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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, 2011  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.  ii  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 iii  2.2  Technologies for Removal of NOM......................................................................... 10  2.2.1  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  3.0  Ozonation .......................................................................................................... 10  Oxidation/Biofiltration...................................................................................... 16  2.2.3.1  Principles of Combined Oxidation/Biofiltration ....................................... 16  2.2.3.2  Effect on NOM .......................................................................................... 17  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  3.3  Batch Biodegradation Experiments .................................................................. 31  3.2.3.1  Batch System ............................................................................................. 31  3.2.3.2  Biomass Analysis ...................................................................................... 33  Analytical Methods .................................................................................................. 35  3.3.1  Glassware .......................................................................................................... 35 iv  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 v  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  5.0  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  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  vi  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  vii  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 viii  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  ix  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 x  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  xi  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 17) 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 xii  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  xiii  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  xiv  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  xv  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  xvi  LIST OF EQUATIONS Equation 2-1 H 2 O 2 + h ⋅ v → 2OH • ..................................................................................... 14 Equation 3-1  Equation 3-2  mg / L ⋅ O3 =  ( A ± B) × N × 24,000 ......................................................... 22 mL ⋅ sample  M produced  M aqueous  V sample  =  V sample  −  M gaseous V KI ⋅Trap ⋅1  −  M gaseous V KI ⋅Trap ⋅2  ......................................... 23  Equation 3-3  M consumed M produced M gaseous M gaseous = − − .......................................... 24 Vsample Vsample V KI ⋅Trap ⋅1 V KI ⋅Trap⋅2  Equation 3-4  IT ⋅ (min) = D ×  Vw 1 × V r J UV × wf × 60 s  ............................................. 30  min  1 − 10 − PL × Abs .......................................................................... 30 PL × Abs × ln(10)  Equation 3-5  wf =  Equation 3-6  H 2 O2 [ ppm] = ( A − Ao ) × 10 × D × (0.7776 * S ) ........................................... 30  Equation 3-7   V sample  VColumn ⋅1  × V harvest =  ....................................... 31  QColumn ⋅1  24 hrs × 60 min hr  Equation 3-8  y = a + b exp(−cx) ............................................................................... 33  mgCaCO3 / L =  Vtitred × N × 50,000 .................................................... 36 Vsample  Equation 3-10  mgCaCO3 / L =  Vtitred × 1000 ................................................................. 36 Vsample  Equation 3-11  SUVA =  Equation 3-9  UV254 × 100[L / mg ⋅ m] ............................................................. 37 DOC  xvii  LIST OF ABBREVIATIONS A254 AMW AOC AOP BAC BDOC BOM DBP DBPFP DOC EBCT GAC H2O2 HAA HAA5 HPB HPL HPSEC HS MW NOM SUVA THM TTHM USEPA UV UV/H2O2 UVA UV254  Ultraviolet absorbance at 254nm wavelength Apparent Molecular Weight Assimilable Organic Carbon Advanced Oxidation Process Biologically Activated Carbon Biodegradable Dissolved Organic Carbon Biodegradable Organic Matter Disinfection By-Product Disinfection By-Product Formation Potential Dissolved Organic Carbon Empty Bed Contact Time Granular Activated Carbon Hydrogen Peroxide Haloacetic Acids Combined total of monochloroacetic acid, dichloroacetic acid, trichloroacetic acid, monobromoacetic acid, and dibromoacetic acid. Hydrophobic Fraction Hydrophilic Fraction High Performance Size Exclusion Chromatography Humic Substances Molecular Weight Natural Organic Matter Specific Ultraviolet Absorbance Trihalomethanes Total Trihalomethanes United States Environmental Protection Agency Ultraviolet Advanced Oxidation Process Using Ultraviolet and Hydrogen Peroxide Ultraviolet Absorbance Ultraviolet Absorbance at 254 nm  xviii  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.  xix  DEDICATION  To my friends and waterkeepers in Kep, Cambodia who serve as a source of constant inspiration and motivation in my life.  xx  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.  1  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.  2  •  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.  3  Figure 1-1- Research plan  4  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). biodegradable (Yavich, 1998).  The non-humic fractions are typically more  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 5  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). 6  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.  7  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  8  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).  9  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 10  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 byproducts 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 11  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 Negligible effect (Kleiser and Frimmel, 2000; Ko et al, 2000; Chin and Bérubé, 2005; Chowdhury et al, 2008; Gunten et al., 2009)  TOC  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) 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)  UVA/SUVA  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)  12  Reported Effect  Parameter Polarity  Decrease in hydrophobic fraction from 54% to 5% following ozonation (Swietlik et al., 2004). 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)  MW  88% increase in compounds less than 500Da, large shift from HMW to LMW. (Hozalski et al., 1999) No effect (Kim et al., 1997)  HAAFP  THMFP  Biodegradability  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) 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 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  13  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 H 2 O 2 + h ⋅ v → 2OH •  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 14  (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 2  14.5 % reduction at 1500mJ/cm 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) TOC  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  MW  Polarity  HAAFP  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) 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) 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). 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).  15  Parameter  THMFP THMFP  Reported Effect 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  2.2.3  Increased in BDOC and biodgradability of NOM (Speitel et al., 2000; Liu et al., 2002; Toor and Mohseni, 2007)  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 16  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 17  (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  TOC  Reported Effect 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)  18  Parameter TOC  UVA Polarity MW  Reported Effect 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) 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) 20% decrease in hydrophobicity (Fahmi et al., 2002) 15-50% reduction in MW (Hozalski et al., 1999) 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).  HAAFP  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) 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)  THMFP  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)  19  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.  20  Table 3-1 - Raw water characteristics  3.1.2  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  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. PRESSURE GAUGE  200mL KI Trap FLOW METER  200mL  COMPRESSED  KI Trap  AIR OZONE GENERATOR  O3  2.5L REACTOR  Figure 3-2 - Schematic of ozonation apparatus  21  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  mg / L ⋅ O3 =  ( A ± B) × N × 24,000 mL ⋅ sample  where A = mL titration for sample, B = mL titration for blank and N is the normality of Na2S2O3  22  6. The final ozone production amount was determined as using Equation 3-2.  M produced Equation 3-2  V sample  =  M aqueous V sample  −  M gaseous V KI ⋅Trap ⋅1  −  M gaseous V KI ⋅Trap ⋅2  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. 250  Concentration (mg O3/L)  200 y = 15.367x + 1.9025 R² = 0.9995 150  Ozone Production (mg/L) 100 Trendline: Ozone Production (mg/L) 50  0 0  2  4  6  8  10  12  14  16  Treatment Time (min)  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.  23  Equation 3-3  M consumed M produced M gaseous M gaseous = − − Vsample Vsample V KI ⋅Trap ⋅1 V KI ⋅Trap⋅2 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.  24  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.  Column 2  Column 1  Table 3-2 - Laboratory apparatus characteristics  Parameter Temperature (°C) Volume (mL)  Setting 21 ± 1 22 ± 1  Diameter (cm)  1  Flow Rate (ml//min) EBCT Volume (mL) Diameter (cm)  1.1 20 min 1000 6.5  Flow Rate (ml//min) EBCT  0.2 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) 25  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.  BAC Column 1  BAC Column 2  Feed Tank Effluent Tank 1  Effluent Tank 2  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.  26  Table 3-3 - Picabiol® granular activated carbon properties  Properties Apparent Density (dry, g/mL) Moisture (as packed, %) Ash (wt. %) Iodine No. (mg I2/g GAC) Uniformity Coefficient Effective Size  Particle Size Distribution  Specification 0.18 - 0.26 5 Max 5% Max 900 min < 1.5 0.85 - 1.1 mm On 10 mesh 10x12 mesh 12x14 mesh 14x16 mesh 16x18 mesh 18x20 mesh Through 20 mesh  Actual 0.22 3.3 3.4% 1125 1.41 1.04 3.2% 16.7% 27.6% 27.2% 18.5% 5.4% 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.  27  6 Column 2 Column 1 Dissolved Organic Carbon (mg/L)  5  4  Experimentation Period 3  2  1  0 Aug, 2009 0  Nov, 2009 5000  Feb, 2010  May, 2010  10000 15000 Bed Volumes Filtered  Aug, 2010 20000  25000  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.  28  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 Lamp  Pump  Photoreactor  Storage Tank  Heat Exchanger  Figure 3-7 - Experimental semi-batch UV/H2O2 reactor  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,  29  irradiation times were calculated based on Equation 3-4 and Equation 3-5 as described in Bolten and Linden (2003). Equation 3-4  Equation 3-5  IT ⋅ (min) = D ×  Vw 1 × V r J UV × wf × 60 s  min  1 − 10 − PL × Abs wf = PL × Abs × ln(10) 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  H 2 O2 [ ppm] = ( A − Ao ) × 10 × D × (0.7776 * S ) 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.  30  Table 3-4 - UV/H2O2 experiment conditions  3.2.3  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  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   V sample  VColumn ⋅1  × V harvest =   QColumn ⋅1  24 hrs × 60 min hr 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, 31  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  Separate experiments performed using both BAC Column 1 & 2  Oxidant  Dose  None Ozone Ozone  -  Ozone AOP AOP AOP  Reaction Times  1 mg/ mg DOC 2 mg/ mg DOC Extended Dose (≈25 mg/mg DOC)  4, 8, 12, 18 hrs; 1, 2, 3, 4, 5, 6, 7 days  2000 mJ/cm2 & 10 mg/L H2O2 4000 mJ/cm2 & 10 mg/L H2O2 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.  32  Equation 3-8  y = a + b exp(−cx) 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 33  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. 5 4.5 4  DOC (mg/L)  3.5 3  0.1 Sodium Azide 0.01 Sodium Azide  2.5  0.05 Sodium Azide 2  Blank 1  1.5  Blank 2  1 0.5 0 0  1  2  3  4  5  6  7  Time (Days)  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.  34  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, Teflonlined 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.  35  •  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.  mgCaCO3 / L =  Equation 3-9  Vtitred × N × 50,000 Vsample  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  mgCaCO3 / L =  Vtitred × 1000 Vsample  where Vtitred is the volume of titrant used, and Vsample is the volume of sample used (25mL). 36  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  SUVA =  UV254 × 100[L / mg ⋅ m] DOC  where UV254 is the absorbance at 254nm (cm-1) and DOC is the dissolved organic carbon content (mg/L).  37  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.  38  4.00  Calibration Data 3.80  Standard Run Checks 3.60  y = -0.3752x + 6.2864 R² = 0.9975  Log ( MW [Da] )  3.40 3.20 3.00 2.80 2.60 2.40 2.20 2.00 5.5  6  6.5  7  7.5  8  8.5  9  Retention Time (min)  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.  39  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 . 40  Table 3-6 - Autofit Peak III deconvolution parameters  Parameter  Setting  Peak Type  Extreme Value 4 Parameter Tailed (Amplitude)  Response Width Response Width Defined at Frequency Domain Filter Amplitude Rejection Threshold Minimum R2 Value  20s Full Width at HalfMaximum 60% 4% > 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).  41  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.  42  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 Incubation Time  20.0 ± 1.0 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.  43  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. 44  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 Injector Type Temperature Detector Type Temperature Oven Initial Temperature Ramp Final Temperature  Setting Splitless 90°C ECD 260°C 30°C, hold for 2 minutes 6°C/min 120°C  Retention times for each of the compounds are summarized in Table 3-9.  45  Table 3-9 - THM retention times (min)  Compound  Retention Time (min)  Chloroform  6.552  Bromodichloromethane Dibromochloromethane IS (1,2 DBP) Bromoform  9.876 13.553 15.6 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.  46  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 HAAesters. 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 47  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 Injector Type Temperature Detector Type Oven Initial Temperature Ramp Final Temperature  Setting Splitless 200°C MS 30°C, hold for 8 minutes 5°C/min for 16 minutes 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  MCAA MBAA DCAA TCAA BCAA IS (1,2,3 TCP) DBAA BDCAA CDBAA Surrogate (2,3 DBPA) TBAA  105 152 83 117 127 75 173 163 205 165 251  64, 77 93, 121 87, 85 119, 141 129, 131 110, 112 171, 175 141, 161 207, 209 167 253, 231  Retention Time (min) 9.124 12.218 12.81 16.002 16.264 16.481 19.27 19.468 22.658 22.72 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.  48  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).  49  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.  Dissolved Organic Carbon (mg/L)  6 5 4 3  2 1 0 Raw Water  Feed Effluent Effluent Effluent Effluent Effluent Effluent Effluent Effluent from from from from from from from Water from (2mg/mg BAC BAC BAC BAC BAC BAC BAC BAC DOC) Column Column Column Column Column Column Column Column 1.1 1.2 1.3 1.4 2.1 2.2 2.3 2.4  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.  50  6  0 -5  Dissolved Organic Carbon (mg/L)  5  4  3 -53  2 -76 1  0 Raw Water  Feed Water (2mg O3/mg DOC)  Effluent from BAC Column 1  Effluent from BAC Column 2  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.  51  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.  Specific UV Absorbance (SUVA)  4 4 3 3 2 2 1 1 0 Raw Water  Feed Effluent Effluent Effluent Effluent Effluent Effluent Effluent Effluent Water from from from from from from from from (2mg/mg BAC BAC BAC BAC BAC BAC BAC BAC DOC) Column Column Column Column Column Column Column Column 1.1 1.2 1.3 1.4 2.1 2.2 2.3 2.4  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.  52  4  0.180 0  0.160  3  0.140  0  0.120  -30 3 -26  0.100  -29  2 -50 2  -65  0.080 0.060  1  UV Absorbance (UVA)  Specific UV Absorbance (SUVA)  4  0.040 -88  1  0.020  0  0.000 Raw Water  Feed Water (2mg O3/mg DOC)  Effluent from BAC Effluent from BAC Column 1 Column 2  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 53  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. 9.00E-03  Raw Water  Response (Absorbance @ 260nm)  8.00E-03  Feed Water (2mg O3/mg DOC)  7.00E-03  Effluent from BAC Column 1  6.00E-03 Effluent from BAC Column 2 5.00E-03 4.00E-03 3.00E-03 2.00E-03 1.00E-03 0.00E+00 0.01  0.1  1  10  100  MW [kDa]  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 54  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.  0.25  Raw Water Feed Water (2 mgO3/mg DOC)  0.2  Effluent from BAC Column 1  0  Effluent from BAC Column 2  Area Count  0  0  0.15 -47  0  0 0.1  -2  -55 -52  -52  -64  0  -35  -23  -68  0.05  -70 -91  -90  -89  -68 -69 -88  -89  -86  0 > 1350 (F1)  1050 - 1350 (F2)  750 - 1050 500 - 750 300 - 500 (F3) (F4) (F5) Apparent Molecular Weight (Da)  < 300 (F6)  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 2 mgO3/mg DOC BAC Column 1 BAC Column 2  0 (15) -47 (39) -55 (21) -91 (26)  0 (7) -52 (20) -64 (8) -90 (17)  0 (7) -52 (4) -68 (7) -89 (18)  0 (11) -35 (14) -70 (10) -89 (21)  0 (13) -23 (17) -69 (6) -88 (17)  0 (11) -2 (18) -68 (6) -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. 55  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.  56  450 400  0  350  THM4 FP  Concentration (ug/L)  0  HAA9 FP  300 250 -45 200 -44  -60  150  Health Canada THM Guideline (2010) 100 50  -67  Health Canada HAA Guideline (2010)  -80  -87  0 Raw Water  Feed Water (2mg O3/mg DOC)  Effluent from BAC Column 1  Effluent from BAC Column 2  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).  57  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. 250 Chloroform (ug/L) 0  Bromodichloroform (ug/L) Dibromochloroform (ug/L)  200  Concentration (ug/L)  Bromoform (ug/L)  150 -52 100  Health Canada THM Guideline (2010)  0 -67 -36  50  0  -73  -20  -92 -54  0  -16  -37  -88  -66  101  0 Raw Water  Feed Water (2mg O3/mg DOC)  Effluent from BAC Column 1  Effluent from BAC Column 2  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 58  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. 300 DCAA (ug/L) TCAA (ug/L) MCAA (ug/L)  250  Concentration (ug/L)  0  200  150  0 -50 -27  Health Canada HAA Guideline (2010)  100  -61 -64  50  -88 0  -70  -59  -73  -97  0 Raw Water  Ozonated (2mg O3/mg DOC)  BAC Column 1  BAC Column 2  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  59  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. 6 0 5  -3%  -3% -13%  3  DOC (mg/L)  4 -38% -44% -60%  2  1  0 Raw Water  Ozonated Ozonated Ozonated UV 1mg/mg DOC 2mg/mg DOC Extended Dose 4000mJ/cm2 & 0mg/L H2O2  UV 2000mJ/cm2 & 10mg/L H2O2  UV 4000mJ/cm2 & 10mg/L H2O2  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.)  60  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.  61  3.5  0.18 0  -7%  0 3  1.5  1  0.14 -28%  -18%  -19% -30%  -45% -65% -51%  UV Absorbance (UVA)  2  0.16  UVA  -15% Specific UV Absorbance (SUVA)  2.5  SUVA  0.12 0.1 0.08 0.06  -70% 0.04  -79% 0.5  -81%  0  0.02 0  Raw Water  Ozonated 1mg/mg DOC  Ozonated 2mg/mg DOC  Ozonated Extended Dose  UV UV UV 4000mJ/cm2 2000mJ/cm2 4000mJ/cm2 & 0mg/L & 10mg/L & 10mg/L H2O2 H2O2 H2O2  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. 62  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.  63  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. 64  0.25  0.2  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 Ozonation  0 0 0  Area Count  0.15  -11 19  -24 -45 -55  0.1  10  -22  -47  0  0 -8  -37 -52  -52  -35  0  4 -7  0.05  -70 -81  -23  -50  -61  -80 -78  -67 -95  -2  -8  -92  -85  -90  -94 -98  -86 -100  -96  -97  -99  0 > 1350 (F1)  1050 - 1350 (F2)  750 - 1050 (F3)  500 - 750 (F4)  300 - 500 (F5)  < 300 (F6)  Molecular Weight (Da)  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.  65  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 1 mgO3/mg DOC 2 mgO3/mg DOC  0 (15) -55 (13) -47 (39)  0 (7) -37 (19) -52 (20)  0 (7) -22 (19) -52 (4)  0 (11) -8 (9) -35 (14)  0 (13) 4 (5) -23 (17)  0 (11) 19 (9) -2 (18)  2000 mJ/cm2 & 10mg/L H2O2  -80 (28)  -80 (13)  -70 (7)  -61 (7)  -67 (6)  -50 (6)  -95 (13)  -94 (34)  -90 (16)  -85 (8)  -86 (20)  -78 (19)  -45 (21) -92 (0)  -24 (10) -98 (0)  -11 (2) -100 (0)  -8 (3) -99 (0)  -7 (15) -97 (0)  10 (18) -96 (0)  2  4000 mJ/cm & 10mg/L H2O2 2  4000 mJ/cm & 0mg/L H2O2 Extended Ozonation  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).  66  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. 600  Health Canada HAA Guideline (2010) Health Canada THM Guideline (2010) 500 22  THM4 FP HAA9 FP  0  Concentration (ug/L)  400  -5 0 -5  300  -6 -16  -28  -45  200  -50  -44  -45  -64 100 -92 0 Raw  Water  4000 mJ/cm2 2000 mJ/cm2 4000 mJ/cm2 Ozonated Ozonated Extended & 0 mg/L & 10 mg/L & 10 mg/L (1mg O3/mg (2mg O3/mg Ozonation DOC) DOC) (25mg O3/mg H2O2 H2O2 H2O2 DOC)  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 67  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.  68  300 Chloroform (ug/L) Bromodichloroform (ug/L) 250  Dibromochloroform (ug/L) Bromoform (ug/L)  Concentration (ug/L)  0 200  -14  Health Canada THM Guideline (2010) -27  150 -40  -41 100  0  3  -2  81 50  43  125  75  -36  -54  0 0  -52  13  349  -52 -54  -20 163  -60 32 -88 646  -16  0 Raw Water 4000 mJ/cm2 2000 mJ/cm2 4000 mJ/cm2 Ozonated Ozonated Extended & 0 mg/L & 10 mg/L & 10 mg/L (1mg O3/mg (2mg O3/mg Ozonation H2O2 DOC) DOC) (25 mgO3/mg H2O2 H2O2 DOC)  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 69  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.  70  350 DCAA (ug/L) TCAA (ug/L)  37  300  MCAA (ug/L)  Concentration(ug/L)  250  8 0  200  Health Canada HAA -27  10  150  Guideline (2010)  -33  0  -16 -50 -27  100  -37  -74  50 0  53  2  -88 -88  -5  -70  -94  -100  0 Raw Water  Ozonated Extended 4000 mJ/cm2 2000 mJ/cm2 4000 mJ/cm2 Ozonated & 0 mg/L & 10 mg/L & 10 mg/L (1mg O3/mg (2mg O3/mg Ozonation DOC) DOC) (25 mg O3/mg H2O2 H2O2 H2O2 DOC)  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 71  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  2  coefficient of correlation (R ) 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. 2.5  Generated Curve Fit  2  90% Confidence Interval  DOC (mg/L)  Actual Data 1.5  1  0.5  0 0  1  2  3  4  5  6  7  8  Time (Days)  Figure 4-17 - Typical biodegradation curve (Showing 90% confidence interval of fitted curve)  72  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 Raw Water 4000 mJ/cm2 & 0 mg/L H2O2 2000 mJ/cm2 & 10 Biomass mg/L H2O2 from 4000 mJ/cm2 & 10 BAC mg/L H2O2 Column Ozonated (1mg O3/mg 1 DOC) Ozonated (2mg O3/mg DOC) Extended Ozonation (25mg O3/mg DOC) Raw Water 4000 mJ/cm2 & 0 mg/L H2O2 2000 mJ/cm2 & 10 Biomass mg/L H2O2 from 4000 mJ/cm2 & 10 BAC mg/L H2O2 Column Ozonated (1mg O3/mg 2 DOC) Ozonated (2mg O3/mg DOC) Extended Ozonation (25mg O3/mg DOC)  Average DOCnon (a) 2.546 (±0.182)  DOCi (b) 2.069 (±0.857)  kDOC(c) 1.857 (±0.505)  2.464 (±0.248)  1.760 (±0.169)  1.751 (±0.834)  1.288 (±0.227)  1.425 (±0.605)  2.300 (±0.668)  0.878 (±0.136)  1.070 (±0.301)  2.604 (±0.389)  2.942 (±0.320)  2.102 (±0.692)  1.632 (±0.686)  2.816 (±0.105)  1.807 (±0.219)  1.632 (±0.462)  0.8467 (±0.018)  1.947 (±0.240)  0.626 (±0.062)  2.383 (±0.250)  2.680 (±0.280)  2.223 (±0.907)  2.030 (±0.300)  2.087 (±0.076)  1.687 (±1.149)  1.255 (±0.653)  1.302 (±0.419)  1.780 (±0.527)  0.962 (±0.010)  0.863 (±0.417)  1.490 (±0.589)  2.570 (±0.153)  2.509 (±0.563)  1.916 (±1.180)  2.429 (±0.176)  2.127 (±0.101)  1.614 (±0.940)  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.  73  3.500  BAC Column 1  0  DOCnon (mg/L)  2.500  BAC Column 2  16  3.000 -3  11 8  0  2 -15  2.000 -49  1.500  -47 -66  1.000  -60  -67 -73  0.500 0.000 Raw Water  4000 2000 4000 Ozonated Ozonated Extended mJ/cm2 & 0 mJ/cm2 & mJ/cm2 & (1mg O3/mg (2mg O3/mg Ozonation mg/L H2O2 10 mg/L DOC) DOC) 10 mg/L (25mg H2O2 H2O2 O3/mg DOC)  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  74  biodegradable organic matter (BAC Column 2) was no better at biodegrading the nonbiodegradable 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. 3.500  Parameter c - Kinetic Rate Constant (k)  BAC Column 1  3.000  BAC Column 2  40 24  2.500 2.000  0 0  -6 -24  -14  -20  -12 -33  -12  -27  1.500 1.000 -66 -80 0.500 0.000 Raw Water 4000 mJ/cm2 2000 mJ/cm2 4000 mJ/cm2 Ozonated Ozonated Extended & 0 mg/L & 10 mg/L & 10 mg/L (1mg O3/mg (2mg O3/mg Ozonation H2O2 H2O2 H2O2 DOC) DOC) (25mg O3/mg DOC)  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).  75  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 76  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. 8.00E-03  Raw Treated 4 hours 8 hours 12 hours 18 hours 1 Day 2 Days 3 Days 4 Days 5 Days 6 Days 7 Days  7.00E-03 6.00E-03  Response  5.00E-03 4.00E-03 3.00E-03 2.00E-03 1.00E-03 0.00E+00 0.01 -1.00E-03  0.1  1  10  100  MW [kDa]  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.  77  1.00E-02 Raw Treated  8.00E-03  Response  Time 1 day 6.00E-03  Time 7 day  4.00E-03  2.00E-03  0.00E+00 0.01  0.1  1 MW [kDa]  10  100  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.  78  0.35  Feed Water - BAC Column 1 1 Day Biodegradation - BAC Column 1 7 Day Biodegradation - BAC Column 1  0.3  Feed Water - BAC Column 2  0  1 Day Biodegradation - BAC Column 2  0  Area Count  0.25  7 Day Biodegradation - BAC Column 2  0.2  0  0 -37 0.15  0 -51  0 -34  -70  0  -36  0.1 -74  -60  -60  0  0  -52 -50  -39  -48 -70  -75  0.05  -62  0  -57 -72  0 -26 -52  0 -50 -63  -65  -64  -66  0 > 1350 (F1)  1050 - 1350 (F2)  750 - 1050 (F3)  500 - 750 (F4)  300 - 500 (F5)  < 300 (F6)  Molecular Weight (Da)  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.)  79  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.  80  0.16  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 2  0.14 0  0 0.12  0  0  0  0  Area Count  0.1  0  0 0  -33  0  -54  0.08 -33  0  0  -50 -54  -58 0.06  -45 -55  -54  -49 -65  -49 -65  0.04  -68  -69  -60 -66  -72  -67  -42 -65  -55  -62 -60  0.02  0 > 1350 (F1)  1050 - 1350 (F2)  750 - 1050 (F3)  500 - 750 (F4)  300 - 500 (F5)  < 300 (F6)  Molecular Weight (Da)  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.)  81  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.  82  0.16  Feed Water - BAC Column 1 1 Day Biodegradation - BAC Column 1  0.14  7 Day Biodegradation - BAC Column 1 Feed Water - BAC Column 2  0.12 0  1 Day Biodegradation - BAC Column 2  0  0  0  7 Day Biodegradation - BAC Column 2 Area Count  0.1 -33 0.08  0  0  -39  -52  0 -52  0.06  -29  -32 0  0 -50  -23 -25 -35  -46  -59  -48 -58  0.04  0  -59  -46 -47  -50  -51  0  0  -39  -25 -43  -39 -45  0.02  0 > 1350 (F1)  1050 - 1350 (F2)  750 - 1050 (F3)  500 - 750 (F4)  300 - 500 (F5)  < 300 (F6)  Molecular Weight (Da)  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.)  83  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.  84  0.07  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 2  0.06  0.05  0 -7 -16 0 -12  Area Count  -14 0.04  0.03 0 0 22  0 -1  0.02  24 34 37 -44  0  0.01  0 -63 -56  -22  48  0  0 -45  -7 1 0  -48  0 -30 -42 0 -34 -41  -94 -89 0 > 1350 (F1)  1050 - 1350 (F2)  750 - 1050 (F3)  500 - 750 (F4)  300 - 500 (F5)  < 300 (F6)  Molecular Weight (Da)  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.)  85  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.  86  0.16  0  0.14 15  24  0  0  0  0.12 0  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 2  -16 0  0  Area Count  0.1  0.08  0  0  0  -44 -52 -39  0.06  -59  -60  -68 -71  0.04  0  0  -58  -61  -73  -76 -82  -79  -58  -76 -83  0.02  -81 -73  -78  -89  -85 0 > 1350 (F1)  1050 - 1350 (F2)  750 - 1050 (F3)  500 - 750 (F4)  300 - 500 (F5)  < 300 (F6)  Molecular Weight (Da)  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.)  87  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.  88  0.07  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 2  0.06  0.05  0  0  0  0  Area Count  0  0  0  0.04 -33  0 -54 0.03  -21  -49  0 -56  -49  0  -50 -52  -57  -50  0  0 -57  0.02  -68  -45  -62  -62  -58  -54 -52  -65  -56  -32 -45 -60 -60  0.01  0 > 1350 (F1)  1050 - 1350 (F2)  750 - 1050 (F3)  500 - 750 (F4)  300 - 500 (F5)  < 300 (F6)  Molecular Weight (Da)  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.)  89  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.  90  0.035  Feed Water - BAC Column 1 1 Day Biodegradation - BAC Column 1 7 Day Biodegradation - BAC Column 1  0.03  Feed Water - BAC Column 2 1 Day Biodegradation - BAC Column 2 7 Day Biodegradation - BAC Column 2  0.025  0 0  Area Count  29 19  0.02 65  54  61 30 0.01  0  0 -11  -9  0 20  2  0  -24 0  0 -18  54  0.015  8  0  -31  1  -41 -35  -18  9  0  0  0 -19  -2  -28 -11  0.005  0 > 1350 (F1)  1050 - 1350 (F2)  750 - 1050 (F3)  500 - 750 (F4)  300 - 500 (F5)  < 300 (F6)  Molecular Weight (Da)  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.)  91  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.  92  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.  93  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. 94  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 preoxidation 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. 95  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 preoxidant 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 96  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.  97  7. Future work should investigate the effect of these treatment processes on membrane fouling.  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In Proceedings of the 16th International Ozone Congress, Las Vegas, NV. Xie, Y.F. & Zhou, H. (2001). Biologically active carbon for HAA removal: Column study. In Proceedings from the 2001 AWWA Water Quality Technology Conference. Nashville, TN. Xie, Y.F., & Zhou, H., (2002). Use of BAC for HAA removal, Part 2: Column study. Journal of American Water Works Association, 94(5), 126 - 135. Xie, Y. F. (2004). Disinfection Byproducts in Drinking Water: Formation, analysis, and control. New York, NY: Lewis Publishers. Yavich, A.A. (1998). The use of ozonation and biological fluidized bed treatment for the control of NOM in drinking water. (Doctoral Dissertation), Michigan State University, East Lansing, MI. Yavich, A.A., Lee, K.H., Chen, K.C., Papa, L. & Masten, S.J. (2004). Evaluation of biodegradability of NOM after ozonation. Water Research, 38(12), 2839 - 2846.  108  APPENDIX A.  OZONATION CALIBRATION DATA  ID  Date  Calibration  Table A-1 - Ozone calibration data  July 19th, 2010 July 19th, 2010 July 20th, 2010 July 20th, 2010 July 21st, 2010 July 21st, 2010 July 21st, 2010 July 21st, 2010 July 21st, 2010 July 22nd, 2010 July 22nd, 2010 July 23rd, 2010 July 25th, 2010 July 25th, 2010 July 31st, 2010 August 8th, 2010  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)  3.00  0.01  20.8  21  0  0.2  50.16  100.32  0.096  100.224  50.112  6.00  0.01  38.7  39.7  0  0.3  94.08  188.16  0.144  188.016  94.008  2.50  0.01  16.1  16.5  0  0.2  39.12  78.24  0.096  78.144  39.072  5.00  0.01  31.7  33.5  0  0.3  78.24  156.48  0.144  156.336  78.168  2.50  0.01  16.5  16.4  0  0.2  39.48  78.96  0.096  78.864  39.432  1.00  0.01  8.5  8.6  0  0.1  20.52  41.04  0.048  40.992  20.496  0.50  0.01  3.8  3.7  0  0.1  9  18  0.048  17.952  8.976  0.25  0.01  1.9  2  0  0  4.68  9.36  0  9.36  4.68  0.50  0.01  3.8  3.6  0  0.1  8.88  17.76  0.048  17.712  8.856  0.50  0.01  3.7  3.6  0  0.1  8.76  17.52  0.048  17.472  8.736  0.75  0.01  5.4  5.6  0  0.1  13.2  26.4  0.048  26.352  13.176  0.75  0.01  5.6  5.8  0  0.1  13.68  27.36  0.048  27.312  13.656  0.67  0.01  5  4.8  0  0.1  11.76  23.52  0.048  23.472  11.736  0.50  0.01  3.8  3.8  0  0.1  9.12  18.24  0.048  18.192  9.096  15.00  0.01  96.4  96.7  0  0.1  231.72  463.44  0.048  463.392  231.696  5.00  0.01  33.7  33.9  0  0.1  81.12  162.24  0.048  162.192  81.096  109  Table A-2 - Ozone treatment data  Treatment  ID  703 1.1 704 1.1 705 1.1 706 1.1 710 1.1 714 1.1 715 1.1 718 1.1 719 1.4 720 1.1 721 1.1 721 2.1 721 2.2 721 2.3 721 2.4 723 1.1 723 1.1 723 1.2 724 1.1 725 1.1 725 1.2 730 1.1 731 1.1 731 1.2 731 1.3 801 1.1 803 1.1 808 1.1 815 1.1 825 1.1 825 1.2  Date  July 3rd, 2010 July 4th, 2010 July 5th, 2010 July 6th, 2010 July 10th, 2010 July 14th, 2010 July 15th, 2010 July 18th, 2010 July 19th, 2010 June 20th, 2010 July 21st, 2010 July 21st, 2010 July 21st, 2010 July 21st, 2010 July 21st, 2010 July 23rd, 2010 July 23rd, 2010 July 23rd, 2010 July 24th, 2010 July 25th, 2010 July 25th, 2010 June 30th, 2010 July 31st, 2010 July 31st, 2010 July 31st, 2010 August 1st, 2010 August 2nd, 2010 August 8th, 2010 August 25th, 2010 August 25th, 2010 August 25th, 2010  Time (min) 0.75 0.75 0.75 0.75 0.75 0.75 0.75 0.75 0.5 0.75 2.5 0.5 0.5 0.5 0.5 0.75 0.75 0.75 0.75 0.75 0.75 0.75 15 0.75 30 45 0.5 5 0.75 2.5 5  N Sodium Thiosulfate 0.01 0.01 0.01 0.01 0.01 0.01 0.01 0.01 0.01 0.01 0.01 0.01 0.01 0.01 0.01 0.01 0.01 0.01 0.01 0.01 0.01 0.01 0.01 0.01 0.01 0.01 0.01 0.01 0.01 0.01 0.01  Primary KI Trap Titration 1.9 1.7 1.4 1.9 2.3 3 2.6 3.2 19 2.8 65 13.7 4.3 0.9 3.1 2.8 3.4 3.8 2.8 25.1 23.9 2.5 46.2 3.4 220 305 3.6 230 1.8 74 236  Secondary Trap KI Titration 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.8 0.1 80 105 0.1 0.8 0.1 75 234  mg O3 (200ml Trap 1) 0.888 0.792 0.648 0.888 1.08 1.416 1.224 1.512 9.12 1.32 31.32 6.624 2.088 0.408 1.488 1.32 1.608 1.872 1.32 12.096 11.424 1.176 22.728 1.608 106.56 147.6 1.752 110.88 0.84 35.76 112.8  mg O3 (200ml Trap 2) 0.048 0.048 0.048 0.048 0.048 0.048 0.048 0.048 0.048 0.048 0.048 0.048 0.048 0.048 0.048 0.048 0.048 0.048 0.048 0.048 0.048 0.048 0.384 0.048 38.4 50.4 0.048 0.384 0 0.24 0.288  Total O3 Produced (mg) 20.1456 20.2416 20.3856 20.1456 19.9536 19.6176 19.8096 20.1936 9.024 19.7136 47.496 11.52 16.056 17.736 16.656 22.39344 19.4256 25.392 19.7136 11.328 12 19.8576 440.28 25.656 781.824 1192.176 16.392 50.928 20.1936 42.864 49.104  Total O3 Produce d (mg/L) 10.0728 10.1208 10.1928 10.0728 9.9768 9.8088 9.9048 10.0968 4.512 9.8568 23.748 5.76 8.028 8.868 8.328 11.19672 9.7128 12.696 9.8568 5.664 6 9.9288 220.14 12.828 309.576 434.568 8.196 25.464 10.0968 21.432 24.552  DOC Raw Water (mg/L) 4.8763 5.1247 4.9957 4.9875 5.3112 4.8865 4.9876 4.8995 5.164 5.0134 5.2443 5.2853 4.8346 4.7217 4.596 5.0646 4.9876 5.1337 5.0646 4.7393 4.6721 5.2347 4.4398 4.8264 4.0277 5.7945 4.8913 4.9583 4.8995  5.1225 4.6883  Total O3 Produced (mg O3/mg DOC ) 2.0657 1.9749 2.0403 2.0196 1.8784 2.0073 1.9859 2.0608 0.8737 1.9661 4.5283 1.0898 1.6605 1.8781 1.8120 2.2108 1.9474 2.4731 1.9462 1.1951 1.2842 1.8967 49.5833 2.6579 76.8617 74.9966 1.6756 5.1356 2.0608 4.1839 5.2369  110  APPENDIX B.  UV/H2O2 TREATMENT DATA Table B-1- UV/ H2O2 experiment conditions  ID Jphh 06/23 1.1 Jphh 06/23 1.2 Jphh 06/23 1.3 Jphh 06/23 1.4 Jphh 06/23 2.1 Jphh 06/23 2.2 Jphh 06/23 2.3 Jphh 06/23 2.4 Jphh 06/26 1.1 Jphh 06/26 1.2 Jphh 06/26 1.3 Jphh 06/26 1.4 Jphh 06/26 2.1 Jphh 06/26 2.2 Jphh 06/26 2.3 Jphh 06/26 2.4 Jphh 06/26 3.1 Jphh 06/26 3.2 Jphh 06/27 1.1 Jphh 06/27 1.2 Jphh 06/27 1.3 Jphh 06/27 1.4  Irradiation Time, IT (min)  H2O2 Dose  Bovine Liver Stock Concentration (mg/L)  Bovine Liver Dosing (mL)  1000  32.7  0 mg/L  500  0.4  2000  1000  32.7  0 mg/L  500  0.4  0.91483  4000  1000  65.4  0 mg/L  500  0.4  0.159  0.91381  4000  1000  65.5  0 mg/L  500  0.4  0.151  0.9179  2000  1000  32.6  500  0.4  0.155  0.91585  2000  1000  32.7  500  0.4  0.157  0.91483  4000  1000  65.4  500  0.4  0.152  0.91739  4000  1000  65.3  500  0.4  0.154  0.91637  2000  900  29.4  500  0.36  0.153  0.91688  2000  900  29.4  500  0.36  0.142  0.92254  4000  900  58.4  500  0.36  0.149  0.91893  4000  900  58.6  500  0.36  0.172  0.90721  2000  1500  49.5  500  0.6  0.169  0.90873  4000  1500  98.8  500  0.6  0.148  0.91944  4000  1500  97.7  0 mg/L  500  0  0.157  0.91483  4000  1500  98.2  0 mg/L  500  0  0.156  0.91534  2000  1500  49.1  0 mg/L  500  0  0.156  0.91534  4000  1500  98.1  0 mg/L  500  0  0.175  0.9057  4000  1500  99.2  500  0.6  0.172  0.90721  4000  1500  99.0  500  0.6  0.158  0.91432  2000  1500  49.1  500  0.6  0.157  0.91483  2000  1500  49.1  500  0.6  UV Dose Volume (mJ/cm2) (mL)  UVA254 (cm-1)  wf  0.155  0.91585  2000  0.157  0.91483  0.157  10 mg/L 10 mg/L 10 mg/L 10 mg/L 10 mg/L 10 mg/L 10 mg/L 10 mg/L 10 mg/L 10 mg/L  10 mg/L 10 mg/L 10 mg/L 10 mg/L  111  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.  112  7  Additional Volatilization (%)  6 5 4 3  Slow Fast  2 1 0  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.  113  Table C-1 - Volatilization of harvested GAC Virgin GAC Volatilization Dish Weight  ID  Dish + GAC  Virgin GAC 1.1080 3.6082 Virgin GAC 1.0791 2.7499 Virgin GAC 1.1087 2.1020 Virgin GAC 1.0804 1.8907 Filter GAC Volatilization  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  3.2279 2.4750 1.8805 1.7017  3.2440 2.5583 1.8140 1.7644  1.4803 1.3025 1.1887 1.1553  2.1199 1.3959 0.7718 0.6213  2.1360 1.4792 0.7053 0.6840  0.3723 0.2234 0.0800 0.0749  82.5702 84.8972 88.6573 89.0497  86.2936  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  Slow Slow Slow Slow Slow Slow Slow Slow Slow Slow Slow Fast Fast Fast  1.1018 1.0904 1.0962 1.0760 1.0753 1.1074 1.0786 1.1014 1.0900 1.0957 1.0758 1.1008 1.0895 1.0952  5.4954 4.9891 4.6407 4.9307 2.1236 2.0499 2.2287 5.7544 4.8918 3.5090 4.5127 1.8131 2.1716 2.4319  3.9964 3.5212 3.1389 3.2027 1.5761 1.5153 1.5821 4.1847 3.4525 2.3734 2.9312 1.3852 1.6189 1.8488  2.0057 1.9736 1.8791 1.9158 1.3323 1.3559 1.3652 2.2448 1.9876 1.6688 1.9011 1.2878 1.3245 1.3813  1.1784 1.1632 1.1611 1.1466 1.0946 1.1268 1.1019 1.1926 1.1604 1.1397 1.1396 1.1177 1.1115 1.1219  2.8946 2.4308 2.0427 2.1267 0.5008 0.4079 0.5035 3.0833 2.3625 1.2777 1.8554 0.2844 0.5294 0.7536  0.9039 0.8832 0.7829 0.8398 0.2570 0.2485 0.2866 1.1434 0.8976 0.5731 0.8253 0.1870 0.2350 0.2861  0.0766 0.0728 0.0649 0.0706 0.0193 0.0194 0.0233 0.0912 0.0704 0.0440 0.0638 0.0169 0.0220 0.0267  0.1239 0.1211 0.1073 0.1151 0.0352 0.0341 0.0393 0.1567 0.1230 0.0786 0.1131 0.0256 0.0322 0.0392  0.0766 0.0728 0.0649 0.0706 0.0193 0.0194 0.0233 0.0912 0.0704 0.0440 0.0638 0.0169 0.0220 0.0267  5.2320 5.4636 5.4167 5.2996 6.1830 5.9166 5.5639 5.7302 5.8632 6.0288 5.9759 4.6929 4.3273 4.3588  Average  5.6976  4.4597  114  APPENDIX D.  BIOFILTRATION RESULTS FOR TOC AND UVA Table D-1- DOC, UVA data for biofiltration  ID  Raw Water DOC (Std Dev)  UVA  SUVA  ID  Treated Water (2mg/mg DOC) 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 7/05 1.1 7/06 1.1 7/07 1.1 7/07 1.2 7/10 1.1 7/14 1.1 7/15 1.1 7/18 1.1 7/19 1.1 7/19 1.4 7/20 1.1 7/21 1.1 7/21 2.1 7/21 2.2 7/21 2.3 7/21 2.4 7/23 1.1 7/23 1.2 7/24 1.1 7/25 1.1 7/25 1.2 7/30 1.1 7/31 1.1 7/31 1.2 7/31 1.3 8/01 1.1 8/03 1.1 803 1.1 825 1.1  5.1247 4.9957 4.9875 5.1104 4.9583 5.3112 4.8865 4.9876 4.8995 5.0896 5.6839 5.0134 5.2853 4.91 4.8346 4.7217 4.596 5.0646 5.1337 5.0646 4.7393 4.6721 5.2347 4.4398 4.8264 4.0277 5.7945 4.8913 4.9223 4.8995  0.075093 0.073391 0.059522 0.0673 0.0489 0.068035 0.08278 0.034424 0.061799 0.1007 0.0821 0.0827 0.0576 0.0704 0.1403 0.132 0.0673 0.0543 0.0446 0.000525 0.1165 0.0547 0.070709 0.006 0.0809 0.1319 0.1627 0.1422 0.056908 0.007096  0.156 0.125 0.162 0.194 0.136 0.190 0.163 0.130 0.166 0.173 0.176 0.127 0.181 0.162 0.128 0.163 0.160 0.158 0.160 0.203 0.163 0.169 0.153 0.141 0.174 0.150 0.193 0.159 0.152 0.153  3.038 2.493 3.247 3.802 2.743 3.585 3.334 2.598 3.396 3.399 3.096 2.527 3.425 3.299 2.648 3.452 3.481 3.120 3.117 4.004 3.439 3.617 2.923 3.176 3.605 3.724 3.331 3.251 3.088 3.123  7/04 1.1 7/05 1.1 7/06 1.1 7/07 1.1 7/07 1.2 7/10 1.1 7/14 1.1 7/15 1.1 7/18 1.1 7/19 1.1 7/19 1.4 7/20 1.1 7/21 1.1 7/21 2.1 7/21 2.2 7/21 2.3 7/21 2.4 7/23 1.1 7/23 1.2 7/24 1.1 7/25 1.1 7/25 1.2 7/30 1.1 7/31 1.1 7/31 1.2 7/31 1.3 8/01 1.1 8/03 1.1 803 1.1 825 1.1  4.868465 4.745915 4.738125 4.85488 4.710385 5.04564 4.642175 4.73822 4.654525 4.7845 4.837635 4.7154 5.021035 4.6411 4.7154 4.391181 4.45812 4.8959 5.0439 4.834086 4.765542 4.578658 5.339394 4.7633 4.8694 3.62493 5.21505 4.40217 4.43007 4.40955  0.072941 0.034136 0.064205 0.030808 0.080567 0.09385 0.08996 0.065116 0.055671 0.0555 0.048563 0.1029 0.003186 0.0346 0.1029 0.014173 0.062726 0.0523 0.0918 0.062503 0.099263 0.017186 0.029089 0.077378 0.0209 0.036364 0.000985 0.076535 0.065962 0.077968  0.116 0.112 0.117 0.11 0.12 0.1 0.118 0.104 0.112 0.109 0.103 0.115 0.111 0.108 0.115 0.106 0.117 0.119 0.118 0.116 0.105 0.105 0.108 0.119 0.12 0.111 0.11 0.125 0.122 0.121  2.382681 2.359924 2.469331 2.265761 2.547562 1.981909 2.541912 2.194917 2.406261 2.27819 2.12914 2.438817 2.2107 2.327035 2.438817 2.413929 2.624425 2.430605 2.33946 2.399626 2.203317 2.293248 2.022701 2.498268 2.464369 3.062128 2.10928 2.839509 2.753907 2.744044  115  Column 1.1  Column 1.2  ID c1.1 c1.1 c1.1 c1.1 c1.1 c1.1 c1.1 c1.1 c1.1 c1.1 c1.1 c1.1 c1.1 c1.1 c1.1 c1.1 c1.1 c1.1 c1.1  DOC 2.5585 2.845 2.915 2.8739 2.7396 2.6032 2.9943 2.8505 1.8807 2.0768 2.567 2.8731 1.6374 1.868 1.858 2.4749 1.8673 1.6415 2.1401  (Std Dev) 0.056 0.0896 0.0307 0.0222 0.0102 0.0278 0.1883 0.0563 0.0353 0.0375 0.0038 0.0387 0.0251 0.0265 0.0146 0.0263 0.0086 0.0202 0.0658  UVA 0.052 0.071 0.069 0.066 0.069 0.07 0.07 0.033 0.037 0.034 0.058 0.066 0.031 0.032 0.036 0.058 0.051 0.046 0.054  SUVA 2.032 2.496 2.367 2.297 2.519 2.689 2.338 1.158 1.967 1.637 2.259 2.297 1.893 1.713 1.938 2.344 2.731 2.802 2.523  c1.1  1.9782  0.0106  0.054  2.730  c1.1  3.0086  0.1572 Column 1.3  0.075  2.493  ID c1.4  DOC 2.5487  ID c1.3 c1.3 c1.3 c1.3 c1.3 c1.3  DOC 2.4422 2.8445 2.8857 2.7753 2.6879 2.658  (Std Dev) 0.0174 0.0388 0.0093 0.0197 0.0721 0.0341  UVA 0.058 0.078 0.072 0.07 0.068 0.067  SUVA  c1.4 c1.4 c1.4 c1.4 c1.4 c1.4 c1.4 c1.4 c1.4 c1.4 c1.4 c1.4 c1.4 c1.4 c1.4  2.0699 2.7137 1.7791 1.863 2.0976 2.4814 3.0319 2.8797 2.1572 2.0717 2.2008 1.9851 2.0756 2.1134 1.873  2.375 2.742 2.495 2.522 2.530 2.521  ID c1.2 c1.2 c1.2 c1.2 c1.2 c1.2 c1.2 c1.2 c1.2 c1.2 c1.2 c1.2 c1.2 c1.2 c1.2 c1.2 c1.2 c1.2 c1.2  DOC 1.4105 2.1604 2.7963 1.3516 1.8969 1.8712 2.1581 1.7933 1.3208 2.6759 2.8325 2.8851 2.0382 1.81 3.0689 3.1687 2.7536 2.8848 2.7341  (Std Dev) 0.0082 0.0059 0.0471 0.0234 0.0357 0.0295 0.0174 0.0033 0.0513 0.0305 0.0286 0.0411 0.0394 0.0349 0.1246 0.0044 0.0616 0.2498 0.0464  UVA 0.028 0.04 0.063 0.025 0.035 0.041 0.053 0.052 0.023 0.069 0.065 0.067 0.056 0.05 0.074 0.074 0.057 0.078 0.073  SUVA 1.985 1.852 2.253 1.850 1.845 2.191 2.456 2.900 1.741 2.579 2.295 2.322 2.748 2.762 2.411 2.335 2.070 2.704 2.670  (Std Dev) 0.0096  UVA 0.062  SUVA 2.433  0.035 0.0279 0.0495 0.0088 0.0214 0.0263 0.0246 0.0748 0.021 0.0316 0.0137 0.0209 0.0087 0.0218 0.0237  0.051 0.072 0.039 0.066 0.038 0.051 0.07 0.07 0.034 0.04 0.052 0.053 0.045 0.041 0.032  2.464 2.653 2.192 3.543 1.812 2.055 2.309 2.431 1.576 1.931 2.363 2.670 2.168 1.940 1.708  Column 1.4  116  Column 2.1 ID c2.1 c2.1 c2.1 c2.1 c2.1 c2.1 c2.1 c2.1 c2.1 c2.1 c2.1 c2.1 c2.1 c2.1 c2.1 c2.1 c2.1 c2.1 c2.1  DOC 1.7927 0.6786 0.9522 1.497 1.3036 1.4422 1.1268 0.9713 0.9121 0.7126 1.3294 1.3034 1.099 1.8723 0.8101 0.7984 1.1518 1.2449 1.1038  (Std Dev) 0.0046 0.0407 0.031 0.0367 0.0107 0.0196 0.0636 0.0345 0.0203 0.0224 0.0223 0.012 0.0109 0.0323 0.057 0.0025 0.0102 0.0154 0.0333  Column 2.2 UVA 0.026 0.011 0.014 0.029 0.019 0.023 0.018 0.016 0.014 0.011 0.024 0.022 0.02 0.035 0.01 0.012 0.018 0.021 0.017  SUVA 1.450 1.621 1.470 1.937 1.458 1.595 1.597 1.647 1.535 1.544 1.805 1.688 1.820 1.869 1.234 1.503 1.563 1.687 1.540  Column 2.3 ID c2.3 c2.3 c2.3 c2.3  DOC 1.3626 0.9923 0.4287 0.6108  (Std Dev) 0.0099 0.0105 0.0196 0.0096  UVA 0.019 0.012 0.006 0.011  SUVA 1.394 1.209 1.400 1.801  ID c2.2 c2.2 c2.2 c2.2 c2.2 c2.2 c2.2 c2.2 c2.2 c2.2 c2.2 c2.2 c2.2 c2.2 c2.2 c2.2 c2.2 c2.2  DOC 1.4958 0.5745 0.7179 0.937 1.5214 1.4938 1.1601 1.779 1.1613 1.2679 0.8409 1.0364 1.0935 1.0643 1.6923 0.9251 0.8752 1.4174  (Std Dev) 0.0031 0.0109 0.0148 0.0271 0.0223 0.0285 0.057 0.0416 0.0299 0.0282 0.0185 0.0258 0.0421 0.0085 0.0628 0.0362 0.0384 0.0087 Column 2.4  UVA 0.021 0.01 0.011 0.016 0.022 0.022 0.02 0.029 0.022 0.023 0.013 0.016 0.011 0.019 0.031 0.013 0.014 0.026  SUVA 1.404 1.741 1.532 1.708 1.446 1.473 1.724 1.630 1.894 1.814 1.546 1.544 1.006 1.785 1.832 1.405 1.600 1.834  ID  DOC  (Std Dev)  UVA  SUVA  c2.4 c2.4 c2.4 c2.4 c2.4 c2.4 c2.4 c2.4 c2.4 c2.4 c2.4 c2.4  1.2809 0.9609 1.7212 1.2298 0.9502 0.8915 0.975 2.142 0.9851 1.5226 1.9644 2.3996  0.0024 0.01 0.0101 0.0261 0.018 0.0127 0.0321 0.0279 0.0103 0.0089 0.0018 0.045  0.017 0.02 0.037 0.013 0.012 0.015 0.015 0.051 0.014 0.023 0.037 0.048  1.327 2.081 2.150 1.057 1.263 1.683 1.538 2.381 1.421 1.511 1.884 2.000  117  APPENDIX E.  OXIDATION HPSEC CHROMATOGRAMS 1  2  3  4  5  7  8  6  9  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  118  1  Figure E-2- HPSEC chromatogram results 1. 4000mJ/cm2, 10mg/L H2O2  119  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.  120  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.  121  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.  122  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.  123  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.  124  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.  125  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.  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. Using Systat Peakfit v4.12, Autofit Peak III Deconvolution.  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. Systat Peakfit v4.12 using Autofit Peak III Deconvolution.  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. Systat Peakfit v4.12 using Autofit Peak III Deconvolution.  129  APPENDIX G.  HAA RESULTS Table G-1 - HAA data run 1  Description  Sample ID  4000,10 626 1.4 1 4000,10 626 1.3 3 Extended 805 1.1 4 c2.1 705 5 Extended 805 1.3 6 Extended 805 1.4 7 Extended 805 1.2 8 c1.2 707 9 2mg 715 11 2mg 713 12 c1.2 710 13 4000,10 627 1.1 14 4000,10 627 1.2 14 DUP 1mg 718 15 2000,10 626 2.1 16 c1.1 707 17 4000,10 627 1.2 18 4000,10 623 1.3 19 Raw 721 2.1 20 Raw 723 1.2 21 Raw 719 1.4 22 Raw 719 1.4 22 DUP 1mg 713 24 1mg 712 25 15 Spike (60) 15 Recover (%) 60 STD  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)  0.000 0.000 0.000 23.673 0.000 0.000 0.000 0.000 0.000 0.000 0.000 32.074 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.000 576.828 98 588.6  0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.000 314.808 104 302.7  0.000 0.000 0.000 0.000 0.000 0.000 1.040 1.606 2.956 1.937 1.197 0.000 0.000 3.597 2.608 2.457 0.000 3.072 21.567 4.902 0.000 3.988 2.596 0.000 102.60429 88 112.59  0.000 0.000 0.000 6.238 0.000 0.000 0.152 0.000 0.000 0.000 0.000 0.463 0.000 0.346 0.227 0.477 0.450 0.331 7.238 0.281 0.416 0.000 0.000 0.000 73.17381 121 60.18  13.218 12.630 1.681 1.651 1.743 1.511 1.591 1.907 2.746 2.665 2.154 3.659 13.072 11.659 7.605 31.605 31.712 3.479 59.843 6.998 15.614 14.540 11.372 9.448 145.35918 110 120  20.706 21.419 14.225 16.900 14.551 16.615 21.269 63.269 98.658 98.687 49.044 67.848 18.071 119.225 73.330 39.841 45.784 34.942 123.438 144.009 115.425 105.479 122.908 106.585 197.51118 110 59.79  0.191 1.780 0.000 0.091 0.000 0.000 0.000 0.000 0.000 0.000 4.318 0.000 2.106 0.000 12.357 0.000 0.000 0.000 0.000 11.926 14.919 14.964 13.069 16.637 180.516 98 184.2  156.429 159.922 9.441 11.707 10.321 11.789 15.571 62.623 93.285 100.573 64.708 80.288 152.449 229.185 152.103 115.856 128.032 155.932 223.440 210.777 233.696 208.757 238.396 214.176 374.00598 92 178.98  0.000 0.000 0.000 17.810 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.000 3.484 0.000 0.000 0.000 0.000 0.000 113.8041 93 122.37  190.545 195.751 25.347 78.069 26.614 29.915 39.622 129.405 197.645 203.862 121.422 184.331 185.698 364.012 248.230 190.237 205.978 197.756 439.010 378.893 380.070 347.728 388.341 346.846  130  Description  Sample ID  c2.2 801 26 c2.2 804 27 c2.2 806 28 c2.1 801 29 c2.1 803 30 2000,10 626 1.2 31 c1.2 806 32 2mg 801 33 2mg 802 33 4000,10 627 34 2000,10 627 1.3 35 2mg 803 36 2mg 804 37 4000,0 626 2.3 38 4000,0 626 2.4 39 c1.1 801 40 c1.1 804 40 DUP 2000,10 627 1.3 41 c1.1 801 42 2000,10 626 1.2 43 Raw 721 2.1 44 Raw 721 2.1 45 4000,0 623 1.1 46 2000,10 627 1.4 47 34 Spike (20) 34 Recover (%) 20 STD  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)  0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.000 174.618 89 196.2  0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.000 118.053 117 100.9  3.038 3.317 3.259 4.061 3.117 3.052 1.508 2.288 2.735 0.000 1.146 0.000 1.823 4.211 0.000 2.336 3.2654 2.418 4.962 19.609 5.017 4.037 0.352 3.478 35.654 95 37.53  0.000 0.429 0.308 0.398 0.234 0.325 0.000 0.314 0.000 0.000 0.256 0.000 0.239 0.488 0.355 0.422 0.000 0.692 0.246 4.835 0.408 0.222 0.426 0.000 18.656 93 20.06  4.074 3.660 3.986 3.919 2.577 8.823 2.163 3.085 2.854 1.381 3.540 3.603 3.766 13.087 12.487 30.549 32.465 36.720 5.085 40.771 9.460 6.244 13.782 10.425 42.540 103 40  40.979 42.650 46.280 49.236 27.838 85.144 74.766 119.049 103.478 45.084 144.853 91.748 96.803 155.531 135.827 32.661 31.185 61.574 61.890 80.563 203.217 139.430 167.094 76.543 59.500 92 19.93  0.000 0.000 0.000 0.000 2.012 11.950 3.953 5.575 2.345 4.399 4.600 5.425 5.475 17.998 16.292 8.597 8.655 11.592 4.594 8.815 10.511 10.321 13.650 14.321 65.361 99 61.4  27.590 23.293 31.693 33.139 19.300 168.803 71.941 104.904 100.035 145.094 135.714 110.487 115.504 302.787 270.210 95.381 86.789 172.901 83.475 146.367 188.253 195.777 292.436 150.478 98.060 48 59.66  0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0 0.000 0.000 2.426 0.000 0.000 0.000 0.000 39.566 97 40.79  75.681 73.349 85.525 90.753 55.079 278.095 154.330 235.214 211.447 195.958 290.108 211.263 223.610 494.101 435.171 169.946 162.359 285.897 160.252 303.386 416.866 356.031 487.740 255.245  131  APPENDIX H.  THM RESULTS Table H-1 - THM data run 1 Bromodichloroform Dibromochloroform Bromoform (ug/L) (ug/L) (ug/L)  Description  S ample ID  Chloroform (ug/L)  Raw 802 Raw 731 1.2 Raw 731 1.2 Raw 731 1.1 Raw 725 1.2 Raw 725 1.1 Raw 725 1.1 Raw 719 1.4 Raw 719 1.4 Raw 719 1.2 Raw 719 1.1 Raw 719 1.1 Raw 707 1.4 Raw 707 1.2 Extended 806 Extended 806 Extended 805 Extended 804 Extended 803 Extended 802 Extended 801 c2.2 806 c2.2 724 c2.2 723 c2.2 719 c2.2 719 c2.2 717 c2.1 806  39 33 32 31 30 27 27 DUP 3 3 DUP  250.804535 206.9451227 204.7230835 264.4803594 157.3051628 211.784019 196.9861091 178.574 167.030  51.10706977 31.63243132 27.16993318 19.13325392 72.78095509 101.553403 95.54887981 95.684 90.174  6.063689458 2.778186312 2.279237894 0 25.23699774 35.16377021 33.31593809 35.985 33.964  0 0 2.573537148  76 2 1 9 7  205.498856 271.333 206.043 170.137 208.882 24.00932068 21.76928435 23.30938468 32.37661894 28.3646767 24.67935672 25.66645486  117.8887309 155.969 119.455 95.855 114.091  65.75337216 61.869 44.448 36.794 43.657  8.836802552 5.467 4.047 3.146 3.842  28.38760902 27.80790972 27.85598276 43.09139428 40.39216478 47.78671664 51.56573015 2.961951409 16.0913155 14.00835355 15.88505235 14.28986189 12.95782043 10.56963021  13.27881389 12.39275519 12.83999739 16.15064574 21.00848481 26.41884547 26.9162005 0 10.0547004 8.642110457 9.231351688 8.821460881 8.035877997 0  c2.1 717 c2.1 708 c1.3 721 c1.3 719 c1.2 805 c1.2 803 c1.2 803 c1.2 801 c1.2 725 c1.2 713 c1.2 713 c1.2 707 c1.1 806 c1.1 805 c1.1 801 c1.1 801 c1.1 801 c1.1 723 c1.1 718 c1.1 718 c1.1 715  0 0 0  2.461003698 3.121 2.979  44 DUP 44 46 45 47 48 79 62 71 70 69 69 DUP 68 67  54.45040949 10.65838967 9.20241938 11.07243045 9.639340614 8.559610743 26.19423468  27.38452356 24.99147686 26.61728637 34.88766049 35.85088398 40.10804452 40.43240802 12.3848969 12.48548776 10.63496849 12.80789526 11.06313313 9.910030354 11.90137728  65 63 13  12.21923085 6.566480383 63.941  4.323988733 7.037528097 28.919  0 8.953098529 9.514  0 5.623485762 0.000  40 61 60 DUP 60 72 59 58 58 DUP 57 56 55 54 66 66 DUP 53 11 DUP 11  42.92812524 67.57416301 67.96797626 59.55193203 17.51249287 78.80912886 134.0903971 120.5987487 100.2366471 78.25103799 64.51433342 89.10700381 59.24951559 42.91749782 136.5448694 64.073 58.826  33.39187239 15.35265811 16.78824546 14.3952766 20.95193513 19.95684368 35.95916834 32.42883821 26.20468464 19.13770853 13.34929493 21.96673422 23.39366873 18.3151619 37.42827607 37.602 33.977  23.46873248 3.648219675 4.107742649 3.529976065 26.70045751 4.52851584 9.295534404 8.389534854 6.749745782 4.349084878 0 0 0 8.025130576 7.856443882 20.474 18.305  5.801638462 0 0 0 12.78411784 0 0 0 0 0 0 0 0 0 0 2.189 2.246  52  56.7601021  15.7898895  3.527770076  0  132  Bromodichloroform Dibromochloroform Bromoform (ug/L) (ug/L) (ug/L)  Description  S ample ID  Chloroform (ug/L)  c1.1 710 c1.1 707 4000,10 6301.4 4000,10 6301.4 4000,10 628 1.2 4000,10 628 1.2 4000,10 628 1.2 4000,10 628 1.1 4000,10 628 1.1 4000,10 627 1.3 4000,10 627 1.3 4000,10 626 1.4 4000,10 626 1.4 4000,10 626 1.3 4000,10 626 1.3 4000,0 731 1.2 4000,0 723 1.2 4000,0 723 1.2 2mg 803 2mg 803 2mg 801 2mg 731 1.2 2mg 731 1.2 2mg 723 1.2 2mg 723 1.1 2mg 723 1.1 2mg 713 2mg 712  64 51 18 16 12 75 12 DUP 38 DUP 38 23 23 DUP 37 36 81 26 35 22 21 6 DUP 6 80 78 34 20  9.063877698 82.81542359 100.097 121.961 91.088 93.67730639 66.271 160.9202888 152.24346 81.67231363 73.65376382 150.2098969 175.4308497 198.3206802 101.5351401 234.06108 156.5054694 152.837 124.295 114.457 61.336 114.3666571 116.0322474 116.520  9.751668923 19.53688122 53.831 54.528 53.968 54.51220053 38.555 32.35952543 30.24480897 51.95056201 47.16427986 16.9799564 10.76951614 14.15201661 46.2841196 51.14474629 99.52207248 94.684 67.713 61.110 79.147 36.61431523 24.51691957 72.016  111.9087153 0 19.970 18.432 29.279 28.3604886 20.862 3.694472598 3.441213521 28.16341428 25.64689683 0 0 0 15.54093654 11.40636839 60.46156947 56.779 25.265 22.808 29.897 11.48246322 5.260213764 42.792  6.806400828 0 0.000 0.000 3.665 4.014777014 2.576 0 0 4.102771205 3.731376557 0 0 0 0 0 9.014687415 8.428 2.029 0.000 2.462 0 0 6.477  24 25 17 14  117.8779411 75.83086314 94.709 111.095  70.5704658 44.69755575 42.827 48.608  41.12016985 25.6838767 14.493 16.276  5.695010945 3.417264377 0.000 0.000  2mg 703 2mg 703 2000,10 627 1.4 2000,10 627 1.4 2000,10 627 1.4 2000,10 627 1.3 2000,10 628 1.4 2000,10 626 1.2 2000,10 626 1.2 2000,10 626 1.2 2000,10 626 1.1 1mg 725 1.1 1mg 725 1.1 1mg 721 2.1 1mg 721 2.1 1mg 719 1.1 1mg 719 1.1 15 mg 802 15 mg 803 15 mg 804  28 28 DUP 8 DUP 10 8 15  90.59996746 62.59834194 135.786 125.994 131.299 132.575 142.4026778 120.4717811  53.14386964 35.85652179 71.283 61.227 68.275 61.402  30.45344812 20.5421347 26.571 22.450 25.107 21.516  3.717114248 2.59409317 2.141 0.000 2.000 0.000  108.5744702 95.08601854 142.5217178 158.7835577 153.6594333 176.5813409 121.6692871 170.342 144.161 94.30235287 72.03931998 75.76708134 33.062  114.4578269 97.41789612 90.39805444 77.10942042 117.7229605 91.30627225 90.94253809 101.8294673 69.24695982 115.781 96.347 56.45637264 51.40218912 44.1113371 21.912  79.80530419 73.71977376 68.53048874 58.19514044 85.33129985 50.63579869 53.25132562 53.99799587 36.6252595 65.386 54.614 24.67210191 25.17019917 14.05863986 19.879  17.57563913 18.83953007 17.95469006 15.05775365 21.38335835 6.823898321 6.49110536 6.72268539 4.668102388 8.725 7.315 4.556008756 2.733811501 0 21.859  107 18.54884  95 18.85581  106 18.75349  121 18.06512  50 43 42 DUP 42 41 77 29 73 74 5 4 81 82 83  65 Spike (20) 65 Recover (%) 20 STD  133  APPENDIX I.  OXIDATION TOC AND UVA DATA  Table I-1 - Raw TOC and UVA data for oxidation conditions  Ozone 2mg O3/mg DOC  Ozone 1mg O3/mg DOC  Treatment  ID JP 7/25 1.1 JP 7/25 1.1 TREATED JP 7/25 1.2 JP 7/25 1.2 TREATED JP 7/21 2.3 JP 7/21 2.3 TREATED JP 7/21 2.4 JP 7/21 2.4 TREATED JP 7/21 2.1 JP 7/21 2.1 TREATED JP 7/21 2.2 JP 7/21 2.2 TREATED JP 7/19 1.4 JP 7/19 1.4 TREATED JP 7/19 1.4 JP 7/19 1.4 TREATED JP 7/21 2.1 JP 7/21 2.1 TREATED JP 7/25 1.2 JP 7/25 1.2 TREATED JP 7/25 1.1 JP 7/25 1.1 TREATED JP 7/25 1.1 JP 7/25 1.1 JP 7/19 1.4 JP 7/19 1.4 TREATED JP 7/21 2.1 JP 7/21 2.1 TREATED JP 7/25 1.1 JP 7/25 1.1 TREATED JP 7/23 1.1 JP 7/23 1.1 TREATED JP 7/23 1.2 JP 7/23 1.2 TREATED JP 7/23 1.1 19.0 JP 7/23 1.1 TREATED JP 7/23 1.1 20.0 JP 7/23 1.1 TREATED JP 7/23 1.2 21.0 JP 7/23 1.2 TREATED JP 7/23 1.2 22.0 JP 7/23 1.2 TREATED JP 731 1.2 RAW 36.0 JP 731 1.2 TREATED JP 731 1.2 RAW JP 731 1.2 TREATED  DOC 4.7393 4.6681 4.6721 4.4361 4.7217 4.6922 4.596 4.5131 4.91 4.3941 4.8346 4.6293 5.6839 5.683 5.6839 5.683 4.91 5.0749 4.6721 4.4361 4.7393 4.7028 4.7393 4.7854 5.6839 5.4763 4.91 4.3941 4.7393 4.6681 5.0646 4.8959 5.1337 5.0439 5.0646 4.7154 5.0646 4.7154 5.1337 4.7845 5.1337 4.6411 4.8264 4.8694 4.8264 4.7633  Std. Dev. 0.1165 0.0655 0.0547 0.01514 0.132 0.0386 0.0673 0.0039 0.0704 0.0417 0.1403 0.0814 0.0821 0.0943 0.0821 0.0943 0.0704 0.101 0.0547 0.01514 0.1165 0.0612 0.1165 0.0436 0.0821 0.0399 0.0704 0.0417 0.1165 0.0655 0.0543 0.0523 0.0446 0.0918 0.0543 0.1029 0.0543 0.1029 0.0446 0.0555 0.0446 0.0346 0.0809 0.0209 0.0809 0.0609  UVA 0.163 0.134 0.169 0.11 0.163 0.152 0.16 0.11 0.162 0.159 0.128 0.127 0.176 0.124 0.176 0.124 0.162 0.1298 0.169 0.11 0.163 0.132 0.163 0.131 0.176 0.149 0.162 0.159 0.163 0.134 0.158 0.109 0.16 0.107 0.158 0.115 0.158 0.115 0.16 0.109 0.16 0.108 0.174 0.12 0.174 0.119  134  0 mg/L H2O2 10 mg/L H2O2  Extended Ozone Dose  4000 mJ/cm2 &  2  2000 mJ/cm & 10 mg/L H2O2  4000 mJ/cm2 &  Treatment  DOC (mg/L) 4.8775  Std. Dev.  UVA  JP 6/26 2.3  0.0948  0.148  JP 6/26 2.3 TREATED  4.2048  0.1682  0.123  ID  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  135  APPENDIX J.  BIODEGRADATION TOC/UV RESULTS Table J-1 - TOC/UV data for biodegradation tests  ID 1.1  TOC DOC standard UV254 Average deviation  ID  TOC DOC standard UV254 Average deviation 2.7633  0.0262  0.037  ID 5.1  TOC DOC standard UV254 Average deviation  1.7211  0.0086  0.019  3.1  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  0.015  136  ID  TOC DOC standard UV254 Average deviation  7.1  1.6137  0.0019  0.016  7.10  0.8666  0.0329  0.011  7.11  0.9981  0.0236  7.12  1.3962  0.0079  7.2  1.5228  7.3  1.4156  7.4  ID 9.1  TOC DOC standard UV254 Average deviation 2.3005  0.0098  0.037  ID 11.10  TOC DOC standard UV254 Average deviation 0.9819  0.0368  0.019  9.10  1.3997  0.0485  0.019  11.1  1.2846  0.0167  0.017  9.11  1.3304  0.0196  0.019  11.11  0.9114  0.0113  0.014  0.014  9.12  1.2377  0.0556  0.011  11.12  0.7586  0.0128  0.011  0.0174  0.017  9.2  2.1872  0.0092  0.036  11.2  1.2921  0.0061  0.016  0.0026  0.015  9.3  1.9324  0.0076  0.03  11.3  1.1752  0.0186  0.016  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  0.024  137  ID  TOC DOC standard UV254 Average deviation  13.10  1.0863  0.0716  0.01  ID 15.10  TOC DOC standard UV254 Average deviation 2.945  0.0298  ID  0.064  17.1  TOC DOC standard UV254 Average deviation 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  0.058  138  ID 19.10  TOC DOC standard UV254 Average deviation 2.8091  0.0638  0.062  ID 21.10  TOC DOC standard UV254 Average deviation 2.5881  0.0617  0.052  ID 23.10  TOC DOC standard UV254 Average deviation 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  0.049  139  ID  TOC DOC standard UV254 Average deviation  25.10  2.43  0.0407  0.058 0.133  25.1  4.0642  0.0861  25.11  1.8741  0.0928  25.2  4.1683  0.0413  25.3  3.7683  25.4  3.4682  25.5  ID  TOC DOC standard UV254 Average deviation  27.10  2.6334  0.0098  0.059 0.142  27.1  4.3956  0.0676  27.11  2.4792  0.0306  0.127  27.2  4.3513  0.039  0.0532  0.104  27.3  4.1297  0.0221  0.097  27.4  4.0908  3.1568  0.0175  0.095  27.5  3.5716  25.6  2.9713  0.0154  0.083  27.6  25.7  2.8446  0.0312  0.077  25.8  2.8201  0.0706  0.061  25.9  2.4995  0.0321  26.10  2.4048  0.0644  ID  TOC DOC standard UV254 Average deviation  31.10  2.3971  0.0323  0.049  31.1  3.7289  0.0834  0.084  31.11  2.3745  0.04  0.049  0.134  31.2  3.3778  0.0288  0.092  0.024  0.114  31.3  3.2189  0.0306  0.084  0.0298  0.157  31.4  3.0494  0.0327  0.078  0.04  0.1  31.6  2.5456  0.0205  0.061  3.5124  0.0416  0.07  31.7  2.58  0.041  0.056  27.7  3.1599  0.0094  0.068  31.8  2.7371  0.0307  0.051  27.8  2.8396  0.0123  0.066  31.9  2.4094  0.1142  0.051  0.058  27.9  2.6344  0.0088  0.059  32.1  3.5608  0.0439  0.096  0.059  28.10  1.8863  0.0435  0.039  32.10  1.9789  0.0495  0.011  0.127  32.11  1.8688  0.0245  0.034  32.2  3.1568  0.0343  0.083  26.1  4.0836  0.0362  0.095  28.1  4.0397  0.0363  26.11  2.2964  0.0255  0.053  28.11  1.8793  0.0234  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  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  0.041  0.029  140  ID  TOC DOC standard UV254 Average deviation  ID 35.10  TOC DOC standard UV254 Average deviation  33.1  3.7655  0.0572  0.106  2.5557  0.042  0.068  33.10  2.3261  0.0445  0.026  35.1  3.8837  0.0838  0.112  33.11  2.055  0.006  0.043  35.11  2.4554  0.0935  0.064  33.2  3.4  0.076  0.094  35.3  3.6077  0.0659  0.111  33.3  3.2089  0.0464  0.087  35.4  3.4793  0.045  33.4  3.3497  0.0388  0.079  35.5  3.3378  0.0565  33.5  3.0381  0.0416  0.076  35.6  3.0293  33.6  2.8636  0.0292  0.057  35.7  33.7  2.5918  0.1329  0.055  33.8  2.3829  0.0311  0.049  33.9  2.401  0.0328  34.10  1.9434  ID 37.1  TOC DOC standard UV254 Average deviation 4.207  0.0842  0.103  37.10  2.7472  0.0167  0.056  37.11  2.6708  0.0171  0.057  37.2  3.7943  0.0475  0.098  0.078  37.3  3.6244  0.0468  0.09  0.092  37.4  3.4318  0.0748  0.087  0.0201  0.086  37.5  3.1491  0.0628  0.063  2.8223  0.0691  0.076  37.6  3.0506  0.0394  0.069  35.8  2.8172  0.0918  0.035  37.7  2.895  0.0599  0.065  35.9  2.5355  0.0105  0.07  37.8  3.0334  0.0579  0.067  0.051  36.1  3.8298  0.0697  0.085  37.9  2.658  0.1279  0.061  0.0395  0.035  36.10  2.4859  0.0158  0.044  38.1  3.9209  0.0791  0.13  0.005  34.1  3.4642  0.0374  0.092  36.11  2.4142  0.0099  0.043  38.10  2.4143  34.11  1.8268  0.0523  0.033  36.2  3.4169  0.0256  0.077  38.11  2.1325  0.054  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  0.056  0.044  141  ID  TOC DOC standard UV254 Average deviation  ID  TOC DOC standard UV254 Average deviation  ID  TOC DOC standard UV254 Average deviation  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  39.2  3.4349  0.0329  0.114  42.6  2.3904  39.3  3.2178  0.0488  0.111  42.7  1.3878  39.4  3.2159  0.0466  0.106  42.8  39.5  2.685  0.0968  0.074  39.7  2.4261  0.0154  0.064  39.8  2.5873  0.0707  39.9  2.4742  40.1 40.2  0.017  15.12 (half 4 hr)  4.8306  0.0724  0.134  0.021  16.0 JP 7/19 1.4 T  5.683  0.0943  0.124  0.054  0.016  16.12 (half 4hr)  4.5109  0.0775  0.139  0.8671  0.0087  0.021  17.0 JP 7/21 2.1 T  5.0749  0.101  0.1298  42.9  0.8011  0.0143  0.014 17.12 (Double 12 hr)  3.116  0.0232  0.062  43.1  2.2747  0.0406  0.026  5.0749  0.101  0.1298  0.064  43.2  2.0469  0.0215  0.019 18.12 (Double 12 hr)  3.2784  0.0304  0.067  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  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  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  18.0 JP 7/21 2.1 T  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) 4.12 (Dup 24hr)  3.676 1.2618  0.0669 0.0091  0.111 0.021  142  ID 20.12 (half 24 hr) 21.0 JP 7/23 1.2 TREATED (2.4) 21.12 (half 8hr)  TOC DOC standard UV254 Average deviation  ID  TOC DOC standard UV254 Average deviation  ID  TOC DOC standard UV254 Average deviation  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  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  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  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  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  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  22.0 JP 7/23 1.2 TREATED 22.12 (Half 8 (2.4) hour) 23.0 JP 7/25 1.1 TREATED 23.12 (Dup (1.17) 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  33.0 JP 626 2.4  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  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  4.269  0.0249  0.136  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  0.036  143  APPENDIX K.  BIODEGRADATION CURVES FOR DOC  7  6  Curve 15.0 BAC Column 1  6  Curve 17.0 BAC Column 1  5  DOC (mg/L)  DOC (mg/L)  5 4 3 Generated Curve Fit 90% Confidence Interval 90% Confidence Interval Actual Data  2 1  4 3 Generated Curve Fit 90% Confidence Interval 90% Confidence Interval Actual Data  2 1  0  0 0  1  2  3  4  5  6  7  0  1  2  Time (Days)  3  4  6  6  7  7  Curve 23.0 BAC Column 1  5  Curve 16.0 BAC Column 2  6  Generated Curve Fit 90% Confidence Interval 90% Confidence Interval Actual Data  5 4  DOC (mg/L)  DOC (mg/L)  5  Time (Days)  3 Generated Curve Fit 90% Confidence Interval 90% Confidence Interval Actual Data  2 1  4 3 2 1  0  0 0  1  2  3  4  5  6  7  0  1  2  Time (Days)  3  4  5  6  7  Time (Days)  Figure K-1 - Biodegradation test results for 1mgO3/mg DOC  144  6  6  Curve 18.0 BAC Column 2  4 3 Generated Curve Fit 90% Confidence Interval 90% Confidence Interval Actual Data  2 1  Curve 24.0 BAC Column 2  5  DOC (mg/L)  DOC (mg/L)  5  4 3 Generated Curve Fit 90% Confidence Interval 90% Confidence Interval Actual Data  2 1  0  0 0  1  2  3  4  5  6  7  0  1  2  Time (Days)  3  4  5  6  7  Time (Days)  Figure K-2 - Biodegradation test results for 1mgO3/mg DOC  145  6  6  Curve 19.0 BAC Column 1  4 3 Generated Curve Fit 90% Confidence Interval 90% Confidence Interval Actual Data  2 1  Curve 21.0 BAC Column 1  5  DOC (mg/L)  DOC (mg/L)  5  4 3 Generated Curve Fit 90% Confidence Interval 90% Confidence Interval Actual Data  2 1  0  0 0  1  2  3  4  5  6  7  0  1  2  3  Time (Days) 6  5  6  7  6  Curve 37.0 BAC Column 1  5 4 3  Generated Curve Fit 90% Confidence Interval 90% Confidence Interval Actual Data  2 1  Curve 20.0 BAC Column 2  5  DOC (mg/L)  DOC (mg/L)  4  Time (Days)  4 3 Generated Curve Fit 90% Confidence Interval 90% Confidence Interval Actual Data  2 1  0  0 0  1  2  3  4  5  6  7  0  1  2  Time (Days)  3  4  5  6  7  Time (Days)  Figure K-3 - Biodegradation test results for 2mgO3/mg DOC  146  5  6  4.5  Curve 22.0 BAC Column 2  4  DOC (mg/L)  DOC (mg/L)  3.5 3 2.5 2 Generated Curve Fit 90% Confidence Interval 90% Confidence Interval Actual Data  1.5 1 0.5  Curve 36.0 BAC Column 2  5 4 3  Generated Curve Fit 90% Confidence Interval 90% Confidence Interval Actual Data  2 1  0  0 0  1  2  3  4  5  6  7  0  1  2  Time (Days)  3  4  5  6  7  Time (Days)  Figure K-4 - Biodegradation test results for 2mgO3/mg DOC  147  3.5  3.5  Curve 40.0 BAC Column 1  DOC (mg/L)  2.5  Generated Curve Fit 90% Confidence Interval 90% Confidence Interval Actual Data  2 1.5  2.5  1.5 1  0.5  0.5  0  0 1  2  3  4  5  6  Generated Curve Fit 90% Confidence Interval 90% Confidence Interval Actual Data  2  1  0  Curve 41.0 BAC Column 1  3  DOC (mg/L)  3  7  0  1  2  3  Time (Days) 3  5  6  7  3  Curve 42.0 BAC Column 2 Generated Curve Fit 90% Confidence Interval 90% Confidence Interval Actual Data  2 1.5 1  1.5 1 0.5  0  0 1  2  3  4  5  6  7  Generated Curve Fit 90% Confidence Interval 90% Confidence Interval Actual Data  2  0.5  0  Curve 43.0 BAC Column 2  2.5  DOC (mg/L)  2.5  DOC (mg/L)  4  Time (Days)  0  1  2  Time (Days)  3  4  5  6  7  Time (Days)  Figure K-5 - Biodegradation test results for extended ozonation  148  5  5  4.5  4.5  Curve 31.0 BAC Column 1  4  3.5  DOC (mg/L)  3.5  DOC (mg/L)  Curve 33.0 BAC Column 1  4  3 2.5 2 Generated Curve Fit 90% Confidence Interval 90% Confidence Interval Actual Data  1.5 1 0.5  3 2.5 2 Generated Curve Fit 90% Confidence Interval 90% Confidence Interval Actual Data  1.5 1 0.5  0  0 0  1  2  3  4  5  6  7  0  1  2  Time (Days) 4.5  5  4  4.5  Curve 32.0 BAC Column 2  4  5  6  7  Curve 34.0 BAC Column 2  4 3.5  3  DOC (mg/L)  DOC (mg/L)  3.5  3  Time (Days)  2.5 2 1.5  Generated Curve Fit 90% Confidence Interval 90% Confidence Interval Actual Data  1 0.5  3 2.5 2 Generated Curve Fit 90% Confidence Interval 90% Confidence Interval Actual Data  1.5 1 0.5  0  0 0  1  2  3  4  Time (Days)  5  6  7  0  1  2  3  4  5  6  7  Time (Days)  Figure K-6 - Biodegradation test results for 4000mJ/cm2 and 0 mg/L H2O2  149  4.5  3.5  4  DOC (mg/L)  3.5  Generated Curve Fit 90% Confidence Interval 90% Confidence Interval Actual Data  3 2.5 2 1.5  Curve 8.0 BAC Column 1  3  Generated Curve Fit 90% Confidence Interval 90% Confidence Interval Actual Data  2.5  DOC (mg/L)  Curve 3.0 BAC Column 1  2 1.5 1  1 0.5  0.5  0  0 0  1  2  3  4  5  6  7  0  1  2  Time (Days) 3  4  5  6  7  2.5 Generated Curve Fit 90% Confidence Interval 90% Confidence Interval Actual Data  2 1.5 1  Curve 13.0 BAC Column 1  2  DOC (mg/L)  Curve 12.0 BAC Column 1  2.5  DOC (mg/L)  3  Time (Days)  Generated Curve Fit 90% Confidence Interval 90% Confidence Interval Actual Data  1.5 1 0.5  0.5 0  0 0  1  2  3  4  Time (Days)  5  6  7  0  1  2  3  4  5  6  7  Time (Days)  Figure K-7 - Biodegradation test results for 2000mJ/cm2 and 10 mg/L H2O2  150  3.5  3  Curve 5.0 BAC Column 2  Generated Curve Fit 90% Confidence Interval 90% Confidence Interval Actual Data  2 1.5  Generated Curve Fit 90% Confidence Interval 90% Confidence Interval Actual Data  2 1.5 1  1 0.5  0.5  0  0 0  1  2  3  4  5  6  7  0  1  2  3  Time (Days)  4  5  6  7  Time (Days)  2.5  Curve 14.0 BAC Column 2  2  DOC (mg/L)  DOC (mg/L)  2.5  Curve 9.0 BAC Column 2  2.5  DOC (mg/L)  3  Generated Curve Fit 90% Confidence Interval 90% Confidence Interval Actual Data  1.5 1 0.5 0 0  1  2  3  4  5  6  7  Time (Days)  Figure K-8 - Biodegradation test results for 2000mJ/cm2 and 10 mg/L H2O2  151  2.5  2.5  DOC (mg/L)  2  Generated Curve Fit 90% Confidence Interval 90% Confidence Interval Actual Data  1.5 1  1 0.5  0  0 1  2  3  4  5  6  7  0  1  2  Time (Days)  3  4  5  6  7  Time (Days)  2  2  1.6  Generated Curve Fit 90% Confidence Interval 90% Confidence Interval Actual Data  1.4 1.2 1 0.8 0.6  1.6 1.2 1 0.8 0.6 0.4  0.2  0.2  0  0 1  2  3  4  Time (Days)  5  6  7  Generated Curve Fit 90% Confidence Interval 90% Confidence Interval Actual Data  1.4  0.4  0  Curve 7.0 BAC Column 2  1.8  DOC (mg/L)  Curve 11.0 BAC Column 1  1.8  DOC (mg/L)  Generated Curve Fit 90% Confidence Interval 90% Confidence Interval Actual Data  1.5  0.5  0  Curve 6.0 BAC Column 1  2  DOC (mg/L)  Curve 1.0 BAC Column 1  0  1  2  3  4  5  6  7  Time (Days)  Figure K-9 - Biodegradation test results for 4000mJ/cm2 and 10 mg/L H2O2  152  2.5  Curve 10.0 BAC Column 2  DOC (mg/L)  2  Generated Curve Fit 90% Confidence Interval 90% Confidence Interval Actual Data  1.5 1 0.5 0 0  1  2  3  4  5  6  7  Time (Days)  Figure K-10 - Biodegradation test results for 4000mJ/cm2 and 10 mg/L H2O2  153  6  6  DOC (mg/L)  5  Generated Curve Fit 90% Confidence Interval 90% Confidence Interval Actual Data  4 3 2  3 2 1  0  0 1  2  3  4  5  6  7  0  1  2  Time (Days)  3  4  5  6  7  Time (Days)  4.5  6  3.5  Generated Curve Fit 90% Confidence Interval 90% Confidence Interval Actual Data  3 2.5 2 1.5  Curve 26.0 BAC Column 2  5  DOC (mg/L)  Curve 35.0 BAC Column 1  4  DOC (mg/L)  Generated Curve Fit 90% Confidence Interval 90% Confidence Interval Actual Data  4  1  0  Curve 27.0 BAC Column 1  5  DOC (mg/L)  Curve 25.0 BAC Column 1  Generated Curve Fit 90% Confidence Interval 90% Confidence Interval Actual Data  4 3 2  1 1 0.5 0  0 0  1  2  3  4  Time (Days)  5  6  7  0  1  2  3  4  5  6  7  Time (Days)  Figure K-11 - Biodegradation test results for raw water samples  154  6  6  Curve 28.0 BAC Column 2  3 2  3 2 1  0  0 1  2  3  4  5  6  Generated Curve Fit 90% Confidence Interval 90% Confidence Interval Actual Data  4  1  0  Curve 38.0 BAC Column 2  5  DOC (mg/L)  4  7  0  1  2  3  Time (Days)  4  5  6  7  Time (Days)  6  Curve 39.0 BAC Column 2  5  DOC (mg/L)  DOC (mg/L)  5  Generated Curve Fit 90% Confidence Interval 90% Confidence Interval Actual Data  Generated Curve Fit 90% Confidence Interval 90% Confidence Interval Actual Data  4 3 2 1 0 0  1  2  3  4  5  6  7  Time (Days)  Figure K-12 - Biodegradation test results for raw water samples  155  APPENDIX L.  BIODEGRADATION TEST ANALYSIS RESULTS FOR DOC Table L-1 - Biodegradation curve analysis results for DOC a  Variables b  c  15  3.114  2.412  1.942  17  2.738  2.257  1.782  1mg, Column 1  23  2.973  1.637  1.171  1mg, Column 2 1mg, Column 2  16 18  2.642 2.599  2.884 2.402  2.612 1.213  1mg, Column 2  24  2.468  2.243  1.924  2mg, Column 1  19  2.870  1.716  1.772  Oxidation  ID  1mg, Column 1 1mg, Column 1  2mg, Column 1 2mg, Column 1  21 37  2.747 2.832  1.748 1.956  1.316 1.808  2mg, Column 2  20  2.336  2.155  1.567  2mg, Column 2 2mg, Column 2  22 36  2.409 2.542  2.058 2.168  1.081 2.193  Extended, Column 1  40  0.84394 1.90845 0.61641  Extended, Column 1  41  0.84951 1.98462 0.63608  Extended, Column 2 Extended, Column 2  42 43  0.68948 1.79511 0.46431 0.61014 1.88826 0.43379  4000,0 Column 1  31  2.50299 1.78627 1.88347  4000,0 Column 1 4000,0 Column 2  33 32  2.42443 1.73288 1.6194 1.98264 2.07546 1.50524  4000,0 Column 2  34  2.0776 2.09951 1.86904  4000,10 Column 1  1  0.88089 1.27537 2.44539  4000,10 Column 1 4000,10 Column 1  6 11  0.95692 0.98943 0.79569 0.94663  2.8685 2.4986  a  Average b  c  2.942  2.102  1.632  2.570  2.509  1.916  S tandard Deviation a stdev b stdev c stdev 0.190  0.091  0.410  0.334  0.407  0.700  2.816  1.807  1.632  0.063  0.130  0.274  2.429  2.127  1.614  0.104  0.060  0.557  0.847  1.947  0.626  0.004  0.054  0.014  0.650  1.842  0.449  0.056  0.066  0.022  2.464  1.760  1.751  0.056  0.038  0.187  2.030  2.087  1.687  0.067  0.017  0.257  0.878  1.070  2.604  0.081  0.179  0.230  # of n 3  t test t 2.92  3  2.92  3  2.92  3 3  2.92 2.92  3  2.92  3  2.92  3 3  2.92 2.92  3  2.92  3 3  2.92 2.92  2  6.314  2  6.314  2 2  6.314 6.314  2  6.314  2 2  6.314 6.314  2  6.314  3  2.92  3 3  2.92 2.92  Error (a)  Error (b)  Error (c)  0.3201  0.6915  0.6862  0.1530  0.5627  1.1798  0.1054  0.2193  0.4623  0.1760  0.1014  0.9397  0.0176  0.2404  0.0621  0.2505  0.2941  0.0963  0.2480  0.1686  0.8337  0.2998  0.0759  1.1485  0.1360  0.3013  0.3885  156  Oxidation  ID  Variables a  b  Average c  a  b  c  0.962  0.863  1.490  S tandard Deviation # of a stdev b stdev c stdev S ampl n  t test  2  t 6.314  2  6.314  4  2.132  4  2.132  4  2.132  4  2.132  3  2.92  3  2.92  3  2.92  3  2.92  3  2.92  4000,10 Column 2  7  0.96049 0.79719 1.58339  4000,10 Column 2  10  0.96361 0.92925 1.39666  2000,10 Column 1  3  1.49012 2.15492 2.47212  2000,10 Column 1  8  1.32546 1.59285 1.63663  2000,10 Column 1  12  1.34841 0.97498 2.00203  2000,10 Column 1  13  0.98829  2000,10 Column 2  5  1.55115 1.57668 1.89486  2000,10 Column 2  9  1.39649  2000,10 Column 2  14  0.81642 1.09256  Raw, Column 1  25  2.66683 2.48096 1.51736  Raw, Column 1  27  2.51378 2.22517 0.50666  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  1.288  1.425  2.300  0.002  0.213  0.093  0.567  0.132  0.627  0.9759 3.08819 1.2366 1.42665  1.255  1.302  1.780  0.387  0.249  0.312  2.0191 2.546  2.383  2.069  2.680  0.835  2.223  0.108  0.235  0.508  0.263  0.591  0.851  Error (a)  Error (b)  Error (c)  0.0098  0.4169  0.5895  0.2267  0.6046  0.6685  0.6530  0.4191  0.5267  0.1821  0.8566  0.9967  0.2502  0.2804  0.9067  157  Table L-2 - Biodegradation analysis of % non-biodegradable for DOC Variables  % nonbiodegra Average dable  Oxidation  ID a  b  c  1mg, Column 1  15  3.114  2.412  1.942  56%  1mg, Column 1  17  2.738  2.257  1.782  1mg, Column 1  23  2.973  1.637  1.171  1mg, Column 2  16  2.642  2.884  2.612  1mg, Column 2  18  2.599  2.402  1.213  1mg, Column 2  24  2.468  2.243  1.924  2mg, Column 1  19  2.870  1.716  1.772  2mg, Column 1  21  2.747  1.748  1.316  2mg, Column 1  37  2.832  1.956  1.808  2mg, Column 2  20  2.336  2.155  1.567  55% 64% 48% 52% 52% 63% 61% 59% 52%  2mg, Column 2  22  2.409  2.058  1.081  2mg, Column 2  36  2.542  2.168  2.193  Extended, Column 1  40  0.84394 1.90845 0.61641  Extended, Column 1  41  0.84951 1.98462 0.63608  Extended, Column 2  42  0.68948 1.79511 0.46431  Extended, Column 2  43  0.61014 1.88826 0.43379  4000,0 Column 1  31  2.50299 1.78627 1.88347  4000,0 Column 1  33  2.42443 1.73288  4000,0 Column 2  32  1.98264 2.07546 1.50524  4000,0 Column 2  34  2.0776 2.09951 1.86904  4000,10 Column 1  1  0.88089 1.27537 2.44539  4000,10 Column 1  6  0.95692 0.98943  2.8685  4000,10 Column 1  11  0.79569 0.94663  2.4986  4000,10 Column 2  7  0.96049 0.79719 1.58339  4000,10 Column 2  10  0.96361 0.92925 1.39666  2000,10 Column 1  3  1.49012 2.15492 2.47212  2000,10 Column 1  8  1.32546 1.59285 1.63663  2000,10 Column 1  12  1.34841 0.97498 2.00203  2000,10 Column 1  13  0.98829  2000,10 Column 2  5  1.55115 1.57668 1.89486  2000,10 Column 2  9  1.39649  2000,10 Column 2  14  0.81642 1.09256  Raw, Column 1  25  2.66683 2.48096 1.51736  Raw, Column 1  27  2.51378 2.22517 0.50666  Raw, Column 1  35  2.45825 1.50135 0.48051  Raw, Column 2  26  2.51434 2.38034 1.54561  Raw, Column 2  28  2.03146 3.02042 1.46405  Raw, Column 2  38  2.4875 2.68266 3.16743  Raw, Column 2  39  2.49896 2.63664 2.71658  1.6194  0.9759 3.08819 1.2366 1.42665 2.0191  54% 54% 31% 30% 28% 24% 58% 58% 49% 50% 41% 49% 46% 55% 51% 41% 45% 58% 50% 50% 53% 43% 52% 53% 62% 51% 40% 48% 49%  Std Dev  N  T  Error  59%  5%  3  2.92  9%  51%  3%  3  2.92  4%  61%  2%  3  2.92  3%  53%  1%  3  2.92  2%  30%  0%  2  6.314  2%  26%  2%  2  6.314  11%  58%  0%  2  6.314  0%  49%  1%  2  6.314  3%  45%  4%  3  2.92  7%  53%  3%  2  6.314  12%  49%  7%  4  2.132  8%  48%  5%  3  2.92  9%  56%  6%  3  2.92  9%  47%  5%  4  2.132  5%  158  APPENDIX M. BIODEGRADATION CURVES FOR SUVA 0.14  0.16  Curve 15.0 BAC Column 1  0.12  Curve 17.0 BAC Column 1  0.14 0.12  0.1  SUVA  SUVA  0.1 0.08 0.06  0.06  Generated Curve Fit 90% Confidence Interval 90% Confidence Interval Actual Data  0.04 0.02  0.08 Generated Curve Fit 90% Confidence Interval 90% Confidence Interval Actual Data  0.04 0.02  0  0 0  1  2  3  4  5  6  7  0  1  2  Time (Days)  3  4  0.16  6  7  0.14  Curve 23.0 BAC Column 1  0.14 0.12  Curve 16.0 BAC Column 2  0.12  Generated Curve Fit 90% Confidence Interval 90% Confidence Interval Actual Data  0.1  SUVA  0.1  SUVA  5  Time (Days)  0.08 0.06  Generated Curve Fit 90% Confidence Interval 90% Confidence Interval Actual Data  0.04 0.02  0.08 0.06 0.04 0.02  0  0 0  1  2  3  4  5  6  7  0  1  2  Time (Days)  3  4  5  6  7  Time (Days)  Figure M-1 - Biodegradation test results for 1mgO3/mg DOC  159  0.16  0.16  Curve 18.0 BAC Column 2  Generated Curve Fit 90% Confidence Interval 90% Confidence Interval Actual Data  0.12  SUVA  0.1 0.08  0.1 0.08 0.06  0.04  0.04  0.02  0.02  0  0 1  2  3  4  5  6  Generated Curve Fit 90% Confidence Interval 90% Confidence Interval Actual Data  0.12  0.06  0  Curve 24.0 BAC Column 2  0.14  SUVA  0.14  7  0  1  2  Time (Days)  3  4  5  6  7  Time (Days)  Figure M-2 - Biodegradation test results for 1mgO3/mg DOC  160  0.14  0.12  Curve 19.0 BAC Column 1  0.12  Curve 21.0 BAC Column 1  0.1  0.1  SUVA  SUVA  0.08 0.08 0.06 Generated Curve Fit 90% Confidence Interval 90% Confidence Interval Actual Data  0.04 0.02  0.06 Generated Curve Fit 90% Confidence Interval 90% Confidence Interval Actual Data  0.04 0.02  0  0 0  1  2  3  4  5  6  7  0  1  2  3  Time (Days) 0.14  5  6  7  0.14  Curve 37.0 BAC Column 1  0.12 0.1  0.1  0.08  0.08  0.06 Generated Curve Fit 90% Confidence Interval 90% Confidence Interval Actual Data  0.04 0.02  Curve 20.0 BAC Column 2  0.12  SUVA  SUVA  4  Time (Days)  0.06 Generated Curve Fit 90% Confidence Interval 90% Confidence Interval Actual Data  0.04 0.02  0  0 0  1  2  3  4  5  6  7  0  1  2  Time (Days)  3  4  5  6  7  Time (Days)  Figure M-3 - Biodegradation test results for 2mgO3/mg DOC  161  0.12  0.14  Curve 22.0 BAC Column 2  0.1  Curve 36.0 BAC Column 2  0.12  Generated Curve Fit 90% Confidence Interval 90% Confidence Interval Actual Data  0.1  SUVA  SUVA  0.08 0.06 Generated Curve Fit 90% Confidence Interval 90% Confidence Interval Actual Data  0.04 0.02  0.08 0.06 0.04 0.02  0  0 0  1  2  3  4  5  6  7  0  1  2  Time (Days)  3  4  5  6  7  Time (Days)  Figure M-4 - Biodegradation test results for 2mgO3/mg DOC  162  0.16  0.16  Curve 31.0 BAC Column 1  Generated Curve Fit 90% Confidence Interval 90% Confidence Interval Actual Data  0.12  SUVA  0.1 0.08  0.12  0.08 0.06  0.04  0.04  0.02  0.02  0  0 1  2  3  4  5  6  Generated Curve Fit 90% Confidence Interval 90% Confidence Interval Actual Data  0.1  0.06  0  Curve 33.0 BAC Column 1  0.14  SUVA  0.14  7  0  1  2  Time (Days) 0.16  4  5  6  7  0.16  Curve 32.0 BAC Column 2  0.12  Generated Curve Fit 90% Confidence Interval 90% Confidence Interval Actual Data  0.1 0.08  0.12  0.08 0.06  0.04  0.04  0.02  0.02  0  0 1  2  3  4  Time (Days)  5  6  7  Generated Curve Fit 90% Confidence Interval 90% Confidence Interval Actual Data  0.1  0.06  0  Curve 34.0 BAC Column 2  0.14  SUVA  0.14  SUVA  3  Time (Days)  0  1  2  3  4  5  6  7  Time (Days)  Figure M-5 - Biodegradation test results for 4000mJ/cm2 and 0mg/L H2O2  163  0.07  0.08  Curve 3.0 BAC Column 1  0.06  Generated Curve Fit 90% Confidence Interval 90% Confidence Interval Actual Data  0.04 0.03  Generated Curve Fit 90% Confidence Interval 90% Confidence Interval Actual Data  0.06 0.05  SUVA  SUVA  0.05  Curve 8.0 BAC Column 1  0.07  0.04 0.03  0.02  0.02  0.01  0.01  0  0 0  1  2  3  4  5  6  7  0  1  2  Time (Days) 0.06  4  5  6  7  0.04  Curve 12.0 BAC Column 1  0.05  Generated Curve Fit 90% Confidence Interval 90% Confidence Interval Actual Data  0.03  Curve 13.0 BAC Column 1  0.035  Generated Curve Fit 90% Confidence Interval 90% Confidence Interval Actual Data  0.03 0.025  SUVA  0.04  SUVA  3  Time (Days)  0.02 0.015  0.02  0.01 0.01  0.005  0  0 0  1  2  3  4  Time (Days)  5  6  7  0  1  2  3  4  5  6  7  Time (Days)  Figure M-6 - Biodegradation test results for 2000mJ/cm2 and 10mg/L H2O2  164  0.06  0.04  Curve 5.0 BAC Column 2  0.035  Generated Curve Fit 90% Confidence Interval 90% Confidence Interval Actual Data  0.03  0.05  Generated Curve Fit 90% Confidence Interval 90% Confidence Interval Actual Data  SUVA  0.04  0.02 0.015  0.03 0.02  0.01 0.01  0.005 0  0 0  1  2  3  4  5  6  7  0  1  2  3  Time (Days)  4  5  6  7  Time (Days)  0.04  Curve 14.0 BAC Column 2  0.035  Generated Curve Fit 90% Confidence Interval 90% Confidence Interval Actual Data  0.03 0.025  SUVA  SUVA  0.025  Curve 9.0 BAC Column 2  0.02 0.015 0.01 0.005 0 0  1  2  3  4  5  6  7  Time (Days)  Figure M-7 - Biodegradation test results for 2000mJ/cm2 and 10mg/L H2O2  165  0.03  0.04  Curve 1.0 BAC Column 1  0.025  Generated Curve Fit 90% Confidence Interval 90% Confidence Interval Actual Data  0.015  Generated Curve Fit 90% Confidence Interval 90% Confidence Interval Actual Data  0.03 0.025  SUVA  SUVA  0.02  Curve 6.0 BAC Column 1  0.035  0.02 0.015  0.01  0.01 0.005  0.005  0  0 0  1  2  3  4  5  6  7  0  1  2  Time (Days) 0.04  4  5  6  7  0.04  Curve 11.0 BAC Column 1  0.035  Generated Curve Fit 90% Confidence Interval 90% Confidence Interval Actual Data  0.03  0.02  0.025 0.02 0.015  0.01  0.01  0.005  0.005  0  0 1  2  3  4  Time (Days)  5  6  7  Generated Curve Fit 90% Confidence Interval 90% Confidence Interval Actual Data  0.03  0.015  0  Curve 7.0 BAC Column 2  0.035  SUVA  0.025  SUVA  3  Time (Days)  0  1  2  3  4  5  6  7  Time (Days)  Figure M-8 - Biodegradation test results for 4000mJ/cm2 and 10mg/L H2O2  166  0.04  Curve 10.0 BAC Column 2  0.035  Generated Curve Fit 90% Confidence Interval 90% Confidence Interval Actual Data  0.03  SUVA  0.025 0.02 0.015 0.01 0.005 0 0  1  2  3  4  5  6  7  Time (Days)  Figure M-9 - Biodegradation test results for 4000mJ/cm2 and 10mg/L H2O2  167  0.2  0.2  Curve 25.0 BAC Column 1  0.18 0.16  Generated Curve Fit 90% Confidence Interval 90% Confidence Interval Actual Data  0.12  0.16  0.1 0.08  0.12 0.1 0.08  0.06  0.06  0.04  0.04  0.02  0.02  0  0 0  1  2  3  4  5  6  7  0  1  2  Time (Days)  3  4  5  6  7  Time (Days)  0.2  0.2  Curve 35.0 BAC Column 1  0.18 0.16  Generated Curve Fit 90% Confidence Interval 90% Confidence Interval Actual Data  0.14 0.12 0.1 0.08  0.16 0.12 0.1 0.08 0.06  0.04  0.04  0.02  0.02  0  0 1  2  3  4  5  6  7  Generated Curve Fit 90% Confidence Interval 90% Confidence Interval Actual Data  0.14  0.06  0  Curve 26.0 BAC Column 2  0.18  SUVA  SUVA  Generated Curve Fit 90% Confidence Interval 90% Confidence Interval Actual Data  0.14  SUVA  SUVA  0.14  Curve 27.0 BAC Column 1  0.18  0  1  2  Time (Days)  3  4  5  6  7  Time (Days)  Figure M-10 - Biodegradation test results for raw water samples  168  0.25  0.2  Curve 28.0 BAC Column 2  Curve 38.0 BAC Column 2  0.18 0.16  Generated Curve Fit 90% Confidence Interval 90% Confidence Interval Actual Data  0.14 0.12  SUVA  0.15 0.1  0.1 0.08 0.06  0.05  0.04 0.02  0  0 0  1  2  3  4  5  6  7  0  1  2  3  Time (Days)  4  5  6  7  Time (Days) 0.2  Curve 39.0 BAC Column 2  0.18 0.16  Generated Curve Fit 90% Confidence Interval 90% Confidence Interval Actual Data  0.14  SUVA  SUVA  0.2  Generated Curve Fit 90% Confidence Interval 90% Confidence Interval Actual Data  0.12 0.1 0.08 0.06 0.04 0.02 0 0  1  2  3  4  5  6  7  Time (Days)  Figure M-11 - Biodegradation test results for raw water samples  169  APPENDIX N. BIODEGRADATION TEST ANALYSIS RESULTS FOR SUVA Table N-1 - Biodegradation curve analysis results for SUVA Oxidation  ID  1mg, Column 1 1mg, Column 1 1mg, Column 1  15 17 23  1mg, Column 2 1mg, Column 2 1mg, Column 2 2mg, Column 1 2mg, Column 1  16 18 24 19 21  2mg, Column 1 2mg, Column 2 2mg, Column 2 2mg, Column 2  37 20 22 36  4000,0 Column 1 4000,0 Column 1 4000,0 Column 2 4000,0 Column 2  31 33 32 34  4000,10 Column 1 4000,10 Column 1 4000,10 Column 1 4000,10 Column 2 4000,10 Column 2  1 6 11 7 10  Variables a b c 0.06455 0.06255 0.83051 0.06081 0.06869 9.0581 0.07041 0.05706 1.286 0.05602 0.06725 1.40967 0.05183 0.07232 1.26796 0.05085 0.07531 1.64377 0.06302 0.05054 2.1454 0.05852 0.04584 1.68405 0.06123 0.05778 1.4891 0.04622 0.06134 1.46622 0.04681 0.0579 1.77716 0.04922 0.06775 2.88359 0.05271 0.06916 1.78344 0.04459 0.08218 1.16448 0.02958 0.09117 1.20847 0.0367 0.09885 1.8782 0.01626 0.01064 6.93199 0.01494 0.01873 6.73574 0.0127 0.01799 6.66209 0.01319 0.02066 9.54416 0.01294 0.01799 7.1755  a  Average b  c  0.067  0.060  1.058  0.004  0.004  0.322  0.053  0.072  1.440  0.003  0.004  0.190  0.061  0.051  1.773  0.002  0.006  0.337  S tandard Deviation a stdev b stdev c stdev  0.047  0.062  2.042  0.002  0.005  0.745  0.049  0.076  1.474  0.006  0.009  0.438  0.033  0.095  1.543  0.005  0.005  0.474  0.015  0.016  6.777  0.002  0.004  0.140  0.013  0.019  8.360  0.000  0.002  1.675  # of n 2 2 2  t test t 6.314 6.314 6.314  3 3 3 3 3  2.92 2.92 2.92 2.92 2.92  3 3 3 3  2.92 2.92 2.92 2.92  2 2 2 2  6.314 6.314 6.314 6.314  3 3 3 2 2  2.92 2.92 2.92 6.314 6.314  Error (a)  Error (b)  Error (c)  0.0185  0.0173  1.4380  0.0046  0.0069  0.3200  0.0038  0.0101  0.5682  0.0027  0.0084  1.2559  0.0256  0.0411  1.9540  0.0225  0.0242  2.1143  0.0030  0.0075  0.2352  0.0008  0.0084  7.4779  170  Oxidation  ID  2000,10 Column 1  3  2000,10 Column 1  8  2000,10 Column 1 2000,10 Column 1  12 13  2000,10 Column 2  5  2000,10 Column 2  9  2000,10 Column 2  14  Raw, Column 1  25  Raw, Column 1  27  Raw, Column 1  35  Raw, Column 2 Raw, Column 2  26 28  Raw, Column 2  38  Raw, Column 2  39  Variables a b c 0.02651 0.02553 3.83604 0.02407 0.03834 2.64703 0.02165 0.02586 2.92244 0.0138 0.0192 9.1839 0.01608 0.01408 1.13352 0.01918 0.03117 1.96156 0.00938 0.0246 9.83805 0.06637 0.1017 1.61297 0.05746 0.10843 0.77662 0.07332 0.07971 2.24371 0.06282 0.10931 1.64948 0.05606 0.12548 2.62282 0.05615 0.10883 1.66028 0.05957 0.10929 1.63307  Average a  b  S tandard Deviation  c  # of S ampl a stdev b stdev c stdev n  0.024  0.030  3.135  0.002  0.007  0.622  0.015  0.023  4.311  0.005  0.009  4.804  0.066  0.059  0.097  0.113  1.544  1.891  0.008  0.003  0.015  0.008  0.736  0.488  t test  3  t 2.92  3  2.92  3 3  2.92 2.92  3  2.92  3  2.92  3  2.92  3  2.92  3  2.92  3  2.92  4 4  2.132 2.132  4  2.132  4  2.132  Error (a)  Error (b)  Error (c)  0.0041  0.0123  1.0493  0.0084  0.0145  8.0996  0.0134  0.0253  1.2407  0.0034  0.0087  0.5199  171  Table N-2 - Biodegradation analysis of % non-biodegradable for SUVA Variables  % nonbiodegra Average dable  Oxidation  ID  1mg, Column 1  15  0.06455 0.06255 0.83051  51%  1mg, Column 1  17  0.06081 0.06869 9.0581  1mg, Column 1  23  0.07041 0.05706  1mg, Column 2  16  0.05602 0.06725 1.40967  1mg, Column 2  18  0.05183 0.07232 1.26796  1mg, Column 2  24  0.05085 0.07531 1.64377  2mg, Column 1  19  0.06302 0.05054 2.1454  2mg, Column 1  21  0.05852 0.04584 1.68405  2mg, Column 1  37  0.06123 0.05778 1.4891  2mg, Column 2  20  0.04622 0.06134 1.46622  47% 55% 45% 42% 40% 55% 56% 51% 43%  2mg, Column 2  22  0.04681 0.0579 1.77716  45% 42% 43% 35% 24% 27% 60% 44% 41% 39% 42% 51% 39% 46% 42% 53% 38% 28% 39% 35% 48% 36% 31% 34% 35%  a  b  c  1.286  2mg, Column 2  36  0.04922 0.06775 2.88359  4000,0 Column 1  31  0.05271 0.06916 1.78344  4000,0 Column 1  33  0.04459 0.08218 1.16448  4000,0 Column 2  32  0.02958 0.09117 1.20847  4000,0 Column 2  34  0.0367 0.09885 1.8782  4000,10 Column 1  1  0.01626 0.01064 6.93199  4000,10 Column 1  6  0.01494 0.01873 6.73574  4000,10 Column 1  11  0.0127 0.01799 6.66209  4000,10 Column 2  7  0.01319 0.02066 9.54416  4000,10 Column 2  10  0.01294 0.01799 7.1755  2000,10 Column 1  3  0.02651 0.02553 3.83604  2000,10 Column 1  8  0.02407 0.03834 2.64703  2000,10 Column 1  12  0.02165 0.02586 2.92244  2000,10 Column 1  13  0.0138 0.0192 9.1839  2000,10 Column 2  5  0.01608 0.01408 1.13352  2000,10 Column 2  9  0.01918 0.03117 1.96156  2000,10 Column 2  14  0.00938 0.0246 9.83805  Raw, Column 1  25  0.06637 0.1017 1.61297  Raw, Column 1  27  0.05746 0.10843 0.77662  Raw, Column 1  35  0.07332 0.07971 2.24371  Raw, Column 2  26  0.06282 0.10931 1.64948  Raw, Column 2  28  0.05606 0.12548 2.62282  Raw, Column 2  38  0.05615 0.10883 1.66028  Raw, Column 2  39  0.05957 0.10929 1.63307  Std Dev  N  T  Error  51%  4%  3  2.92  7%  43%  3%  3  2.92  4%  54%  3%  3  2.92  4%  43%  1%  3  2.92  2%  39%  6%  3  2.92  10%  26%  2%  3  2.92  3%  49%  10%  3  2.92  17%  40%  2%  2  6.314  9%  44%  5%  4  2.132  6%  40%  13%  3  2.92  22%  41%  7%  3  2.92  34%  2%  4  2.132  11%  3%  172  Table N-3 - Biodegradation average curve parameters for BAC Column 1 and BAC Column 2  Average  Oxidation Raw, BAC Column 1 4000,0 BAC Column 1 2000,10 BAC Column 1 4000,10 BAC Column 1 1mg, BAC Column 1 2mg, BAC Column 1 Raw, BAC Column 2 4000,0 BAC Column 2 2000,10 BAC Column 2 4000,10 BAC Column 2 1mg, BAC Column 2 2mg, BAC Column 2  DOCnon (a)  DOCi (b)  kDOC (1/c)  0.066 (±0.013) 0.049 (±0.026) 0.024 (±0.004) 0.015 (±0.003) 0.067 (±0.019) 0.061 (±0.004) 0.059 (±0.003) 0.033 (±0.022) 0.015 (±0.008) 0.013 (±0.003) 0.053 (±0.005) 0.047 (±0.003)  0.097 (±0.025) 0.076 (±0.041) 0.030 (±0.012) 0.016 (±0.008) 0.060 (±0.017) 0.051 (±0.010) 0.113 (±0.009) 0.095 (±0.024) 0.023 (±0.015) 0.019 (±0.008) 0.072 (±0.007) 0.062 (±0.008)  0.784 (±0.749) 0.709 (±0.941) 0.327 (±0.101) 0.147 (±0.005) 0.991 (±1.34) 0.577(±0.174) 0.551 (±0.120) 0.680 (±0.932) 0.498 (±0.658) 0.122 (±0.005) 0.702 (±0.152) 0.53 (±0.286)  0.1  BAC Column 1  Parameter a - UVAresidual  0.09  BAC Column 2  0.08 0.07  3  0 0  0.06  -7 -26 -10 -19  0.05 0.04  -43 -63  0.03 0.02  -75  -78  -78  0.01 0 Raw  4000 mJ/cm2 & 2000 mJ/cm2 & 4000 mJ/cm2 & 0 mg/L H2O2 10 mg/L H2O2 10 mg/L H2O2  Ozonated (1mg O3/mg DOC)  Ozonated (2mg O3/mg DOC)  Figure N-1 - Parameter a for each oxidation scenario for BAC Column 1 and 2  173  2.5  Series1 Series2  Parameter k=1/c - Kinetic Rate Constant 2  1.5  26 1 0  -10  28  24  -26  0 0.5  -10  -4  -58 -81  -78  0 Raw -0.5  4000 mJ/cm2 & 2000 mJ/cm2 & 4000 mJ/cm2 & 0 mg/L H2O2 10 mg/L H2O2 10 mg/L H2O2  Ozonated (1mg O3/mg DOC)  Ozonated (2mg O3/mg DOC)  Figure N-2 - Parameter c for each oxidation scenario for BAC Column 1  174  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.  175  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.  176  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.  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. Measured at time 0, 1 day, 7 days, using biomass from BAC Column 1 and BAC Column 2.  178  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.  179  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.  180  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.  181  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.  182  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.  183  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.  184  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.  185  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.  186  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.  187  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.  188  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.  189  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.  190  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.  191  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.  192  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.  193  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.  194  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.  195  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.  196  APPENDIX Q. 0.25  BIODEGRADATION BAR GRAPH RESULTS 0 0  Area Count  0.2 0.15  0 -37  -48  Raw 1 day 7 days -38  ID 25 RAW Column 1  0 0  0.1  -32  -63  -67  -10 -69  -79  0.05  0-10 -51  -68  0 > 1350 (F1)  1050 - 1350 750 - 1050 500 - 750 300 - 500 (F2) (F3) (F4) (F5) Molecular Weight (Da)  0.25 0  0  0  Area Count  0.2 -31  0.15  -30  0.1  Raw 1 day 7 days -31  ID 27 RAW Column 1  0  0 -32  -57  -61  < 300 (F6)  -73  -62  0.05  -37  0 -32 -50  -66  0 > 1350 (F1) 0.35  1050 - 1350 750 - 1050 500 - 750 300 - 500 (F2) (F3) (F4) (F5) Molecular Weight (Da)  0  Raw 1 day 7 days  0.3 Area Count  0.25  -34  < 300 (F6)  ID 35 RAW Column 1  0.2 0.15  -60  0 -37 -50  0.1 0.05  0 -43 -58  0  0 -40 -47  0  -40-54  -51 -58  0 > 1350 (F1)  1050 - 1350 750 - 1050 500 - 750 300 - 500 (F2) (F3) (F4) (F5) Molecular Weight (Da)  < 300 (F6)  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.  197  0.25 0 0.2 Area Count  Raw 1 day 7 days  0 0  0.15  -39  -48 0.1  -37  -60  0  -60  -73  ID 26 RAW Column 2 0 -23  0  -67  0.05  -48  -10 -56  -71  0  Area Count  > 1350 (F1) 0.2 0.18 0.16 0.14 0.12 0.1 0.08 0.06 0.04 0.02 0  1050 - 1350 750 - 1050 500 - 750 300 - 500 (F2) (F3) (F4) (F5) Molecular Weight (Da) 0  0  0  Raw 1 day 7 days  ID 28 RAW Column 2  0 -48  -52  -78 -84  > 1350 (F1)  < 300 (F6)  0  -53 -73  -53 -75  0 -63 -10-64  1050 - 1350 750 - 1050 500 - 750 300 - 500 (F2) (F3) (F4) (F5) Molecular Weight (Da)  -75  < 300 (F6)  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.  198  0.35  0  Raw 1 day 7 days  0.3 Area Count  0.25 0.2  -52  0  0.15 0.1  -73  0 -58 -82  0.05  ID 39 RAW Column 2  0  0 -58 -80  -64 -75  0 -10-70  -76  -55  0 > 1350 (F1)  1050 - 1350 750 - 1050 500 - 750 300 - 500 (F2) (F3) (F4) (F5) Molecular Weight (Da)  < 300 (F6)  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.  199  Area Count  0.2 0.18 0.16 0.14 0.12 0.1 0.08 0.06 0.04 0.02 0  ID 19 Ozone 2mg Column 1 0 0  Area Count Area Count  -33 -46  0 -41 -52  1050 - 1350 750 - 1050 500 - 750 300 - 500 (F2) (F3) (F4) (F5) Molecular Weight (Da)  ID 21 Ozone 2mg Column 1 0 0  -42 -51 -71  -72  -74  -73  -76  -42 -53  -45 -55  -44 -53  0  Raw Treated Time 1 Day Time 7 Days  -71  < 300 (F6)  0  -34  0 0 -35 -55 -69  > 1350 (F1) 0.2 0.18 0.16 0.14 0.12 0.1 0.08 0.06 0.04 0.02 0  0  0  > 1350 (F1)  0.2 0.18 0.16 0.14 0.12 0.1 0.08 0.06 0.04 0.02 0  0  Raw Treated Time 1 Day Time 7 Days  44  -43 -53 -68  -41 -52 -64  -48 -55 -68  0  0  -20  -55 -76  > 1350 (F1)  < 300 (F6)  Raw Treated Time 1 Day Time 7 Days  ID 37 Ozone 2mg Column 1  -14 -27  -42 -52 -63  1050 - 1350 750 - 1050 500 - 750 300 - 500 (F2) (F3) (F4) (F5) Molecular Weight (Da)  0  -52 -61  -47 -68 -75  0  0 -37 -67 -68  -15  0 -37 -62 -68  1050 - 1350 750 - 1050 500 - 750 300 - 500 (F2) (F3) (F4) (F5) Molecular Weight (Da)  -59 -68  < 300 (F6)  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  200  Area Count  0.2 0.18 0.16 0.14 0.12 0.1 0.08 0.06 0.04 0.02 0  ID 20 Ozone 2mg Column 2 0 0  Area Count Area Count  -33 0  -41 -58 -70  -44 -62 -66  -42 -60 -65  -45 -62 -67  0 0  -42 -60  -63 -59 -64  1050 - 1350 750 - 1050 500 - 750 300 - 500 (F2) (F3) (F4) (F5) Molecular Weight (Da)  ID 22 Ozone 2mg Column 2 0  Raw Treated Time 1 Day Time 7 Days  < 300 (F6)  0  -33  0  -64 -53  0 -41 -50 -73  > 1350 (F1) 0.2 0.18 0.16 0.14 0.12 0.1 0.08 0.06 0.04 0.02 0  0  0  > 1350 (F1) 0.2 0.18 0.16 0.14 0.12 0.1 0.08 0.06 0.04 0.02 0  0  Raw Treated Time 1 Day Time 7 Days  36  -44 -62 -69  -42  -45  -42 -73-66  -69-69  1050 - 1350 750 - 1050 500 - 750 300 - 500 (F2) (F3) (F4) (F5) Molecular Weight (Da)  0  < 300 (F6)  Raw Treated Time 1 Day Time 7 Days  ID 36 Ozone 2mg Column 2  0  -68 -65  0  -22 0 -52 -67  -46 -70 -83  > 1350 (F1)  0  -63 -83  -16 -25 -47 -75  -76  0 -34 -60  -59 -74  1050 - 1350 750 - 1050 500 - 750 300 - 500 (F2) (F3) (F4) (F5) Molecular Weight (Da)  < 300 (F6)  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  201  Raw ID 15 Ozone 1mg Treated Column 1 Time 1 Day Time 7 Days  0.25  Area Count  0.2  0  0 0  -22 0.15  0  -30 -44 -68 -72  0.1  0 -11  0.05  -49 -60  -67 -76  -71 -77  -10 -49 -42  0 -16 -47 -57  0 > 1350 (F1)  1050 - 1350 750 - 1050 500 - 750 300 - 500 (F2) (F3) (F4) (F5) Molecular Weight (Da)  0.18  0 0  0.16  Area Count  0.14  -18  0  Raw ID 17 Ozone 1mg Treated Column 1 Time 1 Day Time 7 Days 0  -23  0.12  0  -29  0.1  < 300 (F6)  -9  -14  -46 -50  0 -10  0.08 -72 -73  0.06 0.04  -75 -75  -63 -59  -76 -73  -55 -52  0.02 0 > 1350 (F1) 0.18 0.16  Area Count  0.14  1050 - 1350 750 - 1050 500 - 750 300 - 500 (F2) (F3) (F4) (F5) Molecular Weight (Da)  ID 23 Ozone 1mg Column 1 0 0  0.1  0  0  0.12 -29 -25  0 -62  -57  -67  0.02  -23  -66  -52 -71  0.04  -10  -25  -31  -47  0.06  0  -29  -26  0.08  Raw Treated Time 1 Day Time 7 Days  < 300 (F6)  -77  -81  -78  0 > 1350 (F1)  1050 - 1350 750 - 1050 500 - 750 300 - 500 (F2) (F3) (F4) (F5) Molecular Weight (Da)  < 300 (F6)  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  202  Raw Treated Time 1 Day Time 7 Days  0.25  Area Count  0.2  0  0  0  ID 16 Ozone 1mg Column 2  -21 0  -29  0.15  0 -6  -17  -43 0.1  0 -7 -78  0.05  -91 -83  -92  -87 -73  -89 -82  -56 -87  -89 -63  0 > 1350 (F1)  1050 - 1350 750 - 1050 500 - 750 300 - 500 (F2) (F3) (F4) (F5) Molecular Weight (Da)  Raw Treated Time 1 Day -18 Time 7 Days  0.18  0 0  0.16  Area Count  0.14  0 -23  0.12  0  -29  0.1 0.08  -64 -55  0.06  ID 18 Ozone 1mg Column 2 0 -9  -14  0.04  -73 -75  -52 -56  0 -10  -61 -73  < 300 (F6)  -54 -81  -78  -73  0.02 0 > 1350 (F1) 0.18 0.16  Area Count  0.14  1050 - 1350 750 - 1050 500 - 750 300 - 500 (F2) (F3) (F4) (F5) Molecular Weight (Da)  0  0  0.12 0.1 0.08  Raw Treated Time 1 Day Time 7 0Days  ID 24 Ozone 1mg Column 2 0 -34 -51  -41  0.06  -68  0.04  -34 0  -12  -56  -65  -60 -67  0 -1  -19  -27  -31  < 300 (F6)  -67  -62  -56 -58  0.02 0 > 1350 (F1)  1050 - 1350 750 - 1050 500 - 750 300 - 500 (F2) (F3) (F4) (F5) Molecular Weight (Da)  < 300 (F6)  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  203  0.25  0  ID 40 Extended O3 Column 1  0.2 Area Count  0 0  0  0.15  Raw Treated Time 1 Day Time 7 Days 0  0  0.1 -99 -89  0.05  -96 -92 -92  -97  -87 -89  -90 -94 -89  -46 -58 -62  -92 -97 -97  -91  0 > 1350 (F1)  1050 - 1350 750 - 1050 500 - 750 300 - 500 (F2) (F3) (F4) (F5) Molecular Weight (Da)  0.18  0 0  0.16  Area Count  0.14  0  Raw Treated Time 1 Day Time 7 Days  ID 41 Ozone 1mg Column 1 0  0  0.12  -61 -57  0.1 0  0.08 0.06 0.04 0.02  < 300 (F6)  -80  -91  -93 -94  -90  -90  -95 -89  -60  -85 -83 -94 -90  -87  -92 -94  0 > 1350 (F1)  1050 - 1350 750 - 1050 500 - 750 300 - 500 (F2) (F3) (F4) (F5) Molecular Weight (Da)  < 300 (F6)  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.  204  0.18 0  0.16  Area Count  0.14  Raw ID 42 Extended O3 Treated Column 2 Time 1 Day Time 7 Days 0  0 0  0  0.12  -61  0.1 0  0.08 0.06  -80  -95  -91  0.04  -92 -99 -98  0.02  -66 -67  -85 -96  -97 -96  -94 -92  -95  0 > 1350 (F1) 0.18 0.16  Area Count  0.14 0.12  -96 -97  1050 - 1350 750 - 1050 500 - 750 300 - 500 (F2) (F3) (F4) (F5) Molecular Weight (Da)  Raw Treated Time 1 Day Time 7 Days 0  ID 43 Extended O3 Column 2  0  -70 0 -73 -73  0.08 -87  -78  -89  0.04 0.02  0  0  0  0.1 0.06  < 300 (F6)  -95 -92  -99 -98  -96 -95  -95  -94  -95 -93  -97 -97  0 > 1350 (F1)  1050 - 1350 750 - 1050 500 - 750 300 - 500 (F2) (F3) (F4) (F5) Molecular Weight (Da)  < 300 (F6)  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.  205  0.18 0.16  Area Count  0.14  0 0  -21  -12 -31  0.12 0.1  0  -42  Raw ID 31 UV 4000,0 Treated Column 1 Time 1 Day Time 7 Days 31  -32  0  1  0 8  -60  0.08  -63  -66  0.06  -55  0 -50  -75  0.04  -47  -80  0.02  -74  -74  0 > 1350 (F1)  1050 - 1350 750 - 1050 500 - 750 300 - 500 (F2) (F3) (F4) (F5) Molecular Weight (Da)  0.18 0.16  0 0 -28  Area Count  0.14  0  -23  -12  4  < 300 (F6)  Raw ID 33 UV 4000,0 Treated Column 1 Time 1 Day Time 7 Days 26  0.12  0  0.1  -49  0.08  -3  0 12  -52  -51  -64  0.06  0  -67  -71  -58  -78  0.04  -79  0.02  -78  -77  0 > 1350 (F1)  1050 - 1350 750 - 1050 500 - 750 300 - 500 (F2) (F3) (F4) (F5) Molecular Weight (Da)  < 300 (F6)  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.  206  0.18 0.16  Area Count  0.14  0 0  0  -22  -35  -12  Raw ID 32 UV 4000,0 Treated Column 2 Time 1 Day Time 7 Days 32  -13  0.12  0  0.1  0  0 10  0.08  -62  -59  0  -69  0.06 -79  0.04  -65  -74 -66  -83  -84  0.02  -86  -83  0 > 1350 (F1)  1050 - 1350 750 - 1050 500 - 750 300 - 500 (F2) (F3) (F4) (F5) Molecular Weight (Da)  0.18 0.16  0 0 -28  0  -23  -12  Area Count  0.14 0.12  < 300 (F6)  Raw ID 34 UV 4000,0 Treated Column 2 Time 1 Day Time 7 Days 26  -18  0  0.1  -3  0 12  0.08  -58  -64  0  0.06 -76  0.04  -75  -79 -85  0.02  -72 -73  -83  -86  -84  0 > 1350 (F1)  1050 - 1350 750 - 1050 500 - 750 300 - 500 (F2) (F3) (F4) (F5) Molecular Weight (Da)  < 300 (F6)  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.  207  Area Count  0.2 0.18 0.16 0.14 0.12 0.1 0.08 0.06 0.04 0.02 0  0  0  0  -92  Area Count Area Count  -74  -85 -87 -78  -84  0  -65 -77  -82 -76  -72  0  -44 -70 -69  -58 -76 -75  1050 - 1350 750 - 1050 500 - 750 300 - 500 (F2) (F3) (F4) (F5) Molecular Weight (Da)  0  < 300 (F6)  Raw ID 8 UV 2000,10 Treated Column 1 Time 1 Day Time 7 Days  0  0  0  -76  -42 -79  -83  -86  -90  > 1350 (F1) 0.2 0.18 0.16 0.14 0.12 0.1 0.08 0.06 0.04 0.02 0  0  -80  > 1350 (F1) 0.2 0.18 0.16 0.14 0.12 0.1 0.08 0.06 0.04 0.02 0  Raw ID 3 UV 2000,10 Treated Column 1 Time 1 Day Time 7 Days  0  -71  -61 -78  -83 -82  -85  0 -80 -68  -84  1050 - 1350 750 - 1050 500 - 750 300 - 500 (F2) (F3) (F4) (F5) Molecular Weight (Da) 0  0  -75 -69  -64  < 300 (F6)  Raw ID 12UV 2000,10 Treated Time 1 Day Column 1 Time 7 Days  0  0  0  -74 -81  -73  -89 -91  > 1350 (F1)  -88  -86  -84 -81  0  -62 -77 -78  -66 -79 -73  1050 - 1350 750 - 1050 500 - 750 300 - 500 (F2) (F3) (F4) (F5) Molecular Weight (Da)  -49 -73 -72  < 300 (F6)  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.  208  0.18  0  0  Raw ID 13UV 2000,10 Treated Column 1 Time 1 Day Time 7 Days  0  0.16  Area Count  0.14 0.12  -68  0.1  0  0  0.08  -65  -75  -31 -43  0  0.06  -81 -71  -59 -97  0.04  -92  -89  -96 -89  0.02  -86  -83  -82 -81  -86  0 > 1350 (F1)  1050 - 1350 750 - 1050 500 - 750 300 - 500 (F2) (F3) (F4) (F5) Molecular Weight (Da)  Raw ID 4 UV 2000,10 Treated Column 2 Time 1 Day Time 7 Days  0.16 0.14  0  0  0  Area Count  0.12 0.1  0  0  0.08 0.06  -92 -85  0.04  -70 -84  -83 -88  -87  < 300 (F6)  -84  -80  -54  -78 -83  0.02  0  -52  -29  -80  -84 -85  -76  0  Area Count  > 1350 (F1) 0.2 0.18 0.16 0.14 0.12 0.1 0.08 0.06 0.04 0.02 0  1050 - 1350 750 - 1050 500 - 750 300 - 500 (F2) (F3) (F4) (F5) Molecular Weight (Da) 0  0  Raw ID 5 UV 2000,10 Treated Time 1 Day Column 2 Time 7 Days  0  0 -82  -70  -79 -93  > 1350 (F1)  -91  -89  0 -59  -87  -92  < 300 (F6)  -62  -83 -87  -48  0 -82  -84 -76  -86 -85  1050 - 1350 750 - 1050 500 - 750 300 - 500 (F2) (F3) (F4) (F5) Molecular Weight (Da)  < 300 (F6)  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.  209  0.18  0  0  Raw ID 9 UV 2000,10 Treated Column 2 Time 1 Day Time 7 Days  0  0.16  Area Count  0.14 0.12 0.1 0.08  -71 -81  -80  0.06  -87  0.04  0  0  -74  -87  -89  0.02  -67  -83  -89  -45 -74  0  -53 -71  -71  -81 -81  -86  0  Area Count  > 1350 (F1) 0.2 0.18 0.16 0.14 0.12 0.1 0.08 0.06 0.04 0.02 0  1050 - 1350 750 - 1050 500 - 750 300 - 500 (F2) (F3) (F4) (F5) Molecular Weight (Da)  0  0  Raw ID 14 UV 2000,10 Treated Column 2 Time 1 Day Time 7 Days  0  0  0  -82 -68  -78  -97 > 1350 (F1)  -98 -98  -42  -58  -94  -98  < 300 (F6)  0  -91 -95  -91  -57 -86 -86  1050 - 1350 750 - 1050 500 - 750 300 - 500 (F2) (F3) (F4) (F5) Molecular Weight (Da)  -85 -85  < 300 (F6)  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.  210  0.18  0  0  Raw ID 1 UV 4000,10 Treated Column 1 Time 1 Day Time 7 Days  0  0.16  Area Count  0.14 0.12  0  0.1  0  0.08 0.04  -95 -92  -94  0.02  -70 -82  0  -95 -91  0.06  -83 -86  -90 -90 -86  -89  -81 -86 -85  -81  -79  0 > 1350 (F1)  1050 - 1350 750 - 1050 500 - 750 300 - 500 (F2) (F3) (F4) (F5) Molecular Weight (Da)  0.18 0.16  0  Raw ID 6 UV 4000,10 Treated Column 1 Time 1 Day Time 7 Days  0  0  Area Count  0.14 0.12  0  0.1  0  0.08 -90  0.04  -85 -86  -91 -92 -87  -96 -94 -88  -91  0.02  -75 -82  0  -93  0.06  < 300 (F6)  -86 -88 -86  -82  -82  0  Area Count  > 1350 (F1) 0.2 0.18 0.16 0.14 0.12 0.1 0.08 0.06 0.04 0.02 0  1050 - 1350 750 - 1050 500 - 750 300 - 500 (F2) (F3) (F4) (F5) Molecular Weight (Da) 0  0  Raw ID 11UV 4000,10 Treated Time 1 Day Column 1 Time 7 Days  0  0  -95 -91  -93 -94  > 1350 (F1)  -95  -89 -93 -92  < 300 (F6)  -90  0 0  -85 -89 -86  -87 -90 -85  1050 - 1350 750 - 1050 500 - 750 300 - 500 (F2) (F3) (F4) (F5) Molecular Weight (Da)  -82 -86 -83  < 300 (F6)  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.  211  0.18  0  0  Raw ID 2 UV 4000,10 Treated Column 2 Time 1 Day Time 7 Days  0  0.16  Area Count  0.14 0.12  0  0  0.1 0.08 -95  0.06  -95 -91  -91  0.04  -92  0.02  -79  -88 -89 -89  -85 -84  -79 -88 -87  -84 -87  -63  0  -81  0  Area Count  > 1350 (F1) 0.2 0.18 0.16 0.14 0.12 0.1 0.08 0.06 0.04 0.02 0  0  0  -94 -94  -93  -88  0  0  0.12  0  0.1 -95 -90  -90 -94  0.02  -94  -88 -92 -92  < 300 (F6)  0  0.08 0.04  -87 -88 -86  -83  Raw ID 10 UV 4000,10 Treated Time 1 Day Column 2 Time 7 Days  0  0.14  0.06  -77 -84 -83  0  1050 - 1350 750 - 1050 500 - 750 300 - 500 (F2) (F3) (F4) (F5) Molecular Weight (Da)  0.16  Area Count  0  -87 -88  -92  -96 -94 -90  -92  < 300 (F6)  Raw ID 7 UV 4000,10 Treated Column 2 Time 1 Day Time 7 Days  0  0  > 1350 (F1) 0.18  1050 - 1350 750 - 1050 500 - 750 300 - 500 (F2) (F3) (F4) (F5) Molecular Weight (Da)  -89  0  -83 -87 -84  -86 -90 -85  -79 -84 -81  0 > 1350 (F1)  1050 - 1350 750 - 1050 500 - 750 300 - 500 (F2) (F3) (F4) (F5) Molecular Weight (Da)  < 300 (F6)  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.  212  APPENDIX R.  BIODEGRADATION PERCENT REMOVAL RESULTS  100  RAW BAC Column 1 ID 26,28,38,39  90 80  Raw N/A Time 1 Day Time 7 Days  Percent Removal  70 60 50 40 30 20 10 0 > 1350 (F1)  1050 - 1350 (F2)  100  750 - 1050 (F3)  500 - 750 (F4)  RAW BAC Column 2 ID 25,27,39  90 80  300 - 500 (F5)  < 300 (F6)  Raw N/A Time 1 Day Time 7 Days  Percent Removal  70 60 50 40 30 20 10 0 > 1350 (F1)  1050 - 1350 (F2)  750 - 1050 (F3)  500 - 750 (F4)  300 - 500 (F5)  < 300 (F6)  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.  213  120  100  Percent Removal  Raw Treated (1mgO3/mgDOC) Time 1 Day Time 7 Days  1mgO3/mgDOC BAC Column 1 ID 15, 17, 23  80  60  40  20  0 > 1350 (F1)  120  750 - 1050 (F3)  1mgO3/mgDOC BAC Column 2 ID 16,18,24  100  Percent Removal  1050 - 1350 (F2)  500 - 750 (F4)  300 - 500 (F5)  < 300 (F6)  Raw Treated Time 1 Day Time 7 Days  80  60  40  20  0 > 1350 (F1)  1050 - 1350 (F2)  750 - 1050 (F3)  500 - 750 (F4)  300 - 500 (F5)  < 300 (F6)  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.  214  120  100  Percent Removal  Raw Treated Time 1 Day Time 7 Days  2mgO3/mgDOC BAC Column 1 ID 19, 21, 37  80  60  40  20  0 > 1350 (F1)  1050 - 1350 (F2)  750 - 1050 (F3)  500 - 750 (F4)  120  Percent Removal  < 300 (F6)  Raw Treated Time 1 Day Time 7 Days  2mgO3/mgDOC BAC Column 2 ID 20,22,36  100  300 - 500 (F5)  80  60  40  20  0 > 1350 (F1)  1050 - 1350 (F2)  750 - 1050 (F3)  500 - 750 (F4)  300 - 500 (F5)  < 300 (F6)  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.  215  140  Raw Treated Time 1 Day Time 7 Days  Extended Ozonation BAC Column 1 ID 40,41  120  Percent Removal  100 80 60 40 20 0 > 1350 (F1)  1050 - 1350 (F2)  750 - 1050 (F3)  500 - 750 (F4)  300 - 500 (F5)  Extended Ozonation BAC Column 2 ID 42,43  120  Raw Treated Time 1 Day Time 7 Days  100  Percent Removal  < 300 (F6)  80  60  40  20  0 > 1350 (F1)  1050 - 1350 (F2)  750 - 1050 (F3)  500 - 750 (F4)  300 - 500 (F5)  < 300 (F6)  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.  216  180  4000mJ/cm2 and 0 mg/L H2O2 BAC Column 1 ID 40,41  160  Percent Removal  140  Raw Treated Time 1 Day Time 7 Days  120 100 80 60 40 20 0 > 1350 (F1)  100 90  1050 - 1350 (F2)  750 - 1050 (F3)  500 - 750 (F4)  300 - 500 (F5)  < 300 (F6)  Raw Treated Time 1 Day Time 7 Days  4000mJ/cm2 and 0 mg/L H2 O2 BAC Column 1 ID 32,34  80 Percent Removal  70 60 50 40 30 20 10 0 > 1350 (F1)  1050 - 1350 (F2)  750 - 1050 (F3)  500 - 750 (F4)  300 - 500 (F5)  < 300 (F6)  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.  217  120  2000mJ/cm2 and 10 mg/L H2O2 BAC Column 1 ID 3,8,12,13  Percent Removal  100  Raw Treated Time 1 Day Time 7 Days  80  60  40  20  0 > 1350 (F1)  120  750 - 1050 (F3)  500 - 750 (F4)  2000mJ/cm2 and 10 mg/L H2O2 BAC Column 1 ID 4,5,9,14  100  Percent Removal  1050 - 1350 (F2)  300 - 500 (F5)  < 300 (F6)  Raw Treated Time 1 Day Time 7 Days  80  60  40  20  0 > 1350 (F1)  1050 - 1350 (F2)  750 - 1050 (F3)  500 - 750 (F4)  300 - 500 (F5)  < 300 (F6)  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.  218  120  4000mJ/cm2 and 10 mg/L H2O2 BAC Column 1 ID 1,6,11  Percent Removal  100  Raw Treated Time 1 Day Time 7 Days  80  60  40  20  0 > 1350 (F1)  120  750 - 1050 (F3)  500 - 750 (F4)  4000mJ/cm2 and 10 mg/L H2O2 BAC Column 2 ID 2,7,10  100  Percent Removal  1050 - 1350 (F2)  300 - 500 (F5)  < 300 (F6)  Raw Treated Time 1 Day Time 7 Days  80  60  40  20  0 > 1350 (F1)  1050 - 1350 (F2)  750 - 1050 (F3)  500 - 750 (F4)  300 - 500 (F5)  < 300 (F6)  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  219  

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