular Weight (Da) ID 13UV 2000,10 Column 1 Raw Treated Time 1 Day Time 7 Days 0 0 0 0 0 0 -92 -83 -70 -52 -54 -29 -85 -88 -84 -78 -84 -80 -87 -84 -83 -76 -85 -80 0 0.02 0.04 0.06 0.08 0.1 0.12 0.14 0.16 > 1350                                                             (F1) 1050 - 1350                                  (F2) 750 - 1050       (F3) 500 - 750                                         (F4) 300 - 500                    (F5) < 300                                       (F6) A re a  Co u n t Molecular Weight (Da) ID 4 UV 2000,10 Column 2 Raw Treated Time 1 Day Time 7 Days 0 0 0 0 0 0 -82 -79 -70 -59 -62 -48 -92 -91 -87 -83 -86 -84 -93 -89 -87 -82 -85 -76 0 0.02 0.04 0.06 0.08 0.1 0.12 0.14 0.16 0.18 0.2 > 1350                                                             (F1) 1050 - 1350                                  (F2) 750 - 1050       (F3) 500 - 750                                         (F4) 300 - 500                    (F5) < 300                                       (F6) A re a  Co u n t Molecular Weight (Da) ID 5 UV 2000,10 Column 2 Raw Treated Time 1 Day Time 7 Days210   Figure Q-14 - Bar graph results for each of the UV2000mJ/cm2 and 10mg/L H2O2 Peakfit analyzed HPSEC chromatograms.  Showing  raw, time 0, 1 day, 7day for BAC Column 2.        0 0 0 0 0 0 -74 -80 -71 -53 -67 -45 -87 -87 -81 -71 -81 -74 -89 -89 -83 -86 -81 -71 0 0.02 0.04 0.06 0.08 0.1 0.12 0.14 0.16 0.18 > 1350                                                             (F1) 1050 - 1350                                  (F2) 750 - 1050       (F3) 500 - 750                                         (F4) 300 - 500                    (F5) < 300                                       (F6) Ar ea  Co u n t Molecular Weight (Da) ID 9 UV 2000,10 Column 2 Raw Treated Time 1 Day Time 7 Days 0 0 0 0 0 0 -82 -78 -68 -58 -57 -42 -98 -98 -94 -91 -86 -85 -97 -98 -95 -91 -86 -85 0 0.02 0.04 0.06 0.08 0.1 0.12 0.14 0.16 0.18 0.2 > 1350                                                             (F1) 1050 - 1350                                  (F2) 750 - 1050       (F3) 500 - 750                                         (F4) 300 - 500                    (F5) < 300                                       (F6) A re a  Co u n t Molecular Weight (Da) ID 14 UV 2000,10 Column 2 Raw Treated Time 1 Day Time 7 Days211   Figure Q-15 - Bar graph results for each of the UV4000mJ/cm2 and 10mg/L H2O2 Peakfit analyzed HPSEC chromatograms.  Showing  raw, time 0, 1 day, 7day for BAC Column 1.  0 0 0 0 0 0 -95 -95 -90 -83 -81 -70 -91 -92 -90 -86 -86 -82 -94 -89 -86 -81 -85 -79 0 0.02 0.04 0.06 0.08 0.1 0.12 0.14 0.16 0.18 > 1350                                                             (F1) 1050 - 1350                                  (F2) 750 - 1050       (F3) 500 - 750                                         (F4) 300 - 500                    (F5) < 300                                       (F6) Ar ea  Co u n t Molecular Weight (Da) ID 1 UV 4000,10 Column 1 Raw Treated Time 1 Day Time 7 Days 0 0 0 0 0 0 -93 -96 -92 -85 -86 -75 -90 -94 -91 -86 -88 -82 -91 -88 -87 -82 -86 -82 0 0.02 0.04 0.06 0.08 0.1 0.12 0.14 0.16 0.18 > 1350                                                             (F1) 1050 - 1350                                  (F2) 750 - 1050       (F3) 500 - 750                                         (F4) 300 - 500                    (F5) < 300                                       (F6) A re a  Co u n t Molecular Weight (Da) ID 6 UV 4000,10 Column 1 Raw Treated Time 1 Day Time 7 Days 0 0 0 0 0 0 -95 -91 -89 -85 -87 -82 -93 -95 -93 -89 -90 -86 -94 -92 -90 -86 -85 -83 0 0.02 0.04 0.06 0.08 0.1 0.12 0.14 0.16 0.18 0.2 > 1350                                                             (F1) 1050 - 1350                                  (F2) 750 - 1050       (F3) 500 - 750                                         (F4) 300 - 500                    (F5) < 300                                       (F6) A re a  Co u n t Molecular Weight (Da) ID 11UV 4000,10 Column 1 Raw Treated Time 1 Day Time 7 Days212   Figure Q-16 - Bar graph results for each of the UV4000mJ/cm2 and 10mg/L H2O2 Peakfit analyzed HPSEC chromatograms.  Showing  raw, time 0, 1 day, 7day for BAC Column 2.  0 0 0 0 0 0 -95 -95 -89 -79 -79 -63 -91 -91 -88 -84 -88 -85 -92 -89 -87 -81 -87 -84 0 0.02 0.04 0.06 0.08 0.1 0.12 0.14 0.16 0.18 > 1350                                                             (F1) 1050 - 1350                                  (F2) 750 - 1050       (F3) 500 - 750                                         (F4) 300 - 500                    (F5) < 300                                       (F6) Ar ea  Co u n t Molecular Weight (Da) ID 2 UV 4000,10 Column 2 Raw Treated Time 1 Day Time 7 Days 0 0 0 0 0 0 -94 -96 -93 -87 -87 -77 -92 -94 -92 -88 -88 -84 -94 -90 -88 -83 -86 -83 0 0.02 0.04 0.06 0.08 0.1 0.12 0.14 0.16 0.18 0.2 > 1350                                                             (F1) 1050 - 1350                                  (F2) 750 - 1050       (F3) 500 - 750                                         (F4) 300 - 500                    (F5) < 300                                       (F6) A re a  Co u n t Molecular Weight (Da) ID 7 UV 4000,10 Column 2 Raw Treated Time 1 Day Time 7 Days 0 0 0 0 0 0 -95 -90 -88 -83 -86 -79 -90 -94 -92 -87 -90 -84 -94 -92 -89 -84 -85 -81 0 0.02 0.04 0.06 0.08 0.1 0.12 0.14 0.16 0.18 > 1350                                                             (F1) 1050 - 1350                                  (F2) 750 - 1050       (F3) 500 - 750                                         (F4) 300 - 500                    (F5) < 300                                       (F6) A re a  Co u n t Molecular Weight (Da) ID 10 UV 4000,10 Column 2 Raw Treated Time 1 Day Time 7 Days213  APPENDIX R. BIODEGRADATION PERCENT REMOVAL RESULTS   Figure R-1 - Percent removal results for each of the Peakfit analysed HPSEC chromatograms raw water samples.  Showing raw, time 0, 1 day, 7day for both BAC Column 1 and BAC Column 2. 0 10 20 30 40 50 60 70 80 90 100 > 1350                                                             (F1) 1050 - 1350                   (F2) 750 - 1050                              (F3) 500 - 750                                           (F4) 300 - 500          (F5) < 300                                                (F6) Pe rc en t R em o v a l RAW BAC Column 1 ID 26,28,38,39 Raw N/A Time 1 Day Time 7 Days 0 10 20 30 40 50 60 70 80 90 100 > 1350                                                             (F1) 1050 - 1350                   (F2) 750 - 1050                              (F3) 500 - 750                                           (F4) 300 - 500          (F5) < 300                                                (F6) Pe rc en t R em o v a l RAW BAC Column 2 ID 25,27,39 Raw N/A Time 1 Day Time 7 Days214    Figure R-2 - Percent removal results for each of the Peakfit analysed HPSEC chromatograms ozonated 1 mgO3/mg DOC water samples.  Showing raw, time 0, 1 day, 7day for both BAC Column 1 and BAC Column 2. 0 20 40 60 80 100 120 > 1350                                                             (F1) 1050 - 1350                   (F2) 750 - 1050                              (F3) 500 - 750                                           (F4) 300 - 500          (F5) < 300                                                (F6) Pe rc en t R em o v a l 1mgO3/mgDOC BAC Column 1 ID 15, 17, 23 Raw Treated (1mgO3/mgDOC) Time 1 Day Time 7 Days 0 20 40 60 80 100 120 > 1350                                                             (F1) 1050 - 1350                   (F2) 750 - 1050                              (F3) 500 - 750                                           (F4) 300 - 500          (F5) < 300                                                (F6) Pe rc en t R em o v a l 1mgO3/mgDOC BAC Column 2 ID 16,18,24 Raw Treated Time 1 Day Time 7 Days215    Figure R-3 - Percent removal results for each of the Peakfit analysed HPSEC chromatograms ozonated 2 mgO3/mg DOC water samples.  Showing raw, time 0, 1 day, 7day for both BAC Column 1 and BAC Column 2.   0 20 40 60 80 100 120 > 1350                                                             (F1) 1050 - 1350                   (F2) 750 - 1050                              (F3) 500 - 750                                           (F4) 300 - 500          (F5) < 300                                                (F6) Pe rc en t R em o v a l 2mgO3/mgDOC BAC Column 1 ID 19, 21, 37 Raw Treated Time 1 Day Time 7 Days 0 20 40 60 80 100 120 > 1350                                                             (F1) 1050 - 1350                   (F2) 750 - 1050                              (F3) 500 - 750                                           (F4) 300 - 500          (F5) < 300                                                (F6) Pe rc en t R em o v a l 2mgO3/mgDOC BAC Column 2 ID 20,22,36 Raw Treated Time 1 Day Time 7 Days216    Figure R-4 - Percent removal results for each of the Peakfit analysed HPSEC chromatograms ozonated 25 mgO3/mg DOC water samples.  Showing raw, time 0, 1 day, 7day for both BAC Column 1 and BAC Column 2.   0 20 40 60 80 100 120 140 > 1350                                                             (F1) 1050 - 1350                   (F2) 750 - 1050                              (F3) 500 - 750                                           (F4) 300 - 500          (F5) < 300                                                (F6) Pe rc en t R em o v a l Extended Ozonation BAC Column 1 ID 40,41 Raw Treated Time 1 Day Time 7 Days 0 20 40 60 80 100 120 > 1350                                                             (F1) 1050 - 1350                   (F2) 750 - 1050                              (F3) 500 - 750                                           (F4) 300 - 500          (F5) < 300                                                (F6) Pe rc en t R em o v a l Extended Ozonation BAC Column 2 ID 42,43 Raw Treated Time 1 Day Time 7 Days217     Figure R-5 - Percent removal results for each of the Peakfit analysed HPSEC chromatograms UV4000mJ/cm2  and 0mg/L H2O2 water samples.  Showing raw, time 0, 1 day, 7day for both BAC Column 1 and BAC Column 2. 0 20 40 60 80 100 120 140 160 180 > 1350                                                             (F1) 1050 - 1350                   (F2) 750 - 1050                              (F3) 500 - 750                                           (F4) 300 - 500          (F5) < 300                                                (F6) Pe rc en t R em o v a l 4000mJ/cm2 and 0 mg/L H2O2 BAC Column 1 ID 40,41 Raw Treated Time 1 Day Time 7 Days 0 10 20 30 40 50 60 70 80 90 100 > 1350                                                             (F1) 1050 - 1350                   (F2) 750 - 1050                              (F3) 500 - 750                                           (F4) 300 - 500          (F5) < 300                                                (F6) Pe rc en t R em o v a l 4000mJ/cm2 and 0 mg/L H2O2 BAC Column 1 ID 32,34 Raw Treated Time 1 Day Time 7 Days218     Figure R-6 - Percent removal results for each of the Peakfit analysed HPSEC chromatograms UV2000mJ/cm2  and 10mg/L H2O2 water samples.  Showing raw, time 0, 1 day, 7day for both BAC Column 1 and BAC Column 2.   0 20 40 60 80 100 120 > 1350                                                             (F1) 1050 - 1350                   (F2) 750 - 1050                              (F3) 500 - 750                                           (F4) 300 - 500          (F5) < 300                                                (F6) Pe rc en t R em o v a l 2000mJ/cm2 and 10 mg/L H2O2 BAC Column 1 ID 3,8,12,13 Raw Treated Time 1 Day Time 7 Days 0 20 40 60 80 100 120 > 1350                                                             (F1) 1050 - 1350                   (F2) 750 - 1050                              (F3) 500 - 750                                           (F4) 300 - 500          (F5) < 300                                                (F6) Pe rc en t R em o v a l 2000mJ/cm2 and 10 mg/L H2O2 BAC Column 1 ID 4,5,9,14 Raw Treated Time 1 Day Time 7 Days219     Figure R-7 - Percent removal results for each of the Peakfit analysed HPSEC chromatograms UV2000mJ/cm2  and 10mg/L H2O2 water samples.  Showing raw, time 0, 1 day, 7day for both BAC Column 1 and BAC Column 0 20 40 60 80 100 120 > 1350                                                             (F1) 1050 - 1350                   (F2) 750 - 1050                              (F3) 500 - 750                                           (F4) 300 - 500          (F5) < 300                                                (F6) Pe rc en t R em o v a l 4000mJ/cm2 and 10 mg/L H2O2 BAC Column 1 ID 1,6,11 Raw Treated Time 1 Day Time 7 Days 0 20 40 60 80 100 120 > 1350                                                             (F1) 1050 - 1350                   (F2) 750 - 1050                              (F3) 500 - 750                                           (F4) 300 - 500          (F5) < 300                                                (F6) Pe rc en t R em o v a l 4000mJ/cm2 and 10 mg/L H2O2 BAC Column 2 ID 2,7,10 Raw Treated Time 1 Day Time 7 Days

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