M.S. THESIS - Peng Pei - Arizona State University

METHYL ISOBORNEOL (MIB) AND GEOSMIN REMOVAL DURING
OZONE – BIOFILTRATION TREATMENT
by
Peng Pei
A Thesis Presented in Partial Fulfillment
of the Requirements for the Degree
Master of Science
ARIZONA STATE UNIVERSITY
December 2003

APPROVED:
METHYL ISOBORNEOL (MIB) AND GEOSMIN REMOVAL DURING
OZONE – BIOFILTRATION TREATMENT
by
Peng Pei
has been approved
December 2003
_______________________________________________________________________ , Chair
_______________________________________________________________________
_______________________________________________________________________
Supervisory Committee
ACCEPTED:
____________________________________
Department Chair
____________________________________
Dean, Graduate College

ABSTRACT
Earthy-musty odors are a prevalent customer complaint for drinking water
utilities. MIB (2-methylisoborneol) and geosmin (trans-1, 10-dimethyl-trans-9-decalol)
are the most common odorants and have threshold odor concentrations of 4 to 10 ng/L.
The general ambient MIB and geosmin concentrations range from 2 to 100 nanogram per
liter (ng/L). Common treatment processes for MIB and geosmin removal include
activated carbon sorption, oxidation and/or biodegradation. The combination of
ozonation and biofiltration processes may be the most efficient for T&O control.
Previous research has primarily focused on ozone-dose versus MIB-removal
relationships, rather than linked ozonation-biofiltration system. A thorough understanding
of ozone-biofiltration mechanisms for MIB and geosmin removal and predictive
relationships are needed to optimize design criteria. This work addresses the needs
through ozonation batch experiment, ozone-biofiltration pilot studies, full-scale utilities
survey, and modeling.
Ozone oxidizes geosmin to a greater extent than MIB in natural waters. Kinetic
oxidation rates of MIB and geosmin in natural waters were controlled by hydroxyl
radicals (HO • ). Second order rate constants between HO • and MIB or geosmin are
8.2×10 9 M -1 s -1 and 1.4×10 10 M -1 s -1 , respectively. Second order rate constants between
molecular ozone and MIB or geosmin are in the range of 0.1 to 1 M -1 s -1 . Biofiltration
after ozonation removes geosmin better than MIB. Filter media type and operation of
filters have the most important effects on MIB and geosmin removals (e.g. Bituminous
GAC > Lignite GAC > Anthracite > Sand). Filter biomass concentration is related to the
III

percentage of MIB or geosmin removals across the biofilters. Surveys of utilities
applying ozone-biofiltration treatment showed that 60-90% removals of MIB, 60-100%
removals of geosmin, and 20-40% removals of TOC could be achieved. Most of the
utilities had MIB and geosmin concentrations under 2 ng/L (the detection limit) in ozone-
biofiltration treated water.
IV

ACKNOWLEDGEMENTS
Many people have contributed to the information presented in this thesis. First of
all, I wish to thank my research advisor and committee chair, Dr. Paul Westerhoff, for his
guidance, advice, and encouragement during Master’s studies. I would like to thank my
committee members, Dr. Peter Fox and Dr. Jordan Peccia for their valuable feedbacks. I
also wish to express my appreciation to persons from cooperating agencies of this project.
This work would not have been done without helping from Dr. Scott Summers and Kerry
Meyer from Colorado University at Boulder, Dr. Zaid Chowdhury, Dr. Sunil Kommineni,
Dr. Shahnawaz Sinha and Aaron Dotson from Malcolm Pirnie Inc. In addition, this
project was founded by America Water Works Association Research Foundation.
I would like to thank Brijesh Nair who helped me in most part of the experiments.
Many thanks to Marisa Masles, Tom Collela, Peter Goguen, Dr. PengFei Chao, and Dr.
Mario Espara-Soto who provided consistent laboratorial assistance. I would like to extend
my acknowledge to my colleagues Dr. Yeomin Yoon, Mohammad Bazaman, and Wontae
Lee for helping in lab work.
Finally, but most importantly, I wish to thank my family and friends. I would like
to take this opportunity to express my deepest gratitude to my parents and my husband,
who always support me with love. Special thanks to my friends and fellow researchers
Qun He, Jixia Li, Wen Chen, Brijesh, and Zhuang Liu for their friendship, caring, and
valuable advice during difficult times.
V

TABLE OF CONTENTS
VI
Page
LIST OF TABLES ……………...………………………………………………...… xi
LIST OF FIGURES …………………………………………………………….…… xiii
CHAPTER 1: INTRODUCTION ……………………………...…………………….. 1
Overview …………………………………………………..……………...… 1
Objectives ….………………………….………...…………………………….. 4
CHAPTER 2: LITERATURE REVIEW…………….…..…………………………… 7
Sources of Earthy-Musty Odors in Natural Systems ………..……………… 7
Control of Earthy-Musty Odors during Drinking Water Treatment Process ..... 9
T&O Treatment Processes Summary ………………………….…..… 9
Oxidation ………………………………………………………….…… 10
Adsorption (Activated Carbon Adsorption) …………………………… 12
Biodegradation in Packed Beds ……………………………………… 13
Ozonation ……………………………………………………………….…….. 14
Mechanisms of Ozone Oxidation of Organic Micropollutants ………... 14
Dose Response Relationships for Taste and Odor Compounds …......… 17
Ozonation Byproducts and Control …………………………………..... 19
Biofiltration ……………………………………………………………….….. 24
Primary Substrate Utilization (AOC/BDOC) ………………………….. 24
Secondary Substrate Utilization (Micropollutants) ……………….…… 25
Effects of Design Factors on Biofiltration Performance ……...……….. 26

CHAPTER Page
VII
Biological Performance ………………….……………...…...………… 31
Biofiltration Models ………………………………………………….… 36
Integrated Ozone-Biofiltration Systems for T&O Removal ……………….… 37
Operational Experience ………………………………………………… 37
Summary of MIB & Geosmin Removal …………………………..…… 39
Overview of Research Gaps ………………………………………………….. 40
CHAPTER 3: EXPERIMENTAL METHODS ……………………………………… 41
Laboratory Ozonation Approach ……………………………………………... 41
Objectives of Natural and DI Water Ozonation …………………...…… 41
Ozonation Methodology ……………………………….……………..… 43
Source Waters and Chemicals …………………………………………. 47
Pilot Tests …………………………………………………………………….. 50
Objectives of Pilot Studies ……………………………………………... 51
Chandler Pilot Facility …………………………………………….…… 53
Squaw Peak Pilot Facility …………………………………………..….. 57
MIB and Geosmin Dosing Method …………………………………….. 61
Utility Survey ……………………………………………………………….... 63
Utilities ID and Treatment Processes ………………………………..… 63
Field Sampling Campaigns …………………………………………….. 69
Analytical Methods …………………………………………………………... 76
GC/MS with SPME Method Description ……………………………… 76

CHAPTER Page
VIII
PCBA Measurement ………………………………………………….... 83
BDOC Measurement …………………………….……..……………… 83
Dissolved O3 Measurement ………………………………………..…… 83
Measurement of Other Parameters …………………………………...… 85
CHAPTER 4: BENCH-SCALE OZONATION EXPERIMENTS ………………..…. 86
Lab Experiment Results and Discussion …………..………………………..... 86
Ozonation of Natural Waters ………………………………………..…. 86
Ozonation of Distilled Water ……………………………………...…… 87
Estimation of Rate Constants …………………………………………... 93
Methanol Effect on Ozonation Experiment ……………………………. 94
Conclusions ……………………………………………………………...…… 98
CHAPTER 5: OZONE-BIOFILTRATION REMOVAL OF MIB & GEOSMIN ---
PILOT STUDIES ……..…………………………………..………… 99
Chandler Pilot Study Results/Discussions ……………………………….….. 99
MIB and Geosmin Feed System …………...………………………….. 100
Ozone-Biofiltration Effects of MIB and Geosmin Removal ……….…. 102
Ozone-Biofiltration Effect of Other Water Parameters …………….…. 111
Disinfection By-products Formation/Removal ……………………...… 115
Summary ………………………………………………………………. 116
Squaw Peak Pilot Study Results/Discussions for MIB Results …………….... 117
Effect of EBCT on MIB Removal ………………………………..…… 119

CHAPTER Page
Effect of Ozonation on MIB Removal ………………………………… 120
Effect of Ozone-Biofiltratoin on MIB Removal …………………….… 121
Effect of Raw Water TOC on MIB Removal …………….………….… 122
Effect of Biomass Concentration on MIB Removal ……..........….…… 123
Effect of Backwash Water on MIB Removal …………….........….…… 124
Effect of Different Filter Media on MIB Removal ………….………..... 125
Effect of Ozone-Biofiltratoin on TOC Removal ………………….…… 126
Bromate Formation ……………………………….……………….…… 128
Summary of Pilot Studies Results ………………………………………..….. 129
CHAPTER 6: FULL-SCALE UTILITY SURVEY…………………….…………… 130
Results and Discussions …………………………………………...………… 130
MIB Removals …………………………………………………...……. 131
Geosmin Removals ……………………………………………….…… 134
TOC Removals ………………………………………………...………. 137
Biomass Results …..…………………………………………...………. 139
Summary of Utility Survey ……………………………………………..…… 141
CHAPTER 7: MODELING OZONE-BIOFILTRATION SYSTEMS …………….... 142
Ozone Module …………………………………………………………….…. 143
Ozone Residual Model …………………………………………..……. 143
MIB and Geosmin Residual Model …………………………………… 143
Bromate Formation Model ……………………………………….…… 145
IX

CHAPTER Page
CT Value Model ………………………………………………….…… 145
Input Parameters for Ozonation Module …...…………………………. 146
Biofiltration Module …………………………………………………………. 148
Solving of Secondary Utilization Equation ………….……………..….. 150
Input Parameters for Bio-filtration Module ……………………………. 151
Ozone-Biofiltration Modeling Results ……………………………………..… 152
Predicting Individual Parameter Effect ……………………………………… 155
Effect of Ozone Dose on MIB & Geosmin Removal ………………. 155
Effect of RCT Value on MIB & Geosmin Removal ………………....…. 157
Effect of Operational Parameters in Biofiltration on MIB Removal ….. 158
Recommendations for Optimizing Ozone-Biofiltration Process …………..… 160
CHAPTER 8: CONCLUSIONS AND RECOMMENDATIONS …………………... 161
REFERENCES …………………………………………………………………..….. 164
APPENDIX
A BATCH OZONATION EXPERIMENTS DATA ………………...…… 181
B PILOT SCALE OZONE - BIOFILTRATION DATA …….....….….…. 188
C FULL SCALE OZONE-BIOFILTRATION DATA ………...……….... 198
X

LIST OF TABLES
Table Page
1.1 Chemical/physical characteristics of MIB and geosmin ………………..…..…. 2
2.1 Percent removal of MIB and geosmin resulting from oxidation …………..….. 10
2.2 MIB and geosmin removals from ozonation tests of different natural waters ... 18
2.3 Odor threshold concentrations and odor types for various aldehydes ……...… 22
2.4 Effect of media and contact time in drinking water biofilters ………….……... 27
2.5 Removal of MIB and geosmin in biofilters …………………………………… 34
3.1 Experimental matrix of ozonation laboratory experiments of natural waters … 45
3.2 Experiment matrix of ozonation experiment in DI water …………………..… 46
3.3 Water quality of natural waters used for laboratory ozonation experiments …. 47
3.4 Filters design of Squaw Peak pilot facility ………………………………….… 59
3.5 Water treatment processes of utilities ……..………………………………….. 64
3.6 Sampling matrix and dates for utilities survey in 2002 and 2003 …………….. 69
3.7 Recovery of MIB and geosmin in the presence of 0.24 mg/L in natural waters 73
3.8 Recovery of MIB and geosmin in the presence of 0.18 mg/L Na3N in Arizona
Canal Water ………………………………………….………………… 74
3.9 Recovery of MIB and geosmin in presence of preservatives in CAP water ….. 74
3.10 Recovery of TOC in presence of preservatives in CAP water .......................... 75
3.11 GC/MS maintenance record during the period of Apr, 2002~Oct, 2003 …..… 80
3.12a MIB analysis method used before December 2002 ……………………...…… 81
3.12b MIB analysis method used after December 2002 …………………………..… 82
XI

Table Page
4.1 RCT values for ozonation tests conducted in DI water …………………….….. 88
5.1 MIB and geosmin decomposition in medical drainage bags …..………...…… 100
5.2 MIB and geosmin decomposition in air tight Teflon bags …… ………...…… 101
5.3 Concentration of MIB and geosmin in bags prepared for Chandler pilot study 102
5.4 MIB results of Squaw Peak pilot study ………………………………………. 119
6.1 MIB removals in utilities ………………………………………………..…… 132
6.2 Geosmin removals in utilities ………………………………………….…….. 135
6.3 TOC removals in utilities …………………………………………………….. 138
7.1 Input Parameters for Ozonation Modeling ………………………………...… 147
7.2 RCT values obtained from lab results of different ozonation conditions ……... 147
7.3 Definations of all parameters used in biofiltration modeling ………………… 149
7.4 Calculation of biofilm specific surface area ( a m ) …………………….……… 151
7.5 Values of biofilm parameters from literature ………………………………… 152
7.6 Input parameters for Figure 7.2 ……………………………………….……… 153
A.1 Distilled water ozonation results …..…………………………….....……...… 182
B.1 Metyyl Isoborneol (MIB, ng/L) result of Chandler pilot test ...….....……...… 189
B.2 Geosmin (ng/L) result of Chandler pilot test ...…..............................……...… 190
B.3 Squaw Peak pilot results ……………………..…..............................……...… 191
C.1 Utilities data table (2002) ..………………………………...…….....……...… 199
C.2 Utilities data table (2003) ..………………………………...…….....……...… 203
C.3 Utilities survey results for ozone-biofiltration treatment of MIB and geosmin 207
XII

LIST OF FIGURES
XIII
Figure Page
2.1 Mechanism of ozone decomposition in water --- initiation, promotion, and
inhibition of radical-type chain reaction ………………………..…..…. 15
3.1 Batch ozonation reactor …………..………………………………………….... 43
3.2 Ozone generation and stock system …………………………………………... 49
3.3 Schematic of Chandler Pilot Test Facility …………………………………..… 54
3.4 Pilot Filters Design and Operation …….........................................................… 54
3.5 Pilot Ozonation System ……..........................................................................… 55
3.6 Pilot Filtration System ……............................................................................… 56
3.7 Schematics of Squaw Peak pilot facility ……................................................… 58
3.8 Gas-sampling bags for stocking MIB solution …….......................................… 62
3.9 MIB and geosmin standard calibration curve ……........................................… 77
3.10 Concentration of 20 ppt QCs during the period of Apr, 2002~Oct, 2003 ......… 78
3.11 Changes of standard curve slop during the period of Apr, 2002~Oct, 2003 ..… 79
4.1 Ozone dose effect on MIB and geosmin oxidation in distilled water ……....… 88
4.2 Effect of pH on MIB and geosmin oxidation in distilled water …………….… 89
4.3 Effect of T-butanol on MIB and geosmin oxidation in distilled water …......… 91
4.4 Relative oxidation removal of MIB and geosmin in ozonation experiments
conducted in distilled water ………………………………………....… 93
4.5 Effect of methanol (0.5 ul/L) on O3 decomposition in distilled water and natural
water …...............................................................................................… 95

XIV
Figure Page
4.6 Effect of methanol (0.5 ul/L) on PCBA decomposition in distilled water and
natural water …...................................................................................… 96
4.7 Effect of methanol (0.5 ul/L) on MIB decomposition in distilled water …....… 97
5.1 Comparison of MIB removals in different filter media at different EBCT and with
and without ozonation …...................................................................… 103
5.2 Biomass concentrations in different filters …................................................… 105
5.3 Effect of Ozone Dose on MIB Removal in Dual-Media Filters …...............… 106
5.4 A Comparison of Percent MIB Removals at Top 6-inches of the Filter and at
bottom of the Filter …........................................................................… 107
5.5 Effect of Influent MIB Concentration on MIB Removals in GAC/Sand Filters
……………………………………………………………………….... 108
5.6 MIB removals at different pHs …..................................................................… 110
5.7 TOC/UV254 Results for Raw, Plant Settled, Filter Influent (Ozonated Water) and
Filter Effluents …...............................................................................… 112
5.8 HPC Results for GAC/Sand and Anthracite/Sand Filtered Waters …...........… 114
5.9 Turbidity Results for Raw, Plant Settled, Filter Influent (Ozonated Water) and
Filter Effluents …...............................................................................… 114
5.10 Bromate concentrations in the effluent of different filters at different ozone doses
…........................................................................................................… 116
5.11 Initial and upon return concentration of MIB stock solutions used in Squaw Peak
pilot study …......................................................................................… 118

Figure Page
5.12 EBCT effects on MIB removals for filters with GAC-B media …...............… 120
5.13 Ozonation effects on MIB removal for different raw water TOC ………….… 121
5.14 MIB removals during filtration with and without ozonation in different filter media
XV
…........................................................................................................… 122
5.15 Raw water TOC effects on MIB removals …................................................… 123
5.16 Biomass concentrations in different GAC media filters …………...………… 124
5.17 Effects of backwash water on different media types ….................................… 125
5.18 Effects of media type on MIB removals in filters with the similar design and
operation …........................................................................................… 126
5.19 TOC removals after biofiltration with or withour ozonation in different filter media
……………………………………………………………………....… 127
6.1 Survey results of utility # 5 …………...……...…………………………….… 130
6.2 Survey results of utility # 6 ………...………...…………………………….… 131
6.3 MIB removals by ozonation in utilities …………...………………………..… 133
6.4 MIB removals by biofiltration in utilities …………...……………………..… 133
6.5 MIB removals by ozone-biofiltration in utilities ….......................................… 134
6.6 Geosmin removals by ozonation in utilities ………………………………..… 135
6.7 Geosmin removals by biofiltration in utilities ……………………………...… 136
6.8 Geosmin removals by ozone-biofiltration in utilities …................................… 136
6.9 TOC removals by biofiltration in utilities ……………………………….....… 138
6.10 TOC removals by ozone-biofiltration in utilities ……………………...…..… 139

Figure Page
6.11 Biomass survey results in seven utilities …………….………………...…..… 140
6.12 Relationships of removals of MIB/geosmin/TOC and biomass concentration at
different utilities …………….……………………………….....…..… 140
7.1 Ozone-biofiltration modeling diagram …......................................................… 142
7.2 Example result of ozone-biofiltration modeling …………………………...… 154
7.3 Predicted O3 dose effects on MIB removal …...............................................… 156
7.4 Predicted O3 dose effects on bromate formation and CT value …………....… 156
7.5 Predicted RCT value effects on MIB removal …............................................… 157
7.6 MIB removals at filter effluent under different super facial velocities and biofilm
specific surface area …......................................................................… 159
C.1 Schematic of Ann Arbor Water Treatment Plant, MI (AAWTP) .................… 214
C.2 Schematic of Central Lake Country Joint Action Water Agency, IL (CLCJA) 215
C.3 Schematic of Chandler Water Treatment Plant, AZ (CWTP) ……………….. 216
C.4 Schematic of Contra Costa Water District, CA (CCWD) ……..…………….. 217
C.5 Schematic of Eagle Mountain Water Treatment Plant, City of Fort Worth, TX
XVI
(EMWTP) ……..………………………………………………..…….. 218
C.6 Schematic of Gilbert Water Treatment Plant, AZ (GWTP) ……...………….. 219
C.7 Schematic of Milwaukee Water Works Linwood Plant, WI (MWW) ...…….. 220
C.8 Schematic of Peoria Greenway Water Treatment Plant, AZ (PGWTP) ...….... 221
C.9 Schematic of Philadelphia Water Treatment Plant, (PWTP) ...…………….... 222

OVERVIEW
CHAPTER 1
INTRODUCTION
Taste and odor (T&O) problems are common in water utilities (Lalezary et al,
1984, 1986a). Earthy-musty odors are the most prevalent T&O customer complaint.
Sources of the earthy-musty odors are usually microbial by-products, such as alicyclic
alcohols 2-methylisoborneol (MIB), trans-1, 10-dimethyl-trans-9-decalol (geosmin),
isopropyl methoxy pyrazine (IPMP), or trichloroanisole (TCA). MIB and geosmin are the
most common odorants and are microbial by-products associated with blue-green algae
and aquatic actinomycetes (Burlingame et al. 1986, Lalezary et al. 1986, Wnorowski
1992). The threshold concentration for detecting these compounds depends on the taste
and odor sensitivity of the individual and it varies from about 4-10 ng/L for MIB and
geosmin (Suffet 1996, Rashash et al. 1997, Elhadi et al. 2003).
Previous research concluded MIB and geosmin are not removed by conventional
treatment processes (coagulation/flocculation/sedimentation/filtration) (Bruce et al. 2002,
Wnorowski 1992). MIB and geosmin have relatively low molecular weights, moderate
hydrophobicity, and moderate solubility (Table 1.1). Air stripping systems are not
economical for MIB and geosmin removal due to their low Henry’s constants (Lalezary
et al. 1984). Powdered activated carbon (PAC) or granular activated carbon (GAC)
adsorption can remove most odorants (Suffet et al. 1995). Chlorine and chlorine-dioxide
are ineffective in removing significant percentages of MIB and geosmin, while ozone can

Table 1.1
Chemical/physical characteristics of MIB and geosmin
Parameter MIB (2-methyisoborneol) Geosmin
Full Name
(1-R-exo)-1,2,7,7tetramethyl
bucyclo-
[2,2,1]-heptan-2-o1
tran-1, 10-dimethyl-trans-9decalol
Molecular Formula C11H20O C12H22O
Molecular Weight
[g/mole]
168 182
Boiling Point [ o C ] 196.7 165.1
Aqueous Solubility [mg/L] 194.5 150.2
Kow 3.13 3.7
Henry’s Law Constant
(atm m 3 /mole)
Structure
Source: Pirbazari et al. 1992.
5.76×10 -5 6.66×10 -5
2

e very effective (Nerenberg et al. 2000). MIB and geosmin are biodegradable, but
information regarding their removal in biological filters used in water treatment plants
(WTP) is limited (Nerenberg et al. 2000). Overall, the more common treatment processes
for MIB and geosmin removal include sorption to activated carbon (PAC or GAC),
oxidation and biodegradation (Hrubec and de Kruijf 1983; Wnorowski 1992). Relevant
chemical characteristics and structures of MIB and geosmin that affect their ability to be
removed by treatment unit processes are given in Table 1.1.
Ozone is efficient in oxidizing MIB and Geosmin as a powerful oxidant. Water
utilities use ozone to achieve multiple objectives includes pathogen inactivation, TOC
removal improvement, mineral oxidation, and synthetic orgainic chemical oxidation.
However, ozonation can produce oxidation by-products of regulatory health or perception
concern: 1) ozonation of natural organic matter (NOM) produces biodegradable dissolved
organic carbon (BDOC) including aldehydes (Carlson and Amy 1997, Langlais et al.
1991, Westerhoff et al. 1996), thus decreasing the bio-stability of effluent water (Servais
et al. 1993); 2) ozonation of waters containing bromide ions (Br - ) form bromate (BrO3 - ),
which is carcinogenic compound and has a maximum contaminant level (MCL) of 10
ug/L (Carlson et al. 1996, Najm and Krasner 1995, Tan and Amy 1991).
Biofiltration removes readily degradable fractions of NOM (i.e., BDOC,
aldehydes), removes DOC and provides biologically stable water. Some evidence exists
that biofiltration also removes MIB and geosmin, but has mainly been evaluated for
dense biofilm systems rather than biologically active sand filters (Nerenberg et al.
2000a). The surface and structural characteristics of different media are critical in
3

affecting the efficiency of the biofilter treatment (Yang et al. 2001). In most WTPs
biofiltration can occur in slow or rapid sand filters under a biologically active mode
(Rittmann et al. 2002a). Previous studies suggested that GAC performs better than sand
and anthracite for biodegradable organic matter (BOM) removal due to their superior
surface and structural characteristics (Lechevallier et al. 1992, Rittmann and Huck 1989).
Use of GAC in biological dual media filters will probably enhance MIB and geosmin
removals.
Ozone-biofiltration is a promising treatment method in T&O problems control.
However, a thorough understanding of reaction mechanisms and predictive relationships
for MIB and geosmin removal has not been reported. Previously, empirical ozone-dose
versus MIB-removal relationships have been developed, without separate molecular
ozone (O3) from hydroxyl radical (HO • ) oxidation mechanisms (Suffet et al. 1995). One
report on O3/ HO • oxidation mechanisms of MIB and geosmin is available (Glaze et al.
1993). Biofiltration has been well studied for BDOC removal, but less information is
available for removal of trace organics. Work with dense biofilms would suggest MIB
biodegradation occurs via secondary substrate pathways. Ozone-biofiltration as a
treatment process must balance disinfection potential, T&O removal, and disinfection by-
products (DBP) production.
OBJECTIVES
This research addresses ozonation mechanisms for MIB and geosmin oxidation,
and links ozone and biofiltration reaction together into a single model. Bench-scale
4

ozonation tests were used to separate O3 vs. HO • oxidation mechanisms for MIB, and
used to estimate corresponding second order rate constants. Full-scale and pilot-scale
biofiltration studies provide information of MIB and geosmin removal in continuous-flow
systems. The goal is to develop an approach capable of selecting an appropriate ozone
dose to meet treatment objectives while achieving good MIB and geosmin control (

geosmin stock solutions and analyzed TOC and MIB and geosmin
samples.
Objective 3. To obtain field data of ozone-biofiltration performance from
current opertating ozone-biofiltration utilities by conducting two
campaigns of utilities survey on effects of T&O control. Peng Pei
conducted the entire surveys and all analysis.
Objective 4. To predict MIB removal by ozone-biofiltration system by
developing a mechanistic Model. Peng Pei conducted all modeling
work.
Researches supporting the above objectives are included in 6 chapters:
• Chapter 1: Introduction
• Chapter 2: Literature review
• Chapter 3: Experimental methods
• Chapter 4: Bench-scale ozonation experiments
• Chapter 5: Ozoen-biofiltration removal of MIB and geosmin ---
pilot studies
• Chapter 6: Full-scale utility survey
• Chapter 7: Mechanistic modeling
6

CHAPTER 2
LITERATURE REVIEW
SOURCES OF EARTHY-MUSTY ODORS IN NATURAL SYSTEMS
Blue-green algae are the most frequent cause of taste and odor problems. Among
the Cyanophyta, the following species of the genera Anabaena, Aphanizomenon,
Microcystis, Oscillatoria, and Phormidium are frequently associated with MIB and
geosmin production (Suffet et al. 1995). Odors produced by these organisms can be
eathy-musty, grassy, or “septic”, depending on species, algal density, and whether the
algae are alive or dying (Suffet et al. 1995).The earthy-smelling compound geosmin was
first detected in blue-green algae by Safferman and colleagues (1976). Although both
earthy (geosmin) and musty (MIB) odorants are produced by blue green algae,
actinomycetes, oscillatoria or closely related genera also produce these odorous
compounds (Tabachek and Yurkowski 1976, Berglind et al. 1983). Further studies
showed that the ability to produce geosmin or MIB seems to be a strain-specific property,
i.e., one that is manifested in certain environmental variants (or subspecies) of various
blue-green algal species. Different strains of the same specie performed different abilities
in producing MIB or geosmin (Suffet et al. 1995).
The actinomycetes have long been recognized as sources of severe earthy-musty
tastes and odors in drinking water. They are a group or bacteria that share some features
with fungi, primarily their growth in the form of a mycelium, a branching network of
filaments (Mallevialle and Suffet 1987). Two important odorous compounds, geosmin
7

and MIB, were first isolated and identified from actinomycete cultures in 1960’s.
Geosmin was reported in 1965 (Gerber and LeChevalier 1965). MIB was reported in
1969 and the author, Gerber, named 2-methylisoborneol (Gerber 1969). Among different
actinomycetes, the genus primarily involved in odor production is Streptomyces (Gerber
1979).
Due to the difficulties in relating MIB and geosmin production quantitatively with
specific culprit species, it has been difficult to predict or monitor the production over
time in a reservoir. Higher nutrient concentration and temperature could be two major
factors that cause taste and odor problems. In a recent survey of over 100 utilities with
taste and odor problems by Summers et al. in 2002, the majority of taste and odor
problems occurred during June through October. Only around 10% of the utilities
reported problems in December through February (Graham 2000). Typical seasonal
patterns of MIB presentation in Arizona lakes have the peak period of June through
October (Westerhoff et al. 2001b). During the peak period, MIB concentrations are
normally the range of 20-80 ng/L though as high as 300 ng/L has been reported in the
central Arizona region (Westerhoff et al. 2001a).
Studies have been conducted to evaluate the MIB biodegradation in lakes. In one
lake, a seasonal transition from actinomycete and cyanobacteria algae that produce
odorants during the summer, to a high population of Bacillus was observed (Hoehn
1965). Soon thereafter, the Bacillus was implied to have been responsible for odorant
biodegrade in the lakes. It was estimated that the biodegradation rates of MIB are on the
magnitude of 1 ng/L/day in the epilimnion and hypolimnion of reservoirs (Westerhoff et
8

al. 2001b). Later work found that the genus pseudomonas isolated from sand filtration
media could be the bacteria primarily responsible for degrading MIB and geosmin
(Oikawa et al. 1995). Since the structure of MIB is similar to camphor that the cam
operon could decompose MIB by a similar pathway as camphor. Those genes in
pseudomonas specie responsible for the degradation were located in chromosomal DNA
(Oikawa et al. 1995).
CONTROL OF EARTHY-MUSTY ODORS DURING DRINKING WATER
TREATMENT PROCESS
T&O Treatment Processes Summary
Previous research on removal of MIB and geosmin in drinking water treatment
plants to

1983). Further studies found that effective and commonly considered treatment processes
of taste and odor problems include sorption to activated carbon, oxidation and
biodegradation (Hrubec and de Kruijf 1983, Wnorowski 1992). Details of the three
commonly considered processes are given in the following sections.
Oxidation
Commonly considered oxidants in water treatment processes include chlorine and
chloramines, chlorine dioxide, potassium permanganate, ozone, and combined oxidants
for advanced oxidation processes. Percentage of removals of MIB and geosmin resulting
different oxidation processes are shown in Table 2.1. As a treatment option for taste and
odor control ozonation and advanced oxidation process using combination of ozone and
hydrogen peroxides/UV light could be the best chooses.
Other oxidation methods, if considered to control taste and odor problems, need
many additional considerations. Many complaints about the taste and odor of drinking
water are directly related to chloramines and chlorine because of their strong swimming
Table 2.1
Percent removal of MIB and geosmin resulting from oxidation
Compound HOCl ClO2 NH2Cl KMnO4 H2O2
Oxidant Dose
Reaction Time
3 mg/L 3 mg/L 3 mg/L 3 mg/L 3 mg/L
(min)
MIB Removal
20 20 20 20 20
(%)
Geosmin
10 2 15 13 29
Removal (%) 16 17 27 15 31
Source: Glaze et al. 1990, Romain et al. 2003.
H2O2+UV O3
10~20mg/L+
86~154mJ/cm 2 0.2 mg/L-min
--- 20
40~70 84
48~92 93
10

pool or bleach-like smell, respectively (Suffet et al. 1995). When ClO 2 was used to
eliminate musty tastes in drinking water, it was reported that customer began to complain
of “chlorinous” and “kerosene” tastes and that ClO 2 escaping from water in customers’
homes and businesses reacted with organic compound in the air to produce not only
kerosene-like odors but cat-urine-like odors as well (Hoehn 1990). Potassium
permanganate has been used for the treatment of tastes and odors in water supplies and as
an alternative to prechlorination since the 1960s. The primary preoxidant uses of
potassium permanganate are to prevent algae and slime growths in water intake, remove
iron and manganese, remove color, and minimize THMs (Colthurst and Singer 1982,
Singer et al. 1980). Potassium permanganate has poor biocidal properties for Escherichia
coli as compared with chlorine compounds or ozone (Weber 1972). Ozone, a powerful
oxidant and disinfectant, has been used in the treatment of drinking water in Europe since
the turn of the century. Principal uses of ozone in Europe were for disinfection and taste-
and-odor control (Langlais et al. 1991, Singer 1990). Other applications of ozonation
include the oxidation of color-causing compounds, synthetic organic chemicals, and
inorganic compounds such as iron and manganese, as well as enhancement of coagulation
and filtration. Advanced oxidation processes using the combined oxidant of ozone and
UV/H2O2 could yield MIB and geosmin removals of 90 to 100 percent, and reduce the
required ozone dosage by 20 to 40 percent (Suffet et al. 1995). More stringent standards
and concerns for disinfection and disinfection by products, particularly chlorination by
products, have prompted more and more water utilities to consider the use of alternative
disinfectants such as ozone.
11

Adsorption (Activated Carbon Adsorption)
Powder activated carbon (PAC) flow through in contact basins or granular
activated carbon (GAC) in packed beds can remove tastes and odors causing compounds
(Hrubec and de Kruijf 1983, Suffet 1993, Wnorowski 1992). PAC is added directly to
raw water before or during coagulation. The amount of a compound adsorbed is affected
by the contact time, PAC dose, PAC source, mixing conditions, and the presence of other
organic compounds in solution. GAC is usually used in dual media filters or post-filter
deep-bed contactor. This enables efficient use of GAC specifically designed for the
removal of taste-and-odor compounds. Breakthrough of organoleptic compounds is a
function of the GAC’s equilibrium capacity, the system contact time, and competitive
adsorption with other organic compounds (Suffet et al. 1995).
PAC contact times are typically between 1 and 4 hours. MIB has a slower rate of
adsorption than geosmin (Lalezary-Craig et al. 1988). It has been shown that the rate and
extent of adsorption of MIB and geosmin can be very dependent on water chemistry
(Knappe et al. 1998, Nwecombe et al. 1997). The maximum adsorption capacity is
affected by (1) the presence of other chemicals that can compete for the available sites on
the activated carbon; (2) water quality changes that change the activated carbon surface
sites, e.g., the presence of a disinfectant that can oxidize the surface of the AC; and (3)
water quality changes that affect the chemical form of the adsorbing chemical, e.g., pH
(Suffet et al. 1995).
12

Biodegradation in Packed Beds
Biological treatment is practiced to achieve four main goals: (1) oxidation of
biodegradable organic matter; (2) Oxidation of NH4 + , NO2 - , Fe2 + , Mn2 + , or other reduced
inorganic species; (3) removal of specific organic compounds that are of particular health
or aesthetic concern; (4) denitrification of NO3 - or NO2 - to N2 (Rittmann and Huck 1989,
Suffet et al. 1995). Biological technologies used in drinking water treatment processes
have two important characteristics: (1) the bacteria are retained by attachment to solid
surfaces; (2) the concentrations of growth substrates are very low and must be removed to
exceedingly low levels. There are three general classes of the attached-growth processes
used in drinking water treatment: (1) the slow sand filter combines biodegradation with
filtration at the top of a bed of small sand (~0.012 in. [0.3 mm]) loaded at a slow rate
(~16.4 ft/d [5 m/d]) (Collins et al. 1991); (2) use either larger granules ( ~0.16 in. [4
mm]) or fluidization of small grains to provide simultaneously large liquid pores and high
biofilm surface area, which can operate with very high liquid loads (160-2300 ft/d [50-
700 m/d]) (Rittmann and Huck 1989); (3) rapid sand filters, granular activated carbon
(GAC) filters, and floc-blanket reactors that accumulate bacteria and allow partial to total
biodegradation, depending on their design purpose (Suffet et al. 1995).
Most of the taste and odor compounds of concern to the water treatment industry
are organic compounds, which can be biodegraded to carbon dioxide and water (i.e.,
mineralized) or biotransformed to less obnoxious compounds. Geosmin and MIB are
expected to be biodegradable, based on their similarity in structure to biodegradable
alicyclic alcohols and ketones (Trudgill 1984). Because MIB and geosmin are present at
13

very low concentrations, they are assumed to be utilized as secondary substrates. Several
studies have demonstrated that bacteria grown on the dissolved organic carbon found in
water supplies can biodegrade geosmin and MIB (Moran and Hodson 1990, Namkung
and Rittmann 1987, Perry and Green 1984, Rittmann 1990). The ability of biofilms
grown on the dissolved organics in natural waters to remove geosmin and MIB by
secondary utilization could be 40-95% depending on the influent concentrations of MIB
and geosmin, filter media types, and the available oxygen concentrations by aeration
system of the filters (Hattori 1988, Lundgren et al. 1988).
OZONATION
Mechanisms of Ozone Oxidation of Organic Micropollutants
Ozonation reactions in natural waters include two types of oxidation pathways:
direct oxidation by the ozone molecule and indirect oxidation by the hydroxyl free radical
(Glaze et al. 1987, Hoigen and Bader 1976, Staehelin and Hoigne 1982). Ozone
decomposition is a complex chain-radical process (Figure 2.1) that may be initiated by
several types of water contaminants such as the hydroxide ion, natural organic matter,
and ferrous ion (Langlais et al. 1991, Staehelin and Hoigne 1985). The lifetime of ozone
depends on several variables including pH, temperature, concentrations of organic
compounds, and type and concentration of inorganic compounds (Hoigen and Bader
1976, Langlais et al. 1991). Higher pH and higher temperature promote ozone
decomposition (Hoigne and Bader 1994). The effect of NOM on ozone consumption is
not well understood. Ozone affects different segments of NOM in different ways (Bose et
14

al. 1994). Water containing structurally different NOM can result in different ozone
decomposition kinetics (Westerhoff et al. 1998).
H +
O3
O2
O3 •-
O3 H2O
Initiation
OH - , H2O2/HO2 - , Fe 2+ , HCOO -
UV, HS, Organic matter…
O2
HO •
O2 •-
HO2 •
Inhibition
HCO3 - /CO3 2- , ter-butanol,
Organic matter
Propagation
Figure 2.1 Mechanism of ozone decomposition in water --- initiation, promotion, and
inhibition of radical-type chain reaction (Source: Staehelin 1985, Langlais 1991).
O2
O3
Organic matter
15

Molecular Ozone
The direct ozonation reactions tend to be highly selective and relatively slow.
Rate constants for direct ozonation reactions are on the order of 10 3 M -1 s -1 (Aieta 1988,
Glaze 1987, Gurol 1985, Hoigen and Bader 1976). In general, under the conditions
employed in drinking water treatment, activated aromatic compounds (e.g. phenol),
olefins, and simple amines would be expected to react with molecular ozone (Hoigen and
Bader 1976, Singer 1990). Organic compounds such as aliphatic acids, aldehydes,
unactivated aromatic compounds (e.g., chlorinated benzenes), and tertiary alcohols are
resistant to molecular ozone oxidation (Glaze 1986, Glaze et al. 1990, Rice 1981, Singer
1990). There is no report on rate constant numbers of molecule ozone with MIB and
geosmin at present.
Hydroxyl Radical
The HO • has been observed to be a less selective and more powerful oxidant than
ozone. Rate constants for HO • reactions are about 10 8 to 10 10 M -1 s -1 (Aieta 1988, Glaze
1987, Hoigen and Bader 1976, Singer 1990). Organic compounds that are resistant to
molecular ozone oxidation, such as aliphatic acids, aldehydes, unactivated aromatic
compounds, and tertiary alcohols are more likely to react with the free radical (Glaze
1986, Glaze et al. 1990, Rice 1981, Singer 1990). Bicarbonate and carbonate ions react
very fast with free radical and can act as hydroxyl radical scavengers (Glaze 1986, Glaze
1988, Hoigen and Bader 1976, Staehelin and Hoigne 1985). It was reported that the rate
constants of HO • with MIB and geosmin are 8.2×10 9 M -1 s -1 and 1.4×10 10 M -1 S -1 ,
16

espectively (Langlais et al. 1991). Para-chlorobenzoic acid (PCBA) was applied, as the
hydroxyl radical probe to measure the HO • concentrations indirectly. The reaction rate of
PCBA with hydroxyl radical (kHO•, PCBA = 5.2 × 10 9 M -1 s -1 ) is much faster than with O3
(kO3, PCBA = 0.15 M -1 s -1 ) (Elovitz and Von Gunten 1999, Haag, and Hoigne, 1981, Neta
1968, Yao and Haag, 1991). T-butanol was nomally applied as the HO • scavenger
because it reacts only slightly with molecular ozone with a rate constant of 0.001 M -1 s -1
while it has a very high reactivity of 6×10 8 M -1 s -1 with HO • (Buxton et al. 1988). A new
term RCT is defined as the ratio of the exposures of HO • and O3 (Elovitz and von Gunten,
1999 & 2000). Equation (EQN 2.1) gives the definition of RCT.
RCT=
•
HO − exp osure
=
O − exp osure
3
∫[
∫
•
HO ] dt
[ O ] dt
3
17
EQN 2.1
The value of ∫[HO • ]dt in Equation EQN 2.1 can be indirectly determined by monitoring
the decrease of an ozone-resistant probe compound (PCBA), whereas the ∫[O3]dt is
calculated from direct ozone measurement as the area under the O3 concentration versus
time curve (von Gunten and Hoigne, 1994).
Dose Response Relationships for Taste and Odor Compounds
Ozonation dose response relationships of MIB and geosmin could vary a lot due
to different water qualities of the raw waters and different ozone doses applied, as shown
in Table 2.2. Disagreements were found between experiments conducted with pure water
and natural waters (Glaze et al. 1990, McGuire and Gaston 1988). This is because the
natural waters contain many substances that can initiate the formation of HO • . As

previously mentioned, HO • is more powerful than O3 as an oxidant for MIB and geosmin.
Therefore, the use of organic free water may have a low RCT (i.e. lower HO •
concentrations) than in natural waters, thus resulting in much lower MIB and geosmin
removals than using natural waters (Glaze et al. 1990, Suffet et al. 1995). Percentages of
MIB and geosmin removals conducted in different studies were given in Table 2.2.
Further bench-scale work conducted by Glaze et al. (1990) studied MIB and geosmin
oxidation in Metropolitan Water District of South California’s other source water (State
Project Water) by ozone and hydrogen peroxide-ozone. MIB and geosmin occurred more
rapidly in State Project Water than in Colorado River Water (CRW), but the final
removals were of the same order of magnitude as for CRW. This could be explained by
two possibilities: (1) the alkalinity of SPW is about two-thirds that of CRW, so the lower
level of hydroxyl radicals’ scavenger (i.e. the alkalinity) gave less competitive for MIB
and geosmin oxidation by hydroxyl radicals; (2) there may had higher levels of initiators
of ozone decompostition in SPW than in CRW, and the faster the ozone decomposition
Table 2.2
MIB and geosmin removals from ozonation tests of different natural waters
Raw Water O3 dose
Removal
% Reference
(mg/l) MIB geosmin
Distilled water 2 15-30 15-30 (Lalezary et al. 1986).
33 50 50
Surface water spiked with 1.5 35-95 35-95 (Lundgren et al. 1988).
50ng/l of MIB and geosmin 7 >95 >95
Methopolitan Water District 4 75 - >99 75 - >99
of Southern California 2 40 35 (Glaze et al. 1990).
& Colorado River water 4 78 89
18

the quicker the oxidation of MIB and geosmin. More details of the MIB and geosmin
oxidation mechanisms, other than simply dose-response relationships, are given in the
former part of this thesis work (Nair 2002):
• Hydroxyl radical (HO • ) accounted for a greater percentage of MIB or
geosmin oxidation relative to molecular ozone oxidation.
• Ozone oxidizes geosmin to a greater extend than MIB.
• MIB and geosmin oxidation increases with increase in ozone dose, pH,
temperature and H2O2.
• MIB and geosmin oxidation is independent of the initial concentration
of the micro pollutant.
Ozonation Byproducts and Control
One of the major benefit for use ozone as a disinfectant instead of chlorine is reduction or
eliminate the formation of various chlorination DBPs. Another set of DBPs (of
ozonation) has been produced and need to be concerned when applying ozonation
process. Most bioassay screening studies have shown that ozonated water induces
substantially less mutagenicity than chlorinated water does. However, little is known
regarding the toxicity and carcinogenicity of many ozone by-products (Glaze 1987). The
type and amount of ozone by-products formed are a function of ozone dose, reaction
time, scavengers, precursor material, and pH. In addition, it is likely that both ozone
reaction pathways, direct reaction with the ozone molecule and indirect reaction with free
19

adicals, play a role in the formation of ozone by-products in natural water (Langlais et
al. 1991, Suffet et al. 1995).
Inorganic Byproducts
The ozonation of bromide and iodide containing waters results in the formation of
brominated and iodinated by-products, which has potential health effects and may also
cause taste and odor problems (Krasner et al. 1993, Suffet et al. 1995). When bromide
and iodide exist in water supplies, ozonation can convert these compounds to HOBr and
HOI, which could induce the following four major groups of reactions with natural
organic matter: (1) produring bromine and iodine containing halomethanes from
haloform reactions; (2) phenol substitution reactions to form bromophenols; (3) amino
acids oxidation to low molecular-weight aldehydes; (4) other brominated disinfection by-
products for substitution or oxidation reactions (Suffet et al. 1993).
The publication of World Health Organization (WHO) temporary guidelines on
bromate, and the formation of undesirable brominated organic by-products (Glaze et al.
1993, Song et al. 1996a, Song et al. 1996c). In 1993, the proposed minimum level of 25
ug/l bromate was included in the drinking water guidelines of the WHO. The USEPA
introduced a MCL for bromate of 10 ug/l.
Bromate (BrO3 - ) formation is via a series of oxidation processes in waters
containing bromide. The major natural source of bromide in ground waters is geological
formations, while the discharge of saline water is the main source of anthropogenic
pollution of surface water. Bromide occurs in nearly every drinking water source at
20

concentrations ranging from

eported to impart tastes and odors to treated water (Anselme 1988a, Liang 1991, Suffet
et al. 1995). Table 2.3 gives the odor threshold concentrations and odor types for various
Table 2.3
Odor threshold concentrations and odor types for various aldehydes
Aldehyde
Odor
Threshold
Concentration,
ug/L Odor Type Reference
Formaldehyde 50000.0 (Mallevialle and Suffet 1987).
Acetaldehyde 4.0 (Gilli 1990).
Propanal 9.5 (Guadagni et al. 1963).
37.0 (Boelens and Van Gemert 1987).
Butanal 9.0 (Guadagni et al. 1963).
15.9 (Shaw 1977). (Ahmed 1978).
18.0 (Boelens and Van Gemert 1987).
Pentanal 12.0 (Guadagni et al. 1963).
42.0 (Boelens and Van Gemert 1987).
Hexanal 4.5 (Guadagni et al. 1963).
9.2 (Shaw 1977). (Ahmed 1978).
4.5 Fruity (Boelens and Van Gemert 1987).
0.3 (Bartels et al. 1989).
4.5 (Gilli 1990).
Heptanal 3.0 (Guadagni et al. 1963).
3.0 Fruity (Boelens and Van Gemert 1987).
Orange-like (Anselme 1988b).
3.0 (Gilli 1990).
Octanal 0.7 (Guadagni et al. 1963).
1.4 Orange-like (Shaw 1977). (Ahmed 1978).
0.7 Orange-like (Boelens and Van Gemert 1987).
Nonanal 1.0 (Guadagni et al. 1963).
2.5 Orange-like (Shaw 1977). (Ahmed 1978).
1.0 (Boelens and Van Gemert 1987).
Fragrant (Anselme 1988b).
1.0 (Bartels et al. 1989).
Decanal 0.1 (Guadagni et al. 1963).
2.0 Orange-like (Shaw 1977). (Ahmed 1978).
0.1 Orange-like (Boelens and Van Gemert 1987).
Undecanal 5.0 (Guadagni et al. 1963).
5.0 Citrus (Boelens and Van Gemert 1987).
Dodecanal 2.0 (Guadagni et al. 1963).
0.5 Orange-like (Shaw 1977). (Ahmed 1978).
2.0 (Boelens and Van Gemert 1987).
3-Methyl butanal 0.15 (Guadagni et al. 1963).
12.0 Sweaty, sickening,
swimming pool
(Hrudey et al. 1988).
2-Methyl butanal 9.0 (Gilli 1990).
2-Methyl propanal 0.9 (Guadagni et al. 1963).
Source: Suffet et al. 1995.
22

aldehydes (Suffet et al. 1995). It was also observed that aldehyde formatted after
chlorination, which indicates that aldehyde formation is not limited to ozonation
(Langlais et al. 1991).
Many researchers have detected low and moderate molecular weight carbonyl
compounds, primarily formaldehyde, in ozonated surface waters (Ferguson 1990, Gilli
1990, Glaze 1986, Kranser 1989, Milter 1990, Milter 1991). Concentrations of C1 to C14
aldehydes have been reported to increase generally after ozonation (Langlais et al. 1991).
However, detection of the types of aldehyde was limited by the analytical method chosen
(Anselme 1988a).
Studies were conducted to quantitatively analyze the aldehydes formation after
ozonation (Glaze 1989, Glaze et al. 1990). Different results were observed from different
source waters. It was suggested that different production of aldehydes could be
contributed to different levels of aldehydes precursors (Glaze 1989). Another explanation
may lie in the differences of the ozone decomposition rate due to different water
qualities. Because aldehydes are probably formed by direct reactions between ozone
molecules and precursors, an increased level of water alkalinity and low levels of total
organic carbon that resulting higher ozone molecules residuals could presumably increase
the aldehydes production amount (Suffet et al. 1995). Different source water composition
could be also a factor that affects the aldehydes formation. Humic substances and organic
acids may be precursors of some of the odor compounds (Thorell 1992). Amino acids
that occur in natural waters may be precursors to the branched aldehydes, e.g., heptanal,
23

octanal, nonanal, and decanal (Hrudey 1989, Hrudey et al. 1988, Hureike 1993). Of these
aldehydes, octanal appeared to have the highest odor potential (Lundgren 1988).
BIOFILTRATION
Primary Substrate Utilization (AOC/BDOC)
Biological processes require electron-donor and electron-acceptor substrates. The
substrates that transfer electrons from the donor to the acceptor and provide the energy to
grow and maintain the bacteria and their primary metabolic functions are defined as
primary substrates (Odencrantz 1990). If primary substrates fall below the minimum
concentration that able to support steady-state biomass (Smin), biomass cannot be
sustained. This minimum primary substrate is important in drinking water biological
treatment processes because primary substrate concentrations in the filtration feeding
waters are very low (Rittmann et al. 1995). The very low concentrations of primary
substrates found in water supplies (simple and complex amino acids, small peptides,
carbohydrates, hydrocarbons, hydrophilic, fatty and carboxylic acids, and some humic
substances) force them to become part of an aggregate of primary substrates in order to
take a significant role in biomass growth (Rittmann et al. 1995). Primary substrates are
also considered the labile fraction (readily biodegradable) of natural dissolved organic
compounds found in drinking water supplies. The other fraction is termed refractory
(slowly biodegradable) and its pool probably contains the humic fraction of organic
matter and other large organic molecules. Therefore, the easily biodegradable fraction of
organic matter (or primary substrates) may be roughly estimated by BDOC and AOC
24

tests. However, AOC is usually considered a small portion of the BDOC because AOC
results are usually lower than BDOC results (expressed as organic carbon) (Zhang et al.
1998).
Secondary Substrate Utilization (Micropollutants)
When a substrate concentration falls below its Smin, it can be biodegraded as a
secondary substrate by bacteria through the use of a more plentiful primary substrate
(Rittmann et al. 1995). Secondary substrate utilization may not yield energy to the cell
due to its low concentration, but if it yields some energy, it can become part of the
aggregate primary substrate (Rittmann et al. 1995). Secondary substrate utilization
equation is (definations of each parameter could be found in Table 7.1):
∂ S
∂x
2
s 0 = Dh
2
∂Ss
ysPMws
− v −a
mK
f Ss
− Klas(
Ss
− )
∂x
H RT
Since the odor threshold concentration for MIB and geosmin is very low (< 10
ng/L), the presence of these compounds in raw drinking water does not support the
growth of microorganisms in biofilters. Hence, MIB and geosmin behave as secondary
substrates because biofilm microorganisms are maintained by the primary substrates.
However, microorganisms capable to biodegrade MIB and geosmin have to be present.
Therefore, the biodegradation rate for MIB and geosmin is function of the total biofilm
biomass, type of microorganisms supported by the primary substrate, and the chemical
nature of the secondary substrate (Rittmann et al. 1995).
cs
25

Effects of Design Factors on Biofiltration Performance
Impact of ozoantion
Table 2.4 shows a summary of operational configuration of ozone-biofiltration
systems. The main benefit of ozonation on NOM include the formation of hydroxyl,
carbonyl, and carboxyl groups by cleavage of double-double carbon bonds, which
increases polarity and hydrophilicity and percentage of lower molecular weight DOC. All
these changes on NOM are reflected in an increase of its biodegradability. The most
important ozonation by-products (carboxylic acids, aldehydes and aldo/ketoacids) are
easily biodegradable and removed by biofilters (> 75 %).
Impact of filter media
Granular activated carbon (GAC) filters usually perform better than anthracite and sand
(A/S) filters because of the ability of GAC to adsorb, remove, and retain biodegradable
components, which can be degraded by the attached bacteria. GAC/sand filters
outperform A/S filters in several aspects: provide better aldehyde removals at colder
temperatures; establish biological BOM removal faster after startup and out-of-service
periods; more resistant to temporary perturbations such as intermittent chlorination.
26

Reactor
Source
water
Pilot,
River
Pilot,
State
Project
Water
(SPW)
Pilot,
Col.
River
Water
Pilot,
SPW
Pilot,
Mille
Iles
River
Pilot,
Ohio
River
Bench,
Synt.
Ozone
Dose
mg/mg
-DOC
Table 2.4
Effect of media and contact time in drinking water biofilters
Media
Type
0.5-1.0 A/AS
GAC/S
GAC
0.5 A/S
GAC/S
0.4 A/S
GAC/S
0.5 A/S
GAC/S
0.4 GAC/S
GAC
0.8 A/S
S
GAC/S
EBCT
min
7.5
7.5-15
14
HLR
m/hr
N/A
1.5-6
5
Substrate
Measasurement
TOC, AOC,
NOX,
THMFP,
DBPs
2-6 7-22 TOC,
aldehydes,
AOC and
NOX
3
3
3-5
3
13
12
9.2
9.2
9.2
15
15
7-15
15
10
10
5
5
5
DOC,
aldehydes,
oxoacids,
AOC and
NOX
Aldehydes,
DOC,
BDOC,
oxalate
TOC,
BDOC,
aldehydes,
AOC, NOX,
THMFP
Biomass
measureement
HPC and
coliform
s
Conclusion Ref.
AOC/TOC
removal better in
GAC/S than A/S
None GAC/S sligthly
better removing
aldehydes than
A/S at cold temp.
None GAC/S removed
formaldehyde
and glyoxal
slightly better
than A/S, at
colder temp.
Phosphol
ipids
GAC/S better
than A/S
BOM removal vs
biomass was not
linear
2-4 S 4-20 0.15 TOC None EBCT did not
affect TOC
removal
Source: Urfer et al. 1997. A, (Lechevallier et al. 1992); B, (Krasner et al. 1993); C,
(Coffey 1995); D, (Prevost and al. 1995); E, (Wang et al. 1995); F, (Hozalski et al. 1995)
Notes: A/S, anthracite/sand dual media; GAC/S, GAC/sand media; S, sand media
A
B
B
C
D
E
F
27

Impact of contact time
Direct correlations have been found between empty bed contact time (EBCT) and
BOM removal, but up to certain economically justifiable level. It has been determined
that for a given EBCT, removal of BOM is independent of hydraulic loading
(Flowrate/filter transversal area), which makes BOM removal in biofilters not limited by
external mass transfer.
Impact of backwashing
The control parameters that control backwashing of biofilters are length and
frequency, use of air scouring and chlorine in backwash water, and accumulation of non-
and biological particles. Biofilter backwashing is necessary to control biomass
accumulation and head loss buildup. Backwashing biofilters with only water is not
efficient enough to remove particles attached to filter media because of the limited
collisions between fluidized media particles. Simultaneous application of air and water at
subfluidization velocities can achieve collapse pulsing conditions to efficiently remove
nonbiological particles without excessively losing biofilm particles. Biofilm particles are
held with greater force than non-biological particles due to sticking effect of extracellular
polymers of biofilm. Some researchers report that the use of chlorinated backwash water
in GAC/S and A/S filters did not affected BOM removal. However, duration of the
backwash procedure and chlorine concentration in the water seems to be more important
28

factors. More research is needed to fully understand the effect of backwashing on
biofilter biomass and BOM removal.
Impact of Temperature
BOM removal in biofilters is theoretically enhanced at higher temperatures
because both mass transfer and microbial kinetics are faster. However, biological filter
media may mitigate these effects. Lower temperatures reduce biodegradation capacities
of biofilters more significantly in A/S filters than GAC/S filters. Only one paper reached
this conclusion. More research may be needed to support this conclusion. The time to
reach steady-state removal increased, whereas the BOM removal decreased when
temperature decreased from approximately 20-25 o C to 10-15 o C.
Impact of Nutrients
COD removal was not affected as C/N ratio varied between 0.18 and 1.5 mg-
COD/mg-N as ammonia in a bench-scale biological aerated filter operated at different
substrate loadings. However, no nitrification was observed at C/N of 1.5 because the
high biofilm detachment rate did not allow nitrifiers establish in the filter. However,
(Ohashi et al. 1995) fed the biofilter high-strength synthetic substrate (30-300 mg/l
COD), which may not be representative of drinking water biofilters.
Since most of the biofilters used in drinking water operate very close to Smin, the
effect of nutrients may not be significant. However, information was not found regarding
this subject. The C/N ratio may have different effects on biofiltration if the N is
29

considered either as ammonia or as organic nitrogen. Ammonia may have a significant
effect on nitrifiers from experience from wastewater reactors, whereas the effect of DON
may be unknown because no literature has been published regarding the effect of DON
on biofilters. AWWARF reports on biofiltration do not deal with the effect of nutrients
on biofiltration.
Impact of pH and other water quality parameters
Bench- and pilot scale biofiltration projects are usually run at natural water pH (7-
8). PH is one of the few water quality parameters that are not usually included in the
experimental matrixes, especially in pilot-scale studies where natural water is used. PH
plays an important role in controlling the final ozonation by-products, which in turn may
control the biodegradation process in the biofilters. Other water quality parameters that
are never mentioned in biofiltration literature are ionic strength and cation concentration.
Since biofilter effluent organic matter is composed mostly of SMPs (Rittmann et al.
2002a), which is controlled by the influent water quality in wastewater biological systems
(ionic strength and cation concentration) (Murthy and Novak 2001). Therefore, it may be
logical to assume that the quantity and quality of organic matter in biofilter effluents may
be highly affected by these parameters. More research is needed to identify the effects of
pH, ionic strength and cation concentration on the effluent water quality of
ozonation/biofiltration systems.
30

Biological Performance
TOC Removal
Biological treatment of water by different types of biofilters is relatively common
in Europe where TOC removal efficiencies were reported to vary between 5 and 75
percent (Bouwer and Crowe 1990).Most processes were generally highly effective in
removing biodegradable TOC, assimilable organic carbon (AOC) (Raymond et al.
1995).TOC removal was affected by NOM source and characteristics, operating
temperature, and ozone dose. It was also reported that TOC removal was not a function
of EBCT in the range of 4 to 20 min. (Raymond et al. 1995).The most effective method
for maximizing TOC removal was to optimize the coagulant dosage (Raymond et al.
1995).
Turbidity Removal
Turbidity is a commonly used parameter to monitor the particulates concentration
during water treatment process. Biological GAC/Sand and A/S filters from pilot-, lab-
and full-scale projects have provided similar turbidity removal with pre-chlorinated,
backwashed A/S filters. All the types of the biofilters can reliably met current guidelines
(NTU< 0.4) (Booth and Idaho 2001, Kommineni et al. 2003).
31

Particle Removal
Changes of particle size distribution through non-biological filters are controlled
by detachment of particles. Turbidity in effluents from pre-chlorinated and biological
filters was similar, but in terms of particle removal, pre-chlorinated filters always
performed better than biological filters. Total bacterial counts in effluents in GAC filters
were higher during bacterial colonization than under steady state condition. This trend
was attributed to the delayed development of protozoan population, which at steady state
removes the produced bacterial biomass.
Head Loss Development and Filter Run Time
Pre-ozonated slow sand filters have reduced filter times because of increased
clogging produced by the excessive accumulation of biofilm. Head loss build up is
consistently higher in non-chlorinated biological and chlorinated backwashed filters than
pre-chlorinated conventional filters because of increased biomass build up at the top of
the filters. Concurrently, biomass build up also reduces the length of filter runs.
Restarting Biological Filters
No significant differences have been determined between pilot scale biological
and non-biological filters in terms of turbidity removal, except for higher initial turbidity
peaks for biological filters than for conventional filters. Elevated bacterial endotoxins
after restarting biological filters have been detected even for short shut down periods (~ 2
hrs). Operational strategies for restarting full-scale biological filters are strongly
32

ecommended (non-stop operation, backwash filters before restart, run to waste for a few
filter volumes after start up).
MIB and Geosmin
MIB and geosmin can be biodegraded by gram-positive bacteria because of their
structure is similar to biodegradable alicyclic alcohols and ketones (Rittmann et al. 1995).
MIB is a bicyclic compound that probably follows monooxygenation steps leading to ring
cleavage and mineralization (Nerenberg et al. 2000a). Geosmin is an alicyclic alcohol
that can be oxidized by a series of dehydrogenase and monooxygenase reactions that lead
to vital metabolic intermediates and mineralization (Nerenberg et al. 2000a). Because of
the low odor threshold concentration of MIB and Geosmin (~ 10 ng/L), they may be used
as secondary substrates by bacteria grown on BOM in natural waters. Several field and
lab-scale experiments have demonstrated that natural-occurring bacteria grown on NOM
can biodegrade MIB and geosmin. Table 2.5 summarizes these reports. It was determined
that slow sand biofiltration was most effective for MIB and geosmin removal (88 to 100
% MIB removal with initial concentrations of 25 and 69 ng/l; 98 % geosmin removal
with initial concentration of 360 ng/l) (Yagi et al. 1988). MIB and geosmin were removed
close to the odor threshold levels in a conventional water treatment plant with no
prechlorination (54 % MIB removal with initial concentration of 120 ng/l; 100 %
geosmin removal for a initial concentration of 120 ng/l) (Ashitani et al. 1988). Slow sand
biofilters effectively removed MIB and geosmin (> 95 % MIB and geosmin removal for
initial concentrations of 50 ng/l) (Lundgren et al. 1988). Different MIB degradation by-
33

products were identified using a new gravel biofilter (Sumitomo 1992). Pilot studies were
also conducted to determine the fate of MIB in a biological filter (Terauchi et al. 1995).
Approximately 70 to 80 % of natural MIB were removed from lake water when initial
concentrations were between 50 and 800 ng/l. When the influent lake water was spiked
with reagent-grade MIB (200 to 1200 ng/l), the average removal increased to 73-83 %. A
honeycomb tube biofilter with river bacteria was spiked with MIB and geosmin to
Reactor Type/
Media
Lab slow sand
filter
Lab CMBR with
glass beads
Lab bench GAC
biofilter
Lab honeycomb
tube biofilter
Rapid sand
biofilter
Pilot biofilter
with porous
granular ceramic
Full-scale rapid
GAC biofilter
Pilot-scale rapid
GAC biofilter
Bentch-scale
GAC filter
N/A = Not available.
Loading
Rate
(m/h)
Table 2.5
Removal of MIB and geosmin in biofilters
Contact
Time
(min)
Raw water
DOC
(mg/l)
Initial
MIB
(ng/l)
MIB
Removal
0.025 480 8-9 50 > 95 (Lundgren et
al. 1988)
0.25 20 1.1 10 5 -10 6 17-44
0.0083 2.4 N/A 56-58 (Yagi et al.
1988)
0.0026-
0.01
%
Ref.
120 2.6 100-115 33-46 (Hattori
1988)
10 8.3 N/A 20-120 8-54 (Ashitani et
al. 1988)
7.1 12.7 N/A 50-750 60-80 (Terauchi et
al. 1995)
5.5-7.7 14.4-20.2 2 9-17 26-64 (Nerenberg
et al. 2000a)
9.8-14.7 4.3-6.3 3 16-56 60-70 (Sinha et al.
2003)
7.5 5.6 1.0-1.1 25-100 20-40 (Elhadi et al.
2003)
34

determine the ability of the bacteria to remove MIB and geosmin (Hattori 1988).
Removal efficiency of MIB and geosmin were approximately 63 and 83 %, respectively,
for initial concentrations of 160 ng/l and 90 ng/l, respectively.
Other T&O compounds
Fishy odors loosely characterized as aldehydes, amines and dimethyl sulfide have
been biodegraded by sand biofilters and aquifer recharge bacteria (Rittmann et al. 1995,
Lundgren et al. 1988). Algae blooms also can produce/release medicinal-antiseptic odors
into the water, which can be easily biodegraded by aerobic bacteria. Aromatic
compounds, specially chlorinated phenolics, are the main compounds related to these
odors (Rittmann et al. 1995). Marshy-swampy-septic odors of biological origin include
hydrogen sulfide, short-chain mercaptans, dimethylsulfide, dimethyldisulfide, and
dimethyltrysulfide. These sulfur-containing compounds can be degraded by aerobic
bacteria (Rittmann et al. 1995). Sand biofilters grown in river water NOM have reported
to use dimethyltrisulfide as secondary substrate (Lundgren et al. 1988).
Biofiltraiton models
Modeling theory
The transient-state, multiple-species biofilm model (TSMSBM) always uses
typical values found in literature for the modeling parameter (Rittmann et al. 2002b). The
model has never been calibrated and a sensibility analysis has not been performed either.
Since the kinetic parameters used by the TSMSBM were taken from wastewater
35

literature, these parameters are expressed in mg of chemical oxygen demand (COD).
Different conversion factors are given to convert mg of BDOC to COD, however, these
factors are always referenced to other literature. After a short research on this literature,
it was determined that it was not clear how the conversion factors were estimated or why
different conversion factors were used for different substrates. More research may be
needed to clarify these discrepancies.
The main clear difference between the TSMSBM and the BIOFILT model is how
substrate biodegradation and biomass growth were modeled (Hozalski and Bouwer
2001). However, the other main difference is that the TSMSBM was performed around
the biofilm, not around the completely mixed reactor as the BIOFILT model did. This
approach eliminated the need of solving the pseudo-analytical (and widely used) steady-
state biofilm model to save time and computational efforts (Saez and Rittmann 1992).
However, by centering the mass balances (substrate and biofilm) for the biofilm, it
eliminated the need for estimating the steady-state flux of substrate into the biofilm (J)
and the substrate concentration at the surface of the biofilm (Ss). This approach assumes
that the effective diffusion layer (Lw) and the diffusion transport of substrate from the
bulk liquid to the biofilm substrate are zero or close. When solving problems, the
TSMSBM assumes that the bulk substrate concentration (S) is equal to Ss. Reasons for
eliminating the molecular diffusion of substrate at the effective liquid layer were not
given (explicitly). In general, the TSMSBM was very innovative in terms of modeling
multiple biofilm species and substrates. However, it falls short in simulating the transport
of compounds through the reactors.
36

Most models mentioned above include the biodegradation of primary substrate
expressed as AOC, BDOC, ammonia, and nitrate, but not biodegradation of secondary
substrates (e.g. MIB and geosmin, or other organic micropollutants). It was reported a
two-step biodegradation model of three taste and odor compounds in a sparged, upflow,
fixed-bed aerobic biofilm reactor (Rittmann et al. 1995). The first step estimates the rate
of primary-substrate utilization and the amount and distribution of biofilm biomass in the
reactor based on the pseudo-analytical steady state model (Saez and Rittmann 1988). The
second step estimates the rate of biodegradation and volatilization of taste-and-odor
compounds. Interesting simulation results are given, but it not reported if the model was
calibrated with lab- or pilot-scale results.
INTEGRATED OZONE-BIOFILTRATION SYSTEMS FOR T&O REMOVAL
Operational Experience
Most of the ozone-biofiltration systems reported in literature deal with the
removal and fate of primary organic substrates defined as NOM, UVA254, DOC, humic
substances, AOC, BDOC, ozonation and chlorination by-products (Carlson and Amy
2001, Graham 1999, Griffini et al. 1999, Hozalski et al. 1999, Huck 1999, Melin et al.
2000, Melin and Odegaard 1999, Melin and Odegaard 2000, Moll and Summers 1999,
Odegaard et al. 1999, Rittmann et al. 2002a, Sumitomo 1992, Urfer and Huck 2000,
Nishijima et al. 2003). These reports have concluded that ozone helps with the
biodegradation filters by hydrolyzing large molecules and making them easier to degrade
by the bacteria in biofilm.
37

The effect of ozonation and biofiltration on MIB and geosmin has not been
extensively studied, limited information is found in literature (Huck et al. 1998,
Nerenberg et al. 2000a). MIB and geosmin removal at a 37.5-MGD full-scale water
treatment facility (Lake Bluff, Illinois) with ozone-biofiltration treatment has been
reported of an overall MIB removal through the facility 65-100 % (Nerenberg et al.
2000a). The water treatment facility had biologically active GAC filters during the test
period, which was in service without regeneration for 6 years. Four sets of results with
ozone doses from 0.66 to 0.88 mg-ozone/mg-DOC were reported. Ozone-biofiltration
removed 26-65 % of an initial MIB concentration of 37-43 ng/l. Another pilot plant, fed
with North Saskatchewan River water, consisted of rapid mix, flocculation,
sedimentation, ozonation, and four biological filters in parallel (three A/S and one GAS/S
filter) had no odors detected after ozonation/biofiltration (Huck et al. 1998). The target
ozone dose was 0.75-1 mg-ozone/mg-DOC. Taste and odors in raw water were identified
by flavor profile analysis and described from grassy, musty, and woody to septic sewage.
Quantitative analysis of raw and treated samples was not performed during these earlier
studies because of lack of experience with the analytical methods at that time.
General conclusions of the ozone enhanced biofiltration treatment process were
summarized as follows (Booth and Idaho 2001, Coffey 1995, Hozalski et al. 1995,
Krasner et al. 1993, Lechevallier et al. 1992, Miltner et al. 1995, Namkung and Rittmann
1987, Wang et al. 1995). First, biofilters with GAC media provided superior performance
compared to anthracite and sand media, and conventionally operated anthracite filters in
terms of particulate removal. However, head loss development and terminal headloss
38

were higher in the biologically active filters compared to the conventionally operated
filter. The GAC filter had the highest terminal head loss. Second, the removal of DOC
and DPB precursors was superior for the GAC filter compared to biologically active
anthracite and conventionally operated anthracite filters (Booth and Idaho 2001). Third,
ozone alone could not eliminate all objectionable odors. Fourth, temperature and
backwash operations are import in biofiltration process.
Summary of MIB and Geosmin Removal
Table 2.5 summarized the percentages of biological removal of MIB in different
studies. Since most of the natural MIB presentations are in the range of ng/L levels, it is
probably used as secondary substrates. From the following apparent results, MIB
removals were the lowest in rapid sand biofilter and completely mixed bioreactor; and
MIB removals achieved the highest percentages in slow sand filter in lab; GAC filters
had fairly consistent middle range removals in lab and full-scale results.
Field operational data suggests that ozone can oxide 10~90% of MIB and
geosmin, and typical biofiltration can remove around 50% of the influent MIB and
geosmin. Ozone to TOC doses in the range of 0.5 to 1.5 mg-O3/mg-TOC have been
reported to remove 50~90% of the influent MIB, with higher ozone doses higher MIB
oxidation (Ferguson 1990, Glaze et al. 1990, Nerenberg et al. 2000).
39

OVERVIEW OF RESEARCH GAPS
In the past reports on ozonation and biofiltration of taste and odor problems, there
was almost none of the reports addressed the mechanisms of ozone oxidation and
biodegradation of taste and odor compounds. Only very few published dose-response
relationships have been developed for ozone oxidation of MIB and geosmin. Most full-
scale water treatment plants that are applying ozonation for taste and odor control
generally operate at quite low ozone doses (< 1 mg-O3/mg-TOC) compared to most of the
ozone doses applied in research. Many literatures were talking about biofiltration process,
but most of them were concentrated on removals of TOC, particulates, and bacteria. The
mechanisms of these removal processes (ozonation and biodegradation), and how to
optimize the overall treatment process to control taste and odor problems, have not been
well documented.
The goal of this project is to optimize the performance of ozone enhanced
biofiltration process for geosmin, MIB, particulate, and BOM removal while considering
other factors such as AOC and DBP formation problem and headloss development.
Quantifying ozonation experiments of MIB and geosmin under changes of different
operational parameters for understanding the oxidation mechanisms were conducted.
Biofiltration process optimization was conducted for MIB and geosmin removal after
optimizing of BOM and particulate removal. Process models, based on existing model
formulations, were developed to facilitate optimization of ozone enhanced biofiltration
design and operating criteria.
40

CHAPTER 3
EXPERIMENTAL METHODS
LABORATORY OZONATION APPROACH
Bench-scale batch ozonation experiments were conducted to understand the
mechanisms of ozonation of MIB and geosmin in geographically different natural waters
and distilled (DI) water. All batch experiments were performed at room temperature
(24±1 0 C). The effect of individual ozonation condition, such as ozone dose, water pH,
initial MIB and geosmin concentration, and water temperature was tested. Ozonation
experiment was designed to understand the role of ozone molecular (O3) and hydroxyl
radicals (HO • ) in MIB and geosmin oxidation processes. Concentration of HO • during
ozonation could be indirectly measured by a common HO • probe compound, p-
chlorobenzoic acid (PCBA), which has high rate constant with HO • and low rate constant
with molecular ozone. Tertiary butanol (t-butanol), that scavenges HO • , was used to
separate the oxidation by O3 from the effects of HO • . T-butanol was selected to separate
the two oxidation mechanisms by O3 and HO • respectively because its reaction rate
constant with molecular ozone (0.001 M -1 s -1 ) could be neglected compared with a rate
constant of 6 × 10 8 M -1 s -1 with HO • radicals (Buxton et al. 1988).
Objectives of Natural and DI Water Ozonation
The goal of the ozonation batch experiment was to understand the MIB and
geosmin ozonation mechanisms through two pathways: MIB and geosmin oxidized by
41

ozone molecules; MIB and geosmin oxidized by HO • radicals, and help in developing
design and operating criteria. For these purposes, natural waters around the U.S. with
different water qualities and distilled (DI) water were conducted with ozonation tests, so
that the experiment results could represent the general trends. Ozonation experiments in
DI water were conducted in an effort to eliminating any effects that may caused from
NOM presentation in natural waters. Effects of individual parameters, such as pH, ozone
dose, and t-butanol presentation, were investigated in MIB and geosmin ozonation
experiment in DI water. MIB and geosmin were artificially introduced before ozone
addition.
To understand the ozonation mechanisms of MIB and geosmin, an orthogonal
experimental matrix was developed and applied in the batch ozonation experiment. The
experimental matrix consists of a baseline condition around which the variables will be
altered one at a time to evaluate the effectiveness of individual parameters:
• Ozone dose
• Hydrogen peroxide dose
• HO • radicals role (t-butanol addition)
• Influent MIB and geosmin concentrations
• pH condition
• Temperature condition
42

Ozonation Methodology
For each ozonation experiment, one of the source waters was spiked in advance
with PCBA, and H2O2 or t-butanol if needed. Then ozone solution was introduced right
after spiking MIB and geosmin into prepared water in a 1-L cylindrical reactor with a
sampling port at bottom (Figure 3.1). A total of 500 ml of the reaction water was
achieved with the required initial ozone concentration (3 to 15 mg/L). A floating Teflon
cover sheet was applied at the surface of the reacting water to minimize volatizing of
MIB, geosmin and O3 and maintain the initial concentration consistency.
Reaction time was counted from the time that ozone solution was introduced.
Residuals of ozone, MIB and geosmin samples were taken at different intervals from the
bottom sampling port in 50 ml centrifugal tubes. Indigo solution was added into each
tube before sampling to quench any ozone residual. The collected 50 ml (with dilution by
indigo solution) samples were firstly analyzed for ozone residual using photo
spectrometer at wavelength 600nm. The left samples were individually stored in 40 ml
Stir Bar at Bottom
Magnetic Mixer
Mixer
Figure 3.1 Batch ozonation reactor
Teflon Cover
Reactor (1L Glass Cylinder)
Sampling Port
43

amber glass vials with zero headspace for future MIB and geosmin analysis. All these
operations were conducted in a time saving manner so that the volatizing loss of MIB and
geosmin was minimized. Concentrations of the samples were corrected using the
corresponding dilution factor.
Natural Water Ozonation Experiment
An orthogonal experimental matrix (Table 3.1) was conducted for each natural
water source. Experimental parameters were varied each at a time from the baseline
conditions to study the individual parameter’s effect. The baseline ozone dose was
chosen such that there was ozone residual between 0.3 to 0.1 mg/L after 10 minutes of
contact time (i.e., CT=1 to 3 mg-min/L). For source waters (W4 and W5) that high TOC
concentrations, perozonation was conducted to reduce the instantaneous ozone demands.
The preozonated waters of W4 and W5 were designated as W4P, W5P respectively.
Preozonation was performed by passing water through a concurrent flow ozone reactor at
0.5 L/min with a hydraulic retention time (HRT) of 40 seconds.
44

Parameter
Testing
Table 3.1
Experimental matrix of ozonation laboratory experiments of natural waters
Ozone Dose
pH MIB & GSM
(ng/L)
H2O2/O3
(mg /mg)
T Butanol
Baseline Baseline(B*) Ambient 50 0 0
H2O2 Baseline(B*) Ambient 50 0.05,0.025 0
PH Baseline(B*) Ambient-1 50 0 0
MIB/GSM Baseline(B*) Ambient 200 0 0
T Butanol Baseline(B*) Ambient 50 0 2
Ozone
Dose
0.5B, 0.75B,
1.25B, 1.5B,
2 B
(mM)
Ambient 50 0 0
Baseline (B*) ozone dose = 2.8,11,3.75,11.125,4.5,10,5 mg/L of ozone for W1, W2, W3,
W4, W4P, W5, W5P respectively
45

DI Water Ozonation Experiment
Table 3.2 gives the experiment matrix of DI water ozonation experiments. Effects
of ozone dose, pH, t-butanol addition, and methanol addition were investigated. Volume
of totlal reaction water was 500 ml for each experiment. PCBA (0.2 mM) was spiked for
all DI water tests to measure HO • concentration. MIB and geosmin initial concentrations
were both 100 ng/L for all tests.
Table 3.2
Experiment matrix of ozonation experiment in DI water
Effect of O3 dose PCBA T-butanol pH
mg/l (uM) (mM)
1 0.2 2 5
Ozone 2 0.2 2 5
Dose 3 0.2 2 5
(with 4 0.2 2 5
t-butanol) 6 0.2 2 5
8 0.2 2 5
Ozone 2 0.2 0 6
Dose 4 0.2 0 6
3 0.2 2 6
pH 3 0.2 2 7
(with 3 0.2 2 8
t-butanol) 2 0.2 0 6
pH 2 0.2 0 7
2 0.2 0 8
2 0.2 7 7
1.25 0.2 1.0 7
T-butanol 1.25 0.2 0.5 7
1.25 0.2 0.1 7
1.25 0.2 0.01 7
1.25 0.2 0 7
46

Source Waters and Chemicals
Five waters from different geographic regions of USA having different TOC,
SUVA, pH and alkalinity values were selected to represent the general source water
quality. As shown in Table 3.3, the five source waters was designated by W1~W5. All
waters were filtered through a 0.45 µm filter, and stored at 4ºC prior to ozonation.
Table 3.3
Water quality of natural waters used for laboratory ozonation experiments
Parameter W1 W2
(Arizona) (Michigan)
Water Body River Impounded
River
W3 W4
(Pennsylvania) (Indiana)
River Reservoi
r
W5
(Texas)
Reservoir
TOC(mg/L) 3.079 7.7 3 4.5 4.88
SUVA
m -1 (mg/L) -1
Alkalinity(mg/l
as CaCO3)
1.6 2.9 2.1 1.9 2.4
175 237.5 59 141 80
TDS (mg/L) 704 391 160 420 161
pH 8.4 8.3 7.6 8 7.9
Bromide(ug/L) 121

All chemicals used in laboratory ozonation tests were analytical grade. Nanopure
water (>18mO) which used for stock solution preparation was made from ultra pure
water system (Nanopure Infinity TM ). MIB and geosmin stock solutions in methanol were
purchased from Sigma Chemical Company (MO, US); MIB and geosmin pure chemicals
were purchased from Wako Chemicals Inc. Hydrogen peroxide (H2O2) solution (3%; or
30,000mg/l) was purchased from Albertson’s store. Pure chemicals of potassium
indigotrisulfonate (Indigo), sodium azide (NaN3), para-chlorobenzoic acid (PCBA) were
purchased from Aldrich Chem. Co. Ultrasonicator was used to help dissolve PCBA into
nanopure water solution. Pure chemicals of sodium phosphate and sodium thiosulfate
were purchased from Mallinckrodt U.S.P. TAC. Tertiary butanol (T-butanol) pure
chemical was puschased from Sigma-Aldrich, Co.
Gaseous ozone was generated from pure oxygen using an OREC TM (Model V5-0,
Phoenix, AZ) or an Osmonics TM ozone generator as shown in Figure 3.2. A liquid ozone
stock solution was prepared by continuously bubbling >45 minutes pure gaseous ozone
through a gas washing bottle (containing 0.5 M sodium phosphate) before entering a 2 L
glass vessel with cold nanopure water in. This vessel with ozone stock was maintained at
a temperature of around 4ºC using an ice bath (Westerhoff et al., 1998) during the whole
period of ozone stock preparation and ozonation experiment. Saturated ozone stock
solution of approximately 40 mg/L and 80 mg/l by OREC TM and Osmonics TM
respectively was usually achieved.
48

OREC
Ozone
Generator
Pure oxygen cylinder
Figure 3.2 Ozone generation and stock system
0.5 M
phosphate
buffer (pH 6) O o
o o
o o
o o
oo
Ice Bath
49

PILOT TESTS
Two separate pilot studies were conducted by MPI during 2002 to 2003 in two
WTPs in the City of Chandler (Chandler) and the City of Squaw Peak (Squaw Peak) in
Arizona. Both of the two plants receive waters predominantly from Salt River Project
(SRP) canal with relatively high concentrations of taste and odor causing compounds
such as MIB and geosmin. The historical concentrations of MIB and geosmin in the plant
source water varied between 10 and 60 ng/L for the months of August through January
(Kommineni et al. 2003). The MIB and geosmin are produced by blue-green algae and
actinomycetes that grow in the canal. The warm climate and the plenty of sunlight create
ideal conditions for algae growth.
Both pilot plants were using the full-scale plant settled water as pilot water
sources to test the ozone-biofiltration effects verses bio-filtration effects without
ozonation on taste and odor controlling and other water quality goals. Two kinds of
filtration media, granular activated carbon (GAC)/sand and anthracite/sand, were tested
in parallel. For evaluation of taste and odor control, results of exhausted media were
applied. Acclimation of the pilot filters was conducted before testing.
Chandler pilot facility was operated over a period of seven months during July
2002 to February 2003, designed specifically to investigate taste and odor control by
ozone-biofiltration treatment. The average ambient concentrations of MIB and geosmin
in Chandler plant settled water were around 1.0~4.2 ng/l (Kommineni et al. 2003).
During the pilot operating period, the City of Chandler occasionally added small doses
50

(5-10 milligrams/L) of powdered activated carbon (PAC) to the raw water to control the
taste and odor problems (Kommineni et al. 2003).
Squaw Peak pilot plant was operated from December 2002 to June 2003 as part of
a water quality master plan for City of Phoenix. The pilot study conducted by MPI was
designed to facilitate development of the design and operating criteria for intermediate
ozonation and filter absorbers. During the period of pilot testing, the Squaw Peak WTP
was practicing enhance coagulation with an average alum dose of 24 mg/L. Sulfuric acid
(approximately 14 mg/L) was added prior to alum to reduce the pH from 8.1 to 7.6~7.8.
Objectives of Pilot Studies
The goal of the Chandler pilot testing was to evaluate the effectiveness of
removing MIB and geosmin removal by Ozone-enhanced biofiltration under different
operating conditions. The pilot study results also help in developing design and operating
criteria. The chandler pilot experiment could be used as supplement of the MIB removal
mechanism studies.
To address this goal, an orthogonal experimental design was developed and
tested. Orthogonal experimental design consists of a baseline condition around which a
variable will be altered one at a time. The orthogonal matrix of experiments was
conducted to evaluate the effectiveness of T&O controlling by changing the following
parameters:
• Ozone dose
51

• Empty bet contact time (EBCT)
• Influent MIB and geosmin concentrations
• pH condition
• Filter media type (GAC vs. anthracite)
Objectives of the Squaw Peak pilot study conducted by MPI include: 1)
evaluating the effectiveness of biologically active GAC filter absorbers for removing
particulates, organics, DBP precursors and taste and odor (T&O) causing compounds; 2)
estimating the GAC media life to comply with the Stage-2 D/DBP Rule; 3) estimating the
effect of ozonation on media life; 4) determining the most appropriate GAC media depth
(or empty-bed contact time (EBCT)) and media type (lignite versus bituminous) for
biological filtration; 5) evaluating the effect of backwashing with chlorinated and
unchlorinated waters on the performance of filter absorbers in terms of removing DBP
precursors and T&O causing compounds; 6) understanding the benefits of ozonation
prior to filtration. Among these goals, the author is concentrating on the result of
removing taste and odor causing compounds, MIB. Effects of the following
parameters/conditions on MIB removals during ozonation and filtration processes were
evaluated in this thesis:
• Filter media type (anthracit, GAC, lignite coal and bituminous coal)
• Backwash water (chlorinated water versus unchlorinated water)
• Influent TOC concentration
• Empty bed contact time (EBCT)
52

Chandler Pilot Facility
As shown in Figure 3.3, the schematic of the Chandler pilot system, the pilot
facility received settled water from the full-scale plant. A portion of the settled water was
spiked with MIB and geosmin and passed through the large, 8-inch diameter filters,
which were designed for evaluation of biofiltration effects without ozonation. The
remaining portion of the water was passed through ozone contactor and dissipation tank,
spiked with MIB and geosmin and passed through the small, 3-inch diameter filters,
which were designed for evaluation of ozone-biofiltration effects. The MIB and geosmin
were continuously spiked into the influent waters of the large and small filters. The
targeted MIB and geosmin concentrations in the spiked influent waters of the small and
large filters were 25 and 50 ng/L, respectively.
Figure 3.4 shows the details of the filters design. Two different types of filter
were used, 3-in diameter and 40-in tall filters (small filters) and 8-in diameter and 40-in
tall filters (big filters). All filters were dual media filters with either GAC/sand or
anthracite/sand as the media. The depth of GAC or anthracite was 20-inches. The depth
of sand media in each filter was 10-inches. The pilot filters were operated at loading
rates of either 4 gallons/minute-foot 2 (gpm/ft 2 ) or 6 gpm/ft 2 . The loading rates at which
each filter was operated are shown in parenthesis underneath each pilot filter in Figure
3.4. Loading rates of 4 gpm/ft 2 and 6 gpm/ft 2 resulted in EBCT of 6.3 minutes and 4.3
minutes, respectively.
53

Full-scale
Raw Water
Pilot-scale
PAC
Coagulation
C F S
Pilot Treated
Ozone Contactor
Dissipation
Flocculation
Plant Settled Water
Sedimentation
MIB/Geosmin
Sodium
Thiosulfate
GAC/
Sand
3-in Filters
MIB/Geosmin
Anthracite/
Sand
Filtration
Figure 3.3 Schematic of Chandler Pilot Test Facility (Source: Kommineni et al. 2003)
Plant Plant Settled Settled Water
Water
Ozone Contactor
Dissipation
Ozonated Ozonated Plant Plant Settled Settled Water Water
6”
20”
10”
(gpm/ft2 (gpm/ft ):
2 (gpm/ft): 2 (gpm/ft ):
2 ):
Sand
Sampling Ports
Port
GAC
Sand
Sand
GAC
Sand
Anthracite
Sand
20”
10”
Figure 3.4 Pilot Filters Design and Operation (Source: Kommineni et al. 2003)
Cl2
GAC/
Sand
(4) (6) (4) (6) (4)
Anthracite/
Sand
8-in Filters
Sand Sand
Backwash With Unchlorinated Plant Filtered Water
54

To minimize adsorption effect of GAC filters, the pilot used aged GAC to
evaluate the removal of MIB and geosmin by biofiltration. The GAC used in the pilot
filters was obtained from one of the Chandler WTP full-scale plant filters. This GAC
was used in the full-scale plant filter for more than three years. All the filters were
acclimated for more than four months prior to performing the experiments. Each
experiment was conducted over a period of one-two weeks.
Ozone was applied in the pilot as an intermediate oxidant. In a counter-flow
contactor, the full scale settled water was ozonated with a residence time of 2-4 minutes,
and then dissipated in a tank that provided an additional 8-10 minutes of contact time.
Sodium thiosulfate was added to the effluent of the ozone dissipation tank to quench any
residual ozone, so that no residual ozone was presenting when the water was feeding to
the four small filters. Digital photos of ozonation and biofiltration systems are shown
respectively in Figures 3.5 and 3.6.
Ozone Generator
Ozone Contactor
Figure 3.5 Pilot Ozonation System (Source: Kommineni et al. 2003)
Dissipation System
55

3-Inch Diameter Filters 8-Inch Diameter Filters Sampling Port
Figure 3.6 Pilot Filtration System (Source: Kommineni et al. 2003)
Parameters such as flow, head loss, turbidity, UV absorbance at 254 nanometers
(UVA254), temperature and pH were measured two-three times per week for ozonation
and each filter. Water samples collected before and after ozonation and biofiltration were
analyzed for MIB, geosmin, TOC, and heterotrophic plate counts (HPCs) (Kommineni et
al. 2003). MIB and geosmin analysis was performed by ASU and laboratory at city of
Phoenix. All the other water parameters were either measured on site by MPI or analyzed
by the laboratory at city of Phoenix. The biological filter performance was assessed in
terms of the removal of MIB, geosmin, TOC, particulates and microbial parameters in
this thesis.
56

Squaw Peak Pilot Facility
As shown in Figure 3.7, the schematic of the Squaw Peak pilot system, the pilot
facility received settled water from the full-scale plant. A portion of the settled water was
spiked with MIB and geosmin and divided into two portions to evaluate filtration
performance with and without ozonation by two groups of filters, respectively. The
remaining portion of the water was treated by reverse osmosis (RO) process to
concentrate the TOC using settled water. This RO-produced high-TOC water was spiked
with MIB and geosmin and divided into two portions to evaluate filtration performance
with and without ozonation by another two groups of filters, respectively. The product of
RO was return to the full-scale plant treatment process through drainage.
Totally twenty filters with four different media types, anthracite/sand dual media
(A/S), bituminous GAC (GAC-B), lignite GAC (GAC-L), and GAC-B/sand dual media
(GAC-B/S), were used in Squaw Peak pilot study. They were grouped into four sets: (A)
filters received plant settled water (SW), (B) filters received ozonated SW (OSW), (C)
filters received the RO-produced high-TOC water (ETOC) and (D) filters received
ozonated ETOC water (OETOC). Each group has four filters with different media type
using unchlorinated water for backwash. Three more filters were used as control filters
using unchlorinated water for backwash, which was designed to evaluate the backwash
effects with chlorinated and unchlorinated water. Two of them with two different media,
A/S and GAC-B/S, are in group (A), served as control filters for unozonated waters. One
of them with A/S media is in group (B), served as control filter for ozonated water. There
is another one more filter in group (A) with GAC-B/S media designed to be applied with
57

Chlorinated
Water
Flash Mixer
Arizona Canal
PAC
Control
Bar Scren
Pre Pre-sedimentation Pre Pre-sedimentation sedimentation
Basin
RWPS
A/S
GAC-B/S
A/S
GAC-B/S
GAC-L
GAC-B
GAC-B/S
RO
Pump/Flush Mixer
Alum, H 2 SO 4 , Poly
Filter Aid
Product to Drain
Plant
Setled
MIB/Geosmin
Water Reject at 50-60% Recovery
Pre-filter
Unchlorinated
Water
1 2 3 4 5 6 7
A/S
GAC-B/S
GAC-L
GAC-B
13 14 15 16
Unchlorinated
Water
Final
Sedimentation
Flocculators
Flocculators Basin
Basin
Plant Setled Water
Ozone Contactor
Ozone
Generator
Ozone Contactor
Chlorinated
Water
Unchlorinated
Water
Anthracite/
Sand Filters
Filters
Reservoirs
Figure 3.7. Schematics of Squaw Peak pilot facility (Source: Internal Report of Malcolm
Pirnie Inc.)
Cl 2
MIB/Geosmin
A/S
A/S
GAC-B/S
GAC-L
GAC-B
Cl 2
8 9 10 1 12
A/S
GAC-B/S GAC-B/S
GAC-L GAC-L
Unchlorinated
Water
GAC-B
17 18 19 20
58

filter aid and evaluated for its effects, which was backwashed with unchlorinated water.
Table 3.4 showed the design of each filter in Squaw Peak pilot facility. Each of
the 20 filters is 3-inch (in) diameter and 15 feet (ft) tall. Media depths that were evaluated
include 20-in (EBCT = 2.2 min), 30-in (EBCT = 3.3 min) and 48-in (EBCT = 5.2 min).
The pilot filters were operated under constant-head and declining flow rate. Average
hydraulic loading rate through the filters was 5.5 gallons/minute-square feet (gpm/sf).
Table 3.4
Filters design of Squaw Peak pilot facility
Filter
EBCT
Backwash
ID Media Description (min) Influent Water
Filter 1 20-in anthracite over 10-in sand 2.3 SW chlorinated
Filter 2 20-in GAC-B over 10-in sand 2.3 SW chlorinated
Filter 3 20-in anthracite over 10-in sand 2.3 SW unchlorinated
Filter 4 20-in GAC-B over 10-in sand 2.3 SW unchlorinated
Filter 5 30-in GAC-L 3.4 SW unchlorinated
Filter 6 48-in GAC-B 5.5 SW unchlorinated
Filter 7 20-in GAC-B over 10-in sand 2.3 SW+filter aid unchlorinated
Filter 8 20-in anthracite over 10-in sand 2.3 OSW chlorinated
Filter 9 20-in anthracite over 10-in sand 2.3 OSW unchlorinated
Filter 10 20-in GAC-B over 10-in sand 2.3 OSW unchlorinated
Filter 11 30-in GAC-L 3.4 OSW unchlorinated
Filter 12 48-in GAC-B 5.5 OSW unchlorinated
Filter 13 20-in anthracite over 10-in sand 2.3 ETOC unchlorinated
Filter 14 20-in GAC-B over 10-in sand 2.3 ETOC unchlorinated
Filter 15 30-in GAC-L 3.4 ETOC unchlorinated
Filter 16 48-in GAC-B 5.5 ETOC unchlorinated
Filter 17 20-in anthracite over 10-in sand 2.3 OETOC unchlorinated
Filter 18 20-in GAC-B over 10-in sand 2.3 OETOC unchlorinated
Filter 19 30-in GAC-L 3.4 OETOC unchlorinated
Filter 20 48-in GAC-B 5.5 OETOC unchlorinated
Notes: SW, settled water
OSW, ozonated settled water
ETOC, elevated TOC water
OETOC, ozonated elevated TOC water
59

Ozone was evaluated in the pilot as an intermediate oxidant. Ozonation was
conducted in two identical counter-flow contactors for SW and ETOC waters. Ozone was
applied at a mass ratio of 0.5 mg/mg-TOC of SW and ETOC waters, respectively.
The pilot used virgin GACs during study period of about seven months from early
December 2002 to the end of June 2003. MIB was introduced after around 5-month’s
operation of the filters. Exhaustion of GAC adsorption was expected to be achieved
within this period, which should allow an evaluation of biological filtration at the later
part of the study. MIB concentrations obtained in this study were spiked using the same
method as Chandler pilot plant, with target concentrations of 50-75 ng/L. MIB stock
solutions were prepared and spiked on site by MPI. Details of MIB dosing method are
discussed later in this chapter.
Parameters such as flow, head loss, turbidity, UVA254, temperature and pH were
measured two-three times per week for ozonations and each filter. Water samples
collected before and after ozonations and filtrations were analyzed for MIB, TOC, and
heterotrophic plate counts (HPCs). MIB removal efficiency was assessed for individual
ozonation process and each filter. MIB analysis was performed by ASU and laboratory at
city of Phoenix. All the other water parameters were either measured on site or analyzed
by other contract laboratories. Only result of MIB from ASU were analyzed and
interpreted in this thesis.
60

MIB and Geosmin Dosing Method
The pilot-scale studies are continuous flow experiment, which requires MIB and
geosmin be spiked continuously into the pipe, and mixed well with the influent water.
Significant consideration was made for the dosing method of MIB and geosmin. Two
types of collapsible dispensing bag, medical drainage bag and airtight gas-sampling bag
were tested for holding MIB and geosmin spiking solution to avoid headspace left during
continuous spiking period. Firstly, medical drainage bags were tried to contain MIB and
geosmin stock solution when pumping it into the pipelines. After around one month
operation, it was decided that the medical bags could not be used for dosing MIB and
geosmin due to volatization problem. Medical bags were designed to be gas permeable.
Significant percentages (>50% lost during one week) of MIB and geosmin stock solution
were volatized through the wall of the bags even though stored in refrigerator. Finally,
airtight gas-sampling bags (Figure 3.8) were used to stock high concentration MIB and
geosmin solution. It was proved that gas-sampling bag (SKC-West Inc., Tedlar bags) has
no MIB and geosmin vilotization issues during up to one month’s stock period in
refrigerator. A digital pump was used to pump the MIB and geosmin solution into pilot
pipes without headspace left in the bag. A mixer was installed in the pipe to provide
mixing of MIB and geosmin solution with the influent water.
61

Figure 3.8 Gas-sampling bags for stocking MIB solution
MIB and geosmin solution (1.5-2.5 mg/L) used for pilot spiking is prepared
according to the following procedures:
1. Dissolve neat (no methanol) MIB and geosmin into to water to prepare stock
solution. Dissolve one vial of pure MIB (20mg/vial, in solide phase) or geosmin
(20mg/vial, in liquid phase) using pure water into 500ml bottles. Bottles were wrapped
with Aluminum foil, capped, mixed for 10 minutes on magnetic stirrer and hold at 4ºC.
2. Dilute the stock solution to determine exact MIB and geosmin concentration.
Stock solutions made in step 1 were diluted into the analytical instrument detection range
of 1~100 ng/l for concentration analysis.
3. Prepare MIB and geosmin spiking solution. Using a 4-liter glass flask covered
with aluminum foil, a predetermined volume of stock solution was added to prepare a 1.5
to 2.5 mg/l spiking solution. The precise spiking solution concentration was quantified by
sample dilution and GC/MS analysis. Due to volatilization of MIB and geosmin during
preparation, a 20% excess of stock solution was used to achieve the target MIB and
geosmin concentration.
62

4. Transfer spiking solution into collapsible dispensing bags. A 10L airtight gas-
sampling bag (SKC-West Inc., Tedlar bags) was used to transport and spike the solution
to the pilot plant. The bags were reinforced with duct tap for holding liquid. Spiking
solution was transferred from the 4-liter glass flask to the bag using a peristaltic pump
with plastic tubing at a flow rate of 30 ml/min. The collapsible dispensing bag was held
in the dark at 4ºC during storage.
5. Spike MIB and geosmin at the pilots. At the pilot plants, the collapsible
dispensing bags were stored in a small refrigerator and pumped through Teflon tubing
exiting a hole drilled in the refrigerator to the pilot pipes at a flow rate of 20 to 40
ml/hour. Each bag was replaced once per week.
UTILITY SURVEY
During this phase of the T&O study, removal of MIB and geosmin across each
unit process in the water treatment plants is investigated. All the utilities chosen are
having both ozonation and biofiltration treatment unit installed and running. MIB and
geosmin samples were taken between June and October so that the MIB and geosmin
reached the peak concentration during the year.
Utilities ID and treatment processes
Table 3.5 shows the utilities ID, source water and treatment process of the
utilities that have been sampled during 2002 and 2003. There were totally nine utilities
participated the sampling campaigns. Details of individual utility setups and operations,
63

Table 3.5
Water treatment processes of utilities
Utility Source
Ozone
Filtre
Utility Name Water Design Flow Coagulation
Dose Filtration Backwash
ID # mg/L Media Water
Ann Arbor Huron flocculation-primary clarifier-
1 Water River flocculation- Lime, Polymer 1.3~2.6 GAC/Sand chlorinated
Treatment
secondary clarifier-CO2
Plant and contactorozonation-filtration
Central
Lake
Well water chloramination-cleanwell
County
ozonation-flocculation-
2 Joint
Action
Water
sedimentation- Hydroxychloride or 0.6 GAC/Sand chlorinated
Agency
Chandler
filtration-cleanwell Hydroxychlorosulfate
Polyaluminum
Water Salt River flocculation-sedimentaion-
3 Treatment Canal filtration- PAC, Alum GAC/Sand chlorinated
Plant chlorination-cleanwell
Contra
Pre-oxidation (NaClO)--
Costa Los Coagulation/Flocculation -
0.7~
4 Water Vaquerous Sedimentation - Intermediate
Ozone - Filtration (GAC/Sand)--
Chlorination and Chloramination-
Alum, Polymer 1.25 GAC/Sand chloraminated
District
Eagle
Reservoir cleanwell
Mountain Eagle ozonation-flocculation-
ozonated
5 Water Mountain sedimentation- Alum 3.4~4.0 Anthracite/ water
Treatment
filtration-ozonation-
Plant
Gilbert
Lake chloramination-cleanwell Sand
Water Salt River
6 Treatment and
Central
presedimentation-coagulation- Alum, Polymer 0.8~1.0 GAC/Sand unchlorinated
Plant Arizona
Project flocculation-filtration-chlorination-
Milwaukee
water cleanwell
Water Lake ozonation-coagulation-
7 Works
Peoria
Michigan sedimentationfiltration-chlorination-cleanwell
Alum 0.9 Coal/Sand chloraminated
Greenway Salt and coagulation-presedimentation-
8 Water Verde ozonation- Alum, Polymer 1.2 GAC unchlorinated
Treatment
flocculation-final sedimentationand
Plant Rivers and
Colorado
chlorination
chlorinated
River filtration-chlorination-chleanwell
Philadelphia Delaware
9 Water River, chloramination
Treatment Schuylkill
Plant River
64

such as filter media, numbers of filters, backwashing water were deliberated in the
following paragraphs.
1). Ann Arbor Water Treatment Plant, MI (AAWTP)
The Ann Arbor Water Treatment Plant applies ozone after primary and secondary
flocculation for multiple purposes, disinfection is the major aim. Additional benefits from
ozone application are reduction of color, taste and odor, and reduction of potentially
harmful chlorinated byproducts. Ozonation unit is followed by filtration system, which
consists of 26 filter beds. Filter media is comprised of 6 inches of silica sand and 18
inches of granular activated carbon (GAC). For filter backwashing, Ann Arbor WTP is
using chlorinated water, with typical chlorine concentration of 3.0mg/l (ppm). The total
backwash time is typically 10 minutes, which could be 20 minutes due to turbidity
problems. Surface wash is also applied at the beginning, and is typically running for 1
minute, which could be 2~3 minutes when having turbidity problems.
2). Central Lake County Joint Action Water Agency, IL (CLCJA)
At Central Lake County Joint Action Water Agency, ozonation is serving as
primary treatment, followed by rapid mixing, flocculation, and sedimentation. Then
GAC/sand filtration is applied before the clear well.
3). Chandler Water Treatment plant, AZ (CWTP)
For filter backwashing, Chandler WTP is using chlorinated water, with typical chlorine
concentration of 2.0 ppm. The average backwash period is approximately 1 hour for both
sides of the filter. A water-scouring device is also applied.
65

4). Contra Costa Water District (CCWD), CA (CCWD)
For filter backwashing, CCWD is using chloraminated water, with typical
chlorine residual concentration of 2.5 ppm. The average total backwash cycle is
approximately 20 minutes, at the following sequence: low rate, 5000gpm, 6min; medium
rate, 10000gpm, 6min; high rate, 28000gpm, 10min. Then the backwashed filter is
waiting to be back in service (in the chloraminted water) for 0.5~48 hours depending on
the operational needs. Air scouring is also applied at the beginning for about 12 minutes
with water drop a few inches below media surface.
5). Eagle Mountain Water Treatment Plant, City of Fort Worth, TX (EMWTP)
The Eagle Mountain Water Treatment Plant applies ozone as a pre-disinfectant to
reduce the potentially harmful chlorinated byproducts, and enhance the flocculation
effect. A combination of Chlorine and ammonia is applied after the following treatment
processes: rapid mixing, flocculation, sedimentation and filtration. Three parallel ozone
contactors are applied to the raw water, and eight parallel filters are applied in between
sedimentation and post disinfection. For filter backwashing, Fort Worth WTP is using
ozonated water, with no ozone residual. The average total backwash cycle is
approximately 20 minutes, with 10-minute backwash at 5600 gallons per minute (gpm).
Air scouring is also applied at the beginning. The filter backwash is computer controlled
and each filter is backwashed and placed back into service automatically. There are three
triggers that can be used to initiate a backwash, which are head loss, turbidity, and run-
time. Currently, Eagle Mountain uses the filter run time trigger to initiate a filter
backwash by placing the filter in the backwash queue.
66

At the beginning of a filter backwash, the filter will automatically draw down to
six inches above the media. The air-scour starts to scour the media for five minutes. At
the five-minute mark, the backwash pump comes on at a low rate of 30% or 3000gpm,
and runs concurrently with the air-scour system, until the level of the water in the filter
reaches approximately six inches below the overflow backwash troughs. At this point,
the air-scour shuts off, and the backwash pumps ramp up to a high rate of 60% or
approximately 5,600 gpm. The high rate backwash sequence lasts approximately 10
minutes, until clear spots start to appear in the water being backwashed through the filter.
At this point, the backwash pumps ramp back down to the low rate of 30% (3000 gpm).
Once flow stabilizes at the low rate, the filter backwash valve closes. Once the valve is
closed, the backwash pumps shut off. The filter is then placed back into service, with a
15-minute ramp time to achieve normal flow through the filter.
6). Gilbert Water Treatment Plant, AZ (GWTP)
The backwash water is the effluent water from the remaining on line filters,
without chlorination. The average total backwash cycle is 20~35 minutes. Air scouring is
also applied at the beginning with water drop to a depth of 8~12 inches above the media.
7). Milwaukee Water Works, WI (MWW)
Milwaukee Water Works receives raw water from Lake Michigan. Ozonation is
applied as primary disinfection process, followed by coagulation and sedimentation. The
settled water is sent to filtration unit, which followed by the clear well. Ammonia is
added as a post disinfectant before the treated water going into the distribution system.
The filter media applied in Milwaukee Water Works is a combination of coal above sand.
67

For filter backwashing, MWW is using the finished water which has been chloraminated,
with typical chlorine residual concentration of 1.0~1.3 ppm. The average total backwash
cycle is 16 minutes, with the surface wash of 2 minutes followed by backwash water flow
of 12 minutes.
8). Peoria Greenway Water Treatment Plant, AZ (PGWTP)
City of Peoria has its water supplied from the Salt and Verde Rivers, and
Colorado River. The Greenway WTP has a design capacity of 16 million gallons per day
(mgd). It incorporates conventional treatment, ozone and GAC filters. Ozone is used to
reduce the total organics present in the water. It’s installed in between pre-sedimentation
and flocculation. GAC filters provide a final polishing of the water before it is
chlorinated and distributed.
9). Philadelphia Water Treatment Plant, (PWTP)
68

Field sampling campaigns
Two sampling campaigns were conducted in August through October 2002 and
May through September 2003. During the first sampling campaign, ten sets of MIB and
geosmin samples were taken from six utilities with some utilities had two set of samples
during different period. Water samples were analyzed for ozonation and biofiltration
effects of MIB, geosmin and TOC. During the second sampling campaign, ten sets of
MIB and geosmin samples were taken from the treatment processes in eight utilities with
two utility had two set of samples during different period. In addition, eight sets of filter
biomass samples were collected during the second sampling campaign. Water samples
were analyzed for MIB, geosmin and TOC in Arizona State University. Biomass data
were analyzed by University of Colorado at Boulder (CU). Utilities provided data of
temperature, pH, ozone dose and filter loading rate. Table 3.6 shows the sampling matrix
of the two campaigns.
Table 3.6
Sampling matrix and dates for utilities survey in 2002 and 2003
Utility ID # 1 2 3 4 5 6 7 8 9
Sampled in 2002 for MIB and
geosmin
8/29
10/15
10/14
8/27
9/03
8/12
8/12
9/23
9/23 9/19
Sampled in 2003 for MIB and
geosmin
5/21
10/11 9/10 6/18 5/05 9/25 5/12 9/10 6/10
Sampled in 2003 for Biomass 5/21 6/10 9/10 5/14 8/24 9/10 6/17
69

Sample collection and shipment
Pre-cleaned amber glass bottles (40-mL), with septa caps are provided for MIB
sampling in advance of a Taste and Odor problem. MIB samples collection time was
timed to meet the period when the raw water has distinctive earthy-musty-moldy odor
that is indicative of MIB or Geosmin.
Samples were collected by utilities from representative sample points:
• Raw water for WTP (Raw)
• Prior to ozone addition (PreO3)
• Effluent from ozonation (PostO3)
• Top of 2 representative biological filters (PreFilt1 & PreFilt2)
• Effluent from both biological filters in #4 (PostFilt1 & PostFilt2)
• Finished water from WTP (Treated)
Water samples were collected from the appropriate location in each WTP by
grabbing samples at >1 ft below the water surface, or from a central sampling location,
from > 1 ft below the surface. If taps are used rather than a bucket or other grab-
sampling device, the tap was allowed to run for 10 minutes prior to sample collection. A
maximum of 8 samples was collected in each set of samples per utility. Two sets of
samples of the same utility were collected at least 1 week apart in between. Once a
sampling was done, it was sent back to ASU immediately by FedEx overnight shipping.
Sampling was conducted by the following procedures:
70

1. Fill the sampling bottles with the sample water all the way to top.
2. Use the provided disposable syringe to remove 1 ml of water sample.
3. Oxidant quenching: All samples were treated with sodium thiosulfate (0.24
g/L) to quench residual ozone or chlorine. Use the provided disposable syringe to add
0.5 mL of the provided sodium thiosulfate (20 g/L stock concentration).
4. Preservation: All samples were treated with sodium azide (0.18 g/L) to prevent
biodegradation of MIB or geosmin, as well as TOC, during shipping and holding prior to
analysis.
5. Cap all the sample bottles, and make sure there have zero-headspace and the
cap is securely tightened. Shake bottle to mix additives with samples.
6. Place each capped sample vial into separate white package shipping bags, fold
bag over tight to seal. Place bagged samples, along with 2 cold-ice bags, in the cooler
provided. Affix an overnight delivery label on the cooler, addressed to ASU.
Sample preservation
Two chemicals, sodium thiosulfate (Na2S2O3, 0.24 g/L) and sodium azide (Na3N,
0.18 g/L), were used to quench ozone residual and preserve sample respectively. Ozone
residual needs to be quenched when left over from the ozonation unit. Sodium thiosulfate
was chosen for quenching ozone during utility sampling. Compared to indigo, Na2S2O3 is
not degraded over a time period of 2-4 weeks. Soduim azide was added as preservative to
keep the bio-stability of the samples during stocking and transportation period. To test if
71

the two chemicals added has any effects on MIB and geosmin recovery during analysis.
Two sets of test were done.
Effect of Na2S2O3 and Na3N on Odorant Detection
Three set of experiments were conducted to demonstrate that both Na3N alone
and a combination of Na3N and Na2S2O3 had no effect on MIB and geosmin recovery.
Different natural waters during different periods through year 2002 and 2003 were tested.
Effects of stocking period of both short-term (24 hours) and long-term (2 weeks) after
preservation were tested.
Five waters (SRP, ANN. AR, PHILA., INDIANA., and TEXAS), with different
water qualities were used to demonstrate that Na2S2O3 alone had no effect on MIB and
geosmin recovery. Equal concentrations of MIB and geosmin were spiked into two vials:
one vial contained only the natural water; another vial contained the natural water and
Na2S2O3 (0.24 g/L). All samples were held in a cold room (4ºC) for 2 days. Table 3.7
summarizes the results. After adding Na2S2O3, recoveries varied from 91% to 113% for
MIB and geosmin. There was not a pattern in recoveries as a function of Na2S2O3 dosing,
and it was concluded that Na2S2O3 had no statistical effect on MIB or geosmin recovery.
72

Table 3.7
Recovery of MIB and geosmin in the presence of 0.24 g/L in natural waters
Source Water SRP ANN.AR PHILA INDIANA TEXAS
No MIB (ng/l)
27 21 22 19 22
Na2S2O3 Geosmin (ng/l) 22 22 22 18 20
with MIB (ng/l)
25 21 22 21 22
0.24 g/L
Geosmin (ng/l)
MIB recovery(%)
21
91
22
104
21
99
20
112
21
101
Na2S2O3 Geosmin recovery(%) 97 104 95 113 105
Notes: recovery = (C0.24mg/L Na2S2O3/Cno Na2S2O3) ×100%, where C is MIB or geosmin
Azizona Canal water was used to demonstrate that Na3N alone had no effect on
MIB and geosmin recovery. Equal concentrations of MIB and geosmin were spiked into
two vials: one vial contained only the natural water; another vial contained the natural
water and Na3N (0.18 g/L). Experiment was conducted in duplicate. All samples were
hold in cold room (4ºC) for around 2 days. Table 3.8 summarizes the results. After
adding in the Na3N, recoveries varied from 96% to 108% for MIB and geosmin. There
was not a pattern in recoveries as a function of Na3N dosing, and it was concluded that
Na3N had no statistical effect on MIB or geosmin recovery.
CAP water was used to demonstrate that both Na3N alone and combination of
Na3N and Na2S2O3 had no effect on MIB and geosmin recovery. Equal concentrations of
MIB and geosmin were spiked into two vials: one vial contained only the natural water;
another vial contained the natural water and Na3N (0.18 g/L), or the natural water and
combination of Na3N (0.18 g/L) and Na2S2O3 (0.24 g/L). Experiment was conducted in
duplicate. Samples were divided into two groups and hold in cold room (4ºC) for 24
hours and 2 weeks, respectively, to test the preservative effect for both short and long
73

Table 3.8
Recovery of MIB and geosmin in the presence of 0.18 g/L Na3N in Arizona Canal Water
Source Water Arizona Canal Water(duplicate tests)
No Na3N
MIB (ng/l)
Geosmin (ng/l)
28
22
24
22
with MIB (ng/l)
28
27
0.18 g/L
Geosmin (ng/l)
MIB recovery(%)
21
108
22
101
Na3N Geosmin recovery(%) 96
97
Notes: recovery = (C0.18mg/L Na3N/CAVG no Na3N) ×100%, where C is MIB or geosmin
Table 3.9
Recovery of MIB and geosmin in presence of preservatives in CAP water
No Na3N &
No Na2S2O3
with
0.18 g/L
Source Water CAP Water ( duplicate tests)
Test Period 24 Hours 2 Weeks
MIB (ng/l) 68 57 67 64
Geosmin (ng/l) 45 39 40 39
MIB (ng/l) - 105
Geosmin (ng/l) - 95
MIB (ng/l) 67 62 58 64
Geosmin (ng/l) 45 42 38 42
MIB recovery(%) 103 98
Na3N Geosmin recovery(%) 104 96
With 0.18
g/L Na3N &
0.24 g/L
MIB (ng/l) 65 66 61 65
Geosmin (ng/l) 43 45 43 44
MIB recovery(%) 105 101
Na2S2O3 Geosmin recovery(%) 105 104
Notes: recovery=(CAVG with preservative/CAVG no preservative) ×100%, where C is MIB or geosmin
74

stoking periods. Table 3.9 summarizes the results. After adding in the Na3N and Na2S2O3,
recoveries varied from 95% to 105% for MIB and geosmin. The results confirmed that
Na3N and Na2S2O3 had no statistical effect on MIB or geosmin recovery for both short
(24 hrs) and long term (2 weeks) stoking.
Effect of Na2S2O3 and Na3N on TOC Detection
Experiments were conducted in CAP water to demonstrate that a combination of
Na3N and Na2S2O3 had no effect on TOC recovery. Effects of preservatives were tested in
CAP water with and without ozonation (2 mg/L for 20 min). Samples with and without
preservatives (Na2S2O3: 0.24 g/L, Na3N: 0.18 g/L) were analyzed for TOC concentration
in triplicates after 3 days stock in cold room (4ºC). Table 3.10 summarizes the results.
After adding preservatives, recoveries varied from 99% to 104% for TOC. There was not
a pattern in recoveries as a function of preservatives dosing, and it was concluded that a
combination of Na2S2O3 and Na3N had no statistical effect on TOC recovery.
Table 3.10 Recovery of TOC in presence of preservatives in CAP water
Source Water Sample Description TOC(mg/L) in triplicates
CAP water
without
ozonation
Water sample only 3.21 3.03 2.88
Water sample+Na3N(0.18g/L)+Na2S2O3(0.24g/L) 3.13 3.06 3.34
TOC Recovery (%) 104%
CAP water Water sample only 2.86 2.90 2.72
after ozonation
(2 mg-O3/L for
20 min)
Water sample+Na3N(0.18g/L)+Na2S2O3(0.24g/L)
TOC Recovery (%)
2.80 2.80
99%
2.80
Notes: recovery = (CAVG with preservative/CAVG no preservative) ×100%, where C is TOC (mg/L)
75

ANALYTICAL METHODS
GC/MS with SPME Method Description
MIB and geosmin were measured using Solid-Phase Micro-extraction method
using Gas Chromatography with Mass Spectroscopy (SPME-GC/MS) (Watson et al.,
2000, Lloyd et al., 1998). 12 ml of sample was added to a 20 ml septum capped vial that
contains 4 gm desiccated sodium chloride (NaCl). An auto sampler was used instead of
manually pre-treating and injecting the samples. The prepared 20 ml capped sample vial
was put on the auto sampler tray, then brought automatically to a magnetic heating and
shaking cell for 6 min at 40 ºC. A SPME fiber (Supelco # 57348 U) was automatically
introduced into the headspace through the septum of the sample vial in the heating cell,
and shaking for 30 minutes. Then the fiber was removed from the vial and inserted into
the gas chromatograph injector at 250 0 C for 6 minutes. The fiber was then retracted into
the holder, removed from the GC inlet and back to the standby position waiting for reuse
for the next sample. Compounds were eluted from the column gas chromatograph to a
mass spectrometer set for selective ion storage (selective mass to charge ratio, m/z values:
MIB = 95, geosmin = 112 and IPMP = 124, 136). Calibration curves were generated
using MIB and geosmin standards that prepared in lab. Standards ranged from 2 ppt to
100 ppt, which represent the detected typical MIB and geosmin concentration range.
Figure 3.9 gives an example of the standard curve with slope of MIB and geosmin
determined as 137.77 and 225.65, respectively.
76

Peak Area
25000
20000
15000
10000
5000
0
MIB
geosmin
y = 225.65x + 59.308
R 2 = 0.9997
y = 137.77x - 76.409
R 2 = 0.9978
0 10 20 30 40 50 60 70 80 90 100
C (ng/L)
Figure 3.9 MIB and geosmin standard calibration curve (08/13/02)
QA/QC
SPME method detection limit for MIB and geosmin was 2 ng/L. The detection
sensitivity was ±15%, which was decided by the standard deviation when running the
same standard samples by the person who developed this method. SPME method for MIB
and geosmin analysis applied in this study was using the external standards for quality
control (QC). A calibration curve was generated first when starting a new cycle of MIB
and geosmin analysis. A QC standard (prepared in lab from the purchased standard
solutions from Wako Inc.) was put in between every 8~15 samples depending on the
stability characteristics of the GC/MS instrument. All QC standards used are at
concentration of 20 ppt. Calibration curve was renewed whenever the QC standards were
77

eyond 15% difference of the standard curve. Figure 3.10 illustrates the concentration of
QCs analyzed with MIB and geosmin samples during the period from April 2002 to
October 2003. The two dotted lines in Figure 3.l0 give the range that the 20-ppt-QC
should be in, which was set to be within 15% difference of the standard curve. Whenever
the QC value was at or out of the range, a new calibration curve was generated.
Many major or miner adjustments of the MIB and geosmin analysis method were
performed during the period from April 2002 to October 2003 due to various causes, such
as column changes, instrument parts replacements, absorption fiber changes, and parts
wearing out and replacements. These led to the changes of calibration slope in different
extents as shown in Figure 3.11. Three major phases of the slope changing could be seen:
?. April 2002~August 2002; ?. September 2002~February 2003; ?. February
2003~October 2003. These were coincided with three filament used during each phase.
20ppt QCs concentration
25
20
15
10
5
0
13-Feb-02 24-May-02 1-Sep-02 10-Dec-02 20-Mar-03 28-Jun-03 6-Oct-03
Date
MIB
Geosmin
high limit
low limit
Figure 3.10 Concentration of 20 ppt QCs during the period of Apr, 2002~Oct, 2003
23 ppt
17 ppt
78

slope of MIB/geosmin
standard curve
700
600
500
400
300
200
100
0
MIB
Geosmin
13-Feb-02 24-May-02 1-Sep-02 10-Dec-02 20-Mar-03 28-Jun-03 6-Oct-03
Date
Figure 3.11. Changes of standard curve slop during the period of Apr, 2002~Oct, 2003
The filament is a part of the detector, mass spectrometer (MS), which generated electrons
to hit the compounds in the trap of MS. Then the amounts of the debris of the compounds
were measured and reported as peaks in the chromatograph. Filament changes affect
instrument sensitivity. Different filament generated different amount of electrons which
produced different amount of debris, and resulted in different peak areas. For a given set
of standard MIB and geosmin samples, a set of higher peaks result in higher slope of the
standard calibration curve, it’s higher sensitivity; while a set of lower peaks result in
lower slope of the standard calibration curve, it’s lower sensitivity. During each phase,
we also can see fluctuations happened. These were because of the changes of the fiber
and parts wearing out. Record of the maintenance of GC/MS is given in Table 3.11.
Two major MIB and geosmin analysis methods were used during the period between
April 2002 and October 2003. Details of the methods are given in Table 3.12. The
changes of the methods, mostly in programming of temperature, were largely due to the
79

changes of columns between column MDN-5 and column DB5-MS. Since even slightly
changes of the stationary phase, the coating on the inner wall, of the column could result
in big difference in retention times of different compounds, which is the major
mechanism of separation. New column came in with the problem of interference peak
given the original setting and program of method. Adjustment made to separate the
interference peak resulted in longer analysis period (from 37.58 minutes to 60.08
minutes) for each MIB and geosmin sample.
Table 3.11
GC/MS maintenance record during the period of Apr, 2002~Oct, 2003
Date Event
12-Jun-02 new fiber, new septum, new injection liner
9-Jul-02 Geosmin has interference peak problems
11-Jul-02 new fiber, new septum
13-Aug-03 new filament
26-Aug-02 new fiber
28-Aug-02 cyclocitrial come in, method was continuously modified
18-Sep-02 new fiber
21-Oct-02 new fiber
5-Nov-02 new filament, new fuse in Combi-Pal
25-Nov-02 fiber crumpled, new fiber, new septum
14-Jan-03 increase EM volts (1350-1500) to increase sensitivity
10-Feb-03 new filament (EM volts=1400)
24-Apr-03 new column DB5-MS(different as the original one)
injection port cleaned
new interference peak
14-May-03 60min-method developed and in use
9-Jul-03 new column MDN-5 (same as the original one)
new injection liner, new septum
14-Jul-03 ASI bungel cord worn out and changed
80

INSTRUMENT CONDITIONS:
Table 3.12a
MIB analysis method used before December 2002
Inlet: Splitless Method:
T&O.
SPME
Carrier Gas: He Cycle: SPME
Vial
Penetr:
Extract
22.0 mm
Heater, degree C: 250 Syringe:
Pre Inc
Fiber time: 30 min
Pressure, psi: 4.5
Time: 3 min Desorb to: Front
Total Flow,
Inc temp,
ml/min: 35~40
*C: 50 Inj Penetr: 44.0 mm
Purge Flow: Agi speed: 600 rpm Tray type: VT32-20
to Split Vent:
Gas Saver: OFF Auxiliary: 250
Thermal
Aux: 250
MS Parameters:
Solvent Delay:
Acq Mode: SIM
Columns: MDN-5 Temperature Program:
Mode: Const Flow Oven: *C/min *C MIN
Inlet: Front Initial: 0 60 1
Detector: MS Ramp1: 5 85 5
Outlet, psi: Ramp2: 1.5 121 24
Pressure: ~4.5 Ramp3: 50 250 2.58
Flow: 1.0 ml/min Ramp4: 0 250 5
Average Velocity: Run Time: 37.58
Chromatograph:
Start
Time(min) Ions(m/z)
MIB 18.6; 24.3 93~98
Geosmin 37.3; 47.5 112
IPMP 23.2 124
Sensitivity and Range of Linearity
Working range of this method is compound and instrument dependent, and is approximately 2.0 to 200
ng/l.
81

INSTRUMENT CONDITIONS:
Table 3.12b
MIB analysis method used after December 2002
Inlet: Splitless Method:
T&O.
SPME
Carrier Gas: He Cycle: SPME
Vial
Penetr:
Extract
22.0 mm
Heater, degree C: 250 Syringe:
Pre Inc
Fiber time: 30 min
Pressure, psi: 4.5
Time: 3 min Desorb to: Front
Total Flow,
Inc temp,
ml/min: 35~40
*C: 50 Inj Penetr: 44.0 mm
Purge Flow: Agi speed: 600 rpm Tray type: VT32-20
to Split Vent:
Gas Saver: OFF Auxiliary: 250
Thermal
Aux: 250
MS Parameters:
Solvent Delay:
Acq Mode: SIM
Columns: MDN-5 Temperature Program:
Mode: Const Flow Oven: *C/min *C MIN
Inlet: Front Initial: 0 60 1
Detector: MS Ramp1: 1 85 25
Outlet, psi: Ramp2: 0.5 95 20
Pressure: ~4.5 Ramp3: 4 121 6.5
Flow: 1.0 ml/min Ramp4: 50 250 2.58
Average Velocity: Run Time: 60.08
Chromatograph:
Start
Time(min) Ions(m/z)
MIB 18.6; 24.3 93~98
Geosmin 37.3; 47.5 112
IPMP 23.2 124
Sensitivity and Range of Linearity
Working range of this method is compound and instrument dependent, and is approximately 2.0 to 200
ng/l.
82

PCBA Measurement
PCBA was measured using HPLC with reverse-phase (RP-18) analytical column
and mobile phase consisting of a mixture of 55% methanol and 45% 10 mM phosphoric
acid. Detection was made using an UV detector set to a wavelength of 234nm.
BDOC Measurement
BDOC sand method was used for BDOC measurement (Nguyen 2002). 60 ml of
biologically active sand were incubated with 150 ml of water sample in 500 ml amber
bottles for one week. Then the acclimated biologically active sand thus formed was put
into another 150 ml of water sample, stayed for 5 days. DOC5 (DOC after 5 days) of this
water was measured and BDOC was the difference of DOC5 and initial DOC. Dissolved
oxygen needed for the bacteria on the sand media was continuously provided by slow
shaking bed, at shaking speed of 100 rpm/min.
Dissolved O3 Measurement
UVA258 Method
Ozone concentrations in the stock solution were determined by direct UV
absorbance at wavelength 258nm (e258nm=3150 M -1 cm -1 ) (Langlais et al, 1991) using
Shimadzu TM UV/VIS spectrophotometer. The detection range of dissolved ozone is 0.15-
14 mg/L. O3 concentration measured by UVA258 method was calculated by:
83

where
Indigo Method
UVA
O3
=
ε
UVA 258nm is UV absorbance at 258 nm
258nm
× MWO3
258nm
MWO3 is molecular weight of O3, which equals to 48000 mg/L
e258nm is absorbity of O3, which equals to 3150 M -1 cm -1
Standard indigo method (Bader et al., 1981) was applied in batch ozonation
experiment. Indigo solution (1mM) was prepared on the day of experiment to minimize
decomposition. No phosphoric acid was added since the MIB and geosmin recovery was
low at pH lower than 5, which possibly due to acid hydrolysis. Indigo had no effect on
MIB and geosmin analysis.
A dilution factor of 1:10 (indigo:water sample) was used for most of the
ozonation samples. When the samples collected were expected to contain more than 5
mg/l of O3 residual, 7.5 mg/L of standard indigo solution was used to quench the O3
residual. The collected samples were measured for ozone residual using Shimadzu TM
UV/VIS spectrophotometer at wavelength 600 nm. All the final measured ozone
concentrations by indigo method were corrected using their corresponding dilution
factors. O3 concentration measured by indigo method was calculated by:
84

where
O
3
( UVA
=
600nm
0
− UVA
ε
600nm
600nm
) × MW
UVA 600nm is UV absorbance of water samples at 600 nm
UVA0 600nm is UV absorbance of blank sample (no O3) at 600 nm
e258nm is absorbity of indogo, which equals to 21000 M -1 cm -1
Measurement of Other Parameters
Solution pH and temperature were measured using Bechman TM pH electrode,
which was calibrated with standard buffers (J.T. Baker TM ). Alkalinities of all the natural
waters were measured using Hach TM kit calorimetric titrate. Dissolved Organic Carbon
(DOC) was determined by a Shimadzu TM TOC Analyzer (Shimadzu Model TOC-
5050A). Bromide and bromate were measured by using a Dionex TM ion chromatography
with elluent solution made up of 9mM carbonate.
O3
85

CHAPTER 4
BENCH-SCALE OZONATION EXPERIMENTS
LAB EXPERIMENT RESULTS AND DISCUSSION
Bench-scale ozonation experiments were conducted in natural waters and distilled
water to understand oxidation mechanisms of MIB and geosmin. Natural water ozonation
experiments were designed to investigate effects of NOM, pH, ordorant initial
concentration, ozone dose and H2O2 addtion on O3 and HO • ratios, and MIB and geosmin
oxidation. Distilled water ozonation experiments were designed to delineate O3 from HO •
oxidation mechanisms in the absence of NOM.
Ozonation of Natural Waters
More than 100 natural water ozonation tests were conducted with 5 different
water sources around U.S.A. Effect of pH, ozone dose, initial MIB and geosmin
concentrations, H2O2, and temperature were evaluated. Results were presented and
discussed in Brijesh Nair’s thesis (Nair 2002). Key results and conclusions of natural
water ozonation were:
• PCBA can be used as a probe of HO • concentration.
• Hydroxyl radicals (HO • ) played a very important role in MIB and geosmin
oxidation relative to molecular ozone.
• MIB and geosmin oxidation increased with increasing ozone dose, pH,
temperature and H2O2 addition.
86

• Ozone oxidized geosmin to greater extent than MIB.
• The percentage removal of MIB or geosmin during ozonation was
independent of their concentrations.
• Addition of small amount of methanol (0.5 ul/L) with the MIB and
Ozonation of Distilled Water
geosmin spike solution had no observable effects on ozone decay or MIB
and geosmin removal in natural waters.
Distilled water experiments were conducted to understand MIB and geosmin
ozonation mechanisms in the absence of NOM reactions. Effects of pH, ozone dose,
methanol and t-butanol, were investigated. Estimation of rate constants of ozone
molecules with MIB and geosmin (kO3) were made by using modeling software,
AQUASIM. Table 4.1 gives all the Rct values obtained from DI water ozonation
experiments conducted under ambient temperature (24°C). RCT values of some
experiments were not calculated due to lack of data or PCBA decomposition too fast.
Table 4.1
RCT values for ozonation tests conducted in DI water
Experiment
ID 1 2 3 4 5 6 7 8 9 10 11
12
pH
O3 dose
6 6 6 6 7 7 7 7 7 7 * *
(mg/l)
T-butanol
0.75 1.25 2 4 1.25 1.25 1.25 1.25 2 2 3 3
(mg/L) 0 0 0 0 0 0.01 0.1 0.5 7 14 0 0
RCT
(mole/mole) 4.01 3.01 2.76 2.65
Notes: * ambient pH
>2.76
0.14
0.09
87
0.21 0.04 0.03 4.08 3.65

O3 Dose Effect
Ozonation experiments conducted in distilled water under different ozone doses
showed that MIB and geosmin removals increased as a function of ozone dose (Figure
4.1). Geosmin removals were slightly higher than MIB removals. MIB and geosmin were
oxidized faster at higher ozone dose. At 3 minutes reaction time, 20% and 5% of the
initial MIB concentration remained at ozone doses of 2 and 4 mg/L, respectively; only
3% and 15% of the initial geosmin remained. RCT values were 2.76 and 2.65 mole/mole
for ozone dose of 2 and 4 mg/L, respectively.
C/Co
1
0.9
0.8
0.7
0.6
0.5
0.4
0.3
0.2
0.1
0
0 5 10 15 20
Time (min)
MIB at 2 mg-O3/L
Geosmin at 2 mg-O3/L
MIB at 4 mg-O3/L
Geosmin at 4 mg-O3/L
Figure 4.1 Ozone dose effect on MIB and geosmin oxidation in distilled water (pH=6;
Initial MIB and geosmin concentration = 100 ng/L)
88

Effect of pH
MIB and geosmin oxidation changed as a function of pH. Removals of geosmin
were slightly higher than MIB at pH = 6, and were almost no difference with MIB at pH
= 7 to 8. As shown in Figure 4.2, percentage of MIB and geosmin removal was plotted
versus time at ozone dose equal to 2 mg/L. Initial MIB and geosmin concentrations were
100 ng/L. PH conditions of reaction water were adjusted to 6, 7, and 8. At 3 minutes
reaction time, 20% remaining of MIB was observed at pH=6, and only 1~3% remaining
were observed at pH=7~8. Around 15% remaining of geosmin was observed at pH=6.
C/Co
1
0.9
0.8
0.7
0.6
0.5
0.4
0.3
0.2
0.1
0
0 5 10 15 20
Time (min)
MIB at pH=6
Geosmin at pH=6
MIB at pH=7
Geosmin at pH=7
MIB at pH=8
Geosmin at pH=8
Figure 4.2 Effect of pH on MIB and geosmin oxidation in distilled water (Ozone dose = 2
mg/L; Initial MIB and geosmin concentration = 100 ng/L)
89

Almost all geosmin were removed within the first minute reaction time at pH=7~8. RCT
value was 2.76 at pH = 6. At pH = 7 and 8, RCT values could not be calculated because
PCBA decomposed too fast. However the actural RCT values at pH = 7 and 8 should be
higher than 2.76 (at pH = 6) for higher HO • concentration at higher pHs.
Effect of T-butanol Addition
T-buantol was spiked into some of the distilled water ozonation tests to scavenge
HO • . Ozonation tests with addition of different concentrations of t-butanol are shown in
Figure 4.3. At pH=7, the percentage of MIB and geosmin remaining increased from
2~3% to 65~75% when t-butanol concentration increased from 0.01 mg/L to 14 mg/L,
with similar percentages remaining of MIB and geosmin. Presentation of t-butanol
resulted in decreased RCT values (from > 2.76 at t-butanol=14 mg/L to 0.03 at t-
butanol=0), which indicated scavenging of HO • .
90

C/C0
1
0.9
0.8
0.7
0.6
0.5
0.4
0.3
0.2
0.1
0
T-butanol = 14 mg/L T-butanol = 0.5 mg/L
T-butanol = 0.1 mg/L T-butanol = 0.01 mg/L
T-butanol = 0 mg/L GSM, T-butanol=14 mg/L
GSM, T-butanol=0.5 mg/L GSM, T-butanol=0.1 mg/L
GSM, T-butanol=0.01 mg/L GSM, T-butanol=0 mg/L
0 2 4 6 8 10
Time (min)
Figure 4.3 Effect of T-butanol on MIB and geosmin oxidation in distilled water (Ozone
dose = 1.25 mg/L; pH = 7)
Role of HO • in ozonation process of MIB and geosmin
HO • radicals are much more important than O3 in MIB and geosmin oxidation
processes. Effects of two parameters, pH and t-butanol, that affect concentration of HO •
during ozonation process were evaluated in distilled water tests. Elevated pH results in
higher concentration of HO • radicals. Presentation of t-butanol scavenges HO • radicals.
Higher HO • concentration led to higher percentage removal of MIB or geosmin.
91

Relative removal of MIB and geosmin
Ozonation experiment of distilled water showed relatively less difference of
removals for MIB and geosmin than were observed in natural water tests. In natural water
tests that geosmin removals were generally 40% higher than MIB removals under same
experiment conditions (Nair 2002). MIB and geosmin relative removals in all distilled
water tests are shown in Figure 4.4. Without t-butanol addition in distilled water, MIB
and geosmin was oxidized by both O3 and HO • , with geosmin oxidized slightly better
than MIB. When t-butanol was added, HO • was efficiently scavenged and was unable to
react with MIB and geosmin; MIB and geosmin were oxidized primarily via O3 reactions
with similar oxidation results. These observations could be possibly explained by the role
of NOM presented in natural waters. Natural organic matter and carbonate alkalinity play
an important role in the ozone decomposition chain reactions by reacting with ozone and
producing hydroxyl radicals (Staehelin et al. 1984). NOM competes against MIB and
geosmin for both O3 and HO • . It is possible that secondary organic or carbonate radicals
affect geosmin oxidation.
92

Percentage of geosmin removed
(1-Geosmin/Geosmino)
1
0.9
0.8
0.7
0.6
0.5
0.4
0.3
0.2
0.1
0
without T-butanol
with T-butanol
1:1 LINE
0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1
Percentage of MIB removed (1-MIB/MIBo)
Figure 4.4 Relative oxidation removal of MIB and geosmin in ozonation experiments
conducted in distilled water
Estimation of Rate Constants
Rate constant of hydroxyl radical reactions (kHO) with MIB (8.2×10 -9 M -1 s -1 ) and
geosmin (9.0×10 -9 M -1 s -1 ) were estimated by Glaze (1998), but there is no reported
estimation of rate constant of molecular ozone with MIB and geosmin (kO3). To
understand the approximate values of kO3, kinetic experiments in natural waters with
presentation of t-butanol were conducted. T-butanol scavenge majority of the HO •
radicals so that the kinetic curves obtained could represent the reaction of MIB and
geosmin with only O3. Experiments with t-butanol levels sufficient to scavenge >95% of
93

HO • indicated no statistically change in MIB or geosmin levels over 15 to 20 minutes of
ozonation. Therefore, kO3 values were assumed small (t < 20 minutes; kO3 < 1 M -1 s -1 ).
Further experiment conducted in distilled water under different pH confirmed that
kO3 values of MIB and geosmin are very small. No observable difference of MIB and
geosmin removals was found for different ozone doses with present of t-butanol within
the ozonation period (20~120 mins). A possible explanation for this fact is that the kO3
values of MIB and geosmin are too small to make any affect within the short reaction
period. Jar test in distilled water was conducted at this point to find MIB and geosmin
removals under different ozone doses given longer reaction period (2~9 days).
A modeling software program, AQUASIM, was applied to fit simultaneously kO3
and kHO by solving a set of differential equations using observed experimental data.
Using lab data obtained from natural water ozonation with t-butanol, the range of values
obtained from AQUASIM varied 3 orders in magnitude (see Appendix), which implies
that some other factors (like carbonate alkalinity) plays a very important role in
determination of kO3 (Nair 2002). For experiments with distilled water kO3 values ranged
from 0.1 M -1 s -1 to 1 M -1 s -1 . These values seem to be quite reasonable as it agrees well
with batch kinetic experiments. For all kinetic experiments conducted with natural water
kO3 values were found to be less than 1 M -1 s -1 (Nair 2002).
Methanol Effect on Ozonation Experiment
All MIB and geosmin in natural water ozonation tests was spiked using stock
solution in methanol. To test if a low concentration (0.5 ul/L) of methanol spiked with a
94

MIB and geosmin solution had effects on MIB and geosmin oxidation, benth-scale
ozonation with presentation of same amount methanol (0.5 ul/L) were conducted in
distilled water and natural water, Central Arizona Project (CAP) water.
As shown in Figure 4.5, methanol effects on ozone decomposition in DI water
were remarkable, but insignificant in natural water. More ozone demand was observed
with presentation of methanol in DI water. At reaction time of 5 minutes, around 20%
more ozone was decomposed with methanol presentation in DI water, while no
observable difference found in CAP water.
Ozone Residual (%)
1
0.9
0.8
0.7
0.6
0.5
0.4
0.3
0.2
0.1
0
DI water, without methanol
DI water, with methanol
Natural water, without methanol
Natural water, with methanol
0 5 10 15 20
Time (min)
Figure 4.5 Effect of methanol (0.5 ul/L) on O3 decomposition in distilled water and
natural water (Ozone dose = 3 mg/L)
95

As shown in Figure 4.6, methanol effects on PCBA decomposition are
significant in DI water, but insignificant in natural water. Less PCBA removals reflects
lower HO • concentrations. At reaction time of 3 minutes, around 10% less PCBA was
decomposed with methanol presentation in DI water, while no observable difference
found in CAP water. This observation could be possibly explained by competition of HO •
by methanol with PCBA, but further experiments are needed for provements. This issue
was not addressed in this work because the focuse is methanol effects on MIB and
geosmin decomposition.
PCBA Residual (%)
1
0.9
0.8
0.7
0.6
0.5
0.4
0.3
0.2
0.1
0
DI water, without Methanol
DI water, with Methanol
Natural water, without Methanol
Natural water, with Methanol
0 5 10 15 20
Time (min)
Figure 4.6 Effect of methanol (0.5 ul/L) on PCBA decomposition in distilled water and
natural water (Ozone dose = 3 mg/L)
96

In both natural water and DI water experiment, methanol addition (0.5 ul/L) had
no effects on MIB and geosmin decomposition. Figure 4.7 showed that methanol addition
had no observable effects on MIB decomposition in DI water. As in natural water,
negligible methanol effects on MIB oxidation were illustrated by its insignificant effects
on decomposition of ozone and PCBA (Figure 4.5 and 4.6).
MIB Residual (%)
1
0.9
0.8
0.7
0.6
0.5
0.4
0.3
0.2
0.1
0
Without methanol
With methanol
0 5 10 15 20
Time (min)
Figure 4.7 Effect of methanol (0.5 ul/L) on MIB decomposition in distilled water (ozone
dose = 5 mg/L)
97

CONCLUSIONS
MIB and geosmin ozonation mechanisms were investigated by conducting bench-
scale ozonation experiment in distilled water and natural waters. The following
conclusions were obtained:
• MIB and geosmin removals increased with increasing in ozone dose, pH,
temperature and H2O2 addition.
• MIB and geosmin percentage removals are independent of their initial
concentrations.
• Relative oxidizing rates of MIB and geosmin in natural waters were
controlled by kHO• values (kHO•, MIB = 8.2*10 9 M -1 s -1 , kHO•, geosmin =
1.4×10 10 M -1 s -1 ); KO3 values of MIB and geosmin are in the range of
0.1~10 M -1 s -1 .
• Ozone oxidizes geosmin to a greater extend than MIB in natural waters.
• Presentation of small amount (0.5 ul/L) of methanol during ozonation has
no observable effects on MIB and geosmin removals in both distilled
water and natural water.
98

CHAPTER 5
OZONE-BIOFILTRATION REMOVAL OF MIB&GEOSMIN---PILOT STUDIES
Pilot studies at Chandler WTP and Squaw Peak WTP were conducted by
Malcolm Pirnie Inc. (MPI) to investigate ozone-biofiltration effects of MIB and geosmin.
Both were using full-scale plant settled Salt River Project (SRP) water as the raw water
source. Effects of different water quality parameters (pH and initial MIB and geosmin
concentration) and operational parameters (ozone dose, EBCT, media type and backwash
water) were evaluated. ASU developed the MIB and geosmin dosing apparatus and
performed all analysis of MIB and geosmin. More than 800 MIB and geosmin samples
generated from the two pilot plants were analyzed by Peng Pei in ASU. Other data (TOC,
UVA254, biomass concentration, THM, HAA, turbidity and pH) were obtained from
Malcolm Pirnie Inc. to support interpretation of MIB and geosmin result and overall
significance of ozone-biofiltration as an efficient means for odorant control.
CHANDLER PILOT STUDY RESULTS/DISCUSSIONS
Chandler pilot plant was designed by MPI specifically for taste and odor control
efficiency by ozone-biofiltration treatment. Average raw water quality at Chandler WTP
had a TOC concentraition of 3.1 mg/L, turbidity of 11.9 NTU, pH of 8.5, alkalinity of
174 mg/L as CaCO3, and bromide concentration of 110 ug/L. MIB removals were
evaluated for different parameters including media type, EBCT, ozone dose, pH, initial
MIB and geosmin concentration. Results of the ozone-biofiltration performance of all
data (MIB, geosmin, TOC, UVA254, etc.) were interpreted for this pilot study.
99

MIB and Geosmin Feed System
MIB and geosmin can diffuse through some plastics. MIB and geosmin solutions
were required to be stocked in collapsible dispensing bags, and pumped continuously
through tubings into the filter influent pipe. Therefore, dense plastics (e.g. Teflon) are
required to contain and transfer MIB and geosmin solutions. High lost rate was observed
when using medical drainage bags to stock MIB and geosmin solutions at the pilot plant.
As shown in Table 5.1, MIB and geosmin lost rate in medical drainage bags were around
3.5 percent/day and 6 percent/day, respectively. It resulted in a 25~40 percent lost of
MIB and geosmin during one week, which is the average period to replace the stock
solution bag.
Chandler
Applied
Bags
Table 5.1
MIB and geosmin decomposition in medical drainage bags
Bag 1 Bag 2
MIB Geosmin MIB Geosmin
Date (mg/L) (mg/L) (mg/L) (mg/L)
11/8/2002 0.95 0.82 0.65 0.57
11/21/2002
Lost Rate
0.44 0.14 0.31 0.12
(percent/day) 4.13 6.38 4.02 6.07
11/21/2002 2.06 2.08 2.01 2.07
12/5/2002
Lost Rate
1.04 0.4 1.09 0.40
(percent/day)
Average Lost
3.54 % 5.77 % 3.27 % 5.76 %
Rate(percent/day) 3.83 % 6.07 % 3.65 % 5.92 %
100

101
The airtight Teflon gas-sampling bags (Figure 3.8) were used to stock high
concentration MIB and geosmin solution (1.5~2.5 mg/L) to prevent volatization. At the
pilot plants, the bags were stored in a small refrigerator and pumped through Teflon
tubing exiting a hole drilled in the wall of the refrigerator to the pilot pipes at a flow rate
of 20 to 40 ml/hour. Each bag was replaced once per week. Table 5.2 shows MIB and
geosmin lost rates were similar (0.5~1.0 percent/day) in the bags. Table 5.3 shows the
MIB and geosmin concentrations prepared through the Chandler pilot study.
ASU TEST
Bags
Chandler
Applied
Bags
Table 5.2
MIB and geosmin decomposition in air tight Teflon bags
Bag 1 Bag 2
Date MIB Geosmin MIB Geosmin
(mg/L) (mg/L) (mg/L) (mg/L)
11/27/2002 1.53 1.04 1.53 1.04
12/9/2002 1.5 1.035 1.37 0.96
12/14/2002 1.26 0.85 1.34 0.95
Average
Decompostion Rate
(percent/day) 1.04 % 1.07 % 0.73 % 0.51 %
11/27/2002 1.53 1.04 1.37 0.95
12/12/2002 1.34 0.96 1.26 0.85
Average
Decompostion Rate
(percent/day) 0.83 % 0.51 % 0.54 % 0.70 %

Table 5.3
Concentration of MIB and geosmin in bags prepared for Chandler pilot study
Concentration (mg/L)
SET # Made Date Checked date MIB Geosmin
1 11/27/2002-1 12/14/2002 1.53 1.04
2 11/27/2002-2 12/14/2002 1.34 0.96
3 12/11/2002-1 12/14/2002 1.51 1.27
4 12/11/2002-2 12/14/2002 1.56 1.28
5 12/17/2002-1 12/18/2002 2.2 3.4
6 12/17/2002-2 12/18/2002 2 2.7
7 12/17/2002-3 12/18/2002 2.4 4.2
8 12/17/2002-4 12/18/2002 2.3 3.9
9 12/17/2002-5 12/18/2002 3 4.2
10 1/8/2003-1 1/14/2003 2.31 1.83
11 1/8/2003-2 1/14/2003 2.77 2.26
12 01/21/03 1/21/2003 1.75 1.3
13 01/22/03 1/24/2003 1.42 1.33
14 1/29/2003-1 1/31/2003 1.86 1.88
15 1/29/2003-2 1/31/2003 1.6 1.48
16 2/9/2003-1 2/12/2003 1.99 2.2
17 2/9/2003-2 2/12/2003 2.47 2.23
Ozone-Biofiltration Effects of MIB and Geosmin Removal
Effect of ozonation on MIB removal
102
In these pilot studies, ozone was applied as an intermediate oxidant. MIB and
geosmin were spiked in the influent water pipe of the small filter columns after ozonation
and dissipation of any ozone residual (Na2S2O3 added). Ozone added to the settled water
oxidized NOM to more biodegradable organic molecules, such as organic acids,
aldehydes and ketoacids (Siddiqui et al., 1997). These smaller molecules of organic by-
products could serve as carbon source for bacteria, which is expected to enhance the
biological activity in the filters and thereby result in higher MIB removals.

103
Figure 5.1 shows the baseline operation conditions with ozone dose of
0.25mg/mg TOC of influent water. Higher removals of MIB were achieved for
unozonated (large, 8-in filters) waters than for ozonated (small, 3-in filters) waters: 91%
removal in large filters and 65%~73% in small filters, respectively. This observation
seems apparently opposite with the above theory and prediction. This could be the results
of operational difference between the large and small filters, which led to different
biomass concentrations as illustrated in Figure 5.2.
Figure 5.2 showed the biomass concentrations in different filters, which could be
a support of the above statements of possibly reasons for low MIB and geosmin removals
in small filters receiving ozonated waters. With the same media, GAC/sand or
anthracite/sand, small filters had around 50% or 70% lower biomass concentrations in
Percent MIB Removal
100
90
80
70
60
50
40
30
20
10
0
GAC/Sand
at 4 gpm/ft2
Ozonated Water; 3-in Diameter Filters
GAC/Sand
at 6 gpm/ft2
EBCT at 4 gpm/ft2 is 6.3 min
EBCT at 6 gpm/ft2 is 4.3 min
Anthracite/Sand
at 4 gpm/ft2
Unozonated Water; 8-in Diameter Filters
Anthracite/Sand
at 6 gpm/ft2
GAC/Sand
at 4 gpm/ft2
Anthracite/Sand
at 4 gpm/ft2
Figure 5.1 Comparison of MIB removals in different filter media at different EBCT and
with and without ozonation (5 data points for each column)

average than big filters, respectively. With the same operational conditions, filters with
anthracite/sand media had around 40%~60% less biomass concentrations than filters with
GAC/sand media.
104
Small filters received waters of varying quality in terms of ozone dose, pH,
peroxide dose, etc. On the other hand, the big filters received unozonated plant settled
water all the time. This might result in lower biomass concentration in the small filters
due to continuously changing environment of the biofilm. In addition, the small filters
were backwashed more rigorously in terms of bed expansion compared to the big filters.
The small and large filters were backwashed using plant filtered water (Figure 3.3 and
3.4). Backwashing was able to expand the small filter media by 50 percent (bed
expansion). On the other hand, due to physical limitations (pipe that carried filtered
water to the pilot facility), only 30 percent bed expansion was achieved during
backwashing of the large filters. Backwashing could cause biofilm detachment from the
media. These operational differences between the small and large filters might answer
why lower biomass concentration and lower MIB removals were observed in the small
filters that fed with ozonated water.

Biomass (nmol PO4/L wet media)
300,000
250,000
200,000
150,000
100,000
50,000
0
Top 1-in of GAC/Anthracite
At 10-in of GAC/Anthracite
Top 1-in of sand
GAC/Sand
at 4 gpm/ft2
Ozonated Water; 3-in Diameter Filters
.
GAC/Sand
at 6 gpm/ft2
Figure 5.2 Biomass concentrations in different filters (1 data point for each column)
105
Different ozone doses resulted in slightly different MIB removals as shown in
Figure 5.3. In all the filters, higher ozone dose (1.0 mg-ozone/mg-DOC) resulted in
slghtly higher MIB removals (by about 1-14 percent). This observation suggested that
excess ozone or very high ozone doses would not be cost effective, though appropriate
ozone addition would enhance the biological uptake of MIB. Since excessively adding of
ozone may result in thorough oxidation (conversion to CO2 and water) of organics, which
is not favorable to biofilm development.
Anthracite/Sand
at 4 gpm/ft2
Unozonated Water; 8-in Diameter Filters
Anthracite/Sand
at 6 gpm/ft2
GAC/Sand
at 4 gpm/ft2
Anthracite/Sand
at 4 gpm/ft2

Percent MIB Removal
100
90
80
70
60
50
40
30
20
10
0
GAC/Sand at 4 gpm/ft2 GAC/Sand at 6 gpm/ft2 Anthracite/Sand
at 4 gpm/ft2
Ozone/TOC of 0.25 (Baseline) (n=5)
Ozone/TOC of 1.00 (n=2)
EBCT at 4 gpm/ft2 is 6.3 min
EBCT at 6 gpm/ft2 is 4.3 min
Anthracite/Sand
at 6 gpm/ft2
Figure 5.3 Effect of Ozone Dose on MIB Removal in Dual-Media Filters (n is number of
data points)
Effect of filter media and biomass concentration on MIB removal
106
Higher biomass concentrations correlated with higher MIB removals, which
could be observed by comparing Figure 5.1 and Fgure 5.2. Higher biomass
concentrations were observed in GAC/sand filters compared to anthracite/sand filters.
Correspondingly, in both ozonated (small) and unozonated (large) filters, higher MIB
removals were observed in GAC/sand filters compared to anthracite/sand filters. All the
filter media were exhausted before evaluation to eliminate MIB and geosmin removals
caused by adsorption.
The biomass concentration in the filter has an important effect on the MIB
removals. As shown in Figure 5.2 of the four small 3-in filters, biomass concentrations in
anthracite/sand filters were more than 50% less than in GAC/sand filters, and

proportionally less MIB removals were observed in Figure 5.1. The higher biomass
concentration in GAC filters could be explained by the fact that GAC is known as better
bioactivity supporter than anthracite by providing better physical support structure (Wang
et al., 1995).
For all the filters, more than 60% of the total MIB removals were achieved within
the top 6-inches of the columns. Some additional removal of MIB occurred in the bottom
24-inches of the columns. Figure 5.4 shows the percent MIB removals at different depth
of the filters. This is also coincide with the distribution of biomass concentrations along
the filter columns: bioactivity is most active at the tops of the filter columns, as shown in
Figure 5.2 biomass concentrations were the highest at filter tops. This observation of high
MIB removal in the top 6-inches is also indicative of the biological up taking of MIB.
Percent MIB Removal
100
90
80
70
60
50
40
30
20
10
0
GAC/Sand
at 4 gpm/ft2
Ozonated Water; 3-in Diameter Filters
GAC/Sand
at 6 gpm/ft2
At 6-Inches from Filter Top (n=3)
Filter Effluent (n=5)
Anthracite/Sand
at 4 gpm/ft2
Unozonated Water; 8-in Diameter Filters
Anthracite/Sand
at 6 gpm/ft2
GAC/Sand
at 4 gpm/ft2
Anthracite/Sand
at 4 gpm/ft2
Figure 5.4 A Comparison of Percent MIB Removals at Top 6-inches of the Filter and at
bottom of the Filter (n is number of data points)
107

Effect of MIB initial concentrations
108
The historical MIB concentrations in the water utilities source water varied
typically between 2 and 100 ng/L. Two experiments were conducted to evaluate the
effect of influent MIB concentrations on the MIB removal percentages at the filter
effluent. Influent MIB concentrations tested were 16ng/L and 56ng/L. Other experiment
parameters were the same for both: ozone dose was 0.25 mg/mg TOC of the influent
water; ambient pH and temperature; same EBCT as either 6.3min or 4.3min. As shown
in Figure 5.5, increasing the influent MIB concentration to 56 ng/L has slightly negative
effects on MIB removals at the filter effluent, but not statistically different from 16 ng/L.
This is true for both EBCT conditions tested. For the GAC/sand filters, the MIB removal
percentages for influent MIB of 56ng/L were between 58% and 67%.
Percent MIB Removal
100
90
80
70
60
50
40
30
20
10
0
Influent MIB of 16 ng/L (n=5)
Influent MIB of 56 ng/L (n=2)
EBCT at 4 gpm/ft2 is 6.3 min
EBCT at 6 gpm/ft2 is 4.3 min
GAC/Sand at 4 gpm/ft2 GAC/Sand at 6 gpm/ft2
Figure 5.5 Effect of Influent MIB Concentration on MIB Removals in GAC/Sand Filters
(n is number of data points)

Effect of empty bed contact time (EBCT) on MIB removal
As shown in previous Figures 5.1, 5.3, and 5.5, consistent result of EBCT effect
on MIB removal could be observed. Higher EBCTs (6.3 min) resulted in slightly better
MIB removals compared to lower EBCTs (4.3 min) for both GAC/sand and
anthracite/sand filters. This is because higher EBCT provide higher residence time for
biological uptake of the secondary substrate (i.e. MIB).
Effect of pH
109
Some water treatment plant controls disinfection byproduct, such as bromate, by
lower the water pH during ozonation. Since water at higher pH has more HO • present,
which served as the ozone decomposing initiator, lower pH condition will reduce
bromate formation during ozonation. Two tests were performed to investigate the effect
on MIB removals during biofiltration only (MIB and geosmin added post ozone) while
lowering the water pH from ambient (~7.9) to 6.5 during ozonation. The other
experiment conditions for both tests remained the same: ozone dose at 0.25mg/mg TOC;
initial MIB concentration at 64~94ng/l; EBCT at either 6.3 min or 4.3 min. Figure 5.6
shows different effects on different media during pH changing. At lower pH conditions,
MIB removals were reduced about 50% on GAC/sand media, with more reduction
observed at longer EBCT; while no significant change of MIB removal was observed on
anthracite/sand media.

Percent MIB Removal
100
90
80
70
60
50
40
30
20
10
0
GAC/Sand at 4 gpm/ft2 GAC/Sand at 6 gpm/ft2 Anthracite/Sand
at 4 gpm/ft2
Ozone/TOC of 0.25 (Ambient pH) (n=5)
Ozone/TOC of 0.25 (pH 6.5) (n=2)
Initial MIB 64-94 ng/L
EBCT at 4 gpm/ft2 is 6.3 min
EBCT at 6 gpm/ft2 is 4.3 min
Figure 5.6 MIB removals at different pHs (n is number of data points)
Anthracite/Sand
at 6 gpm/ft2
These observations suggest that biofilters packed by GAC/sand media are more
sensitive on changes than those packed by anthracite/sand media. Similar observations
were reported in other pilot studies on BDOC removals. GAC was known as a good
supportor for biofilters. Consequtly, the attached bacteria on GAC was easier to be
affected by changing surroundings, such as pH condition.
Geosmin removal
110
Geosmin was prepared at exactly the same way as MIB and spiked
simultaneously with MIB during the entire Chandler pilot study. The results showed that
geosmin is much more ready to be removed than MIB. The target concentrations for MIB
and geosmin were the same, either 25ng/l or 50ng/l. Both MIB and geosmin
concentrations in the stock bags at filter influent were monitored before and after spiking.
No significant differences were observed for MIB ang geosmin concentrations in the bags

going to Chandler and upon return. However, the geosmin concentrations detected at the
filter influent were always < 6 ng/l, and below detection limit (2ng/l) after ozonation and
at the filters effluent. There are two possible reasons for the low geosmin levels. First,
geosmin is much more volatile than MIB despite only slight difference between their
Henry’s law constants (Table 1.1). Second, geosmin is much more readily to attach on
the pipe/tubing wall (Elhadi 2003).
Ozone-Biofiltration Effect of Other Water Parameters
The ozone-biofiltration effect on the two kinds of media was also tested for other
water parameters including particulates removal, total organic carbon (TOC) removal,
and bacterial population concentration in the effluent water. Particulates concentration
was represented by nephlometric turbidity units (NTU); total organic carbon removal was
represented by TOC and UV254 absorbance (represent smaller organics presentation);
bacterial population was represented by heterotrophic plate counts (HPC). All data and
graphs in this section were supplied from MPI.
111

TOC (mg/L)
UV254 (1/cm)
3.0
2.5
2.0
1.5
1.0
0.5
0.0
0.05
0.04
0.03
0.02
0.01
0.00
Raw
Water
Raw
Water
Plant
Settled
Water
Plant
Settled
Water
Ozonated
Water
Ozonated
Water
GAC/Sand
Filtered
Water
(After O 3 )
GAC/Sand
Filtered
Water
(After O 3 )
Anthracite/Sand
Filtered
Water
(After O 3 )
Anthracite/Sand
Filtered
Water
(After O 3 )
Figure 5.7 TOC/UV254 Results for Raw, Plant Settled, Filter Influent (Ozonated Water)
and Filter Effluents
112

Figure 5.7 shows that TOC average concentration was reduced from ~1.4mg/l to
~1.1mg/l after ozone-biofiltration for both GAC/sand and anthracite/sand media, with the
GAC/sand filters performed slightly better than anthracite/sand filters. As shown in
Figure 5.7, lower UV254 values were achieved in GAC/sand filters, which represents that
more percentages of smaller organics were removed in GAC/sand filters. Correlating the
TOC/UV254 results with the results of HPC shown in Figure 5.8, more bacterial
populations were present in GAC/sand filters than in anthracite/sand filters. All these
observations support that the GAC/sand media is a better bioactivity supporter than
anthracite/sand media. So more percentages of smaller molecules of TOC were up taken
in the GAC/sand filters, and resulted in lower TOC and UV254 values in the effluent
waters.
113
Ozone-biofiltration by both the two media, GAC/sand and anthracite/sand,
reduced the water turbidity from an average of ~0.8 NTU to ~0.2 NTU, and achieved the
full-scale plant treatment goal of 0.3 NTU (as shown in Figure 5.9). No visible difference
was observed in terms of particulates removal of the two kinds of media.

HPC (CFUs/mL)
10000
8000
6000
4000
2000
0
GAC/Sand
Filtered
Water
(After O 3 )
Anthracite/Sand
Filtered
Water
(After O 3 )
Figure 5.8 HPC Results for GAC/Sand and Anthracite/Sand Filtered Waters
Turbidity (NTU)
2.0
1.5
1.0
0.5
0.0
Raw
Water
Plant
Settled
Water
Ozonated
Water
GAC/Sand
Filtered
Water
(After O 3 )
Anthracite/Sand
Filtered
Water
(After O 3 )
Figure 5.9 Turbidity Results for Raw, Plant Settled, Filter Influent (Ozonated Water) and
Filter Effluents
114

Disinfection By-products Formation/Removal
Bromate formation
115
One of the disadvantages of ozonation process is oxidation of bromide in the
influent water to bromate, which is known as a carcinogenic product. This is one of the
major concerns when water utilities choosing water purification processes, especially in
areas where sources water has high concentration of bromide. This pilot study examined
bromide and bromate concentrations at the filters effluent. As shown in Figure 5.10, for
both GAC/sand and anthracite/sand media, no bromate (< 2 ug/L) was present in the filter
effluent even after higher ozone dose (1.5 mg/mg TOC) was applied. This was supprising
based upon research results of bromate formation by Chao (2002), where bromate formed
during ozonation of Arizona surface waters. Higher ozone doses were used by Chao
(2002). Using an empirical bromate formation model from Ozekin (Chapter 7), 3~45
ug/L of bromate would be predicted for Chandler water with ozone doses of 0.25~1.5
mg-O3/mg-TOC. Possible reasons for no formation of bromate in Chandler are that
subsequent biofiltration may have reduced BrO3 - back to Br - ; addition of Na2S2O3 would
have decreased dissolved oxygen levels prior to biofiltration, which would favorite
biodegradation process of BrO3 - . It was observed that bromate removal during
biofiltration when the biofilters had acclimated to nitrate. Nitrate was present in Chandler
raw water.

Bromide and Bromate (ug/L)
250
200
150
100
50
0
GAC/Sand
at 4 gpm/ft2
Ozonated Water; 3-in Diameter Filters
GAC/Sand
at 6 gpm/ft2
Anthracite/Sand
at 4 gpm/ft2
Anthracite/Sand
at 6 gpm/ft2
Unozonated Water; 8-in Diameter Filters
Bromide (ug/L) (O3/TOC=1.5 mg/mg)
Bromate (ug/L) (O3/TOC=1.5 mg/mg)
Bromide (ug/l) (O3/TOC=0.25 mg/mg)
Bromate (ug/l) (O3/TOC=0.25 mg/mg)
N/ N/D N/D N/D N/D
N/D
GAC/Sand
at 4 gpm/ft2
Anthracite/Sand
at 4 gpm/ft2
Figure 5.10 Bromate concentrations in the effluent of different filters at different ozone
doses (1 data point for each column)
Summary
116
MIB removals were a function of multiple parameters/conditions: filter media,
ozone doses, EBCTs, initial MIB concentrations, and influent water pH. Among these
parameters, the type and condition of filter media are the most important on MIB
removals; other parameters, within the normal operational ranges, play some, but not
significant roles.
Significant higher MIB removals were observed in GAC/sand filters compared to
anthracite/sand filters. All the filter media were using exhausted materials to eliminate
adsorption effects on MIB and geosmin removals. Increased ozone dose, higher EBCT,
less initial MIB concentration slightly favor the final MIB removals. The fact that most of

the MIB removal occurred within the top 6-inches of the filter correlated with the
observation that biomass concentration is the highest at filter tops, which indicating
predominance of biological up taking/oxidation as opposed to adsorption (to GAC
media).
117
The GAC/sand filters also outperformed anthracite/sand filters in terms of TOC
and UV254 reductions. GAC/sand and anthracite/sand filters have comparable
performance on turbidities; both produced finished water with less than 0.2 NTU. Higher
HPCs were observed in GAC/sand filters compared to anthracite/sand filters, which also
proved more biological activities on GAC/sand media.
Geosmin is much more ready to be removed than MIB. Geosmin were lost during
pipeline (tubings) transportations. At any conditions tested in Chandler pilot plant, more
than 90% of geosmin were removed before entering the filters. Almost all the geosmin
concentrations at filter effluent were below decteciton limit. Possible reasons for the low
geosmin levels are its easier to attach on the pipe/tubing wall (Elhadi 2003).
SQUAW PEAK PILOT STUDY RESULTS/DISCUSSIONS FOR MIB RESULTS
Squaw Peak pilot plant was designed to evaluate the performance for many water
quality parameters of intermediate ozonation and filtration process to meet the Stage-2
D/DBP Rule. Taste and odor problem control is one of the goals. MIB removals were
evaluated for different operational parameters including media type, EBCT, ozonation
and back wash water. Results of ozone-biofiltration performance of only MIB were
interpreted for Squaw Peak pilot as a complement of Chandler pilot study. Average raw

water quality at Squaw Peak WTP had a TOC concentraition of 2.6 mg/L, turbidity of
11.9 NTU, pH of 8.5, alkalinity of 174 mg/L as CaCO3, and bromide concentration of
100 ug/L. MIB dosing method developed by ASU were the same as described in
Chandler pilot work. Figure 5.11 shows initial and upon return concentrations of MIB in
collapsible bages used in Squaw Peak pilot study. MIB decomposition rate (0.5~1.0
percent/day) were similar as in Chandler pilot study (Table 5.2). Table 5.4 gives the MIB
results of Squaw Peak pilot study, and provides information helping to sort through all
the different pilot column acronyms.
MIB Stock Concentration (mg/L) )
2.0
1.5
1.0
0.5
0.0
Initial Concentration
Concentration Upon Return
4/9 4/14 4/19 4/24 4/29 5/4 5/9 5/14 5/19
Date (2003)
Figure 5.11 Initial and upon return concentration of MIB stock solutions used in Squaw
Peak pilot study
118

Sample Lable
Table 5.4
MIB results of Squaw Peak pilot study
MIB Removal (%)
Sampling Date (2003)
4/10 4/16 4/24 4/30 5/8 5/12 5/14
Filter Operation Period (day)
123 129 137 143 151 155 157
119
Average
MIB
Removal
%
Full-scale Settled Water (SW) 1 1 1 1 1 1 1 0
Filter 1 Effluent (F1) - - 0.24 - 0.15 0.04 - 9
Filter 2 Effluent (F2) - - 0.41 0.3 0.54 0.09 - 27
Filter 3 Effluent (F3) - - 0.27 0.15 0.2 0.04 - 13
Filter 4 Effluent (F4) - 0.16 0.49 0.6 0.5 0.57 - 46
Filter 5 Effluent (F5) - 0.18 0.37 0.5 0.51 - - 39
Filter 6 Effluent (F6) - 0.35 0.66 0.77 0.71 0.7 - 64
Filter 7 Effluent (F7) - 0.25 0.42 0.56 0.62 0.41 - 45
Ozonated SW (OSW) - 0.28 0.28 0.35 0.42 0.26 - 32
Filter 8 Effluent (F8) - 0.08 0.48 0.45 0.59 0.34 - 47
Filter 9 Effluent (F9) - - 0.33 0.29 0.5 0.28 - 35
Filter 10 Effluent (F10) - 0.44 0.62 0.55 0.65 0.56 - 56
Filter 11 Effluent (F11) - 0.3 0.51 0.65 0.69 0.65 - 56
Filter 12 Effluent (F12) - 0.55 0.82 0.83 0.83 0.89 - 78
Elevated TOC Water (ETOC) 1 1 1 1 1 1 1 0
Filter 13 Effluent (F13) 0.01 - 0.07 0.03 0.26 0.52 - 15
Filter 14 Effluent (F14) 0.46 - 0.55 0.49 0.66 0.72 - 58
Filter 15 Effluent (F15) 0.58 - 0.57 0.48 0.87 0.9 0.3 54
Filter 16 Effluent (F16) 0.50 0.51 0.67 0.61 0.9 0.95 0.67 69
Ozonated ETOC (OETOC) 0.25 - 0.26 0.15 0.38 0.32 - 27
Filter 17 Effluent (F17) 0.29 0.11 0.52 - - 0.42 0.33 34
Filter 18 Effluent (F18) 0.28 0.35 0.39 - - 0.67 0.46 43
Filter 19 Effluent (F19) 0.44 0.41 0.38 - - 0.41 0.55 44
Filter 20 Effluent (F20) 0.55 0.56 0.68 0.67 - - 0.62 62
Effect of EBCT on MIB Removal
MIB removal increases as EBCT increases. Figure 5.12 shows EBCT effects on
MIB removal for different influent water of the filters with the same media, GAC-B. For
regular plant settled water (SW) and RO concentrated water (ETOC), with (OSW) or

MIB Removal
(1-MIB/MIBo)
1.00
0.80
0.60
0.40
0.20
0.00
EBCT=2.3 min
EBCT=5.5 min
Settled Water Ozonated
Settled Water
Elevated TOC
Water
Figure 5.12 EBCT effects on MIB removals for filters with GAC-B media
Ozonated
Elevated TOC
Water
without ozonation (OETOC), MIB removals are higher (15% on average) for longer
EBCT (5.5 min) than shorter EBCT (2.3 min).
Effect of Ozonation on MIB Removal
120
Ozonation alone could achieve around 30% MIB removals as shown in Figure
5.13. Slightly lower MIB removals were observed at increased TOC concentrations.
Ozonation oxidizes natural organic mater to smaller molecules. TOC is a commonly used
parameter to represent NOM concentration. Higher TOC concentration indicates more
NOM presenting in raw water to compete with MIB during ozonation process.

MIB removal
(1-MIB/MIBo)
1.00
0.80
0.60
0.40
0.20
0.00
Plant Settled Water
(TOC~1.8 mg/L)
O3/TOC = 0.25~0.5 mg/mg
Elevated TOC Water
(TOC~2.9 mg/L)
Figure 5.13 Ozonation effects on MIB removal for different raw water TOC
Effect of Ozone-Biofiltration on MIB Removal
121
Ozone-biofiltration achieved more MIB removals than filtration alone without
ozonation. Figure 5.14 shows biofiltration effects on MIB removals for filters with
different media, with and without ozonation (0.25-0.5 mg-O3/mg-TOC). MIB removals
for filters fed with ozonated water were 15% higher in average than those fed directly
with plant settled water (TOC~1.8 mg/L). More MIB removals during biofiltration
process achieved after ozonation should be accounted for both direct ozone oxidation and
easily biodegradable substance produced by ozonation.

MIB removal
(1-MIB/MIBo)
1.00
0.90
0.80
0.70
0.60
0.50
0.40
0.30
0.20
0.10
0.00
filtration without ozonation
filtration after ozonation (O3/TOC=0.25-0.5 mg/mg)
Anthracite/Sand
(EBCT=2.3min)
GAC-B/Sand
(EBCT=2.3min)
GAC-L
(EBCT=3.4min)
GAC-B
(EBCT=5.5min)
Figure 5.14 MIB removals during filtration with and without ozonation in different filter
media (Filter influent water = plant settled water, TOC~1.8 mg/L)
Effect of Raw Water TOC on MIB Removal
122
MIB removals decreased when raw water TOC increased. As shown in Figure
5.15, MIB removals after ozone-biofiltration treatment were decreased 10% in average
when filter influent TOC increased from 1.8 mg/L to 2.9 mg/L. No statistical effects
observed for filtration without ozonation after elevating TOC.

MIB removal
(1-MIB/MIBo)
1.00
0.80
0.60
0.40
0.20
0.00
Anthracite/Sand
(EBCT=2.3min)
filtration without ozonation
filtration after ozonation (O3/TOC=0.25~0.5mg/mg)
GAC-B/Sand
(EBCT=2.3min)
GAC-L
(EBCT=3.4min)
GAC-B
(EBCT=5.5min)
Anthracite/Sand
(EBCT=2.3min)
GAC-B/Sand
(EBCT=2.3min)
GAC-L
(EBCT=3.4min)
GAC-B
(EBCT=5.5min)
plant settled water (TOC~1.8 mg/l) RO concentrated water(TOC~2.9 mg/l)
Figure 5.15 Raw water TOC effects on MIB removals
Effect of Biomass Concentration on MIB Removal
Proportionaly increased MIB removals were observed with correspondence of
proportionally increased biomass concentrations. As show in Figure 5.16, biomass
concentrations were the highest in 48-in (EBCT=5.5 min) GAC-B filters. Compared to
Figure 5.15, highest MIB removals were observed in GAC-B filters with EBCT of 5.5
min. Similar biomass concentrations in 30-in GAC-B/S (EBCT=2.3 min) and 30-in
GAC-L (EBCT=3.4 min) resulted in similar MIB removals as shown in Figure 5.15 and
5.16. Similar observations were also observed in Chandler pilot study.
123

nmol PO4-Lipid/ cm3 of media
100
90
80
70
60
50
40
30
20
10
0
30-in GAC-B/S
30-in GAC-L
48-in GAC-B
Settled Water Ozonated Settled Water Elevated TOC waters Ozonated Elevated TOC
waters
Figure 5.16 Biomass concentrations in different GAC media filters
Effect of Backwash Water on MIB Removal
Filter Column
124
MIB removals were higher in filters backwashed with unchlorinated water than
with chlorinated water. Figure 5.17 shows effects of backwash water on different media
types. MIB removals increased 5% and 20% when switching backwash water from
chlorinated to unchlorinated water for A/S and GAC-B/S media, respectively.

MIB removal
(1-MIB/MIBo)
1.00
0.80
0.60
0.40
0.20
0.00
backwashed with chlorinated water
backwashed with unchlorinated water
Anthracite/Sand GAC-B/Sand
Figure 5.17 Effects of backwash water on different media types (Filters influent = planted
settled water; EBCT = 2.3 min)
Effect of Different Filter Media on MIB Removal
125
Bituminous coal (GAC-B) media has the best performance among three media
types (GAC-B, GAC-L, and A/S) tested in this study. As shown in Figure 5.18, filters
with media type of GAC-B (EBCT = 2.3 min) and GAC-L (EBCT = 3.4 min) media
achieved around 20% more removals of MIB than of Anthracite/sand media (EBCT = 2.4
min), with GAC-B (with shorter EBCT) performed slightly better than GAC-L. Superior
performances of GAC media than anthracite media in taste and odor control, as well as

MIB removal
(1-MIB/MIBo)
1.00
0.80
0.60
0.40
0.20
0.00
filtration without ozonation
filtration after ozonation (O3/TOC=0.25~0.5mg/mg)
Anthracite/Sand
(EBCT=2.3min)
GAC-B/Sand
(EBCT=2.3min)
GAC-L
(EBCT=3.4min)
Anthracite/Sand
(EBCT=2.3min)
GAC-B/Sand
(EBCT=2.3min)
GAC-L
(EBCT=3.4min)
plant settled water (TOC~1.8 mg/l) RO concentrated water(TOC~2.9 mg/l)
Figure 5.18 Effects of media type on MIB removals in filters with the similar design and
operation
other water treatment goals, were reported frequently (Lechevallier et al. 1992, Rittmann
and Huck 1989). Filter performance also vary a little with different GAC types.
Bituminous coal (GAC-B) was known as better than lignite coal (GAC-L) in terms of
taste and odor control.
Effect of Ozone-Biofiltration on TOC Removal
126
Total organic carbon removal was represented by TOC results in Squaw Peak
pilot study. TOC data and graph in this section were supplied from MPI. Figure 5.19
shows that TOC average concentrations were reduced by 10-20% after biofiltration, with
slightly better performance observed after ozonation. Biofiltration in GAC media

achieved around 10% more reduction of TOC than in anthracite media. Bituminous coal
had slightly better performance than lignite coal under any similar design and operational
conditions.
C/Co, TOC (mg/L)
1.2
1.0
0.8
0.6
0.4
0.2
0.0
30-in A/S (Pilot-Control)
30-in A/S (No-O3)
30-in A/S (with-O3)
30-in GAC-B/S (No-O3)
Figure 5.19 TOC removals after biofiltration with or withour ozonation in different filter
media
30-in GAC-B/S (with-O3)
30-in GAC-L (No-O3)
30-in GAC-L (with-O3)
48-in GAC-B (No-O3)
48-in GAC-B (with-O3)
127

Bromate Formation
No bromate formation was observed by the regular monitoring throughout Squaw
Peak Pilot study, which was similar as observed in Chandler pilot study. The bromide
concentration in both the Squaw Peak WTP settled water and elavated TOC water was in
the range of 80 ug/L to 200 ug/L. The applied ozone doses were in the low range, vairing
between 0.5mg/L to 2.0 mg/L (0.24-0.5 mg-O3/mg-TOC). The detection limit for
bromate was 5 ug/L. Possible reasons for no formation of bromate include the low ozone
dose applied and low bromide concentrations in the infuluent water. It was reported that
at least 180-250 µg/L of bromide concentrations were necessary to produce measurable
levels (greater than 5 µg/L) of bromate when using ozone for primary disinfection
(Krasner et al. 1993, Siddique and Amy 1993). Bromate formation may alos affected by
different natural water matrix.
128

SUMMARY OF PILOT STUDIES RESULTS
129
Biofiltraiton process after ozonation could achieve 40-60% removals of MIB,
with an additional 10-20% removals achieced by ozonation itself. Geosmin removals
were generally higher than MIB. Almost all geosmin could be removed by ozone-
biofiltration process. Both of the two pilot studies were using exhausted filter media from
full-scale plants to eliminate adsorption effects on MIB and geosmin removals.
MIB and geosmin removals were a function of many parameters: filter media, O3
dose, EBCT, initial MIB and geosmin and TOC concentration, water pH, and backwash
water and frequency. Media type and operation of filters have the most important effects
on MIB and geosmin removals. GAC media had the best performance for tasts and odor
control, as well as TOC and particulate removals. GAC made of bituminous coal has
slightly better performance than of luminous coal in terms of MIB and geosmin removal.
Backwashing use chlorinated water could substancially decrese the MIB and geosmin
removals by damaging the biofilm. Increased ozone dose, higher EBCT, less initial MIB
and TOC concentrations slightly favor the final MIB removals. Lowering water pH was
observed having much negative effects on MIB removal in PAC filters than in
anthracite/sand filters.

RESULTS AND DISCUSSIONS
CHAPTER 6
FULL-SCALE UTILITY SURVEY
130
Ozone-biofiltration treatments could reduce MIB concentrations from 0-15 ng/L
to less than 2 ng/L after, geosmin concentrations from 0-12 ng/L to under 2 ng/L, and
TOC concentrations from 1-5.5 mg/L to 1-3.5 mg/L. Figure 6.1 and 6.2 showed two sets
of example results from two utilities. The other survey data of MIB, geosmin, TOC are
given in appendix (Table C.1). All the other experiment results of MIB, geosmin and
TOC reported for the utilities survey campaigns are annually averaged values.
MIB/Geosmin (ng/L) or TOC (mg/L) )
15
10
5
0
RW
SW
Post O3
Figure 6.1 Survey results of utility #5
Eagle Moutain Water Treatment Plant (ID#5) (8/27/2002)
Prefil#1
Postfilt#1
Sampling Location
Prefilt#2
MIB
Geosmin
TOC
Postfilt#2
Treated

MIB/Geosmin (ng/L) or TOC (mg/L) )
15
10
5
0
RW
SW
Post O3
Figure 6.2 Survey results of utility #6
MIB Removals
Gilbert Water Treatment Plant (ID#6) (8/12/2002)
Prefil#1
Postfilt#1
Sampling Location
Prefilt#2
MIB
Geosmin
TOC
No Geosmin Presentation
Postfilt#2
Treated
Table 6.1 gives the percentages of MIB removal in numbers and the reasons of no
data at some points. As shown in Figure 6.3, ozonation alone could achieve 0-85% of
MIB removals of ozone contactor influent concentration, with a general value of 30-40%
removals. Figure 6.4 shows biofiltration alone after ozonation could achieve 0-80% of
MIB removals of filter influent concentration, with a general value of 50-70% removals.
Very low percentage (~ 0 %) removals of biofiltration are typically associated with low
MIB influent concentrations (~ 2 ng/L), which suggestes low margins for biodegradation
and high analytical inaccuracy. The total MIB removals (of sedimentation effluent
concentration) by ozonation and biofiltration are shown in Figure 6.5. A total of 35-90%
131
removals could be acheieved by ozone-biofiltraton, with a general value of 60-90%

emovals. Utility #3 is an exceptional case in this survey. It is the only utility without
ozonation amony the nine utilities. There is almost no MIB removed after sedimentation
in utility #3.
One common phenomenon was that values of total removals of ozone-
biofiltration not equaling the sum of the individual ozonation and biofiltration removals
for both MIB and geosmin and TOC. At such low concentration range (ng/L), it could be
due to concentration changes during transportion in pipes or meaurement inaccuracy.
Possible processes may occure in water transportation pipelines include
biodegradation/production, volatization, and adsorption to the walls.
Table 6.1
MIB removals in utilities
2002 MIB Removal
2003 MIB Removal
Utilities
ID # ozonation biofiltration Total ozonation biofiltration Total
1 85 % 47 % 88 % 33 % 16 % 62 %
2 No MIB present in raw water No sampling
3 No sampling - 1 % 1 %
4 No sampling 37 % 57 % 88 %
5 73 % 65 % 90 % 41 % 1 % 66 %
6 46 % 74 % 89 % 29 % 57 % 88 %
7 11 % 1 % 56 % No MIB present in raw water
8 No sampling 1 % 83 % 79 %
9 43 % 60 % 66 % 46 % 1 % 34 %
Notes: All “MIB Removal (%)” are based on the influent concentrations of the
refered unit treatment process/process train
132

% MIB Removal
100
90
80
70
60
50
40
30
20
10
0
No error bars = only one set of samples collected
1 2 3 4 5 6 7 8 9
Figure 6.3 MIB removals by ozonation in utilities
% MIB Removal
100
90
80
70
60
50
40
30
20
10
0
utilities ID #
No error bars = only one set of samples collected
MIB

% MIB Removal
100
90
80
70
60
50
40
30
20
10
0
ozone-biofiltration-2002
ozone-biofiltration-2003
No error bars = only one set of samples collected
1 2 3 4 5 6 7 8 9
utilities ID #
Figure 6.5 MIB removals by ozone-biofiltration in utilities
Geosmin Removals
Table 6.2 gives the percentages of geosmin removal in numbers and the reasons
of no data at some points. As shown in Figure 6.6, ozonation alone could achieve 0-90%
of geosmin removals, with a general value of 50-60% removals. Figure 6.7 shows
biofiltration alone after ozonation could achieve 0-100% of geosmin removals, with a
general value of 60-100% removals. The total geosmin removals by ozonation and
biofiltration are shown in Figure 6.8. A total of 45-100% removals could be acheieved
by ozone-biofiltraton, with a general value of 70-95% removals. Geosmin concentrations
are generally very low (< 3 ng/L) in most of the utilities, and it is easier to be removed
than MIB. All utilities have geosmin concentration less 2 ng/L in the treated water.
134

Table 6.2
Geosmin removals in utilities
2002 geosmin Removal
2003 geosmin Removal
Utilities
ID # ozonation biofiltration Total ozonation biofiltration Total
1 90 % 47 % 88 % 85 % 10 % 83 %
2 48 % 100 % 100 % No sampling
3 No sampling No geosmin presentation
4 No sampling 55 % 41 % 83 %
5 71 % 78 % 92 % 12 % 1 % 45 %
6 58 % 100 % 100 % 50 % 65 % 82 %
7 1 % 1 % 69 % No geosmin presentation
8 No sampling 1 % 100 % 100 %
9 46 % 57 % 79 % 59 % 13 % 64 %
Notes: All “MIB Removal (%)” are based on the influent concentrations of the
% Geosmin Removal
100
90
80
70
60
50
40
30
20
10
0
refered unit treatment process/process train
No error bars = only one set of samples collected
1 2 3 4 5 6 7 8 9
Figure 6.6 Geosmin removals by ozonation in utilities
utilities ID #
ozonation-2002
ozonation-2003
135

% Geosmin Removal
100
90
80
70
60
50
40
30
20
10
0
No error bars = only one set of samples collected
1 2 3 4 5 6 7 8 9
utilities ID #
Figure 6.7 Geosmin removals by biofiltration in utilities
% Geosmin Removal
100
90
80
70
60
50
40
30
20
10
0
No error bars = only one set of samples collected
ozone-biofiltration-2002
ozone-biofiltration-2003
biofiltration-2002
biofiltration-2003
1 2 3 4 5 6 7 8 9
utilities ID #
Figure 6.8 Geosmin removals by ozone-biofiltration in utilities
136

TOC Removals
Table 6.3 gives the percentages of TOC removal in numbers and the reasons of no
data at some points. There is no observable removal of TOC after ozonation. The
variation, even increase of TOC concentrations during ozonation process could be
possibly explained by bioactivities going on in the dead zones of ozone contact chambers
or ozone dissipation tank. The preservatives added during sampling had no observable
effects on TOC recovery (Chapter 3). At regular TOC range (2-5 mg/L), ozonation could
cause TOC values increased up to 30%, or decreased up to 25%. Figure 6.9 shows
biofiltration alone after ozonation could achieve 0-30% of TOC removals, with a general
value of 15-20% removals. The total TOC removals by ozonation and biofiltration are
shown in Figure 6.10. A total of 15-40% removals could be acheieved by ozone-
biofiltraton, which is as good as, if not better than, the removal achieved by conventional
treatment processes. High removals of TOC by ozone-biofiltration could be explained by
the ozone oxidation mechanisms of NOM. NOM is major composition of TOC.
Ozonation could break big NOM molecules to small ones that are easier to be
biodegraded by bacterias during the following biofiltration process.
137

Table 6.3
TOC removals in utilities
2002 TOC Removal
2003 TOC Removal
Utilities
ID # ozonation biofiltration Total ozonation biofiltration Total
1 1 % 15 % 18 % 26 % 15 % 38 %
2 3 % 24 % 30 % No sampling
3 No sampling - 1 % 19 %
4 No sampling 1 % 31 % 31 %
5 -1 % 18 % 29 % -29 % 16 % 13 %
6 -13 % 26 % 18 % -14 % 16 % 14 %
7 -3 % 1 % 19 % -23 % 17 % 19 %
8 No sampling No TOC data
9 -4 % 21 % 18 % 8 % 22 % 28 %
Notes: All “MIB Removal (%)” are based on the influent concentrations of the
% TOC Removal
100
90
80
70
60
50
40
30
20
10
0
refered unit treatment process/process train
No error bars = only one set of samples collected
1 2 3 4 5 6 7 8 9
Figure 6.9 TOC removals by biofiltration in utilities
utilities ID #
biofiltration-2002
biofiltration-2003
138

% TOC Removal
100
90
80
70
60
50
40
30
20
10
0
No error bars = only one set of samples collected
1 2 3 4 5 6 7 8 9
utilities ID #
Figure 6.10 TOC removals by ozone-biofiltration in utilities
Biomass Results
ozone-biofiltration-2002
ozone-biofiltration-2003
139
As shown in Figure 6.11, biomass concentrations in seven of the utilities varied
from 20 to 300 nmol-PO4/gram-dry-wt. Figure 6.12 showed the relationship of removals
of MIB/geosmin/TOC and biomass concentrations in different utilities in 2003. No
apparant relationship during biofiltraiton was observed. The observation that lack of
correlation of biomass concentration with MIB and geosmin removals from the seven
utilities may be due to the very low MIB and geosmin concentrations. Most utilities had
MIB and geosmin concentrations less than 2 ppt in the filter influent.

Biomass Concentration
(nmol-PO4/g-dry-wt)
300.0
250.0
200.0
150.0
100.0
50.0
0.0
1 2 3 4 5 6 7 8 9
Figure 6.11 Biomass survey results in seven utilities
MIB/Geosmin removed (ng/L)
& TOC removed (mg/L)
1
0.8
0.6
0.4
0.2
0
No Biomass Samples
utilities ID #
0.0 50.0 100.0 150.0 200.0 250.0 300.0
Observed biomass concentration
MIB
geosmin
TOC
Figure 6.12 Relationships of removals of MIB/geosmin/TOC and biomass concentration
at different utilities
140

SUMMARY OF UTILITY SURVEY
Natural occuring MIB and geosmin concentrations were in the range of 0-20 ng/L
in most of the surveid utilities. Ozone-biofiltration could achieve 60-90% removals of
MIB, 60-100% of geosmin, and 20-40% of TOC in general. Most of the utilities had MIB
and geosmin concentrations under 2 ng/L in treated water. TOC removals by ozone-
biofiltration treatment are as good as, if not better than, by conventional treatment
processes.
141
Higher biomass concentration resulted in higher MIB and geosmin removals.
Biofilter maintenance is important in taste and odor control. Backwashing of filters using
chlorinated water could damage the biofilm, and dramatically reduce MIB and geosmin
removals, as observed in utility #1. The second set of water samples in 2003 from utility
#1 was collected after performance of backwashing using chlorinated water. As a contrast
to the first set of samples, almost no MIB and geosmin by biofiltration were observed in
the second set. As a consideration of presenting general observations, the data of samples
collected after backwashing with chlorinated water was not included in taken account in
average values.

CHAPTER 7
MODELING OZONE-BIOFILTRATION SYSTEMS
A process-orientated model was developed as a tool for optimizing ozone doses
in ozone-biofiltration processes. The major purpose of the model was to study the MIB
and geosmin removal mechanisms during biofiltration process. The model considers
odorant (i.e. MIB and geosmin) oxidation, ozonation by-product (i.e. bromate) formation,
microbial inaction during ozonation (i.e. CT credit), and odorant biodegradation across
biofilters. Figure 7.1 illustrates the inputs and outputs of two modules in the model.
BDOC is not directly predicted due to lack of existing models.
Inputs
Outputs
Raw water
quality;
Ozonation
conditions;
Ozonation rate
constants
Ozonation
Module
Bromate
CT
Figure 7.1 Ozone-biofiltration modeling diagram
[MIB]
after ozonation
Biofilm
parameters;
Biofiltraiton
parameters;
Biofiltration
Module
[MIB] after
ozone-biofiltration
142

OZONE MODULE
Ozone Residual Model
An empirical model was used to estimate ozone residuals as a fuction of water
quality and contact time. The empirical model is represented by equation (EQN) 7.1,
which was developed after statistical analysis of ozone decay kinetics in natural waters
during a previous project (Ozekin 1998).
Where
143
[DO3] = 6554(DOC) -1.64 (pH) -4.433 [O3] 1.524 (t) -0.638 (ALK) 0.111 (EQN 7.1)
R 2 = 0.67, F = 128, N = 323, a < 0.0001
[DO3]= Dissolved Ozone (mg/l); 0.05

from lab results that are given in Table 7.1. Ozonation Kinetics of MIB and geosmin
could be expressed by the following equations:
Where
[M] is concentration of MIB or geosmin.
Rearranging EQN 7.2:
Let
We get:
144
dM
− = KO
3[
O3][
M]
+ KHO[
HO][
M]
(EQN 7.2)
dt
−
−
dM
dt
dM
dt
−
dM
dt
= { KO
3[
O3]
+ K
HO
[ HO]}[
M]
= { KO
3[
O3]
+ KHORct
[ O3
]}[ M]
= { KO
3 + KHORct}[
M][
O3]
K '= { KO3
+ KHORct
}
dM
− = K'
[ M][
O3]
dt
For pseudo first order reaction A + B ? Product, we have:
[ B]
B0
B0
= ln + ( B0
− A ) K't
& ln[ B] − ln[ A]
= ln + ( B0
− A0
) K't
[ A]
A
A
ln 0
0
Therefore, we get EQN 7.3 for calculating MIB or geosmin residual at time t:
M 0
ln[ M ] =
ln + ( M 0 −O3
) K'
t + ln[ O3]
0
O
30
0

Bromate Formation Model
145
M 0
M ] = exp{ln + ( M 0 − O3
) K'
t + ln[ O ]} (EQN 7.3)
0
O
[ 3
30
An empirical model was used to estimate bromate formation during ozonation as
a fuction of water quality and contact time. The empirical model is represented by EQN
7.4, which was developed after statistical analysis of bromate formation in ozonation of
natural waters during a previous project (Ozekin 1998).
log[BrO3 - ] = -3.361+0.006(t)+0.249(pH)+1.575log[O3]+1.136log[Br-]-1.267log(DOC)
Where
[BrO3 - ] = bromate concentration formed during ozonation
t = time (min); 1

statistical analysis of CT values in ozonation of natural waters during a previous project
(Ozekin 1998).
Where
T
×
T
10
CT10 = [DO3] × HRT
[DO3] is dissolved ozone residule calculated from equation 7.1
T 10 =0.6 (within the range of 0.2 – 0.9)
T
50
HRT is the hydrolic retension time
Input Parameters for Ozonation Modual
50
146
(EQN 7.5)
The input values for the ozonation model were given in Table 7.1 and 7.2. Initial
water parameters and ozonation conditions were chosen according to the general practical
cases. Rate constants were obtained from the lab ozonation experiment conducted
previously. Selection of Rct value was based on natural water ozonation lab results
(Table 7.2).

Table 7.1
Input Parameters for Ozonation Modeling
Parameter Value Unit
Raw Water Quality Parameters
Bromide

BIOFILTRATION MODULE
148
MIB and geosmin was assumed to follow behave as a secondary substrate in the
biofilter. Therefore, the MIB and geosmin utilization could be expressed from secondary
substrate utilization equation (EQN 7.6) (Suffet 1995). Definations of all parameters used
in biofiltration modeling are given in Table 7.3.
made:
2
∂ Ss
∂Ss
ysPMws
= Dh
− v −a
mK
f Ss
− Klas(
Ss
− ) (EQN 7.6)
∂x
∂x
H RT
0 2
K
f
KmsD
fsB
tanh( BL f )
= (EQN 7.7)
K + D B tanh( BL )
ms
0.
468 −2/
3
K = 1.
33v(Re
m)
Sc
fs
f
ms (EQN 7.8)
B
K
fs
cs
2 f
= (EQN 7.9)
D
X
In order to simplify the modeling process, the following assumptions has been
Assumption 1: In this model, gas phase concentrations of MIB and geosmin are
neglected. Since in practical situations MIB and geosmin are at very low concentrations
(

Table 7.3
Definations of all parameters used in biofiltration modeling
Parameter Unit Defination Ref. EQN
a (dimensionless) coefficient in simplified utilization differential equation EQN 7.12
a m 1/cm
the specific biofilm surface area or area per total reactor
volume EQN 7.6
B (dimensionless) a characteristic biofilm kinetic parameter EQN 7.7
C ng/L MIB or geosmin concentration entering the biofilter Table 7.3
Df s cm 2 EQN 7.7;
/h Diffusivity in biofilm Dfs=0.8Dw
EQN 7.9
Dh cm 2 hydrodynamic dispersion coefficient for a packed-bed
/h
reactor EQN 7.6
dp,eff cm the effective diameter of the packing
Dw cm 2 /h the diffusion coefficient of MIB in water EQN 7.8
E (dimensionless) Porosity of the reactor (dimensionless) Table 7.3
f (dimensionless) shape factor of active carbon partical Table 7.3
Hcs cmw 3 /cmg 3 the Henry's law constant for the secondary substrate EQN 7.6
the first-order flux constant defined by the following EQN 7.6;
Kf cm/h
equation: Kf = [KmsDf sB tanh(B Lf)]/[Kms+Df sB tanh (B Lf)]
the overall mass transfer rate coefficient for the
exchange of the secondary substrate between the water
EQN 7.7
Klas 1/h
phase and the air phase
the overall mass transfer rate codfficient for the
EQN 7.6
Kms cm/h
movement of the substrat EQN 7.7
cm 2 secondary substrate from bulk solution to the outer
/h
surface of the biofilm
K2 cm 3 /mgx/h the mixed second-order rate constant EQN 7.9
Lf cm Biofilm thickness EQN 7.7
Mws mg/mol molecular weight of the secondary substrate EQN 7.6
P dyne cm 2 the hydrostatic pressure at any point in a sparged reactor EQN 7.6
R dyne cm/mol/K the universal gas constant
a modified Reynolds number defined by
EQN 7.6
Rem (dimensionless) Rem = dpeff *v/(0.65*(1-E)*u) EQN 7.8
Sc (dimensionless) the Schmidt number (dimensionless), defined by u/Dw
Ss mg/ cm 3
the secondary substrate (MIB) concentration at a point
within the biofilm EQN 7.6
T K absolute temperature EQN 7.6
tanh (dimensionless) the hyperbolic tangent
u cm 2 /h the kinematic viscosity of water
EQN 7.6;
v cm/h the empty-bed or superficial water velocity in the reactor EQN 7.8
V cm 3 control volume for am calculation Table 7.3
x cm filter depth EQN 7.6
Xf mgx /cm 3 -column the biomass concentration EQN 7.9
ys (dimensionless) mole fraction of secondary substrate in the gas phase EQN 7.6
ρ mgx/cm 3 -biofilm Biofilm density EQN 7.15
? (dimensionless) biofilm coverage of the media Table 7.3
149

150
Assumption 2: Usually, the hydraulic loading rates for the filters and GAC
contactors in biological water treatment processes are relatively high and the effect of
axial hydrodynamic dispersion is negligible (Zhang S. and Huck P.M., 1995).
Calculations showed this to be true for the drinking water biofilters operated by Huck et
al. 1991. Therefore, EQN 7.10 can be simplified to EQN 7.11:
Solving of Secondary Substrate Utilization Equation
Rearrange EQN 7.11:
Let
We get EQN 7.13:
∂Ss
0 = v + amK
f Ss
(EQN 7.11)
∂x
∂S
∂x
a
K
s m f
= −(
) Ss
v
am K f
a = − ( )
(EQN 7.12)
v
∂S
=
∂x
s aSs
EQN 7.13 was solved by Maple 7 using the initial condition:
Ss = C (ng/l) at x = 0 cm
Solvement of EQN 7.13 from Maple 7 is given in EQN 7.14:
(EQN 7.13)
Ss ( x)
= Cexp(
ax)
(EQN 7.14)

151
The solvement of the EQN 7.13 was put into an Excell spreadsheet as a
biofiltration model. MIB or geosmin residuals could be calculated from the model as a
function of filter depth x at steady state.
Input Parameters for Bio-filtration Modual
Input parameters of bilfilters characteristics are obtained from literature or
calculated by the author. Table 7.4 gives the values calculated by the author according to
literature. Table 7.5 gives the values obtained from literature. The value of operational
parameter, super facial water velocity v, was chosen based upon practical operating
ranges, 2-10 gpm/ft 2 , which is equivalent to 400-2500 cm/h.
Table 7.4
Calculation of biofilm specific surface area ( a m )
Parameter Huck's approach Thesis's approach
biofilm coverage (?) 20% 20%
media porosity (E) 0.425 0.425
correction of shape
factor (f) 1.5 1.5
control volume (V) cubic volumn containing one PAC bean 1 cm 3 of the column
partical diameter (dp-60% + dp-10%)/2 deff
equation
A
m
=
( d
6(
1 − E)
φf
+ d
p−
60% p−10%
)
/ 2
A
m
( 1 − E)
φf
=
8(
d / 2)
0.734 (GAC: dpeff = 0.06)
calculated 11.12 (GAC) 0.4318 ( GAC: dpeff = 0.121)
am(cm 2 /cm 3 ) 8.86 (Anthracite) 0.29 (Anthracite: dpeff = 0.152)
eff

Parameter
Table 7.5
Values of biofilm parameters from literature
Parameter
Value Parameter Defination System/Comments Citation
Lf(um) 33-42 Biofilm thickness along filter depth Dual media filter 3
40-56 * GAC contactor 3
E 0.9 Porosity of the reactor a Berl-saddle reactor 1
(dimensionless) 0.39 (dimensionless) GAC RSSCT column 2
0.425 * GAC contractor/dual media filter 3
Am(1/cm) 2.49 the specific biofilm surface area or a Berl-saddle reactor 1
61.61 area per total reactor volume dual media filter 3
50.56 GAC contactor 3
Dw(cm 2 /h) 0.02 Diffusivity of MIB in water 1
0.0175 * GAC contactor 3
u(cm 2 /h) 36 * the kinematic viscosity of water 5
Df s(cm 2 /h) 0.016 * Diffusivity of MIB in biofilm a Berl-saddle reactor 1
0.01 GAC contactor/dual media filter 3
K2(cm 3 the mixed second-order rate
/mgx/h) 8.2 * constant 1
Xf(mgx/cm 3 ) 30 the biomass concentration a Berl-saddle reactor 1
30 * GAC media 3
13.1~58 300 um glass beads 4
dpeff(cm) 0.77 the effective diameter of the a Berl-saddle reactor 1
0.0513 packing GAC pilot column 2
0.0882 dual media filter 3
0.1206 * GAC contactor 3
0.06-0.152 * GAC/sand media 6
Notes: *: value of parameter used in the model of this thesis
Citation: 1, (Suffet 1995); 2, (Raymond 1999); 3, (Zhang 1995); 4, (Rittmann
1986); 5, http://scienceworld.wolfram.com/physics/KinematicViscosity.html; 6,
(Wang 1995)
OZONE-BIOFILTRATION MODELING RESULTS
The results of MIB and geosmin ozone-biofiltration model was combined into a
single excel model, with the output MIB concentration serving as the influent MIB
concentration for the biofiltration model. Figure 7.2 gives an example of the modeling
results of ozone-biofiltration of natural water (SRP water). Input parameters used for
Figure 7.2 are given in Table 7.6.
152

153
As shown in Figure 7.2, the model predicts around 95% removal of MIB after
ozone-biofiltration process. The model prediction is agreed with the results of lab
experiments and utilities survey. With the ozone dose of 1.5 mg/L, which is within the
common range applied in WTPs, more than 80% of MIB and geosmin were removed
during ozonation. Biofiltraiton achieved around 60% removal of the influent MIB.
Bromate formation is

Ozone (mg/L) & CT (mg-min/L)
MIB concentration (ng/l)
1.5
1.0
0.5
0.0
15
10
5
0
0.5
1.0
1.5
2.0
O3 (mg/L)
2.5
Contact Time (min)
CT (mg-min/L)
BrO3 (ug/L)
MIB (ng/L)
Geosmin (ng/L)
3.0
3.5
0 5 10 15 20 25 30 35 40 45 50 55 60 65 70 75
filter depth from top (cm)
Figure 7.2 Example result of ozone-biofiltration modeling
100
90
80
70
60
50
40
30
20
10
0
MIB/Geosmin (ng/L) & BrO3 (ug/L)
154

PREDICTING INDIVIDUAL PARAMETER EFFECT
Effect of Ozone Dose on MIB and Geosmin Removal
Ozone dose was selected to vary within the range of 0.5 to 4.0 mg/L, the common
dosages applied in utilities. All the other parameters used in the simulations (Figure
7.3~7.5) were listed in Table 7.6. As shown in Figure 7.3, predicted MIB removals
increased when increasing ozone dose. This observed trend is coinciding with the
ozonation lab results. At reaction time of 4 minutes, predicted MIB removals increased
from 76% to 98% when increased ozone dose from 0.5 mg/L to 3 mg/L. Predicted MIB
removals were 10~20% higher compared with lab results. This could be possibly due to
the inaccuracy of applied rate constants and Rct values. Figure 7.4 shows the disinfection
level CT increased when increasing ozone dose. However, the concentration of
disinfection by product bromate also increased proportionally with increasing CT value.
155

MIB removal %
100
90
80
70
60
50
40
30
20
10
0
0 1 2 3 4
Contact Time (min)
Figure 7.3 Predicted O3 dose effects on MIB removal
Bromate concentration (ug/L) )
30
20
10
0
BrO3- (O3 = 0.5 mg/L) BrO3- (O3 = 1.5 mg/L)
BrO3- (O3 = 3 mg/L) CT (O3 = 0.5 mg/L)
CT (O3 = 1.5 mg/L) CT (O3 = 3 mg/L)
O3 = 0.5 mg/L
O3 = 1.5 mg/L
O3 = 3 mg/L
0 1 2 3 4
Contact Time (min)
Figure 7.4 Predicted O3 dose effects on bromate formation and CT value
0.8
0.6
0.4
0.2
0
CT value (mg-min/L) )
156

Effect of RCT value on MIB and Geosmin Removal
Rct value was selected to vary in the range of 1E-8~15E-8 mole/mole, which was
decided based on the observed lab results of natural water ozonation. Rct values obtained
from ozonation of natural waters were given in Table 7.2. Rct value is a fuction of many
raw water qualities and ozonation conditions. Within the observed Rct range, MIB
removals at a given set of conditions (Table 7.6) could vary around 20% as shown in
Figure 7.5. This means that the accuracy of selected Rct values for different raw water
quality and ozonaiton conditions could directly affect the model prediction of MIB
removals.
MIB removal %
100
90
80
70
60
50
40
30
20
10
0
0 1 2 3 4
Contact Time (min)
Figure 7.5 Predicted RCT value effects on MIB removal
Rct = 1E-8
Rct = 5E-8
Rct = 10E-8
Rct = 15E-8
157

Effect of Operational Parameters in Biofiltration of MIB Removal
158
Two parameters, super facial water velocity (filter loading rate) v (cm/h) and
specific surface area of the biofilm m a (cm-1 ) in the biofiltration module were picked to
be evaluated for the effects on MIB removals. Parameters were selected based on the
operational possibilities of each parameter. Super facial water velocity v could be easily
controlled during operation. Specific surface area of the biofilm a m is largly depending
on the media type that utilities chose. For instance, a larger a m is expected for GAC
media, as it is known as a better biofilm supporter than anthracite or sand media. The
biofilm density Xf represents the biomass amount by weight, which could be calculated
from biofilm specific surface area, biomass density and biofilm thickness by:
Xf= m f L a × × ρ (EQN 7.15)
where, ρ was assumed in the range of 1000~1500 mg-x/cm 3 -biofilm; Lf was using the
average biofilm thickness through the filter. Depending on the regional water qualities,
favorable water qualities could lead to high biofilm density and large biomass amount,
and vise visa. A reasonable range of values for each parameter was selected according to
literature and empirical experience.
Super facial water velocity was selected to vary within the range of 400~2500
cm/h (2~10 gpm/ft 2 ), the normal operational range for biofilters. Biofilm specific surface
area ( a m ) and the associate biomass concentration were selected to vary within the range
of 0.29~11.12 cm -1 (cm 2 /cm 3 ) that covers a wide range of media types including sand,
anthracite, and GAC and dual media. Biomass concentration Xf was calculated from

Equation 7.15 with ρ = 1200 mg-x/cm 3 -biofilm and Lf (Average) = 46 um. Calculations of
a m for different media types could be found in Table 7.4.
159
As shown in Figure 7.6, a m has a stronger effect on the MIB removals in biofilter
than v. MIB removals decreased from around 100% to ~10% when a m decrease from
11.12 to 0.29 cm -1 . While MIB removals varied by up to 10% at m a

RECOMMENDATIONS FOR OPTIMIZING OZONE-BIOFILTRATION
PROCESS
160
Ozonation alone could achieve 40~90% removals of MIB and geosmin,
denpending on the raw water qualities and applied ozone doses. MIB and geosmin initial
concentratons have slight effects on their removals. The suggested ozone dose is within
the range of 0.25~1.0 mg-O3/mg-TOC. MIB and geosmin removal of 40~60% is desired
during ozonation process. Ozonation time is suggested within 3~6 minutes. High ozone
dosages could cause unacceptable DBP (bromate) formation. Low ozone dosages may
reduce BDOC production during ozonation, decrease TOC removal and biomass
development in the following biofilters, as well as get low CT values.
Biofiltration effects could be controlled through majorly two operational
parameters, superfacial water velocity along the filter and biofilm specific surface area.
Lower water velocities could lead to slightly higher MIB removals. Biofilm specific
surface area and the associate biomass density are the factors reflecting the biomass
amount in the biofilter. Biofilm specific surface area is largly decided by media type.
Generally, GAC media has larger surface area than anthracite and sand media, thus better
performance in removing of MIB and geosmin. For different feeding water qualities and
bacteria type, anthracite/sand or GAC/sand dual media may have performance as well as
GAC media.
Future work is needed to develop more sophisticated BDOC-biomass models that
is capable of predicting active biofilm density. A model capable of predicting Rct value is
needed to predict MIB removals more accurately.

CHAPTER 8
CONCLUSIONS AND RECOMMENDATIONS
161
Results from pilot studies, and full-scale utilities surveies showed MIB and
geosmin could be effectively removed by ozone-biofiltration treatment. Bench-scale lab
ozonation experiments illustrated ozonation mechanisms. Modeling results gave the
guidance of optimization of ozone-biofiltration process through controlling of several
operational parameters.
Objective 1: To understand MIB and geosmin ozonation mechanisms by
conducting bentch-scale lab experiments:
• Ozone oxidizes geosmin to a greater extend than MIB in natural waters.
• MIB and geosmin removals increased with increasing in ozone dose, pH,
temperature and H2O2 addition.
• MIB and geosmin percentage removals were independent of their initial
concentrations.
• HO • was the primary oxidant, with less oxidation occurring via molecular
ozone.
• Relative oxidizing rates of MIB and geosmin in natural waters were
controlled by kHO• values (kHO•, MIB = 8.2×10 9 M -1 s -1 , kHO•, geosmin =
1.4×10 10 M -1 s -1 ); KO3 values of MIB and geosmin are in the range of
0.1~10 M -1 s -1 .

162
• Presentation of small amount (0.5 ul/L) of methanol during ozonation has
no observable effects on MIB and geosmin removals in both distilled
water and natural water.
Objective 2: To evaluate MIB and geosmin removals in continuous flow ozone-
biofiltration system by conducting pilot studies: Pilot studies showed MIB and geosmin
removals were a function of many parameters: O3 dose, initial MIB and geosmin and
TOC concentration, water pH, filter media, EBCT, and backwash water and frequency.
Media type and operation of filters have the most important effects on MIB and geosmin
removals. GAC media had the best performance for tasts and odor control, as well as
TOC and particulate removals. Biofilter maintenance is important in taste and odor
control. Backwashing of filters using chlorinated water could damage the biofilm, and
dramatically reduce MIB and geosmin removals. Within the general operational ranges,
increased ozone dose, higher pH, higher EBCT, less initial MIB and TOC concentrations
slightly favor the final MIB removals. Volatization of MIB and geosmin through some
plastic materials were observed. Dense plastic (Teflon) was suggested to stock and
transfer the MIB and geosmin solutions for continuous flow feed system.
Objective 3: To obtain field data of MIB and geosmin removals in operating full-
scale utilities by conducting utility survies: Utilities survey found that ozone-biofiltration
treatment could achieve 60-90% removals of MIB, 60-100% removals of geosmin, and
20-40% removals of TOC in general. Most of the utilities had MIB and geosmin
concentrations under 2 ng/L in ozone-biofiltration treated water. TOC removals by

ozone-biofiltration treatment are as good as, if not better than, by conventional treatment
processes.
Object 4: To predict MIB and geosmin removals by ozone-biofiltration treatment
by developing a model: Modeling results suggested that CT values and removals of MIB
and geosmin and TOC during ozonation are needed to be balance with DBP (bromate)
formations. The recommended ozone dose is 0.25~1.0 mg-O3/mg-TOC to achieve the
desired MIB and geosmin removal of 40~60% by ozonatin. Ozonation time is suggested
within 3~6 minutes. Biofiltration effects could be controlled through majorly two
operational parameters: filter loading rate (EBCT) and biofilm specific surface area
(biomass concentration). Lower water velocity resulted in slightly higher MIB removals.
Biomass concentration has the most important effects on MIB and geosmin removals
during biofiltration process. GAC media filters had larger biomass concentrations and
better performance in removing MIB and geosmin than anthracite and sand media filters.
163
Future work is needed to develop more sophisticated model to help optimizing
ozonation conditions for individual raw water without conducting experiments. More
ozonation experiments are suggested to obtain Rct values for a wide varity of raw water
qualities and ozonation conditions. A model capable of predicting Rct values could be
developed based on the statistical analysis of the lab results. For similar consideration of
biofiltraion module, developing a BDOC-biomass model that is capable of predicting
active biofilm density is suggested.

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180

APPENDIX A
BATCH OZONATION EXPERIMENTS DATA
181

Table A.1
Distilled water ozonation results
Name of
Water Effect Date
O3
spiked
MIB GSM PCBA
T-but
spd
H202
spd
pH DOC O3/DOC Alkalinity
(mg/l as
Temp Time O3 PCBA MIB GSM OE
(mg/L-
O3/O3o PCBA/Po MIB/MIB0 GSM/GSMo 1-MIB/MIBo 1-GSM/GSMo Rct(x10E8) Commnets
exp source of Exp (mg/l) (ng/L) (ng/L) uM (mg/L) (mg/L) (mg/L) ratio
CaCO3) ( oC) (min) (mg/L) (ug/l) (ng/L) (ng/L)
min) fast
No PCBA
113 DI O3 9/30/2002 1 100 0 0 140 0 5 0 24 0 1 52.5 0 1 1 0 0 1 data MIB rate constant test
-
O3
5 0.504 52.66 0 0.504 1.003047619 0 0.003047619 1
measurement:UVA258
rate 11 0.303 53.05 0 0.303 0.35 0 0.65 1 For MIB samples:
use Indigo to quench
constant 16 0.201 49.18 0 0.201 0.936761905 0 0.063238095 1
O3
28 0.088 49.16 0 0.088 0.936380952 0 0.063619048 1
41 0.018 0 0 0 0 1 1
85 0.087 0 0 0 0 1 1
0 0 0 0 1 1
0 0 0 0 1 1
114 DI O3 9/30/2002 2 100 0 0 140 0 5 0 24 0 2 87.14 0 1 1 0 0 1
5 1.346 63.9 0 0.673 0.733302731 0 0.266697269 1
rate 10 1.144 59.98 0 0.572 0.68831765 0 0.31168235 1 For MIB samples:
use Indigo to quench
constant 15 1.003 70.16 0 0.5015 0.805141152 0 0.194858848 1
O3
20 0.841 60.59 0 0.4205 0.695317879 0 0.304682121 1
30 0.491 67.96 0 0.2455 0.779894423 0 0.220105577 1
40 0.247 67.73 0 0.1235 0.777254992 0 0.222745008 1
0 0 0 0 1 1
0 0 0 0 1 1
115~118 DI O3 9/26/2002 3,4,6,8 100 100 0 140 0 5 0 24 1
No PCBA
data
MIB rate constant test
O3
measurement:UVA258
No PCBA
data MIB rate constant test
1 WRONG:
Spiked both MIB and
1
GSM
rate 1 in methanol
constant 1
119 DI O3 9/30/2002 8 100 0 0 140 0 5 0 24 0 8 0 1 1
2 6.743 0 6.743 1
rate 3 7.290 0 7.29 1 For MIB samples:
use Indigo to quench
constant 4 7.274 0 7.274 1
O3
6 7.098 0 7.098 1
8 6.837 0 6.837 1
12 6.754 0 6.754 1
0 0 1
0 0 1
120 DI O3 9/30/2002 6 100 0 0 140 0 5 0 24 0 6 87.14 0 1 1 0 0 1
3 4.527 59.18 0 0.7545 0.679137021 0 0.320862979 1
rate 5 4.402 60.54 0 0.7336667 0.69474409 0 0.30525591 1 For MIB samples:
use Indigo to quench
constant 8 4.209 60.25 0 0.7015 0.691416112 0 0.308583888 1
O3
10 4.003 64.26 0 0.6671667 0.737434014 0 0.262565986 1
15 3.480 69.53 0 0.58 0.797911407 0 0.202088593 1
0 0 0 0 1 1
0 0 0 0 1 1
0 0 0 0 1 1
121 DI O3 9/30/2002 4 100 0 0 140 0 5 0 24 0 4 79.76 0 1 1 0 0 1
3 3.480 55.28 0 0.87 0.693079238 0 0.306920762 1
1
1
1
1
No PCBA
data
No PCBA
data
MIB rate constant test
O3
measurement:UVA258
MIB rate constant test
O3
measurement:UVA258
No PCBA
data MIB rate constant test
O3
measurement:UVA258
rate 5 3.133 67.73 0 0.78325 0.849172518 0 0.150827482 1 For MIB samples:
use Indigo to quench
constant 10 3.075 66.59 0 0.76875 0.834879639 0 0.165120361 1
O3
15 2.910 58.88 0 0.7275 0.738214644 0 0.261785356 1
182

Name of Water Effect Date
O3
spiked MIB GSM PCBA
exp source of Exp (mg/l) (ng/L) (ng/L) uM (mg/L) (mg/L) (mg/L) ratio
T-but
spd
Table A.1 (Continued)
H202
spd pH DOC O3/DOC Alkalinity Temp Time O3 PCBA MIB GSM OE O3/O3o PCBA/Po MIB/MIB0 GSM/GSMo 1-MIB/MIBo 1-GSM/GSMo Rct(x10E8) Commnets
(mg/l as
(mg/L-
CaCO3) ( oC) (min) (mg/L) (ug/l) (ng/L) (ng/L)
min) fast
20 2.734 58.13 0 0.6835 0.728811434 0 0.271188566 1
25 2.376 51.08 0 0.594 0.640421264 0 0.359578736 1
0 0 0 0 1 1
0 0 0 0 1 1
122 DI O3 9/30/2002 3 100 0 0 140 0 5 0 24 0 3 71.28 0 1 1 0 0 1
3 2.427 51.93 0 0.809 0.728535354 0 0.271464646 1
No PCBA
data MIB rate constant test
O3
measurement:UVA258
rate 5 2.290 60.54 0 0.7633333 0.849326599 0 0.150673401 1 For MIB samples:
use Indigo to quench
constant 10 1.999 55.55 0 0.6663333 0.779320988 0 0.220679012 1
O3
15 1.798 57.6 0 0.5993333 0.808080808 0 0.191919192 1
20 1.550 54.86 0 0.5166667 0.769640853 0 0.230359147 1
30 1.012 60.07 0 0.3373333 0.842732884 0 0.157267116 1
0 0 0 0 1 1
0 0 0 0 1 1
123 DI O3 10/17/2002 12 100 100 0 140 0 6 0 24 0 12 1
No PCBA
data
MIB rate constant test
3 9.310 1 WRONG:
Spiked both MIB and
5 9.067 1
GSM
rate 10 8.152 1 with methanol
constant 15 7.269 1
20 6.415 1
25 5.379 1
124 DI O3 10/17/2002 15 100 100 0 140 0 6 0 24 0 15 1
1
1
No PCBA
data
MIB rate constant test
3 11.794 1 WRONG:
Spiked both MIB and
5 11.398 1
GSM
rate 10 10.651 1 with methanol
constant 15 10.316 1
20 9.509 1
25 8.366 1
140 DI pH 11/15/2002 3 100 0 0 140 0 6 0 24 0 3.000 94.83 0 1 1 0 0
-
1
0.5 2.840 104.12 0 0.9466667 1.097964779 0 0.097964779
-
1
rate 1 2.770 106 0 0.9233333 1.117789729 0 0.117789729 1
constant 2 91.83 0 0.8733333 0.968364442 0 0.031635558 1
3 2.620 89.5 0 0.9 0.943794158 0 0.056205842
-
1
5 2.700 107.36 0 0.7633333 1.132131182 0 0.132131182 1
10 2.290 92.5 0 0.6866667 0.975429716 0 0.024570284
-
1
15 2.060 99.65 0 0.58 1.050827797 0 0.050827797
-
1
20 1.740 96.1 0 #REF! 1.013392386 0 0.013392386 1
141 DI pH 11/15/2002 3 100 0 0 140 0 8 0 24 0 3 72.92 0 1 1 0 0
-
1
0.5 75.29 0 0 1.032501371 0 0.032501371 1
rate 1 2.400 72.81 0 0.8 0.998491498 0 0.001508502 1
constant 2 0 0 0 0 1 1
3 1.836 68.57 0 0.940345584 0 0.059654416 1
5 1.498 67.7 0 0.928414701 0 0.071585299 1
10 1.009 65.84 0 0.4993333 0.902907296 0 0.097092704 1
15 0.629 72.54 0 0.3363333 0.99478881 0 0.00521119 1
20 0.261 0 0.2096667 0 0 1 1
142 DI pH 11/15/2002 3 100 0 0 140 0 7 0 24 0 3 84.625 0 1 1 0 0
-
1
0.5 3.113 86.4 0 1.0376667 1.020974889 0 0.020974889
-
1
rate 1 3.629 87.92 0 1.2096667 1.038936484 0 0.038936484 1
1
1
No PCBA
data
No PCBA
data
183

Table A.1 (Continued)
O3
T-but H202
Name of Water Effect Date
spiked MIB GSM PCBA spd
spd pH DOC O3/DOC Alkalinity Temp Time O3 PCBA MIB GSM OE O3/O3o PCBA/Po MIB/MIB0 GSM/GSMo 1-MIB/MIBo 1-GSM/GSMo Rct(x10E8) Commnets
(mg/l as
(mg/L-
exp source of Exp (mg/l) (ng/L) (ng/L) uM (mg/L) (mg/L) (mg/L) ratio
CaCO3) ( oC) (min) (mg/L) (ug/l) (ng/L) (ng/L)
min) fast
No PCBA
143 DI pH 11/15/2002 0 100 0 0 140 0 7 0 24 0 0 84.625 0 1 0 0 1 data
Control experiment
0.5 0 0 0 0 1 1
rate 1 0 0 0 0 1 1
constant 2 0 0 0 0 1 1
ambient 0.5 38.17 0
rate 1 3.970 25.63 0
constant 2 3.758 17.93 0
3 0 73.97 0 0.874091581 0 0.125908419 1
5 0 76.87 0 0.908360414 0 0.091639586 1
10 0 67.47 0 0.797282127 0 0.202717873 1
15 0 0 0 0 1 1
20 0 76.51 0 0.904106352 0 0.095893648 1
3 3.496 11.68 0
5 2.804 5.70 0
10 1.797 3.86 0
15 1.169 3.15 0
20 0.683 2.60 0
1 DI Methanol 11/15/2002 5 100 0 0 0 0 5.7 0 24 0 5 88.25 35 1 1 1 0 0
ambient 0.5 3.307 32.63 17.51 0.6614 0.369745042 0.500305168 0.630254958 0.499694832
rate 1 3.261 26.93 8.24 0.6522 0.305155807 0.235499294 0.694844193 0.764500706
constant 2 2.624 14.78 5.44 0.5248 0.167478754 0.155516756 0.832521246 0.844483244
3 2.109 10.49 3.46 0.4218 0.118866856 0.098803289 0.881133144 0.901196711
5 1.312 8.23 2.59 0.2624 0.09325779 0.07406053 0.90674221 0.92593947
10 0.480 3.79 2.39 0.096 0.042946176 0.068357114 0.957053824 0.931642886
15 0.262 4.12 1.91 0.0524 0.046685552 0.054517944 0.953314448 0.945482056
20 0.311 4.22 0.86 0.0622 0.047818697 0.024491138 0.952181303 0.975508862
301 DI O3 4/4/2003 2 100 100 0.2 0 0 6.04 0 24 0 2 31.34 130.28 113.25 1 1 1 1 0 0 2.76 rate constant test
No PCBA
data
Use MIB stock in
Methanol
0.5 2.217 23.09 53.99 37.17 1.1085 0.736758137 0.414415106 0.328211921 0.585584894 0.671788079 use MIB/GSM
1 2.087 18.53 45.11 27.28 1.0435 0.591257179 0.346254222 0.240883002 0.653745778 0.759116998 without Methanol
1.5 2.040 15.74 36.66 22.51 1.02 0.502233567 0.281393921 0.198763797 0.718606079 0.801236203
3 2.072 11.44 26.33 15.69 1.036 0.365028717 0.202103162 0.138543046 0.797896838 0.861456954
5 1.962 7.75 18.63 11.38 0.981 0.247287811 0.142999693 0.100485651 0.857000307 0.899514349
10 1.854 4.23 7.67 6.69 0.927 0.134971283 0.058873196 0.059072848 0.941126804 0.940927152
15 1.720 2.77 5.89 3.45 0.86 0.08838545 0.045210316 0.030463576 0.954789684 0.969536424
20 1.571 2.01 4.32 3.49 0.7855 0.06413529 0.033159349 0.030816777 0.966840651 0.969183223
302 DI O3 (pH) 4/4/2003 4 100 100 0.2 0 0 6.04 0 24 0 4 31.34 130.28 113.25 1 1 1 1 0 0 2.65 rate constant test
0.5 4.187 6.86 26.96 15.27 1.04675 0.218889598 0.206938901 0.134834437 0.793061099 0.865165563 use MIB/GSM
1 4.088 5.11 16.68 10.09 1.022 0.163050415 0.128031931 0.089094923 0.871968069 0.910905077 without Methanol
1.5 4.096 3.56 11.96 7.07 1.024 0.113592853 0.091802272 0.062428256 0.908197728 0.937571744
3 3.924 0.89 7.51 4.71 0.981 0.028398213 0.057645072 0.041589404 0.942354928 0.958410596
5 3.924 0.38 4.87 3.32 0.981 0.01212508 0.037381025 0.029315673 0.962618975 0.970684327
10 3.482 0.03 3.28 3.41 0.8705 0.000957243 0.025176543 0.030110375 0.974823457 0.969889625
15 3.291 0 3.19 2.86 0.82275 0 0.024485723 0.025253863 0.975514277 0.974746137
20 2.940 0 2.89 2.77 0.735 0 0.02218299 0.024459161 0.97781701 0.975540839
303 DI pH 4/4/2003 4 100 100 0.2 0 0 7.07 0 24 0 4 31.34 130.28 113.25 1 1 1 1 0 0
0.5 3.361 0.00 6.13 2.93 0.84025 0 0.047052502 0.025871965 0.952947498 0.974128035
PCBA
decompose rate constant test
too fast to
be use MIB/GSM
1 3.881 0.00 3.72 3.29 0.97025 0 0.028553884 0.029050773 0.971446116 0.970949227 without Methanol
1.5 3.654 0.00 2.94 1.93 0.9135 0 0.022566779 0.017041943 0.977433221 0.982958057
3 3.226 0.00 3.08 2.04 0.8065 0 0.023641388 0.018013245 0.976358612 0.981986755
5 2.689 0.00 3.44 2.13 0.67225 0 0.026404667 0.018807947 0.973595333 0.981192053
10 2.017 0.00 2.90 2.11 0.50425 0 0.022259748 0.018631347 0.977740252 0.981368653
184

Name of Water Effect Date
O3
spiked MIB GSM PCBA
exp source of Exp (mg/l) (ng/L) (ng/L) uM (mg/L) (mg/L) (mg/L) ratio
T-but
spd
Table A.1 (Continued)
H202
spd pH DOC O3/DOC Alkalinity Temp Time O3 PCBA MIB GSM OE O3/O3o PCBA/Po MIB/MIB0 GSM/GSMo 1-MIB/MIBo 1-GSM/GSMo Rct(x10E8) Commnets
(mg/l as
(mg/L-
CaCO3) ( oC) (min) (mg/L) (ug/l) (ng/L) (ng/L)
min) fast
15 1.597 0.00 0.39925 0 0 0 1 1
20 1.290 0.00 0.3225 0 0 0 1 1
304 DI control 4/4/2003 0 100 100 0 0 0 5.7 0 24 0 0 0 130.28 113.25 0 0 1 1 0 0
PCBA
decompose
too fast to
rate constant test
ambient 0.5 0 0 131.14 109.61 0 0 0.72 0.96785872 0.28
-
0.03214128 be
use MIB/GSM
1 0 0 135.42 110.4 0 0 1.039453485 0.974834437 0.039453485
-
0.025165563 without Methanol
1.5 0 0 147.40 126.04 0 0 1.131409272 1.112935982 0.131409272
-
-0.112935982
3 0 0 134.00 113.34 0 0 1.028553884 1.000794702 0.028553884
-
-0.000794702 control experiment
5 0 0 135.68 112.35 0 0 1.041449186 0.99205298 0.041449186 0.00794702
10 0 0 153.71 126.92 0 0 0.18 1.120706402 0.82
-
-0.120706402
15 0 0 136.08 116.36 0 0 1.044519496 1.027461369 0.044519496 -0.027461369
20 0 0 0 0 0 0 1 1
305 DI O3 4/4/2003 4 100 100 0.2 0 0 7.07 0 24 0 4 31.34 130.28 113.29 1 1 1 1 0 0
0.5 3.729 0 5.26 4.67 0.93225 0 0.040374578 0.041221644 0.959625422 0.958778356
PCBA
decompose rate constant test
too fast to
be
use MIB/GSM
duplicate 1 3.554 0 3.54 3.28 0.8885 0 0.027172244 0.028952246 0.972827756 0.971047754 without Methanol
of #303 1.5 3.534 0 2.60 2.8 0.8835 0 0.019957016 0.024715332 0.980042984 0.975284668
3 3.240 0 2.47 2.24 0.81 0 0.018959165 0.019772266 0.981040835 0.980227734
5 2.687 0 2.72 2.86 0.67175 0 0.020878109 0.025244947 0.979121891 0.974755053 duplicate of #303
10 1.971 0 3.07 3.57 0.49275 0 0.02356463 0.031512049 0.97643537 0.968487951
15 1.520 0 2.39 1.9 0.38 0 0.018345103 0.016771118 0.981654897 0.983228882
20 1.143 0 2.59 2.32 0.28575 0 0.019880258 0.020478418 0.980119742 0.979521582
306 DI pH 4/4/2003 2 100 100 0.2 0 0 7.07 0 24 0 2 31.34 130.28 113.25 1 1 1 1 0 0
0.5 1.872 0 5.33 3.05 0.936 0 0.040911882 0.026931567 0.959088118 0.973068433
PCBA
decompose rate constant test
too fast to
be use MIB/GSM
1 1.792 0 3.64 3.06 0.896 0 0.027939822 0.027019868 0.972060178 0.972980132 without Methanol
1.5 1.763 0 2.47 3.07 0.8815 0 0.018959165 0.027108168 0.981040835 0.972891832
3 1.610 0 2.09 1.8 0.805 0 0.01604237 0.01589404 0.98395763 0.98410596
5 1.359 0 2.11 1.81 0.6795 0 0.016195886 0.01598234 0.983804114 0.98401766
10 1.157 0 2.04 1.63 0.5785 0 0.015658582 0.014392936 0.984341418 0.985607064
15 0.976 0 2.03 1.47 0.488 0 0.015581824 0.012980132 0.984418176 0.987019868
20 0.830 0 2.18 2.22 0.415 0 0.01673319 0.019602649 0.98326681 0.980397351
307 DI pH (O3) 4/4/2003 2 100 100 0.2 0 0 8.07 0 24 0 2 31.34 130.28 113.25 1 1 1 1 0 0
0.5 1.572 0 1.64 4.75 0.786 0 0.012588271 0.041942605 0.987411729 0.958057395
PCBA
decompose rate constant test
too fast to
be
use MIB/GSM
1 1.452 0 1.08 0 0.726 0 0.008289837 0 0.991710163 1 without Methanol
1.5 1.382 0 1.15 0 0.691 0 0.008827142 0 0.991172858 1
3 1.013 0 1.21 0 0.5065 0 0.009287688 0 0.990712312 1
5 0.773 0 1.04 16.75 0.3865 0 0.007982806 0.992017194 1
10 0.473 0 0.2365 0 0 1 1
15 0.343 0 0.1715 0 0 1 1
20 0.254 0 0.127 0 0 1 1
308 DI O3 4/4/2003 4 100 100 0.2 0 0 8.07 0 24 0 4 31.34 130.28 113.25 1 1 1 1 0 0
0.5 2.759 0 2.30 0 0.68975 0 0.017654283 0 0.982345717 1
PCBA
decompose rate constant test
too fast to
be use MIB/GSM
1 2.735 0 0.90 0 0.68375 0 0.006908198 0 0.993091802 1 without Methanol
1.5 2.587 0 1.47 0 0.64675 0 0.01128339 0 0.98871661 1
3 1.833 0 0.58 0 0.45825 0 0.00445195 0 0.99554805 1
5 1.331 0 0.99 1.13 0.33275 0 0.007599018 0.009977925 0.992400982 0.990022075
10 0.876 0 0.219 0 0 0 1 1
15 0.438 0 0.1095 0 0 0 1 1
20 0.469 0 0.11725 0 0 0 1 1
311 DI O3 4/18/2003 0.75 130 130 0.2 0 0 6.04 0 24 0 0.5 36.5111 143.49 131.3 1 1 1 1 0 0 4.01 rate constant test
0.5 0.699 10.6556 31.68 18.88 1.3988571 0.34 0.220781936 0.143792841 0.779218064 0.856207159 use MIB/GSM
1 0.585 9.0886 19.64 12.36 1.1693233 0.29 0.13687365 0.094135567 0.86312635 0.905864433 without Methanol
1.5 0.537 8.1484 25.40 12.81 1.0740451 0.26 0.17701582 0.097562833 0.82298418 0.902437167
3 0.421 6.268 14.40 6.86 0.8411429 0.2 0.100355425 0.052246763 0.899644575 0.947753237
185

Name of Water Effect Date
O3
spiked MIB GSM PCBA
exp source of Exp (mg/l) (ng/L) (ng/L) uM (mg/L) (mg/L) (mg/L) ratio
T-but
spd
Table A.1 (Continued)
H202
spd pH DOC O3/DOC Alkalinity Temp Time O3 PCBA MIB GSM OE O3/O3o PCBA/Po MIB/MIB0 GSM/GSMo 1-MIB/MIBo 1-GSM/GSMo Rct(x10E8) Commnets
(mg/l as
(mg/L-
CaCO3) ( oC) (min) (mg/L) (ug/l) (ng/L) (ng/L)
min) fast
5 0.445 5.1711 7.44 3.99 0.8902256 0.165 0.051850303 0.030388423 0.948149697 0.969611577
10 0.366 3.134 5.14 2.35 0.732391 0.1 0.035821312 0.017897944 0.964178688 0.982102056
15 0.321 2.3505 1.96 0.76 0.642406 0.075 0.013659488 0.005788271 0.986340512 0.994211729
20 1.7237 1.75 0.47 0 0.055 0.012195972 0.003579589 0.987804028 0.996420411
312 DI O3 4/18/2003 1.25 130 130 0.2 0 0 6.04 0 24 0 1.25 36.9812 143.49 131.3 1 1 1 1 0 0 3.01 rate constant test
313 DI
314 DI
0.5 1.261 0 14.90 10.8 1.0086015 0 0.103839989 0.082254379 0.896160011 0.917745621 use MIB/GSM
1 1.286 36.5111 7.96 5.71 1.028812 0.987288136 0.055474249 0.043488195 0.944525751 0.956511805 without Methanol
1.5 1.255 6.5814 7.58 3.66 1.003982 0.177966102 0.052825981 0.027875095 0.947174019 0.972124905
3 1.226 5.1711 3.32 2.76 0.9804992 0.139830508 0.023137501 0.021020564 0.976862499 0.978979436
5 1.138 4.0742 1.72 0.97 0.9100511 0.110169492 0.011986898 0.007387662 0.988013102 0.992612338
10 1.056 2.6639 0 0.00 0.844415 0.072033898 0 0 1 1
15 0.937 1.7237 0.00 0.00 0.7497143 0.046610169 0 0 1 1
20 0.680 0.7835 0.00 0 0.5443368 0.021186441 0 0 1 1
Tbutanol
4/18/2003 2 130 130 0.2 14 0 7.04 0 24 0 2 36.5111 143.49 131.3 1 1 1 1 0 0 0.0272 rate constant test
0.5 1.946 32.2802 90.90 97.03 0.9728722 0.884120172 0.633493623 0.738994669 0.366506377 0.261005331 use MIB/GSM
1 1.922 31.8101 86.73 92.76 0.961203 0.871244635 0.604432365 0.706473724 0.395567635 0.293526276 without Methanol
1.5 1.860 31.4967 111.84 111.39 0.9299248 0.862660944 0.779427138 0.848362529 0.220572862 0.151637471
3 1.821 31.1833 92.63 96.47 0.9105564 0.854077253 0.645550213 0.734729627 0.354449787 0.265270373
5 1.900 31.34 94.74 100.01 0.9498947 0.858369099 0.66025507 0.761690784 0.33974493 0.238309216
10 1.796 31.0266 93.29 98.7 0.8979248 0.849785408 0.650149836 0.751713633 0.349850164 0.248286367
15 1.755 32.1235 95.21 99.13 0.8774737 0.879828326 0.66353056 0.754988576 0.33646944 0.245011424
20 1.620 30.3998 112.65 98.49 0.8102256 0.832618026 0.78507213 0.750114242 0.21492787 0.249885758
Tbutanol
4/18/2003 2 130 130 0.2 7 0 7.04 0 24 0 2 36.5111 143.49 131.3 1 1 1 1 0 0 0.0416 rate constant test
0.5 1.881 31.8101 104.19 96.01 0.9402707 0.871244635 0.726113318 0.7312262 0.273886682 0.2687738 use MIB/GSM
1 1.945 31.6534 100.53 97.29 0.972391 0.86695279 0.700606314 0.740974867 0.299393686 0.259025133 without Methanol
1.5 1.946 33.3771 97.92 92.46 0.9731128 0.91416309 0.682416893 0.70418888 0.317583107 0.29581112
3 1.923 32.1235 62.64 75.57 0.9616842 0.879828326 0.436546101 0.575552171 0.563453899 0.424447829
5 1.890 31.34 95.69 87.84 0.9449624 0.858369099 0.66687574 0.669002285 0.33312426 0.330997715
10 1.721 30.8699 116.79 84.62 0.8605113 0.845493562 0.813924315 0.644478294 0.186075685 0.355521706
15 1.712 29.3029 105.34 84.17 0.8559398 0.802575107 0.734127814 0.641051028 0.265872186 0.358948972
20 1.547 29.4596 96.65 75.7 0.7735338 0.806866953 0.673566102 0.57654227 0.326433898 0.42345773
315 DI control 4/18/2003 0 130 130 0.2 0 0 7.04 0 24 0 0 36.5111 139.96 131.44 0 1 0.975398983 1.00106626 0.024601017 -0.00106626
control
experiment rate constant test
0.5 0.000 28.0493 106.55 88.56 0 0.768240343 0.742560457 0.67448591 0.257439543 0.32551409 use MIB/GSM
1 0.000 35.8843 117.30 108.59 0 0.982832618 0.81747857 0.827037319 0.18252143 0.172962681 without Methanol
1.5 0.000 35.4142 133.46 122.41 0 0.969957082 0.930099659 0.93229246 0.069900341 0.06770754
3 0.000 37.9214 128.76 121.18 0 1.038626609 0.897344763 0.9229246 0.102655237 0.0770754
5 0.000 36.8245 129.64 119.41 0 1.008583691 0.903477594 0.909444021 0.096522406 0.090555979
10 0.000 36.1977 139.96 131.44 0 0.991416309 0.975398983 1.00106626 0.024601017 -0.00106626
15 0.000 36.1977 124.92 111.95 0 0.991416309 0.870583316 0.85262757 0.129416684 0.14737243
20 0.000 36.5111 118.35 111.82 0 1 0.824796153 0.851637471 0.175203847 0.148362529
316 DI t-butanol 11/11/2003 0 100 100 0.2 0.5 0 7.04 0 24 0 1.25 54.630 59.05 93.7181 2.5 1.496245542 0.411548786 0.71377077 0.588451214 0.28622923
control
experiment
rate constant test
0.5 1.112 40.289 47.24 65.6468 2.224 1.103464327 0.329243745 0.499975829 0.670756255 0.500024171 use MIB/GSM
2 1.031 31.517 28.72 38.2626 2.0621714 0.863206977 0.200134281 0.291413356 0.799865719 0.708586644 without Methanol
4 0.913 21.019 24.32 27.6921 1.8253714 0.575691765 0.169499158 0.21090693 0.830500842 0.78909307
7 0.884 14.009 12.01 12.8863 1.7673143 0.3837011 0.083680638 0.098144272 0.916319362 0.901855728
10 0.848 6.743 6.99 7.20478 1.6969143 0.184693495 0.048726466 0.054872627 0.951273534 0.945127373
0 0 0 0 1 1
317 DI t-butanol 11/11/2003 0 100 100 0.2 0.1 0 7.04 0 24 0 1.25 43.897 63.3183 85.0866 2.5 1.202291823 0.441273456 0.648032144 0.558726544 0.351967856
control
experiment
rate constant test
0.5 1.192 18.15269 20.31 23.3512 2.3849143 0.497182738 0.141515732 0.177845783 0.858484268 0.822154217 use MIB/GSM
2 1.110 7.322055 6.56 6.36321 2.2208 0.200543261 0.045693086 0.048463117 0.954306914 0.951536883 without Methanol
4 0.950 0 1.34 1.84418 1.9008 0 0.009332711 0.014045539 0.990667289 0.985954461
7 0.787 0 0.45 0.99282 1.5730286 0 0.003125332 0.0075615 0.996874668 0.9924385
186

Name of Water Effect Date
O3
spiked MIB GSM PCBA
exp source of Exp (mg/l) (ng/L) (ng/L) uM (mg/L) (mg/L) (mg/L) ratio
T-but
spd
Table A.1 (Continued)
H202
spd pH DOC O3/DOC Alkalinity Temp Time O3 PCBA MIB GSM OE O3/O3o PCBA/Po MIB/MIB0 GSM/GSMo 1-MIB/MIBo 1-GSM/GSMo Rct(x10E8) Commnets
(mg/l as
(mg/L-
CaCO3) ( oC) (min) (mg/L) (ug/l) (ng/L) (ng/L)
min) fast
10 0.701 0 0.00 0.90671 1.4011429 0 0 0.006905643 1 0.993094357
318 DI t-butanol 11/11/2003 0 100 100 0.2 0.01 0 7.04 0 24 0 1.25 45.47855 36.9455 61.9943 2.5 1.245608849 0.257477955 0.472157276 0.742522045 0.527842724
1
control
experiment
rate constant test
0.5 1.186 10.33584 5.52 8.8566 2.3725714 0.28308759 0.038481277 0.067453154 0.961518723 0.932546846 use MIB/GSM
1 1.079 2.868497 1.09 1.46058 2.1586286 0.078565073 0.007564914 0.011123995 0.992435086 0.988876005 without Methanol
1.5 0.915 0 0.17 0.76384 1.8304 0 0.001184752 0.005817517 0.998815248 0.994182483
3 0.794 0 0.00 0.87735 1.5885714 0 0 0.006682056 1 0.993317944
5 0.683 0 0.00 0.68164 1.3654857 0 0 0.005191472 1 0.994808528
319 DI t-butanol 11/11/2003 0 100 100 0.2 0 0 7.04 0 24 0 1.25 44.20817 52.0911 77.5234 2.5 1.210814487 0.363029436 0.590429616 0.636970564 0.409570384
1
control
experiment rate constant test
0.5 1.197 0 1.83 3.19069 2.3945143 0 0.012747774 0.024300755 0.987252226 0.975699245 use MIB/GSM
1 1.076 0 0.32 1.09264 2.1517714 0 0.002241434 0.008321698 0.997758566 0.991678302 without Methanol
1.5 0.974 0 0.00 0.84213 1.9488 0 0 0.006413751 1 0.993586249
3 0.842 0 0.00 0.8617 1.6841143 0 0 0.006562809 1 0.993437191
5 0.811 0 0.00 0 1.6224 0 0 0 1 1
320 DI control 11/11/2003 0 100 100 0.2 1 0 7.04 0 24 0 1.25 48.79224 63.3158 105.959 2.5 1.336367402 0.44125594 0.806997967 0.55874406 0.193002033
1
control
experiment rate constant test
0.5 1.055 30.12352 42.21 61.0789 2.1097143 0.825050962 0.294148952 0.465185605 0.705851048 0.534814395 use MIB/GSM
1 0.855 17.83101 22.23 26.9836 1.7106286 0.48837233 0.15493492 0.205511017 0.84506508 0.794488983 without Methanol
1.5 0.912 7.272944 4.31 6.65286 1.8235429 0.199198161 0.030003886 0.050669181 0.969996114 0.949330819
20
3 0.732 0 2.34 4.15947 1.4637714 0 0.016283369 0.031679145 0.983716631 0.968320855
5 0.824 0 1.15 2.90299 1.6470857 0 0.008047041 0.022109597 0.991952959 0.977890403
322 CAP Methanol 7/9/2003 3 50 50 0.5 0 0 ambient 0 24 0 3 78.35 1 1 0 0 1 1 1.87 Methanol Effect Test
0.5 1.153 19.01743 0.3843048 0.242724017 0 0 1 1
1 0.913 14.29613 0.3043048 0.18246499 0 0 1 1 with methanol
(use 10ug/ml M/G
2 0.515 7.398518 0.1716571 0.09442907 0 0 1 1
stock,
3 0.315 12.06014 0.1051429 0.153926487 0 0 1 1 4ul added)
5 0.124 11.14694 0.0414476 0.142271038 0 0 1 1
10 0.011 6.779926 0.0036571 0.08653383 0 0 1 1
15 0.104 5.722071 0.034819 0.073032171 0 0 1 1
20 0 0 0 0 1 1
187

APPENDIX B
PILOT SCALE OZONE-BIOFILTRATION DATA
188

Samples Raw Settled PO
F1 -
T F1 - B
Table B.1
Methyl Isoborneol (MIB, ng/L) result of Chandler pilot test
F2 -
T F2 - B F3 - T F3 - B F4 - T F4 - B F5 - T F5 - B F6 - T F6 - B SMG(PO) LMG SMG LMG
Old
New
Locations
Locations
9/17/2002 3.05 4.18 -- 2.03 0.63 -- -- 2.53 3.24 -- -- -- -- -- --
9/23/2002 2.09 3.38 -- 1.68 0.74 -- -- 2.24 2.41 -- -- -- -- -- --
10/1/2002 -- 5.39 2.45 1.84 0.00 -- 1.10 2.73 2.29 -- 3.09 2.37 0.00 2.41 0.70
10/8/2002 -- 4.23 3.76 1.65 0.00 -- 0.00 3.62 2.85 -- 2.64 2.05 0.00 1.41 0.72
10/15/2002 -- 3.98 3.94 0.88 0.60 -- 0.94 2.27 1.72 -- 1.85 0.84 0.24 1.38 0.43
10/25/2002 4.75 5.43 -- 3.00 1.09 -- 1.05 2.96 3.21 -- 2.63 1.85 1.24 2.84 1.34
10/28/2002 3.29 4.54 -- 16.55 4.35 -- 6.85 23.82 16.35 -- 21.42 2.78 1.46 7.65 3.23
10/29/2002 -- -- -- -- -- -- -- -- -- -- -- -- -- -- -- 4.45 14.02
11/5/2002 1.42 4.11 1.56 0.85 0.96 2.07 2.11 1.56 2.05 1.54 7.09 3.50 4.12 23.66
11/12/2002 0.70 2.48 1.12 0.34 0.85 1.29 0.47 1.13 1.93 0.34 3.75 1.62 2.88 8.47
11/19/2002 3.18 5.01 3.26 2.66 2.18 2.86 2.62 3.25 2.99 2.10 2.65 2.10 3.73 4.16
11/22/2002 0.65 0.00 0.66 0.00 0.82 6.82
1.73(1.5
No Sodium
Thiosulfate) 5.57
11/26/2002
11/28/2002
(still old
0.69 0.79 0.55 0.33 0.61 1.19 0.56 0.96 2.65 0.81 2.76 1.17 1.83 9.6
bags)
12/3/2002
49.89 53.08 31.26 53.98
(new bags) 1.71 13.75 2.13 30.28
12/10/2002 1.15 2.79 2.48 0.90 3.28 1.58 4.79 3.76 4.27 4.30 2.83 0.00 5.73 2.58 5.37 24.36 4.61 5.69
12/17/2002

Samples Raw Settled PO
F1 -
T
F1 -
B
F2 -
T
Table B.2
Geosmin (ng/L) result of Chandler pilot test
F2 -
B
F3 -
T
F3 -
B
F4 -
T
F4 -
B
F5 -
T
F5 -
B
F6 -
T
F6 -
B SMG(PO) LMG SMG LMG
Old
New
Locations
Locations
9/17/2002 0.83 0.98 -- 0.04 0.03 -- -- 0.43 0.60 -- -- -- -- -- --
9/25/2002 0.40 0.71 -- 0.04 0.13 -- -- 0.22 0.14 -- -- -- -- -- --
10/1/2002 -- 0.88 0.38 0.06 0.00 -- 0.03 0.14 0.08 -- 0.05 0.05 0.00 0.09 0.00
10/8/2002 -- 1.04 0.79 0.04 0.00 -- 0.00 0.49 0.14 -- 0.37 0.04 0.00 0.15 0.00
10/15/2002 -- 1.87 1.15 0.09 0.00 -- 0.04 0.96 0.59 -- 0.86 0.13 0.06 0.30 0.08
10/23/2002 2.93 2.28 -- 0.56 0.37 -- 0.36 0.84 0.65 -- 0.51 0.32 0.35 0.51 0.32
10/28/2002 2.41 2.46 -- 0.86 0.76 -- 0.30 0.79 0.52 -- 1.02 0.54 0.30 0.30 0.30
10/29/2002 -- -- -- -- -- -- -- -- -- -- -- -- -- -- -- 1.22 1.95
11/5/2002 1.42 2.35 0.28 0.00 0.00 0.50 0.66 0.37 0.31 0.00 0.46 0.00 2.24 2.80
11/12/2002 1.80 1.38 0.71 0.13 0.25 0.95 0.58 0.61 0.27 0.22 0.54 0.13 0.88 1.27
11/19/2002 1.52 2.17 0.45 0.10 0.10 0.74 0.52 0.71 0.25 0.11 0.37 0.11 1.04 1.73
0.52 0.00 0.14 0.00 0.82 0.99
0.81(0.79
No Sodium
Thiosulfate) 0.84
11/26/2002 1.68 0.09 0.00 0.04 0.00 0.00 0.00 0.00 0.00 0.00 0 0
11/28/2002 1.19 2.13 0.44 2.02
12/3/2002 0.41 0.85 0 0.95
12/12/2002 0.87 3.67 0.23 0.00 0.50 0.00 1.68 1.15 2.09 1.69 0.13 0.00 0.65 0.00 2.11 3.27 1.92 2.76
12/17/2002

#
date
collected lable
Table B.3
Article I. Squaw Peak Pilot Result
date
analyzed MIB(ng/l) GSM(ng/l)
1 4/10/2003 MP P2T3 RW 4/27/2003 8.3 24.41
2 4/10/2003 MP P2T3 SW 4/27/2003 21.4 7.19
3 4/10/2003 MP P2T3 SW(DUP)
4 4/10/2003 MP P2T3 POH 4/27/2003 20.8 22.04
5 4/10/2003 MP P2T3 PON 4/28/2003 6.1 9.36
6 4/10/2003 MP P2T3 ROC 4/28/2003 27.6 7.77
7 4/10/2003 MP P2T3 F13B 4/28/2003 27.5 5.33
8 4/10/2003 MP P2T3 F14B 4/28/2003 14.8 4.09
9 4/10/2003 MP P2T3 F15B 4/28/2003 11.6 1.69
10 4/10/2003 MP P2T3 F16B 4/28/2003 13.9 13.68
11 4/10/2003 MP P2T3 F17B 4/28/2003 19.7 7.11
12 4/10/2003 MP P2T3 F18B 4/28/2003 19.9 11.67
13 4/10/2003 MP P2T3 F19B 4/28/2003 15.5 13.99
14 4/10/2003 MP P2T3 F20B 4/28/2003 12.5 5.54
15 4/16/2003 MP P2T3 RW 5/3/2003 93.9
16 4/16/2003 MP P2T3 SW 4/28/2003 127.7 3.01
17 4/16/2003 MP P2T3 SW(DUP) 5/3/2003 113.0
18 4/16/2003 MP P2T3 POH 5/3/2003 118.5
19 4/16/2003 MP P2T3 PON 5/3/2003 91.6
20 4/16/2003 MP P2T3 ROC 5/3/2003 87.9
21 4/16/2003 MP P2T3 F1B 5/3/2003 177.3
22 4/16/2003 MP P2T3 F2B 5/3/2003 173.5
23 4/16/2003 MP P2T3 F3B 5/3/2003 132.0
24 4/16/2003 MP P2T3 F4B 5/3/2003 101.4
25 4/16/2003 MP P2T3 F5B 4/28/2003 99.2 2.84
26 4/16/2003 MP P2T3 F6B 5/3/2003 78.0
27 4/16/2003 MP P2T3 F7B 5/3/2003 90.7
28 4/16/2003 MP P2T3 F8B 5/3/2003 110.3
29 4/16/2003 MP P2T3 F9B 5/3/2003 140.0
30 4/16/2003 MP P2T3 F10B 5/3/2003 67.7
31 4/16/2003 MP P2T3 F11B 5/3/2003 83.9
32 4/16/2003 MP P2T3 F12B 5/3/2003 54.2
33 4/16/2003 MP P2T3 F13B 5/3/2003 116.3
34 4/16/2003 MP P2T3 F14B 5/3/2003 99.4
35 4/16/2003 MP P2T3 F15B 4/28/2003 82.7 1.36
36 4/16/2003 MP P2T3 F16B 5/3/2003 42.7
37 4/16/2003 MP P2T3 F17B 5/3/2003 104.9
38 4/16/2003 MP P2T3 F18B 5/3/2003 77.4
191

Table B.3 (Continued)
date
date
# collected lable
analyzed MIB(ng/l) GSM(ng/l)
39 4/16/2003 MP P2T3 F19B 5/3/2003 69.6
40 4/16/2003 MP P2T3 F20B 5/3/2003 51.5
41 4/24/2003 MP P2T3 RW 4/26/2003 296.4 7.53
42 4/24/2003 MP P2T3 SW 4/26/2003 175.1 7.66
43 4/24/2003 MP P2T3 SW(DUP) 4/27/2003 202.9
44 4/24/2003 MP P2T3 POH 4/26/2003 110.3 6.91
45 4/24/2003 MP P2T3 PON 4/26/2003 136.7 6.69
46 4/24/2003 MP P2T3 ROC 4/26/2003 148.7 6.54
47 4/24/2003 MP P2T3 F1T 4/26/2003 160.3 6.65
48 4/24/2003 MP P2T3 F1B 4/26/2003 143.1 5.38
49 4/24/2003 MP P2T3 F2T 4/26/2003 130.6 5.65
50 4/24/2003 MP P2T3 F2B 4/26/2003 111.1 5.87
51 4/24/2003 MP P2T3 F3T 4/26/2003 148.1 6.27
52 4/24/2003 MP P2T3 F3B 4/26/2003 137.5 6.96
53 4/24/2003 MP P2T3 F4T 4/26/2003 100.9 4.00
54 4/24/2003 MP P2T3 F4B 4/26/2003 96.6 5.77
55 4/24/2003 MP P2T3 F5T 4/26/2003 127.3 6.49
56 4/24/2003 MP P2T3 F5B 4/26/2003 118.8 5.38
57 4/24/2003 MP P2T3 F6T 4/26/2003 106.7 4.23
58 4/24/2003 MP P2T3 F6B 4/26/2003 63.8 5.04
59 4/24/2003 MP P2T3 F7T 4/26/2003 132.9 6.98
60 4/24/2003 MP P2T3 F7B 4/26/2003 109.5 5.93
61 4/24/2003 MP P2T3 F8B 4/26/2003 97.7 5.42
62 4/24/2003 MP P2T3 F9B 4/26/2003 126.1 8.56
63 4/24/2003 MP P2T3 F10B 4/26/2003 72.1 2.83
64 4/24/2003 MP P2T3 F11B 4/26/2003 92.3 6.14
65 4/24/2003 MP P2T3 F12B 4/26/2003 34.7 0.83
66 4/24/2003 MP P2T3 F13B 4/26/2003 138.9 5.85
67 4/24/2003 MP P2T3 F14B 4/26/2003 66.5 4.19
68 4/24/2003 MP P2T3 F15B 4/26/2003 64.3 4.76
69 4/24/2003 MP P2T3 F16B 4/26/2003 49.2 5.10
70 4/24/2003 MP P2T3 F17B 4/26/2003 70.7 3.58
71 4/24/2003 MP P2T3 F18B 4/27/2003 90.5
72 4/24/2003 MP P2T3 F19B 4/27/2003 92.8
73 4/24/2003 MP P2T3 F20B 4/27/2003 47.1
74 4/30/2003 MP P2T3 RW 5/21/2003 2.8 2.32
75 4/30/2003 MP P2T3 SW 5/21/2003 85.1 2.23
76 4/30/2003 MP P2T3 SW(DUP) 5/21/2003 86.7 2.34
77 4/30/2003 MP P2T3 POH 5/21/2003 34.8 2.15
78 4/30/2003 MP P2T3 POH(dup) 5/30/2003 40.0
79 4/30/2003 MP P2T3 PON 5/21/2003 65.9 1.92
192

#
date
collected lable
Table B.3 (Continued)
date
analyzed MIB(ng/l) GSM(ng/l)
80 4/30/2003 MP P2T3 PON(dup) 5/30/2003 46.3
81 4/30/2003 MP P2T3 ROC 5/21/2003 51.8 3.02
82 4/30/2003 MP P2T3 ROC(dup) 5/30/2003 36.5
83 4/30/2003 MP P2T3 F1B 5/21/2003 86.0 2.44
84 4/30/2003 MP P2T3 F2B 5/30/2003 60.0
85 4/30/2003 MP P2T3 F3B 5/22/2003 72.8 2.08
86 4/30/2003 MP P2T3 F4B 5/22/2003 34.2 1.29
87 4/30/2003 MP P2T3 F5B 5/22/2003 42.8 1.55
88 4/30/2003 MP P2T3 F6B 5/22/2003 20.0 1.20
89 4/30/2003 MP P2T3 F7B 5/30/2003 37.8
90 4/30/2003 MP P2T3 F8B 5/30/2003 46.8
91 4/30/2003 MP P2T3 F9B 5/22/2003 61.1 0.98
92 4/30/2003 MP P2T3 F10B 5/22/2003 38.7 0.20
93 4/30/2003 MP P2T3 F11B 5/22/2003 30.4 0.00
94 4/30/2003 MP P2T3 F12B 5/23/2003 14.7 0.00
95 4/30/2003 MP P2T3 F13B 5/23/2003 42.9 1.77
96 4/30/2003 MP P2T3 F14B 5/23/2003 22.6 0.00
97 4/30/2003 MP P2T3 F15B 5/23/2003 23.0 0.00
98 4/30/2003 MP P2T3 F16B 5/23/2003 17.0 0.00
99 4/30/2003 MP P2T3 F17B 5/23/2003 43.1 0.00
100 4/30/2003 MP P2T3 F18B 5/23/2003 35.5 0.00
101 4/30/2003 MP P2T3 F19B 5/23/2003 40.0 0.00
102 4/30/2003 MP P2T3 F20B 5/23/2003 14.4 0.00
103 5/8/2003 MP P2T3 blk mib new 5/30/2003 0.6
104 5/8/2003 MP P2T3 blk mib old 5/30/2003 3.7
105 5/8/2003 MP P2T3 RW 5/23/2003 14.8 0.73
106 5/8/2003 MP P2T3 SW 5/23/2003 38.4 0.81
107 5/8/2003 MP P2T3 SW(DUP) 5/23/2003 66.0 1.42
108 5/8/2003 MP P2T3 POH 5/23/2003 31.6 1.02
109 5/8/2003 MP P2T3 PON 5/23/2003 30.1 0.04
110 5/8/2003 MP P2T3 ROC 5/23/2003 51.0 1.78
111 5/8/2003 MP P2T3 F1B 5/23/2003 44.1 0.80
112 5/8/2003 MP P2T3 F2B 5/30/2003 24.2
113 5/8/2003 MP P2T3 F3B 5/23/2003 41.9 0.52
114 5/8/2003 MP P2T3 F4B 5/23/2003 26.0 0.24
115 5/8/2003 MP P2T3 F5B 5/23/2003 25.7 0.00
116 5/8/2003 MP P2T3 F6B 5/24/2003 15.3 0.00
117 5/8/2003 MP P2T3 F7B 5/30/2003 19.9
118 5/8/2003 MP P2T3 F8B 5/30/2003 21.5
119 5/8/2003 MP P2T3 F9B 5/24/2003 26.3 0.00
120 5/8/2003 MP P2T3 F10B 5/24/2003 18.0 0.00
193

Table B.3 (Continued)
date
date
# collected lable
analyzed MIB(ng/l) GSM(ng/l)
121 5/8/2003 MP P2T3 F11B 5/24/2003 16.1 0.00
122 5/8/2003 MP P2T3 F12B 5/24/2003 8.8
123 5/8/2003 MP P2T3 F13B 5/24/2003 37.7
124 5/8/2003 MP P2T3 F14B 5/24/2003 17.4
125 5/8/2003 MP P2T3 F15B 5/24/2003 6.9
126 5/8/2003 MP P2T3 F16B 5/24/2003 5.1
127 5/8/2003 MP P2T3 F17B 5/24/2003 66.3
128 5/8/2003 MP P2T3 F18B 5/24/2003 51.0 0.00
129 5/8/2003 MP P2T3 F19B 5/24/2003 63.6 0.13
130 5/8/2003 MP P2T3 F20B 5/24/2003 30.4
131 5/12/2003 MP P2T3 blk 5/30/2003 81.5
132 5/12/2003 MP P2T3 RW 5/30/2003 0.5
133 5/12/2003 MP P2T3 SW 5/30/2003 32.0
134 5/12/2003 MP P2T3 SW(DUP) 5/30/2003 212.1
135 5/12/2003 MP P2T3 POH 5/30/2003 27.7
136 5/12/2003 MP P2T3 PON 5/30/2003 23.6
137 5/12/2003 MP P2T3 ROC 5/31/2003 40.5 2.30
138 5/12/2003 MP P2T3 F1B 5/31/2003 30.7 1.00
139 5/12/2003 MP P2T3 F2B 5/31/2003 29.1 0.62
140 5/12/2003 MP P2T3 F3B 5/31/2003 30.7 0.86
141 5/12/2003 MP P2T3 F4B 5/31/2003 13.8 0.00
142 5/12/2003 MP P2T3 F5B 5/31/2003 174.7 2.96
143 5/12/2003 MP P2T3 F6B 5/31/2003 9.7 0.00
144 5/12/2003 MP P2T3 F7B 5/31/2003 18.9 0.00
145 5/12/2003 MP P2T3 F8B 5/31/2003 21.2 0.32
146 5/12/2003 MP P2T3 F9B 5/31/2003 23.1 0.32
147 5/12/2003 MP P2T3 F10B 5/31/2003 14.2 0.00
148 5/12/2003 MP P2T3 F11B 5/31/2003 11.3 0.00
149 5/12/2003 MP P2T3 F12B 5/31/2003 3.4 0.00
150 5/12/2003 MP P2T3 F13B 5/31/2003 19.5 0.68
151 5/12/2003 MP P2T3 F14B 5/31/2003 11.5 0.00
152 5/12/2003 MP P2T3 F15B 5/31/2003 3.9 0.00
153 5/12/2003 MP P2T3 F16B 5/31/2003 2.0 0.00
154 5/12/2003 MP P2T3 F17B 5/31/2003 23.6 0.30
155 5/12/2003 MP P2T3 F18B 5/31/2003 13.3 0.00
156 5/12/2003 MP P2T3 F19B 5/31/2003 24.0 0.20
157 5/12/2003 MP P2T3 F20B 5/31/2003 132.2 1.77
158 5/14/2003 MP P2T3 blk 5/24/2003 24.7 0.00
159 5/14/2003 MP P2T3 SW 5/24/2003 152.0 3.80
160 5/14/2003 MP P2T3 POH 5/24/2003 77.8 1.83
161 5/14/2003 MP P2T3 ROC 5/24/2003 62.8 2.44
194

Table B.3 (Continued)
date
date
# collected lable
analyzed MIB(ng/l) GSM(ng/l)
162 5/14/2003 MP P2T3 ROC(dup) 5/24/2003 53.4 2.28
163 5/14/2003 MP P2T3 F13B 5/24/2003 58.3 1.48
164 5/14/2003 MP P2T3 F15B 5/30/2003 40.5 0.90
165 5/14/2003 MP P2T3 F16B 5/30/2003 19.4 0.00
166 5/14/2003 MP P2T3 F17B 5/30/2003 51.8 0.98
167 5/14/2003 MP P2T3 F18B 5/30/2003 42.3 0.20
168 5/14/2003 MP P2T3 F19B 5/30/2003 34.9
169 5/14/2003 MP P2T3 F20B 5/30/2003 29.3
170 6/18/2003 MP P2T3 POH 7/27/2003 36.1 2.44
171 6/18/2003 MP P2T3 F12B 7/26/2003 13.8 0.00
172 6/18/2003 MP P2T3 F13B 7/26/2003 42.1 2.06
173 6/18/2003 MP P2T3 F15B 7/27/2003 9.0 0.00
174 6/18/2003 MP P2T3 F16B 7/27/2003 11.5 0.01
175 6/18/2003 MP P2T3 F17B 7/27/2003 34.1 1.60
176 6/18/2003 MP P2T3 F18B 7/27/2003 2.4 0.00
177 6/18/2003 MP P2T3 F19B 7/27/2003 1.8 0.00
178 6/18/2003 MP P2T3 F20B 7/27/2003 25.5 0.74
179 6/20/2003 MP P2T3 RW 8/9/2003 5.2 5.32
180 6/20/2003 MP P2T3 SW 8/9/2003 45.4 5.19
181 6/20/2003 MP P2T3 SW(DUP) 8/10/2003 56.1 4.77
182 6/20/2003 MP P2T3 POH 8/9/2003 31.3 3.30
183 6/20/2003 MP P2T3 PON 8/10/2003 30.1 3.54
184 6/20/2003 MP P2T3 F13B 8/10/2003 36.8 3.42
185 6/20/2003 MP P2T3 F15B 8/10/2003 10.9 1.15
186 6/20/2003 MP P2T3 F16B 8/10/2003 8.6 1.24
187 6/20/2003 MP P2T3 F17B 8/10/2003 25.5 2.47
188 6/20/2003 MP P2T3 F18B 8/10/2003 6.5 0.98
189 6/20/2003 MP P2T3 F19B 8/10/2003 7.0 0.90
190 6/20/2003 MP P2T3 F20B 8/10/2003 24.1 1.91
191 6/24/2003 MP P2T3 RW 8/2/2003 6.0 3.61
192 6/24/2003 MP P2T3 SW 8/2/2003 37.2 4.18
193 6/24/2003 MP P2T3 POH 8/2/2003 30.2 2.53
194 6/24/2003 MP P2T3 PON 8/2/2003 31.0 2.57
195 6/24/2003 MP P2T3 ROC 8/2/2003 58.9 6.42
196 6/24/2003 MP P2T3 F1B 8/2/2003 43.5 4.51
197 6/24/2003 MP P2T3 F2B 8/2/2003 35.7 3.02
198 6/24/2003 MP P2T3 F3B 8/2/2003 30.7 3.05
199 6/24/2003 MP P2T3 F4B 8/2/2003 3.3 0.00
200 6/24/2003 MP P2T3 F5B 8/2/2003 5.3 0.00
201 6/24/2003 MP P2T3 F6B 8/6/2003 4.2 0.00
202 6/24/2003 MP P2T3 F7B 8/6/2003 17.3 0.68
195

Table B.3 (Continued)
date
date
# collected lable
analyzed MIB(ng/l) GSM(ng/l)
203 6/24/2003 MP P2T3 F8B 8/6/2003 25.9 2.40
204 6/24/2003 MP P2T3 F9B 8/6/2003 26.5 2.04
205 6/24/2003 MP P2T3 F10B 8/6/2003 2.3 0.00
206 6/24/2003 MP P2T3 F11B 8/6/2003 2.6 0.00
207 6/24/2003 MP P2T3 F12B 8/6/2003 7.2 0.00
208 6/24/2003 MP P2T3 F13B 8/6/2003 22.3 1.96
209 6/24/2003 MP P2T3 F14B 8/6/2003 8.5 0.05
210 6/24/2003 MP P2T3 F15B 8/6/2003 6.6 0.00
211 6/24/2003 MP P2T3 F16B 8/9/2003 8.8 0.21
212 6/24/2003 MP P2T3 F17B 8/9/2003 22.7 1.21
213 6/24/2003 MP P2T3 F18B 8/9/2003 5.6 0.00
214 6/24/2003 MP P2T3 F19B 8/9/2003 5.2 0.00
215 6/24/2003 MP P2T3 F20B 8/9/2003 19.2 0.61
216 6/26/2003 MP P2T3 RW 7/27/2003 4.2 3.61
217 6/26/2003 MP P2T3 SW 7/27/2003 44.6 5.52
218 6/26/2003 MP P2T3 POH 7/27/2003 15.9 2.29
219 6/26/2003 MP P2T3 PON 7/27/2003 35.5 2.72
220 6/26/2003 MP P2T3 ROC 7/27/2003 31.3 6.17
221 6/26/2003 MP P2T3 F1B 7/27/2003 59.7 6.04
222 6/26/2003 MP P2T3 F2B 7/27/2003 46.7 4.07
223 6/26/2003 MP P2T3 F3B 7/27/2003 44.4 3.87
224 6/26/2003 MP P2T3 F4B 7/27/2003 3.1 0.00
225 6/26/2003 MP P2T3 F5B 7/27/2003 4.8 0.00
226 6/26/2003 MP P2T3 F6B 7/27/2003 5.7 0.00
227 6/26/2003 MP P2T3 F7B 7/27/2003 25.3 0.67
228 6/26/2003 MP P2T3 F19B 7/31/2003 4.0 0.0
229 6/26/2003 MP P2T3 F20B 7/31/2003 14.7 1.2
230 6/26/2003 MP P2T3 F1T 7/31/2003 52.0 5.7
231 6/26/2003 MP P2T3 F2T 7/31/2003 48.1 5.0
232 6/26/2003 MP P2T3 F3T 7/31/2003 44.0 4.7
233 6/26/2003 MP P2T3 F4T 7/31/2003 12.4 0.3
234 6/26/2003 MP P2T3 F5T 7/31/2003 15.9 0.4
235 6/26/2003 MP P2T3 F6T 7/31/2003 32.0 2.6
236 6/26/2003 MP P2T3 F7T 7/31/2003 35.2 3.4
237 6/26/2003 MP P2T3 F8T 8/1/2003 34.5 3.1
238 6/26/2003 MP P2T3 F9T 8/1/2003 33.2 3.0
239 6/26/2003 MP P2T3 F10T 8/1/2003 10.2 0.0
240 6/26/2003 MP P2T3 F11T 8/1/2003 11.5 0.1
241 6/26/2003 MP P2T3 F12T 8/1/2003 24.3 1.3
242 6/26/2003 MP P2T3 F13T 8/1/2003 21.8 4.4
243 6/26/2003 MP P2T3 F14T 7/31/2003 10.1 0.8
196

Table B.3 (Continued)
date
date
# collected lable
analyzed MIB(ng/l) GSM(ng/l)
244 6/26/2003 MP P2T3 F15T 7/31/2003 8.8 0.8
245 6/26/2003 MP P2T3 F16T 7/31/2003 22.8 3.8
246 6/26/2003 MP P2T3 F17T 7/31/2003 15.1 2.3
247 6/26/2003 MP P2T3 F18T 8/1/2003 7.9 0.2
248 6/26/2003 MP P2T3 F19T 8/1/2003 6.8 0.0
249 6/26/2003 MP P2T3 F20T 8/1/2003 16.3 2.1
250 6/27/2003 MP P2T3 SW 8/1/2003 204.0 5.4
251 6/27/2003 MP P2T3 PON 8/1/2003 193.1 4.0
252 6/27/2003 MP P2T3 F1B 8/1/2003 316.8 6.8
253 6/27/2003 MP P2T3 F2B 8/1/2003 266.6 4.6
254 6/27/2003 MP P2T3 F3B 8/1/2003 278.6 5.2
255 6/27/2003 MP P2T3 F4B 8/1/2003 245.7 2.0
256 6/27/2003 MP P2T3 F5B 8/1/2003 257.1 2.1
257 6/27/2003 MP P2T3 F6B 8/1/2003 208.6 2.5
258 6/27/2003 MP P2T3 F7B 8/1/2003 167.1 1.8
259 6/27/2003 MP P2T3 F8B 8/1/2003 198.0 3.8
260 6/27/2003 MP P2T3 F9B 8/1/2003 175.2 3.0
261 6/27/2003 MP P2T3 F10B 8/1/2003 127.6 1.0
262 6/27/2003 MP P2T3 F11B 8/2/2003 7.4 0.0
263 6/27/2003 MP P2T3 F12B 8/2/2003 187.7 1.8
264 7/28/2003 MP P2T3 POH 8/2/2003 288.1 4.2
265 7/28/2003 MP P2T3 ROC 8/2/2003 301.7 8.7
266 7/28/2003 MP P2T3 F13B 8/2/2003 178.9 3.1
267 7/28/2003 MP P2T3 F14B 8/2/2003 112.5 1.0
268 7/28/2003 MP P2T3 F15B 8/2/2003 134.1 1.5
269 7/28/2003 MP P2T3 F16B 8/2/2003 93.2 1.1
270 7/28/2003 MP P2T3 F17B 8/2/2003 142.8 2.2
271 7/28/2003 MP P2T3 F18B 8/2/2003 83.1 0.6
272 7/28/2003 MP P2T3 F19B 8/2/2003 165.7 1.2
273 7/28/2003 MP P2T3 F20B 8/2/2003 112.5 1.5
Notes: MP: Macollm Pirnie Inc.
P2T3: Job number
F1 T ~ F20 T: Filter # 1 Top ~ Filter # 20 Top
F1 B ~ F20 :B Filter # 1 Bottom ~ Filter # 20 Bottom
RW: Raw water
SW: Settled water
POH: Post ozonated High TOC water
PON: Post ozonated Normal TOC water
ROC: High TOC water
197

APPENDIX C
FULL SCALE OZONE-BIOFILTRATION DATA
198

Table C.1
Utilities data table (2002)
Utility name Location DATE DATE MIB GSM TOC
sampled analyzed (ng/l) (ng/l) (mg/l) O3 dose(mg/l) Water PH
Gilbert raw 12,Aug 17,Aug 6.04 1.48 1.349
Gilbert pre O3 12,Aug 17,Aug 5.9 1.12 1.316
Gilbert Post O3 12,Aug 17,Aug 3.03 0.52 1.502
Gilbert Pre filt 1 12,Aug 17,Aug 2.51 0.37 1.431
Gilbert post filt 1 12,Aug 17,Aug 0.57 0 1.128
Gilbert pre filt 2 12,Aug 17,Aug 1.99 0.43 1.324
Gilbert post filt 2 12,Aug 17,Aug 0.7 0 1.174
Gilbert treated 12,Aug 17,Aug 0.88 0 1.136
Gilbert raw 12,Aug 17,Aug 6.03 1.45 1.532
Gilbert pre O3 12,Aug 17,Aug 5.17 1.14 1.336
Gilbert Post O3 12,Aug 17,Aug 2.93 0.42 1.488
Gilbert Pre filt 1 12,Aug 17,Aug 2.03 0.32 1.626
Gilbert post filt 1 12,Aug 17,Aug 0.59 0 1.079
Gilbert pre filt 2 12,Aug 17,Aug 2.47 0.31 1.465
Gilbert post filt 2 12,Aug 17,Aug 0.52 0 1
Gilbert treated 12,Aug 17,Aug 0.97 0 1.209
WTP Water Quality data
Fort Worth raw 27,Aug 29,Aug 11.88 7.11 4.480 7.67
Fort Worth pre O3 27,Aug 29,Aug 12.65 7.26 4.665 7.67
Fort Worth Post O3 27,Aug 29,Aug 3.92 2.66 4.863 3.55
8.73
Fort Worth Pre filt 1 27,Aug 29,Aug 2.67 2.27 4.308 8.73
Fort Worth post filt 1 27,Aug 29,Aug 0.85 0.57 3.502 8.25
Fort Worth pre filt 2 27,Aug 29,Aug 2.54 2.67 4.359 8.73
Fort Worth post filt 2 27,Aug 29,Aug 0.83 0.83 3.552 8.25
Fort Worth treated 27,Aug 29,Aug 0.91 0.66 3.606
8.25
Filter loading
rate
1A= 4.3MG
2A= 4.0MG
flow
rate(MGD)
55.9
55.9
199

Table C.1 (Continued)
Utility name Location DATE DATE MIB GSM TOC
WTP Water
Quality data
sampled analyzed (ng/l) (ng/l) (mg/l) O3 dose(mg/l) Water PH
Fort Worth raw 03,Sep 13,Sep 13.73 6.94 4.82 7.58
Fort Worth pre O3 03,Sep 13,Sep 12.45 6.43 5.239 7.58
Fort Worth Post O3 03,Sep 13,Sep 2.78 1.35 5.151 3.42
8.76
Fort Worth Pre filt 1 03,Sep 13,Sep 4.32 1.96 4.424 8.76
Fort Worth post filt 1 03,Sep 13,Sep 1.88 0.15 3.799 8.38
Fort Worth pre filt 2 03,Sep 13,Sep 4.47 2.11 4.105 8.76
Fort Worth post filt 2 03,Sep 13,Sep 1.39 0.46 3.269 8.38
Fort Worth treated 03,Sep 13,Sep 0.96 0.38 3.462
Ann Arbor raw 29,Aug 13,Sep --- --- 4.558 7.8/7.3 river/well
8.38
Filter loading
rate
1A= 4.26MG
2A= 4.27MG
flow
rate(MGD)
Ann Arbor pre O3 29,Aug 13,Sep 9.47 22.01 2.486 7.7 21.7
Ann Arbor Post O3
Pre filt
29,Aug 13,Sep 1.39 1.94 2.515 7.700
Ann Arbor 1(#17) 29,Aug 13,Sep 1.34 2.02 2.332
2.25
9.300 17.94/2.95
Ann Arbor post filt 1
pre filt
29,Aug 13,Sep 0.99 0.5 1.959 9.300 river/well
Ann Arbor 2(#11) 29,Aug 13,Sep 1.59 2.2 2.393 9.300 2.45 gal/min-ft2
Ann Arbor post filt 2 29,Aug 13,Sep 1.4 0.84 2.043 9.300
Ann Arbor treated 29,Aug 13,Sep 0.96 0.49 2.038
Ann Arbor raw 15,Oct 20,Oct 3.02 4.46 4.675
9.300
8.2/7.4
RIVER/WELL
Ann Arbor pre O3 15,Oct 20,Oct 2.84 4.42 2.676 7.400 15.9
Ann Arbor Post O3
Pre filt
15,Oct 20,Oct 0.41 0.79 2.604 7.4
Ann Arbor 1(#17) 15,Oct 20,Oct 1.32 1 2.556 1.94
9.3 1.1 MGD
Ann Arbor post filt 1
pre filt
15,Oct 20,Oct 0.44 0.43 2.244 9.3
2.36 gal/min-ft2
Ann Arbor 2(#9) 15,Oct 20,Oct 1.14 1.15 2.607 9.3 1.1 MGD
Ann Arbor post filt 2 15,Oct 20,Oct 0 0.03 2.126
9.3
60
60
12.17/2.96
200

Table C.1 (Continued)
Utility name Location DATE DATE MIB GSM TOC
WTP Water
Quality data
sampled analyzed (ng/l) (ng/l) (mg/l) O3 dose(mg/l) Water PH
Filter loading
rate
flow
rate(MGD)
Ann Arbor treated 15,Oct 20,Oct 0.52 0.39 2.207 9.3 river/well
Philadelphia raw 19,Sep 26,Sep 5.25 4.52 3.644 7.8 30.8 gpm
Philadelphia pre O3 19,Sep 26,Sep 4.45 3.83 2.854 6.6 6 gpm
Philadelphia Post O3 19,Sep 26,Sep 2.53 2.07 2.974 6.6 4 gpm
Philadelphia Pre filt 1 19,Sep 26,Sep 3.79 1.85 2.969 6.6 4 gpm
Philadelphia post filt 1 19,Sep 26,Sep 1.5 0.8 2.332 6.7 4.0 gpm/ft2 0.8 gpm
Philadelphia
Philadelphia
Philadelphia
Milwaukee raw 23,Sep 27,Sep 0.5 1.05 1.835
Milwaukee pre O3 23,Sep 27,Sep 0.71 0.51 1.83
Milwaukee Post O3 23,Sep 27,Sep 0.54 0.59 1.875
Milwaukee Pre filt 1 23,Sep 27,Sep 0.58 0.1 1.482
Milwaukee post filt 1 23,Sep 27,Sep 0.68 0.1 1.454
Milwaukee pre filt 2 23,Sep 27,Sep 0.49 0.11 1.453
Milwaukee post filt 2 23,Sep 27,Sep 0.32 0.08 1.56
Milwaukee treated 23,Sep 27,Sep 0.27 0.11 1.53
Milwaukee raw 23,Sep 03,Oct 0.56 2.9 2.065
Milwaukee pre O3 23,Sep 03,Oct 0.38 0.47 1.868
Milwaukee Post O3 23,Sep 03,Oct 0.43 0.56 1.919
Milwaukee Pre filt 1 23,Sep 03,Oct 0.65 0.21 1.459
Milwaukee post filt 1 no sample
Milwaukee pre filt 2 broken
0.9
201

Table C.1 (Continued)
Milwaukee post filt 2 23,Sep 03,Oct 0.54 0.28 1.451
Milwaukee treated 23,Sep 03,Oct 0.21 0.19 1.534
CLCJA raw 14,Oct 20,Oct 0 1.99 1.89
CLCJA pre O3 14,Oct 20.Oct 0 1.15 2.033
CLCJA Post O3 14,Oct 20.Oct 0 0.6 1.964
CLCJA Pre filt 1 14,Oct 20.Oct 0 0.39 1.915
CLCJA post filt 1 14,Oct 20.Oct 0 0 1.503
CLCJA pre filt 2 14,Oct 20.Oct 0 0.55 1.838
CLCJA post filt 2 14,Oct 20.Oct 0 0 1.336
CLCJA treated 14,Oct 20.Oct 0 0 1.513
202

Table C.2
Utilities data table (2003)
Utility name Location DATE DATE MIB GSM TOC
sampled analyzed (ng/l) (ng/l) (mg/l)
Gilbert RW 9/25/2003 9/26/2003 2.5 0.8 1.3
Gilbert SW 9/25/2003 9/26/2003 13.8 2.4 1.3
Gilbert Post O3 9/25/2003 9/26/2003 9.8 1.2 1.5
Gilbert Pre filters 9/25/2003 9/26/2003 7.6

Table C.2 (Continued)
Utility name Location DATE DATE MIB GSM TOC
sampled analyzed (ng/l) (ng/l) (mg/l)
WTP
Water
Quality
data
O3
dose(mg/l)
Ann Arbor pre filt 2(#22) 5/21/2003 5/22/2003

Table C.2 (Continued)
Utility name Location DATE DATE MIB GSM TOC
sampled analyzed (ng/l) (ng/l) (mg/l)
Milwaukee Post O3 5/12/2003 5/18/2003 2 2.3 2.3
Contra Costa WD post filt 4 6/18/2003 7/24/2003 >2 >2 1.5
Contra Costa WD treated 6/18/2003 7/24/2003 >2 >2 1.6
WTP
Water
Quality
data
O3
dose(mg/l)
2.605
Water
PH
Filter
loading
rate
flow
rate(MGD)
205

Table C.2 (Continued)
Utility name Location DATE DATE MIB GSM TOC
sampled analyzed (ng/l) (ng/l) (mg/l)
WTP
Water
Quality
data
O3
dose(mg/l)
Chandler WTP Raw 9/10/2003 9/10/2003 8.9 4.4 2.1 7.83 40
Chandler WTP SW 9/10/2003 9/11/2003 4.4 0.6 1.6 40
Chandler WTP Prefilters 9/10/2003 9/10/2003 3.1 0.4 40
Chandler WTP Prefilters (Dup) 9/10/2003 9/10/2003 3.2 0.8 O3 was
40
Chandler WTP Postfil #2 9/10/2003 9/10/2003 3.2 0.0
NOT applied
3.7
40
Chandler WTP Post filt #4 9/10/2003 9/10/2003 3.5 0.0 1.6 gpm/sqft 40
Chandler WTP treated 9/10/2003 9/10/2003 4.1 0.0 1.3 7.35
Design
40
Chandler WTP
rate = 4.6
Water
PH
Filter
loading
rate
flow
rate(MGD)
Peoria WTP Raw 9/10/2003 9/11/2003 14.2 1.5 8.23 10.047
Peoria WTP SW 9/10/2003 9/11/2003 10.5 0.1 10.728
Peoria WTP Post O3 9/10/2003 9/11/2003 17.9 2.1 instrument 7.67
Peoria WTP Prefilters 9/10/2003 9/11/2003 11.9 1.2 problem 7.69
Peoria WTP Prefilters (Dup) 9/10/2003 9/11/2003 9.6 1.2
1.2
Peoria WTP Postfil #1 9/10/2003 9/11/2003 2.0 0.0
Peoria WTP Post filt #6 9/10/2003 9/11/2003 1.5 0.0
Peoria WTP treated 9/10/2003 9/11/2003 2.2 0.0
7.82
2.65
gpm/ft2
0.92
gpm/ft2
206

1.
AAWTP
Water
samples
Biomass
samples
1.
AAWTP
Water
samples
Biomass
samples
Table C.3
Utilities survey results for ozone-biofiltration treatment of MIB and geosmin
207
Sampling
8/23/2002 10/15/2002
location MIB Geosmin TOC MIB Geosmin TOC
(ng/L) (ng/L) (mg/L) (ng/L) (ng/L) (mg/L)
Raw --- --- 4.6 3.02 4.46 4.7
Pre O3 9.47 22.01 2.5 2.84 4.42 2.7
Post O3 1.39 1.94 2.5 0.41 0.79 2.6
Prefilt 1 1.34 2.02 2.3 1.32 1 2.6
Postfilt 1 0.99 0.5 2.0 0.44 0.43 2.2
Prefilt 2 1.59 2.2 2.4 1.14 1.15 2.6
Postfilt 2 1.4 0.84 2.0 0 0.03 2.1
Treated 0.96 0.49 2.0 0.52 0.39 2.2
Top
3in of
filters
1
Sampling
5/21/2003 10/11/2003
location MIB MIB MIB MIB Geosmin TOC
(ng/L) (ng/L) (ng/L) (ng/L) (ng/L) (mg/L)
Raw 2.6 2.6 2.6 9.2 6.8
Pre O3 1.7 1.7 1.7 15.1 11.9
Post O3 1.1 1.1 1.1 12.8 3.3
Prefilt 1 0.8 0.8 0.8 10.0 2.6
Postfilt 1 0.6 0.6 0.6 12.6 0.8
Prefilt 2 0.9 0.9 0.9 10.5 2.2
Postfilt 2 0.8 0.8 0.8 9.9 0.7
Treated 0.7 0.7 0.7 12.8 0.7
Top
3in of
filters
1 67.4 nmole-PO4 - /g-dry wt

2.
CLCJA
Water
samples
Biomass
samples
3.
CWTP
Water
samples
Biomass
samples
Table C.3 (Continued)
Sampling
2002 2003
location MIB Geosmin TOC MIB Geosmin TOC
(ng/L) (ng/L) (mg/L) (ng/L) (ng/L) (mg/L)
Raw 0 2.0 1.9
Pre O3 0 1.2 2.0
Post O3 0 0.6 2.0
Prefilt 1 0 0.4 1.9
Postfilt 1 0 0 1.5
Prefilt 2 0 0.6 1.8
Postfilt 2 0 0 1.3
Treated 0 0 1.5
1 302.4 nmole-PO4 - 2
/g-dry wt
304.1 nmole-PO4 - Top
3in of
filters 3
/g-dry wt
219.9 nmole-PO4 - /g-dry wt
Sampling
2003
location
MIB Geosmin TOC
(ng/L) (ng/L) (mg/L)
Raw 8.9 4.4 2.1
SW 4.4 0.6 1.6
Prefilt 1 3.1 0.4
Postfilt 1 3.2 0
Prefilt 2 3.2 0.8
Postfilt 2 3.5 0 1.6
Treated 4.1 0 1.3
1 121.6 nmole-PO4 - /g-dry wt
2 153.6 nmole-PO4 - Top
3in of
filters 3
/g-dry wt
113.2 nmole-PO4 - /g-dry wt
208

4.
CCWD
Water
samples
Biomass
samples
8.
PGWTP
Water
samples
Biomass
samples
Table C.3 (Continued)
Sampling
6/11/03 2003
location MIB Geosmin TOC MIB Geosmin TOC
(ng/L) (ng/L) (mg/L) (ng/L) (ng/L) (mg/L)
Raw 2.3 10.4 3.3 2.6 13.4 3.6
Pre O3 2.1 8.4 2.4 2.8 10.6 2.4
Post O3 1.3 4.1 2.4 1.8 4.5 2.4
Prefilt 1 1.1 3.0 2.2 1.1 3.1 2.5
Postfilt 1 0 1.5 1.8 1.1 2.8 1.6
Prefilt 2 1.0 2.3 2.8 0.6 2.7 2.3
Postfilt 2 0 1.3 1.6 0.5 1.0 1.5
Treated 0 1.8 1.8 0.6 2.3 1.6
Top 1
3in of 2
filters 3
Sampling
2003
location
MIB Geosmin TOC
(ng/L) (ng/L) (mg/L)
Raw 14.2 1.5
Pre O3 10.5 0.1
Post O3 17.9 2.1
Prefilt 1 11.9 1.2
Postfilt 1 2.0 0
Prefilt 2 9.6 1.2
Postfilt 2 1.5 0
Treated 2.2 0
1 186.4 nmole-PO4 - /g-dry wt
2 184.8 nmole-PO4 - Top
3in of
filters 3
/g-dry wt
172.2 nmole-PO4 - /g-dry wt
209

5.
EMWTP
Water
samples
Biomass
samples
5.
EMWTP
Water
samples
Biomass
samples
Table C.3 (Continued)
Sampling
8/27/2002 9/03/2002
location MIB Geosmin TOC MIB Geosmin TOC
(ng/L) (ng/L) (mg/L) (ng/L) (ng/L) (mg/L)
Raw 11.9 7.1 4.5 13.7 6.9 4.8
Pre O3 12.7 7.2 4.7 12.5 6.4 5.2
Post O3 3.9 2.7 4.9 2.8 1.4 5.2
Prefilt 1 2.7 2.3 4.3 4.3 2.0 4.4
Postfilt 1 0.9 0.6 3.5 1.9 0.2 3.8
Prefilt 2 2.5 2.7 4.4 4.5 2.1 4.1
Postfilt 2 0.8 0.8 3.6 1.4 0.5 3.3
Treated 0.9 0.7 3.6 1.0 0.4 3.5
Top 1
3in of 2
filters 3
Sampling
5/5/2003
location
MIB Geosmin TOC
(ng/L) (ng/L) (mg/L)
Raw 2.1 2.9 4.7
Pre O3 2.0 2.3 4.7
Post O3 1.2 2.0 6.0
Prefilt 1 0.7 1.6 4.7
Postfilt 1 0.8 1.7 4.0
Prefilt 2 0.7 1.5 4.9
Postfilt 2 3.8 1.9 4.1
Treated 0.7 1.3 3.6
1 102.1 nmole-PO4 - 2
/g-dry wt
86.2 nmole-PO4 - Top
3in of
filters 3
/g-dry wt
76.7 nmole-PO4 - /g-dry wt
210

6.
GWTP
Water
samples
Biomass
samples
6.
GWTP
Water
samples
Biomass
samples
Table C.3 (Continued)
Sampling
8/12/2002 8/12/2002
location MIB Geosmin TOC MIB Geosmin TOC
(ng/L) (ng/L) (mg/L) (ng/L) (ng/L) (mg/L)
Raw 6.0 1.5 1.3 6.0 1.5 1.5
Pre O3 5.9 1.1 1.3 5.2 1.1 1.3
Post O3 3.0 0.5 1.5 3.0 0.4 1.5
Prefilt 1 2.5 0.4 1.4 2.0 0.3 1.6
Postfilt 1 0.6 0.0 1.1 0.6 0.0 1.1
Prefilt 2 2.0 0.4 1.3 2.5 0.3 1.5
Postfilt 2 0.7 0 1.2 0.5 0 1.0
Treated 0.9 0 1.1 1.0 0 1.2
Top 1
3in of 2
filters 3
Sampling
9/25/2003
location MIB Geosmin TOC
(ng/L) (ng/L) (mg/L)
Raw 2.5 0.8 1.3
Pre O3 13.8 2.4 1.3
Post O3 9.8 1.2 1.5
Prefilt 1 7.6 1.3 1.4
Postfilt 1 4.7 0.4 1.1
Prefilt 2 7.7 1.2 1.3
Postfilt 2 1.9 0.5 1.2
Treated 1.6 0.3 1.1
Top
3in of
filters
1
211

7.
MWW
Water
samples
Biomass
samples
7.
MWW
Water
samples
Biomass
samples
Table C.3 (Continued)
Sampling
9/23/2002 9/23/2002
location MIB Geosmin TOC MIB Geosmin TOC
(ng/L) (ng/L) (mg/L) (ng/L) (ng/L) (mg/L)
Raw 0.5 1.0 1.8 0.6 2.9 2.1
Pre O3 0.7 0.5 1.8 0.4 0.5 1.9
Post O3 0.5 0.6 1.9 0.4 0.6 1.9
Prefilt 1 0.6 0.1 1.5 0.7 0.2 1.5
Postfilt 1 0.7 0.1 1.5
Prefilt 2 0.5 0.1 1.5
Postfilt 2 0.3 0.1 1.6 0.5 0.3 1.5
Treated 0.3 0.1 1.5 0.2 0.2 1.5
Top 1
3in of 2
filters 3
Sampling
5/12/2003
location
MIB Geosmin TOC
(ng/L) (ng/L) (mg/L)
Raw 0 0.8 1.9
Pre O3 0 0.8 1.9
Post O3 0 0.6 2.3
Prefilt 1 0 0.2 1.9
Postfilt 1 0 0.4 1.6
Prefilt 2 0 0.6 1.8
Postfilt 2 0 0.5 1.5
Treated 0 0.8 1.6
1 26.9 nmole-PO4 - 2
/g-dry wt
25.5 nmole-PO4 - Top
3in of
filters 3
/g-dry wt
No sample
212

9.
PWTP
Water
samples
Biomass
samples
9.
PWTP
Water
samples
Biomass
samples
Table C.3 (Continued)
Sampling
9/13/2002
location MIB Geosmin TOC
(ng/L) (ng/L) (mg/L)
Raw 5.3 4.5 3.6
Pre O3 4.5 3.8 2.9
Post O3 2.5 2.1 3.0
Prefilt 3.8 1.9 3.0
Postfilt 1.5 0.8 2.3
Top 1
3in of 2
filters 3
Sampling
6/10/2003
location MIB Geosmin TOC
(ng/L) (ng/L) (mg/L)
Bax Raw 2.5 2.8 4.7
Bax Pre O3 3.7 2.8 2.3
Bax Post O3 1.5 1.0 2.2
Bax Postfilt 1.7 0.9 1.7
Bel Raw 1.1 2.8 3.3
Bel Pre O3 1.1 2.8 2.4
Bel Post O3 1.1 1.3 2.1
Bel Postfilt 1.4 1.1 1.6
1 53.1 nmole-PO4 - 2
/g-dry wt
110.8 nmole-PO4 - Top
3in of
filters 3
/g-dry wt
No sample
213

From Huron River
& Well
Lime (CaO)
Primary Rapid Mix
Pump Station
(To Distribution System)
Reservoir
Flocculators
(Slow Mix
Basin)
Primary Clarifer
Clean Well
Notes: Filter Back Wash: use chlorinated water; with typical chlorine concentration 3.0 ppm; typical cycle 10 minutes; with the
surface wash of 1 minutes at the beginning of backwash.
Figure C.1 Schematic of Ann Arbor Water Treatment Plant, MI (AAWTP)
NH2Cl
Well Water & CO2
Polymer
Rapid Mix
Fluoride
Filtration
Flocculators
(Slow Mix
Basin)
GAC/Sand Dual Media
Phosphate
NaOH
CO2
Contactor
Ozone
Contactors
214
Secondary Clarifer

Raw Water
Pump Station
(To Distribution System)
H3PO4
KMnO4
Clean Well
Ozone Contactors
Primary Disinfection
Hydroxychloride or
Hydroxychlorosulfate
Filtration
GAC/Sand Dual Media
Inclined Plate
Sedimentation
Notes: Filter Back Wash: use Chlorinated water; with typical chlorine concentration 0.6-0.9 ppm; typical cycle 15 minutes; with air
scouring for 2 minutes, and low wash/air for 2 mins at the beginning of backwash.
H2SiF6
NaOCl
Polyaluminum
Rapid
Mix
Slow Mix Basin
Flocculation
215

Figure C.2 Schematic of Central Lake Country Joint Action Water Agency, IL (CLCJA)
From Salt River
Canal
Bar Screen
Pump Station
(To Distribution System)
PAC
CO2
Contactor
Clean Well
Pre sedimentation
Fluoride)
Chlorine
Filtration
GAC/Sand Dual Media
Notes: Filter Back Wash: use the chlorinated water; with typical chlorine concentration 2.0 ppm; typical 60 minutes for both sides of
the filter; use a water scouring device.
Alum
R
In Line Rapid Mix
Slow Mix Basin
Coagulation
216

Figure C.3 Schematic of Chandler Water Treatment Plant, AZ (CWTP)
Raw Water
Pump Station
(To Distribution System)
H2SO4 Alum
NaClO Cationic Polymer
Clean Well
NH3
Fluoride
Caustic Soda
Slow Mix Basin
NaClO
Filtration
GAC/Sand (44/5 in)
Nonionic Polymer
Flocculation
Nonionic Polymer
Sedimentation
Ozone Contactors
Intermediate Ozonation
217

Notes: Filter Back Wash: use the chloraminated water; average backwash cycle uses 300-400k gal/wash; Air scouring is applied at the
beginning for about 12 minutes.
Figure C.4 Schematic of Contra Costa Water District, CA (CCWD) s
218

Raw Water
Pump Station
(To Distribution System)
Ammonia
From Eagle Mountain
Lake
Clean Well
Ozone Contactors
Primary Disinfection
Ammonia
Chlorine
Lime
Fluoride
NaOH
Chlorine & Ammonia
Filtration
Anthracite/Sand
Notes: Filter Back Wash: use the ozonated water; with no ozone residual; average total backwash cycle is 20 minutes; air scouring is
applied at the beginning for about 5 minutes.
Rapid
Mix
Figure C.5 Schematic of Eagle Mountain Water Treatment Plant, City of Fort Worth, TX (EMWTP)
Chlorine & Ammonia
Slow Mix Basin
Flocculation
Sedimentation
219

Salt River & Central
Arizona Project
Water
Pump Station
(To Distribution System)
Disinfectant
Bar Screen
Clean Well
Pre Sedimentation
Notes: Filter Back Wash: use the filtrated water without chlorination; average total backwash cycle is 20-35 minutes; Air scouring is
applied at the begining.
Figure C.6 Schematic of Gilbert Water Treatment Plant, AZ (GWTP)
Coagulant
Disinfectant
Filtration
GAC/Sand Dual Media
Mixing Chamber
Flocculation Basin
Ozone Contactors
220

Raw Water
Pump Station
(To Distribution System)
Ammonia
From Lake Michigan
Clean Well
Ozone Contactors
Primary Disinfection
Fluoride
Notes: Filter Back Wash: use the finished water (chloraminated); with typical chlorine residual 1.0~1.3 ppm; average total backwash
cycle is 16 minutes; with the surface wash of 2 minutes followed by backwash water flow of 12 minutes.
Figure C.7 Schematic of Milwaukee Water Works Linwood Plant, WI (MWW)
Chlorine
Alum
Filtration
Coal/Sand Dual Media
Rapid
Mix
Slow Mix Basin
Flocculation
Sedimentation
221

Salt and Verde
Rivers & Colorado
River Water
Pump Station
(To Distribution System)
Coagulant
Aid Polymer
Bar Screen Pre Mix Basin
Clean Well
Pre Sedimentation
Basin
Sodium
Hydroxide
Hydrofluosilicic
Acid
Chlorine
Notes: Filter Back Wash: use unchlorinated and chlorinated water; chlorine residual is 1.2 mg/L in chlorinated water; normal total
backwash cycle is 19 min; air scouring is applied for 3 min at the beginning.
Figure 7.8 Schematic of Peoria Greenway Water Treatment Plant, AZ (PGWTP)
Ozone
Contactors
Filtration
GAC Media
Aluminum
Sulfate/Ferric
Chloride
Filter Aid Polymer
Chlorine
Coagulant
Aid Polymer
Chlorine
Flash & Rapid Mixing
Flocculators
(Slow Mix Basin)
Final Sedimentation
222

Notes: Filter Back Wash:
Figure 7.9 Schematic of Philadelphia Water Treatment Plant, (PWTP)
Process Not Clear (Use Chloramination)
223