COVERING CHLORINE CONTACT BASINS AT THE ......COVERING CHLORINE CONTACT BASINS AT THE KANAPAHA WATER...
Transcript of COVERING CHLORINE CONTACT BASINS AT THE ......COVERING CHLORINE CONTACT BASINS AT THE KANAPAHA WATER...
COVERING CHLORINE CONTACT BASINS AT THE KANAPAHA WATER RECLAMATION FACILITY: EFFECTS ON CHLORINE RESIDUAL,
DISINFECTION EFFECTIVENESS, AND DISINFECTION BY-PRODUCT FORMATION
By
HEATHER L. FITZPATRICK
A THESIS PRESENTED TO THE GRADUATE SCHOOL OF THE UNIVERSITY OF FLORIDA IN PARTIAL FULLFILLMENT OF THE
REQUIREMENTS FOR THE DEGREE OF MASTER OF ENGINEERING
UNIVERSITY OF FLORIDA
2005
Copyright 2005
by
Heather L Fitzpatrick
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ACKNOWLEDGMENTS
I would like to thank my supervisory committee members (Dr. Paul Chadik, Dr.
David Mazyck, and Dr. Benjamin Koopman) for their input and assistance during this
investigation. Special thanks go to my supervisory committee chair (Dr. Chadik) for his
technical support and guidance during this study; they were of immeasurable significance
to this research and to me. Also, I would like to thank the Gainesville Regional Utilities
staff for their support throughout the course of this research. The help of Christina Akly
in the field and at the University of Florida was of great importance and greatly
appreciated. I would also like to thank my family, friends, and especially my husband for
their continuous support during my graduate career.
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TABLE OF CONTENTS page ACKNOWLEDGMENTS ................................................................................................. iii
LIST OF TABLES............................................................................................................ vii
LIST OF FIGURES .............................................................................................................x
ABSTRACT..................................................................................................................... xvi CHAPTER 1 INTRODUCTION ........................................................................................................1
Pilot Study ....................................................................................................................5 Full-Scale Study............................................................................................................7 Clarifier Chlorine Addition...........................................................................................7
2 REVIEW OF LITERATURE .......................................................................................9
Nitrification/Denitrification..........................................................................................9 Chlorine Disinfection..................................................................................................10
Free Chlorine .......................................................................................................11 Combined Chlorine .............................................................................................12 Break-Point Chlorination.....................................................................................13 Contact Time .......................................................................................................14
Disinfection By-Product Formation ...........................................................................15 Sunlight/UV Irradiation ..............................................................................................23
3 MATERIALS AND METHODS ...............................................................................27
Measured Parameters..................................................................................................27 Global Solar Radiation ........................................................................................27 Ultraviolet Radiation ...........................................................................................27 Total and Free Chlorine Residual........................................................................28 Total Suspended Solids .......................................................................................29 Total Coliform.....................................................................................................29 Trihalomethane (THM) .......................................................................................30 Haloacetic Acid (HAA).......................................................................................30 pH ........................................................................................................................31
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Conductivity ........................................................................................................31 Dissolved Oxygen ...............................................................................................32
Sampling .....................................................................................................................32 Pilot Scale System ......................................................................................................32
Wastewater Feed System Materials.....................................................................34 Chlorine Dosing...................................................................................................37 Pump Test ............................................................................................................37
Full Scale ....................................................................................................................38 Calculations ................................................................................................................40
Disinfection By-Product Data Normalization .....................................................40 Trihalomethane normalization .....................................................................40 Haloacetic acid normalization......................................................................42
Average Radiation ...............................................................................................43 Standard Deviation ..............................................................................................44 Paired T-Test .......................................................................................................44 Linear Correlation ...............................................................................................45
4 DISCUSSION: PILOT-SCALE BASIN ....................................................................47
Solar Radiation/Temperature......................................................................................47 Chlorine Residual .......................................................................................................50
Free Chlorine .......................................................................................................51 Total Chlorine......................................................................................................57
Disinfection By-Products............................................................................................60 Trihalomethane....................................................................................................61 Haloacetic Acid ...................................................................................................74
5 DISCUSSION: FULL-SCALE STUDY ....................................................................86
Chlorine Residual .......................................................................................................86 Free Chlorine .......................................................................................................86 Total Chlorine......................................................................................................89
Disinfection By-Products............................................................................................91 Trihalomethane....................................................................................................91 Haloacetic Acid .................................................................................................101
6 DISCUSSION: MEASURED PARAMETERS .......................................................112
Temperature..............................................................................................................112 Total Coliform ..........................................................................................................112 Total Suspended Solids.............................................................................................113 pH .............................................................................................................................114 Conductivity .............................................................................................................115 Dissolved Oxygen.....................................................................................................115
7 CONCLUSIONS ......................................................................................................117
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APPENDIX
A PILOT-SCALE BASIN DESIGN ............................................................................121
B FLUOROSCEIN TRACER ANALYSIS .................................................................122
C CHLORINE DOSING CALCULATIONS ..............................................................126
D COMPILED DATA..................................................................................................127
E PILOT-SCALE DATA.............................................................................................139
F FULL-SCALE DATA ..............................................................................................157
G GAS CHROMATOGRAPHY INFORMATION.....................................................165
H T-TEST AND PEARSON COEFFICIENT TABLES.............................................172 LIST OF REFERENCES.................................................................................................175
BIOGRAPHICAL SKETCH ...........................................................................................178
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LIST OF TABLES
Table page 3-1 Chlorine contact basin dimension ratios. .................................................................33
3-2 Pilot chlorine contact basin dimension.....................................................................33
4-1 Normalization factors used to normalize OPAQ TTHM effluent concentrations to TRANS TTHM effluent concentrations...................................................................68
4-2 Normalization factors used to normalize OPAQ HAA(5) effluent concentrations to TRANS HAA(5) effluent concentrations.................................................................80
5-1 Normalization factors used to normalize COV TTHM effluent concentrations to UNCOV TTHM effluent concentrations..................................................................97
5-2 Normalization factors used to normalize COV HAA(5) effluent concentrations to UNCOV HAA(5) effluent concentrations..............................................................108
A-1 South chlorine contact basin ..................................................................................121
A-2 North chlorine contact basin ..................................................................................121
A-3 Pilot basin. ..............................................................................................................121
B-1 Fluoroscein tracer at KWRF pilot basin, clear top.................................................122
B-2 Conditions during tracer analysis. ..........................................................................123
B-3 Flouroscein F curve calculation. ............................................................................124
B-4 The F curve values. ................................................................................................125
C-1 Chlorine dosing during pilot-scale study. ..............................................................126
C-2 Acid and base addition during pilot-scale study. ...................................................126
D-1 Pilot-scale study compiled and calculated parameter data.....................................127
D-2 Pilot-scale study compiled chlorine data and differences. .....................................128
D-3 Pilot-scale study compiled TTHM data and differences. .......................................129
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D-4 Pilot-scale study compiled TTHM and normalization factors. ..............................130
D-5 Pilot-scale study compiled normalized TTHM’ data and differences....................131
D-6 Pilot-scale study compiled HAA(5) data. ..............................................................132
D-7 Pilot-scale study compiled normalized HAA(5) data. ...........................................133
D-8 Pilot-scale study compiled differences in HAA(5) and HAA(5)’ data. .................134
D-9 Full-scale study compiled and calculated parameter data. .....................................135
D-10 Full-scale study compiled chlorine data and differences. ......................................135
D-11 Full-scale study compiled TTHM data and differences. ........................................136
D-12 Full-scale study compiled TTHM and normalization factors. ...............................136
D-13 Full-scale study compiled normalized TTHM’ data and differences.....................137
D-14 Full-scale study compiled HAA(5) data.................................................................137
D-15 Pilot-scale study compiled normalized HAA(5) data. ...........................................138
D-16 Full-scale study compiled differences in HAA(5) and HAA(5)’ data. ..................138
E-1 Trihalomethane mass concentrations in the pilot-scale study. ...............................139
E-2 Trihalomethane molar concentrations in the pilot-scale study...............................142
E-3 Haloacetic acid mass concentrations in the pilot-scale study.................................144
E-4 Haloacetic acid molar concentrations in the pilot-scale study. ..............................146
E-5 Pilot-scale study chlorine effluent concentrations..................................................148
E-6 Pilot-scale probe parameter data. ...........................................................................151
E-7 Pilot-scale data provided by GRU laboratory. .......................................................154
F-1 Trihalomethane mass concentrations in the full-scale study..................................157
F-2 Trihalomethane molar concentrations in the full-scale study. ...............................159
F-3 Haloacetic acid mass concentrations in the full-scale study. .................................160
F-4 Haloacetic acid molar concentrations in the full-scale study. ................................161
F-5 Full-scale study chlorine effluent concentrations...................................................162
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F-6 Full-scale probe parameter data. ............................................................................163
F-7 Full-scale data provided by GRU...........................................................................164
H-1 Pilot-scale t-test values ...........................................................................................172 H-2 Full-scale t-test values ............................................................................................172
H-3 Pilot-scale Pearson coefficient and linear correlation value...................................173
H-4 Full-scale Pearson coefficient and linear correlation values ..................................174
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LIST OF FIGURES
Figure page 1-1 Kanapaha Water Reclamation Facility flow diagram. ...............................................1
1-2 Overhead layout of the KWRF...................................................................................2
1-3 Wastewater process from filtration through chlorination. .........................................2
1-4 Chlorine addition at the clarifiers...............................................................................8
2-1 Percent of free chlorine compound (HOCl and OCl-) versus pH.............................11
2-2 Breakpoint chlorination: Species of chlorine residuals present during chlorination when ammonia is present. ........................................................................................14
2-3 The THM species. ....................................................................................................16
2-4 The HAA(5) species.................................................................................................17
2-5 Predicted versus the observed concentration of CHCl3 for the entire model development database from the 1993 AWWA report. .............................................22
2-6 Predicted versus the observed concentration of DCAA for the entire model development database from the 1993 AWWA report. .............................................23
3-1 Radiometer, pyranometer, and datalogger setup. .....................................................28
3-2 Pilot basin system setup. ..........................................................................................35
3-3 Pilot scale setup; chlorine and acid/base solution containers, solution pumps, influent water spigot, static mixers, t-split, TRANS and OPAQ basins. .................36
3-4 Full-scale setup. (a) Uncovered side of the basin. (b) Covered side of the basin during the full-scale study. .......................................................................................38
3-5 Sampling points in the post-aeration basin and North chlorine contact basin for the full-scale study. ........................................................................................................39
4-1 Average global horizontal radiation versus the average UV radiation.....................48
4-2 The effluent temperature of the TRANS and OPAQ basins plotted versus the average UV radiation exposure of the TRANS basin over the HRT. ......................49
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4-3 Difference in effluent temperature of the basins (TRANS-OPAQ) plotted versus the average UV radiation over the HRT. .......................................................................50
4-4 Free chlorine residual sampling sets in particular residual ranges for the TRANS and OPAQ basins. ....................................................................................................52
4-5 Free chlorine residual difference of the TRANS and OPAQ basins (TRANS-OPAQ) plotted versus average UV Radiation over the HRT of the wastewater in the basin for all pilot studies. ............................................................53
4-6 Free chlorine residual difference of the OPAQ and TRANS basins (TRANS-OPAQ) plotted versus average UV radiation over the HRT of the wastewater in the basin for baseline parameters. .....................................................54
4-7 Free chlorine difference of the TRANS and OPAQ basins (TRANS-OPAQ) plotted versus the difference in temperature for all of the pilot studies. ..............................55
4-8 Free chlorine difference of the TRANS and OPAQ basins (TRANS-OPAQ) plotted versus the difference in temperature for baseline parameters. .................................56
4-9 Total chlorine residual sampling sets in particular residual ranges for the TRANS and OPAQ basins. ....................................................................................................58
4-10 Total chlorine residual difference of the OPAQ and TRANS basins (TRANS-OPAQ) plotted versus average UV Radiation over the HDT of the wastewater in the basin for all pilot studies. ...................................................................................59
4-11 Total chlorine residual difference of the TRANS and OPAQ basins (TRANS-OPAQ) plotted versus the difference in temperature between the basins................60
4-12 The TTHM effluent mass concentrations for the TRANS and OPAQ basins are shown in range increments. ......................................................................................62
4-13 The TTHM effluent molar concentrations for the TRANS and OPAQ basins are shown in range increments. ......................................................................................62
4-14 Difference in TTHM concentration between the TRANS and OPAQ sides (TRANS-OPAQ) separated into mass concentration ranges. ..................................64
4-15 Difference in TTHM concentration between the TRANS and OPAQ sides (TRANS-OPAQ) separated into molar concentration ranges. .................................64
4-16 Difference in TTHM effluent mass concentration of the TRANS and OPAQ basins (TRANS-OPAQ) plotted versus the difference in free chlorine residual of the TRANS and OPAQ basins. ......................................................................................65
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4-17 Difference in TTHM effluent molar concentration of the TRANS and OPAQ basins (TRANS-OPAQ) plotted versus the difference in free chlorine residual of the TRANS and OPAQ basins. ......................................................................................65
4-18 Difference in TTHM mass effluent concentration between the TRANS and OPAQ basins (TRANS-OPAQ) plotted versus the difference in free chlorine residual between the TRANS and OPAQ basins for baseline runs. ......................................66
4-19 Speciation of the THM formation in the TRANS effluent on a mass basis sampled at 9 am on August 23, 2004......................................................................................67
4-20 Normalized TTHM effluent mass concentrations for the TRANS and OPAQ basins are shown in range increments. ................................................................................69
4-21 Normalized TTHM effluent molar concentrations for the TRANS and OPAQ basins are shown in range increments. .....................................................................69
4-22 Difference in TTHM’ concentration between the TRANS and OPAQ sides (TRANS-OPAQ) separated into mass concentration ranges. ..................................70
4-23 Difference in TTHM’ concentration between the TRANS and OPAQ sides (TRANS-OPAQ) separated into molar concentration ranges. .................................71
4-24 Difference in normalized TTHM mass concentration of the TRANS and the OPAQ basins (TRANS-OPAQ) plotted versus the average UV radiation. exposure over the HRT. .........................................................................................................................72
4-25 Difference in normalized TTHM molar concentration of the TRANS and the OPAQ basins (TRANS-OPAQ) plotted versus the average UV radiation exposure over the HRT............................................................................................................73
4-26 The HAA(5) effluent mass concentrations for the TRANS and OPAQ basins are shown in range increments. ......................................................................................75
4-27 The HAA(5) effluent molar concentrations for the TRANS and OPAQ basins are shown in range increments. ......................................................................................75
4-28 Difference in HAA(5) concentration between the TRANS and OPAQ sides (TRANS-OPAQ) separated into mass concentration ranges. ..................................76
4-29 Difference in HAA(5) concentration between the TRANS and OPAQ sides (TRANS-OPAQ) separated into molar concentration ranges. .................................76
4-30 Difference in HAA(5) mass concentration of the TRANS and the OPAQ basins (TRANS-OPAQ) plotted versus the difference in free chlorine residual of the TRANS and OPAQ basins (TRANS-OPAQ). .........................................................77
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4-31 Difference in HAA(5) molar concentration of the TRANS and the OPAQ basins (TRANS-OPAQ) plotted versus the difference in free chlorine residual of the TRANS and OPAQ basins (TRANS-OPAQ). .........................................................78
4-32 Speciation of the HAA(5) formation in the OPAQ effluent on a mass basis sampled at 12 pm on August 30, 2004. ..................................................................................79
4-33 The HAA(5)’ effluent mass concentrations for the TRANS and OPAQ basins are shown in range increments. ......................................................................................81
4-34 The HAA(5)’ effluent molar concentrations for the TRANS and OPAQ basins are shown in range increments. ......................................................................................81
4-35 Difference in HAA(5)’ concentration between the TRANS and OPAQ sides (TRANS-OPAQ) separated into mass concentration ranges. ..................................82
4-36 Difference in HAA(5)’ concentration between the TRANS and OPAQ sides (TRANS-OPAQ) separated into molar concentration ranges. .................................83
4-37 Difference in HAA(5)’ effluent mass concentration of the TRANS and OPAQ basins (TRANS-OPAQ) plotted versus the average UV radiation exposure over the HRT. .........................................................................................................................84
4-38 Difference in HAA(5)’ effluent molar concentration of the TRANS and OPAQ basins (TRANS-OPAQ) plotted versus the average UV radiation exposure over the HRT. .........................................................................................................................84
5-1 Free chlorine residual of the UNCOV and COV side effluents separated into concentration ranges.................................................................................................87
5-2 Difference in free chlorine residual between the UNCOV and COV sides (UNCOV-COV) separated into concentration ranges..............................................88
5-3 Free chlorine difference of the UNCOV and COV basin sides plotted versus the difference in temperature. ........................................................................................89
5-4 Total chlorine residual of the UNCOV and COV side effluents separated into concentration ranges.................................................................................................90
5-5 Total chlorine difference of the UNCOV and COV basin sides plotted versus the difference in temperature. ........................................................................................91
5-6 The TTHM effluent mass concentrations for the UNCOV and COV sides are shown in range increments. ......................................................................................92
5-7 The TTHM effluent molar concentrations for the UNCOV and COV sides are shown in range increments. ......................................................................................93
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5-8 Difference in TTHM concentration between the UNCOV and COV sides (UNCOV-COV) separated into mass concentration ranges.....................................94
5-9 Difference in TTHM concentration between the UNCOV and COV sides (UNCOV-COV) separated into molar concentration ranges. ..................................94
5-10 Difference in the TTHM effluent mass concentration between the UNCOV and COV sides (UCOV-COV) plotted versus the difference in free chlorine residual of the UNCOV and COV sides (UCOV-COV)............................................................95
5-11 Difference in the TTHM effluent molar concentration between the UNCOV and COV sides (UCOV-COV) plotted versus the difference in free chlorine residual of the UNCOV and COV sides (UCOV-COV)............................................................96
5-12 Speciation of the TTHM formed in the UNCOV side sampled at 9 am on August 25, 2004. ...................................................................................................................96
5-13 The TTHM’ mass concentration instances separated into concentration ranges for the UNCOV and COV side. .....................................................................................98
5-14 The TTHM’ molar concentration instances separated into concentration ranges for the UNCOV and COV side. .....................................................................................99
5-15 Difference in TTHM’ concentration between the UNCOV and COV sides (UNCOV-COV) separated into mass concentration ranges...................................100
5-16 Difference in TTHM’ concentration between the UNCOV and COV sides (UNCOV-COV) separated into molar concentration ranges. ................................101
5-17 The HAA(5) effluent mass concentrations for the UNCOV and COV sides are shown in range increments. ....................................................................................102
5-18 The HAA(5) effluent molar concentrations for the UNCOV and COV sides are shown in range increments. ....................................................................................103
5-19 Difference in HAA(5) concentration between the UNCOV and COV sides (UNCOV-COV) separated into mass concentration ranges...................................104
5-20 Difference in HAA(5) concentration between the UNCOV and COV sides (UNCOV-COV) separated into molar concentration ranges. ................................104
5-21 Difference in HAA(5) effluent mass concentration of the UNCOV and COV sides versus the difference in free chlorine residual of the UNCOV and COV sides.....105
5-22 Difference in HAA(5) effluent molar concentration of the UNCOV and COV sides versus the difference in free chlorine residual of the UNCOV and COV sides.....106
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5-23 Speciation of the HAA(5) formation in the COV effluent on a mass basis sampled at 12 pm on August 25, 2004. ................................................................................107
5-24 The HAA(5)’ effluent mass concentrations for the UNCOV and COV basin sides are shown in range increments. ..............................................................................109
5-25 The HAA(5)’ effluent molar concentrations for the UNCOV and COV basin sides are shown in range increments. ..............................................................................109
5-26 Difference in HAA(5)’ concentration between the UNCOV and COV sides (UNCOV-COV) separated into mass concentration ranges...................................110
5-27 Difference in HAA(5)’ concentration between the UNCOV and COV sides (UNCOV-COV) separated into molar concentration ranges. ................................111
6-1 Total coliform and temperature plotted against sampling time on July 14, 2004. .113
6-2 Total suspended solids and temperature plotted against sampling time on July 14, 2004. .......................................................................................................................114
6-3 pH and temperature plotted against sampling time on July 14, 2004. ...................114
6-4 Conductivity and temperature plotted against sampling time on July 14, 2004. ...115
6-5 The D.O. and temperature plotted against sampling time on July 14, 2004..........116
B-1 Fluoroscein versus sampling time. .........................................................................124
B-2 The F curve.............................................................................................................125
G-1 Trihalomethane GC for spiked sample...................................................................165
G-2 Trihalomethane GC for blank sample. ...................................................................166
G-3 Trihalomethane GC for field sample......................................................................167
G-4 Haloacetic acid GC for spiked sample. ..................................................................169
G-5 Haloacetic acid GC for blank sample.....................................................................170
G-6 Haloacetic acid GC for field sample. .....................................................................170
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Abstract of Dissertation Presented to the Graduate School
of the University of Florida in Partial Fulfillment of the Requirements for the Degree of Master of Engineering
COVERING CHLORINE CONTACT BASINS AT THE KANAPAHA WATER RECLAMATION FACILITY: EFFECTS ON CHLORINE RESIDUAL,
DISNIFECTION EFFECTIVENESS, AND DISINFECTION BY-PRODUCT FORMATION
By
Heather L. Fitzpatrick
May 2005
Chair: Paul A. Chadik Major Department: Environmental Engineering Sciences
It is commonly understood that sunlight, specifically ultraviolet (UV) radiation,
degrades chlorine and thus reduces chlorine residual in uncovered chlorine contact
basins. Its effect on disinfection by-product (DBP) formation, however, has not been
significantly studied. A pilot and full-scale study were performed at the Kanapaha Water
Reclamation Facility (KWRF) to investigate the effect of UV radiation on chlorine
residual, disinfection-by-product formation, and inactivation of bacteria.
For both the pilot and full-scale studies, two chlorine disinfection processes were
setup in parallel, for effluent parameter comparisons. One process allowed for the
exposure of the wastewater to UV radiation. In the other process an opaque cover was
used to prevent solar radiation exposure of the wastewater during chlorine disinfection.
Preventing UV radiation exposure of wastewater provided higher chlorine residuals (on
average 0.4 and 0.7 mg/L free chlorine higher) for pilot and full-scale averages
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respectively. Extent of chlorine loss from UV radiation exposure was directly
proportional to the UV exposure intensity during chlorine disinfection. Both processes,
with and without UV radiation exposure, provided adequate total coliform inactivation.
To compensate for the difference in effluent conditions (such as chlorine residual
and temperature), the effluent DBP concentrations were normalized. In the normalization
process, non-exposed effluent DBP concentrations were normalized to UV-exposed
effluent DBP concentrations using normalization factors. Normalization factors were
calculated from parameter data collected during each sampling run. By preventing UV
radiation exposure during chlorine disinfection, free chlorine residual was found to be
significantly higher, and also the total trihalomethane effluent concentration was found to
be significantly less (on average 17.1 and 7.5 µg/L less for normalized concentrations)
than for pilot and full-scale averages, respectively. In the full-scale study haloacetic acid
(HAA(5)) concentration was significantly less in the process that prevented UV radiation
exposure (on average, 39.0 µg/L less). However, the pilot-scale did not show the same
degree of HAA(5) concentration difference; thus, no significant difference was found
between the UV radiation exposed and non-exposed processes. Preventing UV radiation,
if it does not lessen HAA(5) formation, does not increase formation.
Our studies provide evidence contrary to common theory that an increase in free
chlorine during chlorination will result in higher DBP formation. The significance lies in
using chlorine disinfection processes where wastewater is covered to prevent UV-
radiation exposure. When used it could lower the amount of chlorine loss, and help to
lower DBP formation.
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CHAPTER 1 INTRODUCTION
The Kanapaha Water Reclamation Facility (KWRF), owned and operated by
Gainesville Regional Utilities (GRU), treats wastewater from the west side of
Gainesville, Florida, and its outlying areas. The plant uses a modified Ludzak-Ettinger
process to treat the wastewater.1 The plant operation promotes biological removal of
nitrogen and carbonaceous biological oxygen demand (CBOD). After the aeration
basins, the wastewater moves to the clarifiers (where solids are removed). Then the
wastewater flows through filters (which remove the fine particles that did not settle out in
the clarifiers). The wastewater is then collected in a clearwell, sent to the post-aeration
basin, and then disinfected in the chlorine contact basins (Figure 1-1).
Figure 1-1. Kanapaha Water Reclamation Facility flow diagram.
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The plant (Figure 1-2) was recently expanded from a 10 million gallon per day
(MGD) to a 14 MGD capacity. A schematic of the wastewater process from filtration
through the chlorine contact basins is shown in (Figure 1-3).
Figure 1-2. Overhead layout of the KWRF.
Figure 1-3. Wastewater process from filtration through chlorination.
6 - Filters
Post-Aeration Basins
North Chlorination Basin
South ChlorinationBasin
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From the clarifiers, the wastewater is sent to six filters setup in parallel. The filter
effluents combine into a single 100,000-gallon clearwell. Chlorine gas is injected into
the pipe as the wastewater flows from the post-aeration basin to the first of two chlorine
contact basins, to begin the disinfection stage of the treatment process. The two chlorine
contact basins are setup in series (the North and the South chlorine contact basins). The
first chlorine contact basin (the North basin), with a volume of 0.16 MG, is part of the
original plant. The wastewater then flows to a second chlorine contact basin (the South
basin) with a volume of 0.57 MG. The South basin was added after the original plant
was built, to increase treatment capacity. A previous study at the KWRF determined that
the North and South basins together model as 60 tanks-in-series while the North basin
models as 100 tanks-in-series separately.2
As stated, the KWRF relies on chlorine to disinfect the wastewater. Enough
chlorine gas is injected to create sufficient free chlorine to meet the chlorine demand of
the wastewater and leave enough effluent residual to meet the standards set by the
Environmental Protection Agency (EPA) and upheld by the Florida Department of
Environmental Protection (FDEP). According to the KWRF permit, the effluent must
have at least a 1 mg/L Cl2 free chlorine residual. In the chlorination process at the
KWRF, the contact basins are open to the environment; allowing the wastewater to be
exposed to UV radiation from sunlight. The UV radiation acts as a catalyst to reduce the
free chlorine (Equation 1-1). This reduction leads to an appreciable amount of chlorine
loss due to UV radiation exposure.
2222 OClHHOCl UV ++⎯→⎯ −+ (1-1)
4
Since the KWRF injects treated wastewater into deep wells in the Floridan aquifer
(a drinking water source), and is used in reuse applications, the finished wastewater must
meet EPA and DEP permit requirements. Disinfection by-product formation is of
increasing concern, since these by-products are linked to harmful health effects.
Pregeant1 using wastewater from the KWRF showed a positive correlation between free
chlorine residual and THM formation. As the chlorine residual was increased the THM
concentration formed also increased, given that there were THM precursors left in the
wastewater to react. 1
In a previous study performed by the Integrated Product and Process Design
(IPPD) team sponsored by Gainesville Regional Utilities (GRU) in 2001-2002 the
chlorine loss at the KWRF was investigated.2 Most chlorine loss was assumed to result
from chlorine decay by ultraviolet (UV) irradiation (Equation 1-1). Thus it was
suggested that covering the basin would decrease chlorine loss caused by this
mechanism.
The IPPD study provided good insight into the hydrodynamic behavior of the
treated wastewater as to flows through the chlorine contact basins and the disinfection
process at the KWRF. The study comprises two days worth of data compilation, March
19th and January 24th, for chlorine concentration, total trihalomethane (TTHM)
concentration, and the volume of water irradiated by sunlight. In the study one side of
the chlorine contact basin was covered with a polypropylene tarp while the other side was
left open. The covered side of the basin had a higher chlorine residual than the
uncovered basin verifying a definite correlation between sunlight exposure and chlorine
degradation.2 The study also showed that as the sunlight intensity increased from winter
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to summer months, the chlorine loss within the uncovered basin increases also. The
study provided some unexpected results: the total trihalomethane (TTHM) concentrations
were actually lower in the covered basin than the control, or uncovered basin.2 This
phenomenon is opposite of that found in the Pregeant1 study and is contrary to common
theory, where a higher residual produced a higher trihalomethane (THM) concentration.
One aspect of this study was to further investigate the phenomenon found by the IPPD
team.
In order to further ascertain the impact of solar radiation, ultraviolet (UV) and
visible radiation, on the chlorination process in the wastewater treatment plant, a research
plan was proposed to and accepted by the Gainesville Regional Utilities. One focus of
this study is the UV radiation catalysis of the oxidation reaction of water by chlorine to
form oxygen and the chloride ion, Equation 1-1. Also, this study reviews the impact of
UV radiation and global horizontal radiation on bacterial inactivation and disinfection by-
product (DBP) formation.
This study involves both a pilot and full-scale investigation of the chlorination
process at the KWRF to determine to what extent solar radiation affects chlorine residual,
disinfection effectiveness, and disinfection by-product formation.
Pilot Study
The pilot basin study involved two pilot basins scaled after the KWRF chlorine
contact basins. One basin was equipped with an opaque acrylic cover to block solar
radiation from entering and coming in contact with the water during chlorination. The
second basin was equipped with an UV transmitting clear acrylic, or UV-TRANS®, cover
that allowed solar radiation, both UV and visible radiation, to come in contact with the
water during chlorination.
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The feed water for the pilot basins had gone through the plant filters but was not
chlorinated by the plant chlorination system. The feed water to the pilot basins was first
dosed with a known concentration of chlorine (NaOCl), and then split into two equal
streams before entering the pilot basins.
The pilot basin study makes it possible to keep flow rate and chlorine dosage
constant which was not possible in the full-scale study. It also enabled the control and
variation of flow rates, pH levels, and chlorine dose to determine the extent of their
involvement in the effects of solar radiation on the chlorination process and water quality
parameters.
KWRF average, minimum, and maximum chlorine dosage, pH, and flow rates were
used in this phase of the study. The KWRF’s effluent wastewater had a total chlorine
residual minimum of 1.4 mg/L as Cl2, an average of 2.8 mg/L as Cl2, and a maximum of
4.8 mg/L as Cl2 according to data provided by GRU for 2003. In the pilot study the
average plant value was used as the pilot baseline value while chlorine dosing that
produces water with minimum and maximum residual values was also tested. The
influent pH, or raw pH, experienced at the KWRF does not vary much from a neutral pH,
around 7. Thus, for this experiment a pH of 7 was used as the baseline value while pH
values of 6 and 8 were also tested to determine the influence of pH on the pilot system.
In the pilot study a baseline hydraulic retention time (HRT) of 2.75 h was used. A longer
HRT of 3.81 hrs was also tested to amplify the effect of radiation on water quality
parameters in this study. The KWRF average and maximum HRT in the chlorine contact
basins is approximately 1.8 and 4.4 h, respectively.
7
Full-Scale Study
A full-scale study was also implemented to further investigate the effect of solar
radiation on the disinfection chlorination stage of the wastewater treatment under normal
operating conditions. The full-scale study was performed on the North basin and did not
include the south basin.
In the North basin the flow is split immediately into two parallel streams after it
enters the basin. Chlorine gas is injected into the pipe that transfers the wastewater from
the post-aeration basin to the North chlorine contact basin. In the full-scale study one
half of the basin was covered with polypropylene tarps and the other half was left
uncovered. As in the pilot-scale study the effect of UV radiation on the chlorine residual,
disinfection effectiveness, and disinfection by-product formation was investigated. The
full-scale study was performed to determine the effect of covering the basin under
standard plant chlorination procedures so no special adjustments were made. Just as in
the pilot study, the UV radiation impact on chlorine residual, disinfection effectiveness,
and DBP formation was examined.
Clarifier Chlorine Addition
The KWRF has recently installed chlorine injection pipes in the clarifiers
(Figure 1-4). The chlorine addition was implemented to reduce algae growth in the weirs
of the clarifiers. The chlorine addition at the clarifiers, however, would also result in the
formation of DBP and could have a lingering effect on chlorine residual and demand.
This would lead to inaccuracies in data collected during the pilot and full-scale studies.
In order to prevent the interference caused by the chlorine dosing of the clarifiers the
chlorine dosing of the clarifiers was ceased at 4 pm the day prior to sampling and
remained turned off until 4 pm the day of the testing. Sampling and analysis of the pilot
8
basin feed wastewater indicated that ceasing the addition of chlorine in the clarifiers at
4:00 pm ensured that the chlorine residual and TTHM concentrations were below
detection at 9:00 am the next morning.
Figure 1-4. Chlorine addition at the clarifiers.
9
CHAPTER 2 REVIEW OF LITERATURE
Nitrification/Denitrification
Nitrogen is incorporated into all living things, and is also present in the atmosphere.
Nitrogen is taken from the atmosphere by nitrogen-fixing bacteria and through the action
of electrical discharge during storms.3,4 Although nitrogen is necessary for life, if too
much nitrogen is fed into a receiving body of water an over production of algae and other
aquatic life can occur, or eutrophication.4,5 Also, organic nitrogen compounds and
ammonia exert a chlorine demand. A higher chlorine dose would be required to achieve
adequate disinfection if organic nitrogen and ammonia were not removed prior to
disinfection.6 Domestic raw wastewater contains mostly organic and ammonia nitrogen,
or Kjeldahl nitrogen.5
One of the major treatment processes at the KWRF is the use of biological
nitrification and denitrification to remove nitrogen from the wastewater. The autotrophic
nitrifying bacteria group, Nitrosomonas, under aerobic conditions oxidizes ammonia and
ammonium to form nitrite (Equation 2-1).3,4,5,7 Nitrite can then be oxidized further by the
bacteria group Nitrobacter to form nitrate (Equation 2-2).3,4,5,7 The aerobic oxidation of
organic nitrogen to inorganic nitrogen, nitrification, is carried out in the aeration basins
and also in the newly installed carousel at the KWRF.
+− ++⎯⎯⎯⎯ →⎯+ HOHNOONH asNitrosomon 42232 2223 (2-1)
−− ⎯⎯⎯ →⎯+ 322 22 NOONO rNitrobacte (2-2)
10
After the ammonia and ammonium are converted to nitrite and nitrate it can be
reduced to nitrogen gas by facultative anaerobic bacteria, such as Pseudmonas.3,5,7 It is
presumed that any nitrate present is reduced to nitrite and then to nitrogen gas. The
overall denitrification is shown in (Equation 2-3). At the KWRF the reduction of nitrite
and nitrate to nitrogen gas, denitrification, takes place in the anoxic basins and in the
newly installed carousel.
−− +++⎯⎯ →⎯+ )(675356 22233 OHOHCONOHCHNO bacteria (2-3)
Chlorine Disinfection
Disinfection of wastewater can be dated back to the late 1800s with the use of
chlorinated lime for odor control and the treatment of fecal material from hospitals.8
Because of the known health problems inflicted on humans by microbial organisms,
disinfection of wastewater has become a mainstream procedure. The disinfection of
wastewater helps prevent bacterial contamination of drinking water sources, thus, aiding
in the control of waterborne diseases. Chlorine is one of the most widely used
disinfectants for both potable and wastewater treatment because of its relatively low cost
and effectiveness as a disinfectant when compared to other alternatives.6,8 At
atmospheric pressure and room temperature chlorine exists as a poisonous yellow gas.8
For the purpose of water and wastewater treatment chlorine gas is pressurized as a dry,
liquefied gas and is stored in steel cylinders to make it easier to store and apply. During
chlorine disinfection three types of reactions can occur: oxidation, addition, and
substitution.9
11
Free Chlorine
In wastewater the chlorine gas is added to water and hydrolyzes to hypochlorus
acid (HOCl) and the hypochlorite ion (OCl-) (Equations 2-4 and 2-5).4,6,7 Together,
HOCl and OCl- are called free chlorine.
−+ ++→+ ClHHOClOHCl 22 (2-4)
+− +→ HOClHOCl (2-5)
Studies show HOCl to be a more efficient disinfectant and a stronger oxidant than
OCl- hence HOCl is the desired species when disinfecting.8,10 The pKa for HOCl is 7.5at
25˚C, thus, at a pH of 7.5 HOCl and OCl- exist in equal concentrations. If the pH is
below 7.5 the predominant species is HOCl while at a pH above 7.5 OCl- predominates.4
The percentage of free chlorine as HOCl and OCl- is dependent on the pH and
temperature conditions (Figure 2-1).4 Most wastewater treatment facilities operate in a
range where the HOCl species is prevalent thus increasing their disinfection efficiency
and lowering the chlorine dose required to achieve disinfection.6
Figure 2-1. Percent of free chlorine compound (HOCl and OCl-) versus pH.
12
Chlorine can react with many chemicals, inorganic and organic, present in the
wastewater stream. The amount of chlorine dissipated during these reactions is referred
to as the chlorine demand the wastewater possesses and dictate the amount of chlorine
that must be added to achieve a specific chlorine residual and good disinfection.
Combined Chlorine
In the presence of ammonia (NH3) the free chlorine species HOCl will react to form
chloramines that consist of monochlroamine (NH2Cl), dichloriamine (NHCl2), and
nitrogen trichloride (NCl3).4,6,10 (Equations 2-6, 2-7, and 2-8).
OHClNHHOClNH 223 +→+ (2-6)
OHNHClHOClClNH 222 +→+ (2-7)
OHNClHOClNHCl 232 +→+ (2-8)
Chloramines have the capacity to disinfect wastewater but are not as effective as
free chlorine. All domestic wastewaters contain organic nitrogen compounds, including
amino acids and proteins.6,8 Chlorine reacts with these organic nitrogen compounds to
form organic chloramines. Though these organic chloramines contribute to the combined
chlorine concentration they have no known disinfecting capability.6,8 Organic
chloramines show up as combined chlorine in the iodometric and DPD chlorine residual
methods.8 The speciation of inorganic chloramines is more related to the pH of the
wastewater and the chlorine to ammonia molar ratio and not as much on the contact time
of ammonia and HOCl.6,8 Under normal operating conditions monochloramine
predominates. As the pH decreases below neutral (pH=7) and as the Cl2:N mass ratio
13
value increases from 3:1 up to 7:1 the formation of dichloramine is favored. As the pH
continues to decrease nitrogen trichloride will form.6
The chloramine hydrolysis reactions will result in the release of ammonia, which
could play a role in nitrification (i.e. formation of NO3-). The decomposition of
dichloramine increases as the pH and alkalinity increase.6,8 This makes dichloramine less
stable than monochloramine under normal wastewater conditions. The decomposition of
monochloramine occurs in essentially two reactions the first being hydrolysis and the
following being the acid catalyzed reaction with the generated free chlorine and results in
the formation of dichloramine and ammonia in the wastewater.6,8
Break-Point Chlorination
In order to form HOCl in the presence of ammonia or other organic nitrogen
enough Cl2 gas must be added to reach and pass what is called the breakpoint
(Figure 2-2).4 The process is therefore termed breakpoint chlorination. Beyond the
breakpoint free chlorine is dominant and makes up a large percentage of the total
chlorine. However, also present beyond the breakpoint are what are termed “irreducible”
or “nuisance” chlorine residuals that show up in total chlorine residual measurements but
do not have the disinfecting capabilities that free chlorine possesses.6 The organic
chloramines and, if present, nitrogen trichloride contribute to the irreducible chlorine
residual.
14
Figure 2-2. Breakpoint chlorination: Species of chlorine residuals present during chlorination when ammonia is present.
Compounds other than ammonia and organic nitrogen compounds can exert a
chlorine demand; the demand exerted is related to their concentration in the wastewater.
For example, inorganic substances such as the sulfide, sulfite, nitrite, iron (II), and
manganese (II) ions all can exert a chlorine demand.8 If ammonia is present in the
wastewater stream the demand these species exert is reduced and sometimes even
eliminated.8
Contact Time
One of the most important parameters in chlorine disinfection is contact time.
Inactivation of pathogens increases with an increase in contact time. The disinfection
effectiveness is expressed as Ct; where C is the disinfectant concentration, and t is the
contact time necessary to inactivate the desirable amount of the pathogenic organism.3,7
In essence, the longer the provided contact time, the subsequently less chlorine is
15
necessary to achieve sufficient disinfection. Based on a comprehensive pilot plant study
Collins et al. developed an equation to determine bacterial inactivation at wastewater
treatment plants (Equation 2-9).6 The equation fits best where good initial mixing
followed by plug flow conditions occur. The wastewater at the KWRF is first filtered
prior to chlorine disinfection. Accordingly, the initial bacterial concentration would
probably range from 3,000 to 10,000 coliforms per 100 mL.6
3]23.01[ −⋅+= ctyy o (2-9)
yo = initial bacterial concentration prior to chlorination y = bacterial concentration at end of contact chamber or at time T in minutes c = initial chlorine concentration t = contact time in minutes
The model can be used to predict bacterial inactivation in wastewater given the
HRT provided in the disinfection chamber. As the model demonstrates, the disinfection
of wastewater with chlorine depends greatly on chlorine concentration addition as well as
contact time. The KWRF uses chlorine contact basins, described earlier, to provide the
contact time necessary to inactivate the indicator organisms, total and fecal coliforms.
As wastewater chlorine demand changes the chlorine addition is altered to provide
adequate disinfection.
Disinfection By-Product Formation
Though the chlorination of wastewater is beneficial in inactivating disease-causing
organisms it can also cause the formation of potentially harmful and carcinogenic
compounds. According to epidemiological studies there is a correlation between water
chlorination and rectal and bladder cancer cases.11 When organic compounds or
precursors such as natural organic matter (NOM), humic and fulvic acids, are present
16
during chlorination they may react with the free chlorine to form what are collectively
called disinfection-by-products (DBPs).4
The main concern for public health surrounds the formation of DBPs known as
trihalomethanes (THMs) and haloacetic acids (HAAs). Because of the public health
concern surrounding these compounds, the federal Environmental Protection Agency
(EPA) has imposed a maximum concentration allowed in drinking water. As of 2004 the
regulatory drinking water MCL standards for TTHM and HAA(5) are 80 µg/L and 60
µg/L, respectively.12 THM species include chloroform (CHCl3), a known human
carcinogen, bromoform (CHBr3), bromodichlormethane (CHBrCl2), and
dibromochlormethane (CHBr2Cl) (Figure 2-3). The five HAA species that are currently
under regulation include monochloroacetic acid (MCAA), monobromoacetic acid
(MBAA), dichloroacetic acid (DCAA), dibromoacetic acid (DBAA), and trichloroacetic
acid (TCAA) (Figure 2-4).8,13 There are several factors that can affect the formation of
these DBPs, such as, temperature, pH, precursor concentration, chlorine dose, contact
time, and bromide concentration.
Figure 2-3. The THM species.
Chloroform
H
Cl
C Cl
Cl
Bromoform
H
Br
C Br
Br
Bromodichloromethane
H
Cl
C Cl
Br
Dibromochloromethane
H
Cl
C Br
Br
17
Figure 2-4. The HAA(5) species.
The natural organic matter (NOM) present in wastewater is a precursor for DBPs
during chlorination.11 The NOM is measured as dissolved organic carbon (DOC) or total
organic carbon (TOC). NOM consists largely of aromatic compounds, thus, studies have
found that aromaticity was a good surrogate for the prediction of DBP formation.14,15 In
general, as the NOM concentration increases the DBP formation during chlorination also
increases. This increase in DBP formation is the result of an increase in these DBP
precursors but also is due to the increase in chlorine demand exerted by the NOM.11
With the increase in chlorine demand a higher chlorine dose is necessary to maintain the
required chlorine residual. The increase in chlorine dose will result in an increase in DBP
formation. In one study, lower molecular weight NOM compounds resulted in a higher
H
Cl O
H
C C OH
Monochloroacetic acid (MCAA)
Br
H
O
H
C C OH
Monobromoacetic acid (MBAA)
Cl
Cl O
H
C C OH
Dichloroacetic acid (DCAA)
Dibromoacetic acid (DBAA)
Br O
H
C C OH Br
Trichloroacetic acid (TCAA)
Cl
Cl O
C C OH
Cl
18
total trihalomethane (TTHM) yield.16 In general, as the molecular weight of the NOM
present in the water or wastewater decreased the TTHM yield increased.16 In one study,
findings showed that when chlorine is applied to water containing NOM the hydrophobic
NOM fraction resulted in a higher DBP formation than the equivalent hydrophilic
fraction.17 Through the oxidation of NOM with chlorine intermediate compounds may
form.11 These intermediates are further oxidized by chlorine, or bromine, to form DBPs.
Generally, as precursor concentration, NOM, increases so does the DBP production, but
it will tend to plateau and even decline after the residual chlorine is exhausted.1 The
apparent decrease in THM production shown in the study done by Pregeant et al. which
was carried out at high precursor concentrations was hypothesized to result from the
predominance of THM intermediates when excess precursors existed.1 The reactions that
result in the direct formation of DBP tend to occur more quickly and form earlier during
the chlorination process than those that have an intermediate step.11
Environmental factors such as bromide concentration and the amount of natural
organic matter affect the amount of DBPs formed during chlorination. Chlorine oxidizes
the bromide ion forming hypobromous acid (HOBr) and hyprobromite (OBr-) ion,
depending on the pH.18 The hypobromous acid and, to a lesser extent, the hypobromite
ion react with DBP precursors by oxidation and substitution reactions to form brominated
DBPs.11,18 As the bromide concentration increases the chlorinated HAA concentration
decreases.18 Given the same chlorine dosing, the addition of the bromide ion results in an
increase in the HAA concentration. Studies have also shown that the hypobromous acid
oxidizes NOM more readily than hypochlorous acid.11,18,19 In one study it was
determined that bromine reacted ten times faster with NOM isolates than chlorine.19 The
19
presence of the bromide ion (Br-) in the wastewater stream can greatly alter the speciation
and formation of THM and HAA during chlorination.18 The free chlorine oxidizes the
Br- to hypobromous acid (HOBr) (Equation 2-10); HOBr will ionize as the pH increases
to OBr-.
−− +→+ ClHOBrBrHOCl (2-10)
The bromide ion can have a substantial effect on the mass concentration of DBP as
bromine has a greater molecular weight, 80, than chlorine, 35.5. The DBPs formed when
HOBr reacts with organic precursors have a higher molecular weight than those with
chlorine. This is a concern as the EPA MCLs for DBP are on a mass basis, µg/L, and
not a molar basis.
As the temperature of the wastewater increases so does the HAA and THM
concentrations. The pH has a variable effect on the DBP concentration. Studies have
found that as the pH is increased from 6 to 8, the THM formation also increased but
resulted in a lower HAA formation.11,17,20 When the pH is lowered from a neutral pH to 6
the HAA formation increased.11,17
A longer chlorine contact time will result in a higher DBP formation because more
time is allowed for chlorine to react with NOM. An increase in contact time will allow
those reactions that require intermediate steps more time to react to completion. The
formation of THM increases as time allowed for reaction with free chlorine increases, or
the contact time, though the rate of formation is not constant. The chlorine dose has a
similar effect on DBP formation as the dose increases so does the DBP concentration
20
sometimes reaching a plateau.1 The chlorine dose can also affect the speciation of DBP as
the dose increases the ratio of THM to total halogenated DBP ratio also increases.
Modeling of DBP formation. Disinfection by-product formation modeling helps
to predict the amount of DBP formed during the chlorination of a feed water if the
necessary parameters are known. The EPA has developed disinfection/disinfection by-
product rule models to predict THM and HAA formation to determine operational and
economic impacts of setting new MCLs.13 The models used to predict THMs were
developed by Malcome Pirnie and models used to predict HAAs were developed by Dr.
Charles Haas, contracted by the AWWA D/DBP Technical Advisory Workgroup
(TAW).13 Since the KWRF provides tertiary wastewater treatment where additional
solids are removed by the six media filters the EPA models developed for drinking water
are applicable..
AWWA contracted Montgomery Watson to develop new model equations for
individual THM and HAA species and published the findings in a March 1993 report.13
Environmental parameters used in the formation of the model equations include bromide
concentration, TOC, ultraviolet light absorbance at 254 nm, temperature, chlorine dose,
pH, and reaction time. Using the basic equation (Equation 2-11)13, as a guideline the
coefficients for each environmental variable were determined through a step-wise
regression model procedure for individual THM and HAA species.
gfedcba TIMEUVBRDOSECLTEMPpHTOCkDBP )()254()()2()()()( ∗−∗∗∗∗∗∗= (2-11)
k, a, b, c, d, e, f, and g are empirical constants
21
The program STATVIEW® was used in the step-wise regression procedure to determine
the coefficients. Another study showed that if the data is available nitrate, calcium, and
alkalinity could be used in the prediction of THM formation.21
Chloroform made up the majority of the TTHM concentrations in this study and
thus the AWWA model equation for chloroform (Equation 2-12) 13 was used to normalize
the sampling sets; an explanation of the normalization method used is in the Materials
and Methods section.
269.0874.0254
404.01561.02
018.1161.1329.03 ]01.0[][][064.0 tUVBrDoseClTpHTOCCHCl += − (2-12)
1254
122
3
/
//
)()(
/
−
−
=
=
−==
=°=
=
cmUVLmgBr
ClLmgDoseClLmgTOC
hrsTimetCeTemperaturT
LgCHCl µ
The model predicted chloroform concentration is plotted versus the observed
chloroform concentration for the whole model development database from the March
1993 AWWA report (Figure 2-5).13 A perfect prediction would result in a slope of 1, the
farther from the perfect prediction line the less accurate the prediction.13 The prediction
versus the actual chloroform coincides better from 0 to 200 µg/L than concentrations
greater than 200 µg/L. Typical wastewater TTHM concentrations do not exceed
200 µg/L.13
22
Figure 2-5. Predicted versus the observed concentration of CHCl3 for the entire model development database from the 1993 AWWA report.
The AWWA model equation for dichloroacetic acid (DCAA) was used to
normalize HAA(5) concentrations of the sampling sets, an explanation of the
normalization method is in the Materials and Methods section. The relationship of the
variable environmental parameters in the formation of the HAA(5) species DCAA is
shown in (Equation 2-13).13
726.0239.0568.01480.0
2665.0291.0 ]254[]01.0[][][][605.0 −+= −− UVtBrDoseClTempTOCDCAA (2-13)
CTempLmgBr
ClLmgDoseClLmgTOC
hrsTimetLgDCAA
o=
=
−==
==
− /
//
)(/
122
µ
23
The model predicted DCAA concentration was plotted versus the observed DCAA
concentration for the whole model development database from the March 1993 AWWA
report (Figure 2-6).13 The predicted concentrations do not correlate perfectly with the
observed values, however, the points lie close to the perfect prediction line, slope =1, and
is sufficiently accurate.13
Figure 2-6. Predicted versus the observed concentration of DCAA for the entire model development database from the 1993 AWWA report.
Sunlight/UV Irradiation
At the KWRF, chlorine disinfection of wastewater occurs in an open flow-through
basin. This allows sunlight to come in contact with the chlorinated water. Aqueous
chlorine is unstable when exposed to sunlight, which results in the degradation of free
chlorine within the wastewater stream (Equation 2-14).7
2222 OClHHOCl UV ++⎯→⎯ −+ (2-14)
24
The cost of this loss can add up since more chlorine is needed to achieve the
desired disinfection. In the 2002 IPPD study the chlorine residual was substantially
greater in a covered basin versus an exposed basin given the same initial chlorine dose
and contact time.10 The amount of chlorine loss to solar irradiation depends on the length
of exposure and the volume of wastewater irradiated, which in turn depends on the angle
of incidence between the sun and chlorine contact basin and the turbidity. In most cases
the photodecay of HOCl is assumed to follow a first-order reaction.22
The ultraviolet (UV) radiation degrades chlorine and is that portion of the
electromagnetic spectrum between wavelengths of 100 and 400 nm. UV radiation is then
divided into vacuum UV (100-200 nm), UV-C (200-280 nm), UV-B (280-320 nm), and
UV-A (320-400 nm).22
The transmittance of solar radiation through a medium is dependent on several
factors including the type (e.g. glass) and thickness of the medium, the angle of
incidence, and the specific wavelength or bands of radiation. Pyrex glass (borosilicate
type), is opaque to UV-B radiation and has maximum transmission at 340 nm and higher,
this is the UV-A portion of the spectrum.22 Plastics, such as, polystyrene (i.e. Lucite) and
methylmethacylate (i.e. Plexiglass) can have a higher radiation transmittance than glass at
wavelengths greater than 290 nm. Thus, these plastic materials have greater transmission
of germicidal solar radiation at wavelengths from 300 to 400 nm.22 In this study an
acrylic UV-transparent plastic was used as it allowed solar radiation, UV and global, to
come in contact with the wastewater during chlorination and was cost effective.
The sunlight inactivation of microorganisms in water and wastewater is
proportional to the sunlight intensity, contact surface area, and atmospheric temperature
25
and is inversely proportional to water depth.23,24,25 Sunlight inactivation, or disinfection,
is also dependant on the bacterial contamination load of the water, the more bacteria to
inactivate the longer the necessary exposure time.24 Turbidity and color also play a big
role in the inactivation of microorganisms through sunlight exposure.24,25 In one study, it
was reported that turbidity inversely affected the kill rate for all bacteria tested.23 In
general, a higher turbidity will require a longer sunlight exposure to obtain adequate
disinfection.23
Besides the inactivation of microorganisms, absorption of sunlight also tends to
increase the temperature of the exposed water. At higher water temperatures, greater
than 70°C, the bacterial inactivation is greater than at lower water temperatures, less than
65 °C.25,26 Studies have determined through the implementation of dark experiments
runs, chlorine dosing experiments that are performed with no sunlight exposure, that solar
radiation was the primary disinfecting factor when the water temperature was 9 to
26°C.27,28 According to sensitivity studies, fecal coliform were the most sensitive
microorganisms to sunlight inactivation among those microorganism tested, such as,
somatic coliphages and bacteriaphages.26,28,29
One concern of covering the chlorination basin is the removal of the natural
disinfecting property of sunlight. Though the chlorine dose will be higher in the covered
basin this may or may not coincide with higher coliform inactivation as the contribution
of sunlight to the wastewater disinfection process has yet to be quantified. The extent
sunlight will affect the chlorination process depends on how much sunlight reaches the
water in the basin. The different wavelengths within the sunlight spectrum have different
coliform inactivation potentials. As explained in Acra et al. the inactivation of coliform
26
bacteria decreases exponentially as the wavelength of light increases from 260 nm to 850
nm.22 Thus, the destruction of coliforms, and expectantly other bacteria too, is most
efficient at the lower wavelengths (260 nm to 350 nm), and is least efficient at the higher
wavelengths (550 nm to 850 nm). Thus, the UV-B and UV-A portions of the spectrum
possess the greatest inactivation potential.22
Wavelengths below 290 nm should not be included when considering solar
radiation, as they do not reach the surface.22 This phenomenon is due to diffusion, or
scattering, and absorption of light before it reaches the surface.22 The solar UV-A
intensity changes as the Earth’s angle of tilt changes. The highest intensity of UV-A
occurs during the summer months while the peak maximum and minimum occur at the
summer and winter solstice, respectively.22 Thus, the inactivation of coliforms by
sunlight is greater during the summer months. Also, chlorine loss is expected to be
highest during the summer as the degradation of chlorine is catalyzed by UV light.
27
CHAPTER 3 MATERIALS AND METHODS
Measured Parameters
Global Solar Radiation
Global solar radiation, or light, between 285 and 2800 nm wavelength was
measured using a Black and White Pyranometer (8-48) manufactured by Eppley
Laboratory, Newport, Rhode Island.
Ultraviolet Radiation
Ultraviolet radiation with a wavelength of 295 to 385 nm was measured using a
Total Ultraviolet Radiometer (TUVR) manufactured by Eppley Laboratory, Newport,
Rhode Island.
The radiometer and pyranometer were located on location at the KWRF
approximately 0.5 m from the pilot basin system. Radiation measurements for both
instruments were recorded every 5 minutes throughout the pilot and full-scale runs. The
millivolt outputs from the pyranometer and radiometer were stored in a Campbell
Scientific CR510 datalogger. The datalogger was powered using the Campbell Scientific
PS100 Power Supply and Charging Regulator. Using the Campbell Scientific SC32B
Optically Isolated RS-232 interface the data were transferred from the datalogger to the
laptop computer for analysis. The radiometer, pyranometer, and datalogger setup is
shown in (Figure 3-1).
28
Figure 3-1. Radiometer, pyranometer, and datalogger setup.
Total and Free Chlorine Residual
Both total and free chlorine residual were measured in the inlet and effluent
samples for the pilot and full-scale experiments. The DPD method was used with the
HACH DR 2000 Spectrophotometer to determine total and free chlorine residual in the
field. The method was equivalent to the US EPA 330.5 method for wastewater, standard
method 8167 for total chlorine and standard method 8021 for free chlorine residual. A
sample of wastewater was collected from the respective sampling area and diluted using
deionized water when necessary. According to a chlorine residual test performed on June
10, 2004 the deionized water resulted in no chlorine residual addition nor a chlorine
demand.
The HACH DR 2000 spectrophotometer wavelength calibration was performed on
June 10, 2004 and again on August 6, 2004. In both calibration events the wavelength
did not need to be adjusted demonstrating that the spectrophotometer was still in line and
CR510 Datalogger
Radiometer
Pyranometer
29
was giving accurate readings. A chlorine residual calibration was also preformed on
those days, using chlorine free glassware, by comparing the residual concentration
reading from the DR2000 field spectrophotometer to that of the lab HACH DR2010
spectrophotometer, no difference was observed between the two readings.
Total Suspended Solids
The KWRF lab uses EPA method 160.2 to measure the total suspended solid
concentrations in the effluent wastewater samples. Samples were taken from the inlet
and the two effluents for the pilot and full-scale studies. Plastic one-gallon containers
were used in the collection of samples for the total suspended solids analysis. Directly
after collection the samples were taken to the KWRF lab and refrigerated until analyzed,
the time between collection and placement in the refrigerator did not exceed 15 minutes.
Total Coliform
The KWRF lab uses Standard Method 9222B to analyze the wastewater samples to
determine the total coliform population of the samples. Total coliform counts were
measured in lieu of fecal coliform since fecal coliform are more easily inactivated than
other species that make up total coliforms. Fecal coliform are also more easily damaged
by UV radiation than other total coliform species. Samples were taken from the inlet and
the two effluents for the pilot and full-scale studies. Glass 1 L Whatman containers and
100 mL plastic containers, for pilot basin inlet samples (pre-chlorination), were
autoclaved and supplied by the KWRF lab and used in the collection of wastewater
samples for the total coliform analysis. Directly after collection the samples were taken
to the KWRF lab and refrigerated until analyzed, the time between collection and
placement in the refrigerator did not exceed 15 minutes.
30
Trihalomethane (THM)
The THM speciation and concentration was determined following the EPA Method
624, method for organic chemical analysis of municipal and industrial waste.30 Dr. M.
Booth performed the THM sample analyses at the University of Florida, Department of
Environmental Engineering and Sciences Analytical Sciences Lab (ASL). The following
materials were used in the sampling stage of the THM analysis:
• 40 mL amber glass VOA sampling vials • Teflon septa • Sodium Thiosulfate, to quench chlorine residual • Tekmar 3100 Purge-and-Trap Concentrator • Finnigan Trace 2000 GC/MS • Gas-Chromatograph: Restek Rtx-VMS capillary column, 30m x 0.32 mm I.D.,
1.8 µm film thickness • Mass Spectrometer: Electron Ionization, 34 amu to 280 amu in 0.4 seconds
Sample GC/MS curves as well as THM analysis conditions can be found in
Appendix G. For the pilot basin system the THM samples were collected at the effluent.
Both the inlet and effluent samples were collected for the full-scale system. The samples
were stored on ice directly after collection and transferred to the ASL for analysis at the
end of each sampling day. The samples were then stored in the lab refrigerator until they
were analyzed. In all instances, the samples were analyzed within the suggested holding
period.
Haloacetic Acid (HAA)
The HAA speciation and concentration was determined following the EPA Method
552.2, determination of haloacetic acid and dalapon in drinking water by liquid-liquid
extraction, derivation and gas chromatography with electron capture detection.31 The
derivation and methylation of the HAA samples were performed at the University of
31
Florida ASL. The following materials were used in the sampling stage of the HAA
analysis:
• 40 mL amber glass VOA sampling vials • Teflon septa • Ammonium Chloride, to quench chlorine residual • Hewlett-Packard 5890 Series II GC/ECD • Gas-Chromatograph: Restek DB5MS Capillary Column, 30m x 0.25 mm I.D., 0.25
um film thickness
Sample GC/ECD curves as well as HAA analysis conditions can be found in
Appendix G. For the pilot basin system the HAA samples were collected at the effluent.
Both the inlet and effluent samples were collected for the full-scale system. The samples
were stored on ice directly after collection and transferred to the ASL for analysis at the
end of each sampling day. The samples were then stored in the lab refrigerator until they
were analyzed. The methylation procedure was performed within 3 days of sample
collection, well within the suggested holding time. Dr. M. Booth then analyzed the
methylated samples within the suggested holding period.
pH
The pH of the feed and effluent streams for the pilot and full-scale studies was
measured using the Orion model 290A pH meter with the 9157BN-thermo temperature
compensating probe. Every morning, prior to sampling, the pH meter was calibrated
using 3-point calibration with pH buffer solutions 4, 7, and 10.
Conductivity
The conductivity of the feed and effluent streams for the pilot and full-scale studies
was measured using the Fisher Scientific 09-328 Automatic Temperature Compensation
Conductivity probe. The conductivity probe meter was calibrated every morning using a
0.01 N KCl solution.
32
Dissolved Oxygen
The dissolved oxygen (DO) of the feed and effluent streams for the pilot and full-
scale studies was measured using the YSI Dissolved Oxygen/Temperature Meter (YSI
Model 57/ YSI 5739). Every morning the probe was checked for air bubbles from
membrane weakening. If air bubbles were present then the probe solution and membrane
were replaced.
Sampling
Wastewater sampling from the respective location (i.e. inlet or effluent in the pilot
or full-scale system) and parameter was collected in a manor to limit aeration while also
obtaining a good representative sample. The parameters that were analyzed by the
KWRF lab, TSS and total coliform, were stored in the lab refrigerator directly after a
sampling. The KWRF samples were put in the refrigerator within 15 minutes of
collection. Those samples that were analyzed at the University of Florida Department of
Environmental Engineering and Sciences ASL, THM and HAA, were stored on ice after
collection and then transported to the lab after the last sample of the day was collected.
The samples were then transferred to a refrigerator located in the ASL where they were
then analyzed using their respective method.
Pilot Scale System
The plant chlorine contact basins, North and South, (Table 3-1) are setup in series
where the wastewater first flows through the smaller and older North basin and then
through the larger South basin before it is finally deep well injected, used as reclaimed
water, or sent to the emergency holding pond. Each pilot basin (Table 3-2) was designed
to simulate the hydraulic retention time (HRT), flow pattern, and dimension ratios
through both the North and South chlorine contact basins. For example, the length to
33
width ratios seen in the two full-scale basins were averaged and used in the pilot basin
design. Full calculations can be found in Appendix A.
Table 3-1. Chlorine contact basin dimension ratios. South CCB North CCB Pilot basin L:W 1.2 L:W 1.0 L:W 1.1 L:H 6.3 L:H 5.3 L:H 5.8 W:H 5.2 W:H 5.3 W:H 5.3 C:W 0.1 C:W 0.1 C:W 0.1 No. of channels 8 No. of channels 10 No. of channels 9
L: Length, H: Height, W: Width, C: Channel Width
Table 3-2: Pilot chlorine contact basin dimension. Pilot basin dimensions
Length (ft) 4.0 Width (ft) 3.7 Height (ft) 0.7 No. channels 9
One basin was equipped with an opaque acrylic cover to block solar radiation from
entering and coming in contact with the wastewater during the disinfection step of the
treatment process. The second basin was equipped with an UV transmitting clear acrylic,
or UV-TRANS®, cover that will allow solar radiation, both UV and visible radiation, to
come in contact with the wastewater during disinfection. Thus, the basin with the UV
radiation transparent cover was termed the TRANS basin and the basin that prevented
UV and solar radiation exposure of the wastewater during the disinfection stage of
treatment was termed the OPAQ basin.
Each basin had one inlet and one outlet that have ¼ inch brass barbs, which allows
for the connection of the ¼ inch plastic tubing. The Analytical Research Systems Inc.
located in Micanopy, Florida constructed the basins to specifications presented to them.
A fluoroscein tracer analysis was performed on one of the basins to determine the flow
34
pattern of the pilot basins. It was determined that each pilot basin modeled as 41 tanks-
in-series with a t10 value of 61 minutes. The tracer analysis was performed with a flow
rate of 42 GPH, a HRT of 107 minutes, the full calculations are shown in Appendix B.
The feed water for the basins had gone through the plant filters but not the chlorine
contact basin. The feed water to the pilot basins was first dosed with a known
concentration of chlorine (NaOCl), and then split into two equal streams before entering
the pilot basins. The chlorine solution preparation is explained in the Chlorine Dosing
section. The chlorine solution was stored in a Nalgene container and added to the pilot
process using a Cole-Palmer Variable Speed Economy Driver pump with an Easy Load
LC-07518-60 head. A second pump and pump head was available for acid or base
addition for some experimental runs, again stored in a Nalgene container and added to the
pilot process using a Cole-Palmer Variable Speed Economy Driver pump with an Easy
Load LC-07518-60 head. Two static mixers were in place to give adequate mixing.
Flowmeters were in place on both basins to ensure steady and equal flow rates. The pilot
scale setup schematic and photographs of the system setup are shown in (Figure 3-2 and
Figure 3-3), respectively.
Wastewater Feed System Materials
• Tygon tubing o ½ inch ID o ¼ inch ID
• Static mixer, OD 5⁄8 inch, ID ½ inch • Barbed male pipe NPT connectors:
o Thread 1⁄8 inch, tube ID 1⁄16, clear polypropylene o Thread 1⁄4 inch, tube ID 1⁄4, natural polypropylene o Thread 1⁄4 inch, tube ID 1⁄2, natural polypropylene
• Female tee, pipe size ¼ inch, PFA • Female reducer, NPT(F) x NPT(F): ¼ x 1⁄8 inch, PVC • Barbed connector, 1⁄16 x 1⁄16 inch, Clear Polypropylene
35
Pump
Pump
Cl2
Acid
Stat
ic M
ixer
St
atic
Mix
er
Flow
Met
er
Flow
Met
er
TRANS Basin OPAQ Basin
Figure 3-2. Pilot basin system setup.
36
Figure 3-3. Pilot scale setup; chlorine and acid/base solution containers, solution pumps, influent water spigot, static mixers, t-split, TRANS and OPAQ basins.
Ten pilot-scale runs were performed at the KWRF. The experimental matrix was
as follows:
• 3 baseline runs o HRT = 2.75 h o Chlorine dose = 7.5-8.0 mg/L Cl2 o pH = no acid/base adjustment
• 3 low flow runs o 2 low flow runs/average chlorine dose
HRT = 3.81 hours Chlorine dose = 9-12 mg/L Cl2 pH=No acid or base adjustment
o 1 low flow run/high chlorine dose HRT = 3.81 h Chlorine dose = 16 mg/L Cl2 pH = no acid or base adjustment
• 1 high chlorine residual o HRT = 2.75 h o Chlorine dose = 8.2 mg/L Cl2 o pH= no acid or base adjustment
37
• 1 low chlorine residual o HRT = 2.75 h o Chlorine dose = 6.5 mg/L Cl2 o pH= no acid or base adjustment
• 1 low pH o HRT = 2.75 h o Chlorine dose = 7 mg/L Cl2 o pH = increased pH (H2SO4 addition) effluent average = 6
• 1 high pH o HRT = 2.75 h o Chlorine dose = 7 mg/L Cl2 o pH= lowered pH (NaOH addition) effluent average = 9
Chlorine Dosing
Clorox bleach (NaOCl) was diluted in order to make the chlorine solutions for the
pilot scale study. The standard method Iodometric method I, standard method 4500 Cl B,
was used to determine the total chlorine concentration in the concentrated Clorox
solution. The concentrated Clorox solution was then diluted with deionized water to
provide the desired concentration for dosing in the pilot basin experimental runs. Prior to
use the chlorine dosing solution concentration was measured to determine the actual
concentration. The full calculation for all of the chlorine solutions used to chlorinate the
pilot basins can be seen in Appendix C.
Pump Test
In order to determine the pump rate provided by the different settings on the Cole-
Palmer Variable Speed Economy Driver pump with an Easy Load LC-07518-60 head a
pump test was performed. The tube used in the system to provide solution dosing was
placed in a graduated cylinder filled with tap water. The beginning volume was recorded,
the pump was then set at a numbered position on the pump, the pump was started, and
then the volume was recorded after a certain time laps had occurred.
38
Full Scale
In the full-scale study the North basin was used since it was the first basin in the
series of the two chlorine contact basins and the wastewater had yet to be exposed to UV
radiation while containing chlorine. The influent wastewater was split at the inlet into
two parallel streams. The North basin is 58 ft long and 59 ft wide. A previous study at
the KWRF determined that the North and South basins together model as 60 tanks-in-
series while the North basin models as 100 tanks-in-series separately.2 One of the
parallel streams of the basin, 58 ft by 30 ft area, was covered with three polypropylene
tarps to prevent the wastewater from being exposed to UV radiation, the (COV) side.
The other side of the basin was left exposed to sunlight radiation, the (UNCOV) side
(Figure 3-4 (a)). The tarps were held down by concrete blocks (Figure 3-4 (b)), while
ropes were tide to rings located along the sides of the tarps. The ropes were then tied to
concrete blocks located on the ground along the sides of the basin. The concrete blocks
holding down the tarps were then removed. There were three full-scale experimental
runs performed for this study at the KWRF.
Figure 3-4. Full-scale setup. (a) Uncovered side of the basin. (b) Covered side of the basin during the full-scale study.
The flow rates and chlorine dose for the full-scale study were the consequence of
the KWRF operation on the days of the study and were recorded by the operators in the
39
daily operations log. The daily operations logs were used to formulate the discharge
monitoring report (DMR) for the Department of Environmental Protection (DEP).
Sampling points in the post-aeration basin and North chlorine contact basin for the
full-scale study are shown in (Figure 3-5). The sampling points are as follows:
1. Post-aeration basin effluent; wastewater sample directly prior to chlorine injection
2. North chlorine contact basin inlet; where the wastewater first enters the basin and directly prior to splitting into parallel flows
3. Covered side effluent; directly prior to recombination of parallel flows and the South basin
4. Uncovered side effluent; directly prior to recombination of parallel flows and the South basin
Figure 3-5. Sampling points in the post-aeration for the full-scale study.
Post-Aeration
Basin
North ChlorineContact Basin
(2)
(3)
basin and North chlorine contact basin
(1)
(4)
40
Calculations
Disinfection By-Product Data Normalization
To determine if other factors (i.e. UV and global radiation) are affecting the DBP
formation in the pilot and full-scale systems the TTHM and HAA(5) concentrations were
normalized to variable parameters (e.g. temperature) that are known to affect their
formation. Among the parameter differences, there was a definite temperature
differentiation between the TRANS and OPAQ basin in the pilot scale system and also
between the COV and UNCOV sides of the North chlorine contact basin in the full-scale
system resulting from absorption of radiation by the exposed wastewater. Temperature
data can be found in the discussion sections and also in Appendix E and F.
Trihalomethane normalization
To compensate for the difference in effluent conditions, such as, chlorine residual,
temperature, and pH the effluent TTHM concentrations were normalized. Normalization
factors for temperature, pH, and free chlorine residual were used to adjust the
concentrations. Since chloroform makes up the majority of the TTHM in every sampling
set, the modeling equation for coliform was used in the normalization of the THM
concentrations. (Equation 3-1) shows the relationship of chloroform formation to
temperature, pH, chlorine residual, and contact time. The model was taken from a March
1993 American Water Works Association report on modeling DBP formation during
chlorination at potable water treatment plants.13
269.0874.0254
404.01561.02
018.1161.1329.03 ]01.0[][][064.0 tUVBrDoseClTpHTOCCHCl += − (3-1)
)()(
/3
hrsTimetCeTemperaturT
LgCHCl
=°=
= µ
LmgBr
ClLmgDoseClLmgTOC
/
//
122
=
−==
−
1254
−= cmUV
41
In the normalization process the OPAQ basin and COV side effluent TTHM
concentrations were normalized to TRANS basin and UNCOV side effluent TTHM
concentrations, respectively. Normalization factors were calculated from parameter data
collected during each sampling run. The equation for each parameter normalization
factor was developed from Equation 3-1. Equations 3-2, 3-3, and 3-4 are the pH,
chlorine residual, and temperature normalization factor equations, respectively, for the
normalization of TTHM concentration of the OPAQ basin to the TTHM concentration of
the TRANS basin. The free chlorine residual was used in the normalization process. The
equations for the full-scale study were the same except the parameters of the COV and
UNCOV sides were used.
pH Normalization Factor
161.1
⎟⎟⎠
⎞⎜⎜⎝
⎛=
OPAQ
TRANS
pHpH
(3-2)
Chlorine Residual Normalization Factor
561.0
⎟⎟⎠
⎞⎜⎜⎝
⎛=
OPAQ
TRANS
ClCl
(3-3)
Temperature Normalization Factor
018.1
⎟⎟⎠
⎞⎜⎜⎝
⎛=
OPAQ
TRANS
TT
(3-4)
In order to normalize the OPAQ basin, or COV side of the North basin, the effluent
TTHM concentration was multiplied by these normalization factors. The normalized
TRANS and OPAQ basin, or UNCOV and COV sides, TTHM concentrations were then
compared to determine if other parameters (i.e. solar radiation) had any influence on the
TTHM formation.
42
Haloacetic acid normalization
In order to compensate for the difference in effluent conditions (i.e., chlorine
residual) the effluent HAA concentrations were normalized. Normalization factors for
temperature and free chlorine residual were used to adjust the concentrations. Since
DCAA makes up the majority of the HAA(5) in the greatest number of sampling sets
compared with the other species the model equation for DCAA was used in the
normalization of the HAA(5) concentrations. Equation 3-5 shows the relationship of
DCAA formation to temperature and chlorine residual. The model was taken from a
March 1993 American Water Works Association report on DBP formation during
chlorination at potable water treatment plants.13
239.0665.0
568.01480.02
726.0291.0
][
]01.0[][]254[][605.0
tTemp
BrDoseClUVTOCDCAA −− +−=(3-5)
LmgBr
ClLmgDoseClLmgTOC
hrsTimetCeTemperaturTemp
LgDCAA
/
//
)()(
/
122
=
−==
=°=
=
−
µ
In the normalization process the OPAQ basin and COV side effluent HAA(5)
concentrations were normalized to TRANS basin and UNCOV side effluent HAA(5)
concentrations, respectively. Normalization factors were calculated from parameter data
collected during each sampling run. The equation for each parameter normalization
factor was developed from Equation 3-5. Equations 3-6 and 3-7 are the temperature
and chlorine residual normalization factor equations, respectively, for the normalization
of HAA(5) concentration of the OPAQ basin to the HAA(5) concentration of the TRANS
43
basin. The free chlorine residual was used in the normalization process. The equations
for the full-scale study were the same except the parameters of the COV and UNCOV
sides were used.
Temperature Residual Normalization Factor
665.0
⎟⎟⎠
⎞⎜⎜⎝
⎛=
OPAQ
TRANS
eTemperatureTemperatur
(3-6)
Chlorine Residual Normalization Factor
480.0
⎟⎟⎠
⎞⎜⎜⎝
⎛=
OPAQ
TRANS
ClCl
(3-7)
In order to normalize the OPAQ basin, or COV side of the North basin, the effluent
HAA(5) concentration was multiplied by these normalization factors. The normalized
TRANS and OPAQ basin, or UNCOV and COV sides, HAA(5) concentrations were then
compared to determine if other parameters (i.e. solar radiation) had any influence on the
HAA(5) formation.
Average Radiation
The average UV and global solar radiation exposure of the wastewater over the
HRT of the wastewater in the pilot basin was calculated for each sampling set. Equations
3-8 and 3-9 were used to calculate the UV and global solar radiation, respectively.
Average UV radiation HRT
UVHRTt
t∑=
== 0 (3-8)
UV= UV radiation readings taken every 5 minutes (mW/cm2) t =minutes of retention time in the pilot basin
HRT=hydraulic retention time (min)
44
Average global solar radiation HRT
GSRHRTt
t∑=
== 0 (3-9)
GSR=Global solar radiation reading taken every 5 minutes (mW/cm2) t =minutes of retention time in the pilot basin
HRT=hydraulic retention time (min)
Standard Deviation
The standard deviation is a measure of how different values are from the average or
mean value (Equation 3-10).
( ))1(
22
−
−= ∑ ∑
nnxxn
STD (3-10)
STD = Standard Deviation n = number of arguments
x = value of argument (n)
Paired T-Test
The paired t-test was the statistical method used to determine if there were
statistical differences between sets of collected data from the pilot and full-scale studies.
The paired t-test is a variation of the standard t-test and is used to compare two treatment
methods where experiments are performed in pairs and the differences are of interest.
Since sample collection was performed in pairs in the pilot and full-scale studies and the
differences in the collected data sets are of interest, the paired t-test was appropriate to
use. The t*-value used in the paired t-test was calculated using Equation 3-11.
nS
DtD
δ−=* (3-11)
samples ofnumber ndeviation StandardS 0
differenceMean D value* t *t
D
===
==δ
45
The t* values are then compared with the t-value for a given degree of freedom and
level of significance. If a t* value is greater than the t-value in the standard Student t
table, the difference is said to be significant to the degree found in the table.
Linear Correlation
In order to evaluate the linear correlation between two difference parameters the
one tailed t-test with the Pearson product moment correlation coefficient. The Pearson
Product momentum, r, varies between –1 and 1 and is unitless. An r-value of –1 and 1
represents a perfect negative and perfect positive correlation, respectively. The larger the
absolute value of the Pearson product momentum the stronger is the degree of linear
relationship between the two parameters. The Pearson Product momentum was
calculated using Equation 3-12.
[ ] [ ] 2122
12
1
)()(
))((
∑∑
∑−−
−−= =
yyxx
yyxxr
ii
n
iii
xy (3-12)
To determine if the linear correlation was significantly different from zero a
significance t-test was performed. First, two test hypothesis were established the first
being the null hypothesis, H0, where the correlation is assumed to be zero. The second
hypothesis, H1, assumes the other case where the correlation is greater than zero. The
one tailed t-test was used to determine which hypothesis was valid. The t* value used in
the correlation determination was calculated using Equation 3-13.
212*
rnrt−
−= (3-13)
46
If the calculated t* value was greater than the t critical value, tc, for a given level of
significance for the set degrees of freedom than the second hypothesis, H1, was accepted
to be true. The degrees of freedom for the linear correlation t-test was n-2. If the t*
values was found to be less than the tc the null hypothesis was accepted and the H1
hypothesis was rejected.
47
CHAPTER 4 DISCUSSION: PILOT-SCALE BASIN
As stated previously, the pilot basin with the opaque cover that prevented solar
radiation exposure of the wastewater was termed the OPAQ basin. The basin with the
transparent cover that allows solar radiation (UV and global radiation) exposure of the
wastewater was termed the TRANS basin. For consistency, the comparisons between the
TRANS and OPAQ basin in all cases have the OPAQ basin effluent concentration
subtracted from the TRANS basin effluent concentration. The paired t-test statistical
analysis, along with the Pearson product momentum correlation coefficient, values used
in the following pilot-scale study discussion can be found in Appendix H.
Solar Radiation/Temperature
In this study, wastewater that had been treated by the KWRF through filtration was
put through one of two parallel pilot chlorine contact basins. The basins were identical
except that one pilot basin was covered with a plastic cover that allows UV and global
radiation to pass and come in contact with the wastewater (TRANS), while the second
basin was covered with a black plastic cover that was opaque to both the UV and global
radiation thus preventing the wastewater from becoming exposed to radiation (OPAQ).
The linear correlation between UV and global radiation is shown in Figure 4-1.
The Pearson product momentum correlation coefficient for this relationship was 0.996
and the resulting t-test showed a 99% confidence in a liner correlation between UV and
global radiation. Since, the radiation patterns match each other so well, only UV
radiation was used in the analysis of chlorine residual, DBP, and other parameter data.
48
0
20
40
60
80
100
120
0.00 1.00 2.00 3.00 4.00 5.00
Average UV Radiation (mW/cm2)
Ave
rage
Glo
bal H
oriz
onta
ls R
adia
tion
(mW
/cm
2)
Figure 4-1. Average global horizontal radiation versus the average UV radiation over the HRT.
Solar radiation increases the temperature of exposed water. The TRANS basin had
a translucent cover allowing for the exposure to UV radiation during the chlorine
disinfection resulting in the increase in effluent temperature. As the average UV
radiation intensity increased during the day, the pilot basin effluent temperature also
increased. The effluent temperatures of both the pilot basins are plotted versus the
average UV radiation (Figure 4-2). An increase in solar radiation also results in an
increase in air temperature as well as the heating of the basins themselves. The
wastewater used in OPAQ basin was not exposed to solar radiation during the chlorine
disinfection process. However, before the pilot basins, the wastewater went through
previous KWRF treatment processes in which it was exposed to solar radiation. So it was
expected that the OPAQ basin effluent temperature would rise due to these conditions.
49
25.0
27.0
29.0
31.0
33.0
35.0
0.00 20.00 40.00 60.00 80.00 100.00 120.00
Average UV Radiation (mW/cm2)
Tem
pera
ture
(°C
)
TRANS (TEMP) OPAQ (TEMP)
Figure 4-2. The effluent temperature of the TRANS and OPAQ basins plotted versus the average UV radiation exposure of the TRANS basin over the HRT.
To determine if the difference in UV radiation exposure of the basins caused the
effluent temperatures to differ, statistical paired t-tests were performed and the difference
in the effluent temperatures of the TRANS and OPAQ basins was plotted versus the
average UV radiation the wastewater was exposed to while in the pilot basin (Figure 4-3).
The results of the paired t-test showed a 99% confidence level that the basin effluent
temperatures were different. Therefore, the opaque cover of the OPAQ basin resulted in
a significantly lower effluent temperature. The Pearson product momentum correlation
coefficient for the relationship between the effluent temperature differences and the
average UV radiation exposure was 0.884 resulting in a 99% confidence in a linear
correlation. Thus, the higher effluent temperature of the TRANS basin over the OPAQ
basin can be attributed to an increase in the average solar radiation exposure while in the
basin. An increase in water temperature enhances the rate of reactions according to the
Arrhenius law. Therefore, the increase in water temperature results in an increase of
chlorine consumption in a variety of reactions and consequently results in lower chlorine
50
residual. Also, an increase in temperature will increase the formation of DBP, both
HAA(5) and TTHM, other variables being held constant.
0.0
1.0
2.0
3.0
4.0
0.00 1.00 2.00 3.00 4.00 5.00
Average UV Radiation (mW/cm2)
Tem
pera
ture
(°C
)
Figure 4-3. Difference in effluent temperature of the basins (TRANS-OPAQ) plotted versus the average UV radiation over the HRT.
Chlorine Residual
The chlorine residual was monitored during each experimental run of the pilot
basins; a constant chlorine dose was set for each pilot run. During the baseline runs the
HRT was 2.75 h and the chlorine dosing was kept between 7.5 and 8.0 mg/L Cl2, in
order to replicate full scale residual conditions, from between 4 pm the day prior to
sampling to 2 pm the day of the sampling. Because it was a pilot study, environmental
conditions like solar radiation and influent wastewater composition could not be
controlled. However, solar radiation, UV and global radiation, as well as pH,
temperature, dissolved oxygen, and conductivity were measured during the pilot studies
to determine the effect, if any, these factors have on chlorine residual and disinfection-
by-product (DBP) formation.
Because the pilot study used filtered wastewater from the KWRF the composition
of the wastewater was not controlled. Depending on the composition of the incoming
∆ ∆
51
wastewater the chlorine demand and the DBP formation potential could change during
the course of the experimental run. The filtered wastewater was dosed with chlorine and
then split into the two parallel pilot basins. Though the influent wastewater could have
fluctuated in chlorine demand and DBP formation potential, each basin received the same
influent wastewater with the same pH and chlorine dose. Since it was a comparison
study of the two basin setups on the effect of solar radiation on chlorine residual,
disinfection effectiveness, and DBP formation, the fact that the influent wastewater
composition was not constant did not affect the outcome of the study. Accordingly,
statistical analyses were made with the paired t-test.32
Free Chlorine
As previously stated, KWRF uses Cl2 gas addition to disinfect the wastewater prior
to discharge, or reuse. The regulatory agencies, EPA and Florida DEP, require the
KWRF effluent to have a free chlorine residual of at least 1 mg/L Cl2. Other than the
chlorine demand of the wastewater, UV radiation also exerts some chlorine demand in
the wastewater, as shown earlier in Equation 1-1. Thus, enough chlorine must be
added to meet the chlorine demand of the wastewater, compensate for the UV radiation
exposure reduction, as well as maintain a sufficient effluent residual.
The effluent free chlorine residual data for the (TRANS-OPAQ) pilot basins was
partitioned into range increments for comparison (Figure 4-4). Most samples were in the
>2.0 mg/L Cl2 residual range increment for both the TRANS and OPAQ basins.
However, the OPAQ basin had a greater number of samples, 11, than the TRANS basin,
8, at the >2 mg/Cl2 residual increment. The higher chlorine residual ensures a greater
chemical disinfection potential.
52
0
2
4
6
8
10
12
<0.5 0.5-1.0 1.0-1.5 1.5-2.0 >2.0
Free Chlorine (mg/L Cl2)
# of
Insta
nces
TRANS Free Cl2 OPAQ Free Cl2
Figure 4-4. Free chlorine residual sampling sets in particular residual ranges for the TRANS and OPAQ basins.
The only difference between the two basins was the exposure to UV radiation, in
order to determine if this was the cause of the chlorine residual differences and to
ascertain if the differences between the two basins was statistically different, the
difference in the free chlorine residual of the (TRANS-OPAQ) basins for each
experimental run was plotted versus the average UV radiation the wastewater was
exposed to over the respective HRT (Figure 4-5). The majority of the points of the plot
were negative and were in the fourth quadrant, showing that the OPAQ basin effluent had
a higher chlorine residual than the TRANS basin in almost all of the sampling runs. Only
in three sampling times was the TRANS basin effluent free chlorine residual higher than
the OPAQ effluent. The largest free chlorine difference between the two basins was
-2.40 mg/L Cl2 (TRANS-OPAQ) at an average UV radiation exposure of 3.77 mW/cm2.
The average difference of free chlorine residual between the TRANS and OPAQ basins
53
for the 30 pilot study sampling sets was –0.44 mg/L Cl2. According to the paired t-test
analysis, there was 99% confidence that the free chlorine concentrations of the TRANS
and OPAQ basins were statistically different. The Pearson product momentum
correlation coefficient for the difference in effluent free chlorine residuals and the
average UV radiation was -0.405 signifying a 95% confidence that there was a negative
linear correlation. Thus, as the average UV radiation increased the difference in the
effluent free chlorine residuals of the basins increased.
-3.00-2.50-2.00-1.50-1.00-0.500.000.501.001.50
0.00 1.00 2.00 3.00 4.00 5.00
Average UV Radiation (mW/cm2)
Free
Chl
orin
e R
esid
ual
(mg/
L C
l2)
Figure 4-5. Free chlorine residual difference of the TRANS and OPAQ basins (TRANS-OPAQ) plotted versus average UV Radiation over the HRT of the wastewater in the basin for all pilot studies.
A plot of only the baseline runs is shown in Figure 4-6. As in the plot of all
experimental runs, Figure 4-6 shows the OPAQ basin, the basin that was not exposed to
UV Radiation, had a greater free chlorine residual in all of the runs, except in one
sampling instance. According to the paired t-test method there was a 99% confidence
level that the TRANS and OPAQ basin effluent free chlorine residuals were different
∆
54
during the baseline experiments. Using the paired t-test method the Pearson product
momentum correlation coefficient was -0.574 resulting in a 99% confidence that there
was a linear correlation between the difference in effluent free chlorine concentration and
UV radiation exposure of the wastewater for the baseline experiments.
-1.50
-1.00
-0.50
0.00
0.50
1.00
1.50
0.00 1.00 2.00 3.00 4.00 5.00
Average UV Radiation (mW/cm2)
Free
Chl
orin
e R
esid
ual
(mg/
L C
l2)
Figure 4-6. Free chlorine residual difference of the OPAQ and TRANS basins (TRANS-OPAQ) plotted versus average UV radiation over the HRT of the wastewater in the basin for baseline parameters.
Since UV radiation catalyzes the reduction of HOCl, it was to be expected that the
TRANS (UV and global radiation translucent plastic covered) basin would have a lower
effluent free chlorine residual than the OPAQ basin. The plots in Figures 4-5 and 4-6
support this expectation during the pilot study.
It is also commonly accepted, given that the chlorine dosing is constant, that as the
water or wastewater temperature increases, the amount of chlorine residual will decrease.
The difference in the free chlorine residual of the TRANS and OPAQ basins is shown
versus the difference in temperature between the basins (Figure 4-7). All except two
∆
55
points were in the fourth quadrant, showing that TRANS had higher temperatures but
lower effluent free chlorine residuals than the OPAQ basin. Using the paired t-test
method the Pearson product momentum correlation coefficient was 0.334 resulting in a
95% confidence that there was a linear correlation between the difference in effluent free
chlorine concentration and the difference in temperature.
-3.00
-2.00
-1.00
0.00
1.00
2.00
0.0 1.0 2.0 3.0 4.0
Temperature (°C)
Free
Chl
orin
e R
esid
ual (
mg/
L C
l2)
Figure 4-7. Free chlorine difference of the TRANS and OPAQ basins (TRANS-OPAQ) plotted versus the difference in temperature for all of the pilot studies.
A plot of only the baseline runs is shown in Figure 4-8. As in the plot of all
experimental runs, the TRANS basin had higher effluent temperatures and lower effluent
free chlorine residual. The higher temperature causes a faster rate of chlorine reduction,
so the cause for greater chlorine loss in the TRANS basin was, in part, the result of this
phenomenon. According to the paired t-test the Pearson product momentum correlation
coefficient was 0.319 but did not result in a significant linear correlation between the
∆
∆
56
difference in effluent free chlorine concentration and the difference in temperature for the
baseline experiments.
-1.50
-1.00
-0.50
0.00
0.50
1.00
1.50
0.00 1.00 2.00 3.00 4.00
Temperature (°C)
Free
Chl
orin
e R
esid
ual (
mg/
L C
l2)
Figure 4-8. Free chlorine difference of the TRANS and OPAQ basins (TRANS-OPAQ) plotted versus the difference in temperature for baseline parameters.
As expected, the TRANS, or UV and global radiation translucent plastic covered
basin had higher effluent temperatures than the OPAQ, or opaque covered, basin this
would contribute to the difference in chlorine residual. The one instance where the
TRANS basin free chlorine residual was higher than the OPAQ basin occurred on
7/14/2004 at 9 am. Prior to this time, during the HRTs for the samples taken at 9 am on
that day, a significant flow meter fluctuation was noticed and was adjusted for subsequent
sampling times on that day.
The pilot basin system was setup to simulate the hydraulic retention time (HRT),
flow pattern, and dimension ratios of the North and South chlorine contact basins that
were setup in series at the KWRF. However, the pilot system scale was much smaller
than that of the full-scale and thus the volume of water contained in the basins were less
than that of the full-scale. Thus, solar radiation had a greater effect on the pilot basin
∆
∆
57
temperature differences than the full-scale basin temperature differences. The average
temperature difference between the TRANS and OPAQ basins during the pilot study was
1.5 ºC while the average difference in temperature between the UNCOV and COV in the
full-scale sides was 0.3ºC.
Total Chlorine
As stated previously, the total chlorine residual is a measure of the free and any
combined chlorine present. Since the KWRF uses biological processes, nitrification and
denitrification, to remove ammonia nitrogen present in the wastewater, it is unlikely that
chloramines would form. The KWRF operators add enough chlorine to pass the
breakpoint where free chlorine residual is formed. Thus, the difference in total and free
chlorine is what is termed “irreducible chlorine residual”1; though there are no inorganic
chloramines present, there is a difference in the total and free chlorine residuals. The
irreducible residual could be due, in part, to the presence of dichloramine and
trichloramine.
Since total chlorine residual consists mostly of free chlorine, the results and
relationships between the total chlorine residual and other parameters should be
comparable to those of the free chlorine residual. The environmental conditions that
result in a lowering of the free chlorine residual would also result in a decrease in the
total chlorine residual.
The effluent total chlorine residual data for the TRANS and OPAQ pilot basins was
partitioned into range increments for comparison (Figure 4-9). The most samples were in
the > 2.0 mg/L Cl2 residual range increment for both the TRANS and OPAQ basins.
However, the OPAQ basin had a greater number of samples, 22, than the TRANS basin,
15, at the >2 mg/Cl2 residual increment. As stated before, since the total chlorine residual
58
was composed mostly of free chlorine the results were similar to those shown for free
chlorine residual.
0
5
10
15
20
25
<0.5 0.5-1.0 1.0-1.5 1.5-2.0 >2.0
Total Chlorine (mg/L Cl2)
# of
Inst
ance
s
TRANS Total Cl2 OPAQ Total Cl2
Figure 4-9. Total chlorine residual sampling sets in particular residual ranges for the TRANS and OPAQ basins.
The difference in the total chlorine residual of the (TRANS-OPAQ) basins is
shown versus the average UV radiation the wastewater was exposed to over the HRT
(Figure 4-10). The majority of the points were negative and were in the fourth quadrant,
showing that the OPAQ basin had higher effluent total chlorine residual than the TRANS
basin in nearly all of the sampling runs. Only in four sampling sets was the TRANS
basin effluent total chlorine residual higher than the OPAQ effluent. The largest total
chlorine difference between the two basins was -2.50 mg/L Cl2 (TRANS-OPAQ) at an
average UV Radiation exposure of 2.55 mW/cm2. The average difference of total
chlorine residual between the TRANS and OPAQ basins for the 30 pilot-scale sampling
sets was -0.50 mg/L Cl2 with a standard deviation of 0.67 mg/L Cl2. According to the
paired t-test method there was a 99% confidence level that the TRANS and OPAQ basin
59
effluent total chlorine residuals were different. Also, using the paired t-test method the
Pearson product momentum correlation coefficient was -0.281 and did not result in a
significant linear correlation between the difference in effluent total chlorine
concentration and UV radiation exposure of the wastewater. Thus, the total chlorine
difference was not significantly affected by the increases in the average UV radiation,
although the irradiated basin had significantly less total chlorine residual than the covered
basin.
-3.00-2.50-2.00-1.50-1.00-0.500.000.5011.00
0.00 1.00 2.00 3.00 4.00 5.00
Avg UV Radiation (mW/cm2)
Tota
l Chl
orin
e R
esid
ual (
mg/
L C
l2)
Figure 4-10. Total chlorine residual difference of the OPAQ and TRANS basins (TRANS-OPAQ) plotted versus average UV Radiation over the HDT of the wastewater in the basin for all pilot studies.
The difference in the total chlorine residual of the (TRANS-OPAQ) basins is
shown versus the difference in temperature between the basins (Figure 4-11). All except
two points were negative and were in the fourth quadrant, showing that TRANS had a
higher temperature but lower total chlorine residual than the OPAQ basin. Using the
paired t-test method the Pearson product momentum correlation coefficient was -0.227
and did not result in a significant linear correlation between the difference in effluent
total chlorine concentration and difference in temperature.
∆
60
-3.00
-2.00
-1.00
0.00
1.00
0.0 1.0 2.0 3.0 4.0
Temperature (°C)
Tota
l Chl
orin
e R
esid
ual (
mg/
L C
l2)
Figure 4-11. Total chlorine residual difference of the TRANS and OPAQ basins (TRANS-OPAQ) plotted versus the difference in temperature between the basins.
The basin with the higher effluent temperature also had significantly lower free and
total chlorine residual. Though, there was a 99% confidence level that the total chorine
residual was different between the two basins there was no significant correlation
between that difference and the exposure to UV radiation or difference in temperature.
Though it is important to note that solar radiation exposure of the wastewater does result
in an increase in water temperature, it is difficult to separate the effect of temperature
increase and UV radiation on the difference in chlorine residual in the TRANS and
OPAQ pilot basins.
Disinfection By-Products
The chlorination of KWRF wastewater ensures the safety of reuse water users and
prevents coliform and other bacterial contamination from entering the Floridan aquifer, a
drinking water source. Besides the consumption of chlorine through the disinfection
process, the reaction of chlorine with humic substances, extracellular algal products, and
other DBP precursors not only reduces the chlorine residual but also induces the
∆
∆
61
formation of DBP. Because of the known carcinogenic health effects attributed to the
presence of DBP in drinking water, the EPA had placed an 80 µg/L limit on TTHM
concentration and a 60 µg/L limit on HAA(5) concentration. Although there are other
known disinfection by-products only trihalomethanes and haloacetic acids are regulated
by the EPA in the drinking water regulations and thus were the only DBP measured in
this study.
Several factors affect the extent of DBP formation, such as, chlorine dose,
temperature, pH, and contact time. It is commonly known that as the chlorine dosing is
increased during chlorination the amount of DBP that forms also increases.6 An increase
in temperature will also result in an increase in DBP formation.6
Trihalomethane
The TTHM concentration of effluent samples was analytically determined using
GC/MS instrumentation. The TTHM concentration in this study refers to a composite of
four molecules (chloroform, bromodichloromethane, dibromochloromethane, and
bromoform). In order to compare TTHM formation on a collective basis the mass
concentrations should be converted to a common unit and then summed. Molarity was
used as the common unit for this study as it is widely used. The THM speciation for each
of the sampling runs can be seen in Appendix E.
The TTHM effluent mass concentrations were separated into range increments and
plotted in a histogram (Figure 4-12). The concentrations are raw values in that they were
not normalized to pH, temperature, nor chlorine dose. The OPAQ basin had the same
number of samples, nine, in each range up to 150 µg/L and then only three samples in the
>200 µg/L range. Most of the effluent TTHM concentrations fell within the 50-100 µg/L
62
range for the TRANS basin, one sample in the 150-200 µg/L range, and three samples
>200 µg/L range. The TTHM effluent molar concentrations were separated into range
increments and plotted in a histogram (Figure 4-13). Most of the effluent TTHM
concentrations fell within the 0.5-1.0 µmole/L range for the TRANS basin and in the less
than 0.5 µmole/L for the OPAQ basin.
02468
101214
<50 50-100 100-150 150-200 >200
TTHM (µg/L)
# of
Inst
ance
s
TRANS TTHM OPAQ TTHM
Figure 4-12. The TTHM effluent mass concentrations for the TRANS and OPAQ basins are shown in range increments.
0
3
6
9
12
15
18
<0.5 0.5-1.0 1.0-1.5 1.5-2.0 >2.0
TTHM ( moles/L)
# of
Inst
ance
s
TRANS TTHM OPAQ TTHM
Figure 4-13. The TTHM effluent molar concentrations for the TRANS and OPAQ basins are shown in range increments.
µ
63
Previously, it was shown that the OPAQ basin, the basin with the cover that
prevented the wastewater from being exposed to UV radiation, had higher effluent free
chlorine residual than the TRANS basin for the majority of the pilot runs. Common
theory would then lead to the conclusion that the OPAQ basin, with a higher chlorine
residual, would result in a higher THM formation as well. The difference in the TRANS
and OPAQ TTHM mass and molar effluent concentrations for all of the pilot basin
experimental runs is shown as a histogram (Figures 4-14 and 4-15), respectively. The
differences in TTHM concentrations were the actual concentrations in the effluent
sample; the concentrations were not normalized for the differences in chlorine residual,
temperature or pH. There were 10 sampling sets of a total of 30 experimental sampling
sets where the OPAQ basin had a higher TTHM concentration than the TRANS basin.
Of the 10 sampling sets where the OPAQ basin had a higher TTHM effluent
concentration than the TRANS basin, 9 coincided with the OPAQ basin effluent having a
higher free chlorine residual that the TRANS basin. Also, of the sampling sets where the
OPAQ basin effluent had a higher TTHM concentration than the TRANS basin, 3 were
on the July 28, 2004 and 3 were on August 2, 2004. Both of those days were non-
baseline experimental pilot runs. On July 28th sodium hydroxide (NaOH) was added to
increase the influent pH to the basins. On August 2nd the flow rate was reduced from the
baseline flow rate of 28 GPH (HRT of 2 h and 45 min) to 20 GPH (HRT of 3 h and 50
min). In the rest of the 30 sampling sets the TRANS basin mass effluent concentration
was higher than that of the OPAQ basin. The average difference of effluent TTHM mass
concentration between the TRANS and OPAQ basins for the 30 pilot-scale sampling sets
was 6.9 µg/L with a standard deviation of 29.1 µg/L. The average difference of effluent
64
TTHM molar concentration between the TRANS and OPAQ basins for the 30 pilot-scale
sampling sets was 0.05 µmole/L with a standard deviation of 0.22 µmoles/L. According
to the paired t-test there was no significant difference between the TTHM effluent
concentration of the TRANS and OPAQ basins, mass or molar despite the typically
higher chlorine residual in the OPAQ basin.
02468
1012
<=0 0-8 8-16 16-24 >24
∆TTHM (µg/L)
# of
Inst
ance
s
Figure 4-14. Difference in TTHM concentration between the TRANS and OPAQ sides (TRANS-OPAQ) separated into mass concentration ranges.
0
5
10
15
20
<=0 0-0.25 0.25-0.50 0.50-0.75 >0.75
∆TTHM (µmoles/L)
# of
Inst
ance
s
Figure 4-15. Difference in TTHM concentration between the TRANS and OPAQ sides (TRANS-OPAQ) separated into molar concentration ranges.
65
The difference in TTHM effluent concentration is plotted versus the difference in
free chlorine residual for mass and molar concentrations (Figures 4-16 and 4-17),
respectively. Using the paired t-test method, with the Pearson product momentum
correlation coefficient, neither the mass nor the molar TTHM concentration difference
correlates to a significant degree with the difference in free chlorine residual.
-100-50
0
50100150
-3.00 -2.00 -1.00 0.00 1.00 2.00
∆Free Chlorine (mg/L Cl2)
TTH
M (
g/L)
Figure 4-16. Difference in TTHM effluent mass concentration of the TRANS and OPAQ basins (TRANS-OPAQ) plotted versus the difference in free chlorine residual of the TRANS and OPAQ basins.
-1.00
-0.50
0.00
0.50
1.00
-3.00 -2.00 -1.00 0.00 1.00 2.00
∆Free Chlorine (mg/L)
TTH
M
(m
oles
/L)
Figure 4-17. Difference in TTHM effluent molar concentration of the TRANS and OPAQ basins (TRANS-OPAQ) plotted versus the difference in free chlorine residual of the TRANS and OPAQ basins.
∆ µ
∆ µ
66
The difference in the TRANS and OPAQ TTHM mass effluent concentrations for
baseline pilot basin experimental runs is plotted versus the difference in free chlorine
residual (Figure 4-18). In only one sample during the baseline runs was the OPAQ basin
TTHM effluent concentration higher than that of the TRANS basin. This one sample out
of nine sampling sets coincided with a higher free chlorine residual in the OPAQ basin
than the TRANS basin. Using the paired t-test the difference in TTHM effluent
concentration does not correlate to a significant degree with the difference in free
chlorine residual in the baseline experiments.
-50
-25
0
25
50
75
100
125
-1.50 -1.00 -0.50 0.00 0.50 1.00 1.50
Free Chlorine Residual (mg/LCl2)
TTH
M (
g/L
)
Figure 4-18. Difference in TTHM mass effluent concentration between the TRANS and OPAQ basins (TRANS-OPAQ) plotted versus the difference in free chlorine residual between the TRANS and OPAQ basins for baseline runs.
As stated previously, trihalomethane formation is affected by environmental
conditions, such as, temperature, pH, and free chlorine residual. The pH, temperature,
and free chlorine residual differences of the basins need to be addressed to allow an
accurate comparison of the trihalomethane formation in the two basins. In order to
compensate for the differences between these parameters in the basins’ effluents the
µ∆
∆
67
TTHM concentrations were normalized. The manner in which the TTHM concentrations
were normalized is explained in the methods section. Each of the basin effluents,
TRANS and OPAQ, were sampled and trihalomethane concentrations were measured
during every sampling event and time.
The TTHM formation for all of the sampling runs for both the TRANS and OPAQ
basins was, for the most part, as chloroform. Chloroform made up at least 70%, by mass,
of the TTHM formed for both basins during each of the sampling runs of the chlorination
pilot study (Figure 4-19).
74%
22%
4%
0%
Chloroform BromodichloromethaneDibromochloromethane Bromoform
Figure 4-19. Speciation of the THM formation in the TRANS effluent on a mass basis sampled at 9 am on August 23, 2004.
Because chloroform makes up 70% or higher, by mass, of the TTHM formed in the
pilot basins the THM model for chloroform formation was used in the normalization of
the OPAQ basin effluent TTHM concentration to that of the TRANS basin.
The average, minimum, and maximum values of the normalization factors used to
normalize the OPAQ effluent TTHM concentrations to the TRANS effluent TTHM
concentrations are shown in (Table 4-1). All TTHM normalized data can be found in
68
Appendix D. The average values of these normalization factors give an idea of how
much the difference in the parameter affects the TTHM concentration of the two basins.
The farther the normalization factor is from 1 the greater the parameter contributes to the
TTHM concentration difference between the basins. The free chlorine residual
normalization factor deviates the most from 1, with a value of 0.85, and thus is the
determining factor in the difference of the TTHM concentration between the two basins.
The chlorine residual having the greatest effect on the TTHM concentration difference of
the two basins is important in that in almost all of the cases the OPAQ basin had a higher
free chlorine residual effluent than the TRANS basin, however, the OPAQ basin in
almost all cases had a lower TTHM effluent concentration.
Table 4-1. Normalization factors used to normalize OPAQ TTHM effluent concentrations to TRANS TTHM effluent concentrations.
pH normalization
factor
Temperature normalization
factor
Chlorine residual
normalization factor
OPAQ OPAQ OPAQ Average 1.00 1.05 0.85 Maximum 1.06 1.13 1.44 Minimum 0.92 1.00 0.46
The TTHM mass concentration comparison was a good way to examine how the
two basin systems compare with EPA DBP drinking water standards. The effluent
normalized total trihalomethane (TTHM’) mass and molar concentrations were separated
into range increments and plotted in a histogram (Figure 4-20 and 4-21), respectively.
The TRANS basin effluent TTHM’ concentrations fell mostly in the 50-100 µg/L range
while the OPAQ basin TTHM’ effluent concentrations fell mostly in the less than 50
µg/L range. Similarly, the TRANS basin TTHM’ molar concentrations fell mostly in a
concentration range increment higher than the those of the OPAQ basin, 0.5-1.0 and <0.5
69
µmole/L respectively. The results show the TRANS basin tending to produce effluent
TTHM’ concentrations in a higher range than the OPAQ basin over several operating
conditions, described in Chapter 3 Materials and Methods.
02468
101214
<50 50-100 100-150 150-200 >200
TTHM' ( g/L)
# of
Inst
ance
s
TRANS TTHM' OPAQ TTHM'
Figure 4-20. Normalized TTHM effluent mass concentrations for the TRANS and OPAQ basins are shown in range increments.
02468
10121416
<0.5 0.5-1.0 1.0-1.5 1.5-2.0 >2.0
TTHM' ( moles/L)
# of
Inst
ance
s
TRANS TTHM' OPAQ TTHM'
Figure 4-21. Normalized TTHM effluent molar concentrations for the TRANS and OPAQ basins are shown in range increments.
µ
µ
70
The difference in the normalized TTHM concentration (∆TTHM’) was separated
into mass concentration ranges (Figure 4-22). In only seven sampling sets was the
OPAQ basin TTHM’ concentration higher than the TRANS basin effluent concentration.
Most sampling sets of the TTHM mass concentration difference were in the >24 µg/L
range, with 10 sampling sets. There were then five sampling sets where the difference
between the TRANS and OPAQ basin were in the 0 to 8 µg/L and five sampling sets in
the 8 to 16 µg/L ranges. Using the paired t-test method there was a 99% confidence level
that there was a difference between the TRANS basin TTHM’ concentration and the
OPAQ basin TTHM’ concentration.
0
2
4
6
8
10
<0 0-8 8-16 16-24 >24TTHM' ( g/L)
# of
Inst
ance
s
Figure 4-22. Difference in TTHM’ concentration between the TRANS and OPAQ sides (TRANS-OPAQ) separated into mass concentration ranges.
The difference in the normalized TTHM concentration was separated into molar
concentration ranges (Figure 4-23). Again, the histogram shows that in only seven
sampling sets did the OPAQ basin have a higher TTHM concentration than the TRANS
basin. Most sampling sets of the TTHM molar concentration difference were in the 0 to
µ∆
71
0.25 µmoles/L range. There were then two sampling sets where the difference between
the TRANS and OPAQ basin were in the 0.25 to 0.50 µmoles/L and two sampling sets in
the 0.50 to 0.75 µmoles/L ranges. Using the paired t-test method there was a 99%
confidence level that there was a difference between the TRANS basin TTHM’
concentration and the OPAQ basin TTHM’ concentration. Thus, the TRANS basin
TTHM’ concentrations were significantly higher than the OPAQ basin TTHM’
concentrations.
02468
101214161820
<0 0-0.25 0.25-0.50 0.50-0.75 >0.75TTHM' ( moles/L)
# of
Insta
nces
Figure 4-23. Difference in TTHM’ concentration between the TRANS and OPAQ sides (TRANS-OPAQ) separated into molar concentration ranges.
The difference in the normalized TTHM mass concentrations were plotted versus
the average UV radiation exposure of the TRANS basin over the HRT (Figure 4-24).
The majority of the points, all but 7, were in the first quadrant meaning that the OPAQ
basin had a lower normalized TTHM effluent concentration than the TRANS basin in
almost all of the sampling periods. The average difference of the normalized effluent
TTHM concentration between the TRANS and OPAQ basins for the 30 pilot-scale
µ∆
72
sampling sets was 17.1 µg/L with a standard deviation of 31.6 µg/L. Using the paired t-
test the normalized difference in TTHM effluent concentration does not correlate to a
significant degree with the average UV radiation exposure.
-80.0-60.0-40.0-20.0
0.020.040.060.080.0
100.0120.0140.0
0.00 1.00 2.00 3.00 4.00 5.00Average UV Radiation (mW/cm2)
TTH
M' (
g/L
)
Figure 4-24. Difference in normalized TTHM mass concentration of the TRANS and the OPAQ basins (TRANS-OPAQ) plotted versus the average UV radiation. exposure over the HRT.
The difference in the normalized TTHM molar concentrations was plotted versus
the average UV radiation the TRANS basin was exposed to over the HRT (Figure 4-25).
The majority of the points, all but 7, were in the first quadrant meaning that the OPAQ
basin had a lower TTHM effluent concentration than the TRANS basin in almost all of
the sampling periods. The average difference of the normalized effluent TTHM molar
concentration between the TRANS and OPAQ basins for the 30 pilot-scale sampling sets
was 0.13 µmoles/L with a standard deviation of 0.24 µmoles/L. Using the paired t-test
the normalized difference in TTHM effluent concentration does not correlate to a
significant degree with the average UV radiation exposure.
µ∆
73
-0.60-0.40-0.200.000.200.400.600.801.00
0.00 1.00 2.00 3.00 4.00 5.00
Average UV Radiation (mW/cm2)
TTH
M' (
mol
es/L
)
Figure 4-25. Difference in normalized TTHM molar concentration of the TRANS and the OPAQ basins (TRANS-OPAQ) plotted versus the average UV radiation exposure over the HRT.
The fact that in all but seven sampling sets the OPAQ basin had a lower TTHM
concentration than the TRANS basins was contrary to the common theory that a higher
residual will result in a higher TTHM concentration. The TTHM and chlorine data
analysis suggest that the chlorine disinfection process tends to produce less TTHMs if
UV radiation and solar radiation exposure of the wastewater was prevented. The data
also validate the common concept that UV radiation catalyzes the reduction of free
chlorine (HOCl).
The data analyses suggest that the OPAQ basin, with the opaque cover that
prevents wastewater exposure to UV radiation during the chlorination disinfection
process, for the majority of sampling sets, had a lower formation of THM than the
TRANS basin. This phenomenon contrasts with the more common theory that a higher
chlorine residual will result in a greater formation of THM. The difference between the
basins was the exposure of the wastewater to UV radiation during the chlorination
disinfection process. The data and statistical analysis suggest that preventing UV
∆ µ
74
radiation and solar radiation exposure of wastewater during the chlorine disinfection
stage at the KWRF had two benefits:
1. The prevention of chlorine loss to the free chlorine reduction reaction by removing the UV radiation as the catalyst
2. A lower THM concentration than with the conventional method of allowing UV radiation to come in contact with wastewater during the chlorine disinfection stage in the KWRF treatment process.
Haloacetic Acid
The HAA(5) concentration of an effluent sample is the summed values of the
monochloroacetic acid (MCAA), monobromoacetic acid (MBAA), dichloroacetic acid
(DCAA), dibromoacetic acid (DBAA), and trichloroacetic acid (TCAA) concentrations
calculated for the said sample using the GC/ECD. The HAA(5) speciation for each of the
sampling runs can be seen in Appendix E. In order to compare HAA(5) formation on a
collective basis the mass concentrations should be converted to a common unit and then
summed. The HAA(5) wastewater effluent samples taken from the OPAQ basin on June
23, at 9am, and the TRANS basin on July 14, at 2 pm, and July 26, at 9 am, were
damaged prior to analysis and were not used in the pilot-study discussion.
The HAA(5) effluent mass concentrations were separated into range increments
and plotted in a histogram (Figure 4-26). The concentrations are raw values in that they
were not normalized to temperature or chlorine residual. Most of the effluent HAA(5)
concentrations fell within the less than 50 µg/L range for the TRANS basin and the
OPAQ basin, with 11 and 17 samples respectively. The HAA(5) effluent molar
concentrations were separated into range increments and plotted in a histogram
(Figure 4-27). Most of the effluent HAA(5) concentrations fell within the less than
0.5 µmole/L range for the TRANS basin and the OPAQ basin, with 24 and 25 samples,
75
respectively. It is good to note that the majority of the TRANS and OPAQ basin HAA(5)
effluent concentrations fall in the range that is below the proposed EPA standard.
02468
1012141618
<50 50-100 100-150 150-200 >200HAA (µg/L)
# of
Inst
ance
s
TRANS HAA OPAQ HAA
Figure 4-26. The HAA(5) effluent mass concentrations for the TRANS and OPAQ basins are shown in range increments.
048
1216202428
<0.5 0.5-1.0 1.0-1.5 1.5-2.0 >2.0
HAA ( moles/L)
# of
Inst
ance
s
TRANS HAA OPAQ HAA
Figure 4-27. The HAA(5) effluent molar concentrations for the TRANS and OPAQ basins are shown in range increments.
The difference in the HAA(5) concentrations (∆HAA(5)) were separated into mass
and molar concentration ranges in (Figure 4-28 and 4-29), respectively. In eighteen of
the twenty-seven sampling sets the TRANS basin HAA(5) mass concentration was higher
than the OPAQ basin effluent concentration and in sixteen of the twenty-seven sampling
sets the TRANS basin molar concentration was greater than the OPAQ basin
µ
76
concentration. In the HAA(5) mass concentration difference histogram the most
sampling sets were in the <=0 µg/L range due to the concentrations being distributed
amongst the higher ranges. The average difference in HAA(5) effluent mass
concentration was 7.22 µg/L with a standard deviation of 32 µg/L. Most sampling sets in
the HAA(5) molar concentration difference histogram were in the 0-0.25 µmole/L range,
with thirteen sampling sets. The average difference in HAA(5) effluent molar
concentration was 0.02 µmole/L with a standard deviation of 0.26 µmoles/L. Using the
paired t-test method it was determined that there was no significant difference between
the TRANS and OPAQ effluent HAA(5) concentrations.
02468
10
<=0 0-8 8-16 16-24 >24∆HAA (µg/L)
# of
Inst
ance
s
Figure 4-28. Difference in HAA(5) concentration between the TRANS and OPAQ sides (TRANS-OPAQ) separated into mass concentration ranges.
0
5
10
15
<=0 0-0.25 0.25-0.50 0.50-0.75 >0.75HAA ( moles/L)
# of
Inst
ance
s
Figure 4-29. Difference in HAA(5) concentration between the TRANS and OPAQ sides
(TRANS-OPAQ) separated into molar concentration ranges.
µ∆
77
The difference in HAA(5) effluent mass concentrations of the TRANS and OPAQ
basins was plotted versus the difference in free chlorine residual of the TRANS and
OPAQ basins (Figure 4-30). As stated previously, in eighteen of the twenty-seven
sampling sets the TRANS basin HAA(5) effluent mass concentrations were higher than
those of the OPAQ basin. Using the paired t-test method, with the Pearson product
momentum correlation coefficient, it was determined that there was no significant
correlation between the difference in HAA(5) mass concentration and the difference in
free chlorine residual.
-100
-75
-50
-25
0
25
50
75
100
-3.00 -2.00 -1.00 0.00 1.00 2.00Free Chlorine Residual (mg/L Cl2)
HA
A (
g/L
)
Figure 4-30. Difference in HAA(5) mass concentration of the TRANS and the OPAQ basins (TRANS-OPAQ) plotted versus the difference in free chlorine residual of the TRANS and OPAQ basins (TRANS-OPAQ).
The difference in HAA(5) effluent molar concentrations of the TRANS and
OPAQ basins was plotted versus the difference in free chlorine residual of the TRANS
and OPAQ basins in (Figure 4-31). In sixteen of the twenty-seven sampling sets the
TRANS basin HAA(5) effluent concentrations were higher than those of the OPAQ
∆ µ
∆
78
basin. Using the paired t-test method, with the Pearson product momentum correlation
coefficient, it was determined that there was no significant correlation between the
difference in HAA(5) molar concentration and the difference in free chlorine residual.
-0.80-0.60-0.40-0.200.000.200.400.600.80
-3.00 -2.00 -1.00 0.00 1.00 2.00Free Chlorine Resdual (mg/L Cl2)
HA
A (
mol
es/L
)
Figure 4-31. Difference in HAA(5) molar concentration of the TRANS and the OPAQ basins (TRANS-OPAQ) plotted versus the difference in free chlorine residual of the TRANS and OPAQ basins (TRANS-OPAQ).
Neither the HAA(5) concentration or the TTHM concentration effluent differences
correlate with the difference in effluent free chlorine residual.
In the HAA(5) analysis in all but three of the thirty sampling sets the DCAA made
up the highest percentage of the HAA(5)s. Thus, the HAA(5) OPAQ basin effluent
HAA(5) concentrations were normalized to the HAA(5) TRANS basin effluent using the
temperature and free chlorine concentration DCAA normalization factors. The speciation
of HAA(5) in the OPAQ basin effluent during a baseline run on August 30, 2004 taken at
12 pm is shown with species percentage (Figure 4-32). In this case, DCAA made up 58%
of the HAA(5) mass concentration.
∆ µ
∆
79
0%
0%
58%
0%
42%
MCAA MBAA DCAA DBAA TCAA
Figure 4-32. Speciation of the HAA(5) formation in the OPAQ effluent on a mass basis sampled at 12 pm on August 30, 2004.
Like THM formation, HAA(5) formation is affected by environmental conditions,
such as, temperature and free chlorine residual. In order to compensate for the
differences between these parameters in the basins’ effluents the HAA(5) concentrations
were normalized. All HAA(5) normalized data can be found in Appendix D.
Normalized HAA(5) concentrations, mass and molar, are denoted as HAA(5)’. Though
DCAA did not make up the highest percentage in all sampling sets it did make up the
highest percentage of the HAA(5) concentrations in the most numerous sampling sets.
The average, minimum, and maximum values of the normalization factors used to
normalize the OPAQ effluent HAA(5) concentrations to the TRANS effluent HAA(5)
concentrations is shown (Table 4-2). The average values give an idea of how much the
difference in the parameter affects the HAA(5) concentration of the two basins. The
farther the normalization factor is from 1 the greater the parameter contributes to the
HAA(5) concentration difference between the basins. The free chlorine residual
normalization factor deviates the most from 1, with an average value of 0.86, and thus is
80
the determining factor in the difference of the HAA(5) concentration between the two
basins according to the model. The chlorine residual having the greatest effect on the
HAA(5) concentration difference of the two basins is important in that in almost all of the
cases the OPAQ basin had a higher free chlorine residual effluent than the TRANS basin,
however, the OPAQ basin in eighteen of the twenty-seven sampling sets had a lower
normalized HAA(5) mass effluent concentration.
Table 4-2. Normalization factors used to normalize OPAQ HAA(5) effluent concentrations to TRANS HAA(5) effluent concentrations.
Temp (°C) Normalization
Factor
Chlorine Residual
Normalization Factor
OPAQ OPAQ Average 1.03 0.86
Maximum 1.08 1.36 Minimum 1.00 0.51
The HAA(5)’ effluent mass concentrations were separated into range increments
and plotted in a histogram (Figure 4-33). Similar to the raw HAA(5) histogram, most of
the effluent HAA(5)’ concentrations fell within the less than 50 µg/L range for the
TRANS basin and the OPAQ basin, with eleven and sixteen samples respectively. The
HAA(5)’ effluent molar concentrations were separated into range increments and plotted
in a histogram (Figure 4-34). Similar to the raw HAA(5) histogram, most of the effluent
HAA(5)’ molar concentrations fell within the less than 0.5 µmole/L range for the TRANS
basin and the OPAQ basin, with twenty-five and twenty-six samples, respectively.
Similar to the raw HAA(5) concentrations, the majority of the TRANS and OPAQ basin
HAA(5)’ effluent concentrations fall in the range that is below the proposed EPA
standard.
81
0
4
8
12
16
20
<50 50-100 100-150 150-200 >200
HAA' ( g/L)
# of
Inst
ance
s
TRANS HAA' OPAQ HAA'
Figure 4-33. The HAA(5)’ effluent mass concentrations for the TRANS and OPAQ basins are shown in range increments.
0
5
10
15
20
25
30
<0.5 0.5-1.0 1.0-1.5 1.5-2.0 >2.0
HAA' ( moles/L)
# of
Inst
ance
s
TRANS HAA' OPAQ HAA'
Figure 4-34. The HAA(5)’ effluent molar concentrations for the TRANS and OPAQ basins are shown in range increments.
The difference in the HAA(5)’ concentrations (∆HAA(5)’) were separated into
mass and molar concentration ranges in (Figure 4-35 and 4-36), respectively. In eighteen
µ
µ
82
of the twenty-seven sampling sets the TRANS basin HAA(5)’ mass concentration was
higher than the OPAQ basin effluent concentration and in nineteen of the thirty sampling
sets the TRANS basin molar concentration was greater than the OPAQ basin
concentration. In the HAA(5)’ mass concentration difference histogram the same number
of sampling sets were in the <=0 µg/L range. The average difference in HAA(5)’ effluent
mass concentration was 9.05 µg/L with a standard deviation of 31.9 µg/L. Most
sampling sets in HAA(5)’ molar concentration difference histogram were in the 0-0.25
µmole/L range, with fourteen sampling sets. The average difference in HAA(5)’ effluent
molar concentration was 0.04 µmole/L with a standard deviation of 0.25 µmoles/L.
Using the paired t-test method it was determined that there was no significant difference
between the TRANS and OPAQ effluent HAA(5) concentrations.
0123456789
10
<=0 0-8 8-16 16-24 >24
HAA' ( g/L)
# of
Inst
ance
s
Figure 4-35. Difference in HAA(5)’ concentration between the TRANS and OPAQ sides (TRANS-OPAQ) separated into mass concentration ranges.
µ∆
83
02468
101214
<=0 0-0.25 0.25-0.50 0.50-0.75 >0.75HAA' ( moles/L)
# of
Inst
ance
s
Figure 4-36. Difference in HAA(5)’ concentration between the TRANS and OPAQ sides (TRANS-OPAQ) separated into molar concentration ranges.
The HAA(5)’ concentration differences histograms are visually similar to those of
for the HAA(5) concentration differences histograms but are slightly shifted in favor of a
greater difference in the OPAQ and TRANS basin effluent concentrations. This results
from the normalization process, for every sampling set where the OPAQ basin effluent
free chlorine residual was higher that that of the TRANS basin the HAA(5), DCAA,
formation equation favored a higher OPAQ effluent HAA(5) concentration over the
TRANS basin effluent. However, since the opposite was the case, the OPAQ basin had
in all but the three sampling sets a higher free chlorine effluent residual than the TRANS
basin, the normalization factor for free chlorine residual was, in all but those three
sampling sets, less than one. In the twenty-seven sampling sets where the OPAQ basin
effluent free chlorine residual was greater than that of the TRANS basin, the OPAQ basin
effluent HAA(5)’ concentrations were greater than the raw, non-normalized, effluent
HAA(5) concentrations which in turn increased the difference in the TRANS and OPAQ
basin effluent concentrations for those sampling sets.
µ∆
84
The difference in HAA(5)’ effluent mass and molar concentrations was plotted
versus the average UV radiation exposure of the wastewater while in the pilot basin, over
the HRT (Figure 4-37 and Figure 4-38), respectively. According to the paired t-test
method, using the Pearson product momentum correlation coefficient, there was no linear
correlation between the difference in effluent HAA(5)’ mass or molar concentrations and
the average UV radiation exposure while in the pilot basins, the HRT.
-100.0-75.0-50.0-25.0
0.025.050.075.0
100.0
0.00 1.00 2.00 3.00 4.00 5.00Avg UV Radiation (mW/cm2)
HA
A' (
g/L
)
Figure 4-37. Difference in HAA(5)’ effluent mass concentration of the TRANS and
OPAQ basins (TRANS-OPAQ) plotted versus the average UV radiation exposure over the HRT.
-0.80-0.60-0.40-0.200.000.200.400.600.80
0.00 1.00 2.00 3.00 4.00 5.00Avg UV Radiation (mW/cm2)
HA
A' (
mol
es/L
)
Figure 4-38. Difference in HAA(5)’ effluent molar concentration of the TRANS and
OPAQ basins (TRANS-OPAQ) plotted versus the average UV radiation exposure over the HRT.
µ∆
µ∆
85
Though the average difference between the TRANS and OPAQ basin were
negative for the HAA(5) effluent concentrations showing on average that the OPAQ
basin had a higher HAA(5) effluent concentration than the TRANS basin the average
difference was positive for the HAA(5)’ effluent concentrations. Showing that when
differences in free chlorine residual were taken into account the TRANS basin effluent
HAA(5) concentration exceeded that of the OPAQ basin. Though the paired t-test did
not show a statistical difference between the OPAQ and TRANS basin HAA(5) and
HAA(5)’ effluent concentration the number of sampling sets where the TRANS basin had
a higher effluent concentration than the OPAQ basin were greater.
86
CHAPTER 5 DISCUSSION: FULL-SCALE STUDY
As stated previously, the North chlorine contact basin was studied in the full-scale
experiments. The North basin flow splits into two parallel streams directly after entering
the basin, after a mixing zone. The North basin plan view as well as the full-scale study
sampling points are shown in Figure 3-4. A gate is also present that enables the
possibility of having one side operational while the other is serviced or given routine
maintenance. One side of the basin was covered with polypropylene tarps that prevent
solar radiation exposure of the wastewater. In this discussion the side covered with the
tarps was termed the COV side. The other side of the basin that was left uncovered
allowed for the solar radiation exposure of the wastewater and was termed the UNCOV
basin. For consistency, the comparisons between the UNCOV and COV sides of the
basin in all cases have the COV side effluent concentration subtracted from the UNCOV
side effluent concentration. The paired t-test statistical analysis, along with the Pearson
product momentum correlation coefficient, values used in the following full-scale study
discussion can be found in Appendix H.
Chlorine Residual
Free Chlorine
The effluent free chlorine residual data for the UNCOV and COV side streams are
partitioned into range increments in a histogram for comparison (Figure 5-1). The most
samples were in the 2.5-3.0 mg/L Cl2 residual range increment for the COV side. The
87
UNCOV side of the basin had the same number of samples, three, in the 1.5-2.0, 2.0-2.5,
and the 2.5-3.0 mg/L Cl2 ranges. The COV side had more samples than the UNCOV in
the 2.5-3.0 mg/L Cl2. In the >3.0 mg/L Cl2 range the COV effluent had two samples
while the UNCOV effluent did not have a free chlorine residual that high. This point is
significant because of the chlorine residual requirement described earlier; a higher
chlorine residual ensures a great disinfection potential.
0
1
2
3
4
5
6
7
1.0-1.5 1.5-2.0 2.0-2.5 2.5-3.0 >3.0Free Chlorine (mg/L Cl2)
# of
Inst
ance
s
UNCOV Free Cl2 COV Free Cl2
Figure 5-1. Free chlorine residual of the UNCOV and COV side effluents separated into concentration ranges.
The difference in free chlorine of the UNCOV and the COV side was split into
concentration ranges and plotted in a histogram (Figure 5-2). In all sampling sets, the
COV side had a higher free chlorine residual than the UNCOV side. The range with the
most numerous sampling sets was at the –1.0 to –0.75 and the –0.50 to –0.25 mg/L Cl2
ranges, with 3 samples each. The average difference of free chlorine residual between
the UNCOV and COV sides for the 9 full-scale sampling sets was –0.71 mg/L Cl2 with a
88
standard deviation of 0.25 mg/L Cl2. Results from the statistical analysis, using the
paired t-test method, indicate that there was a 99% confidence that the COV and UNCOV
side effluent free chlorine residuals were statistically different. Thus the cover over the
COV side stream helped to lower free chlorine loss from the UV radiation reduction
reaction, shown in (Equation 1-1).
0
1
2
3
4
5
6
<-1.0 -1.0- -0.75 -0.75- -0.50 -0.50- -0.25 >-0.25-0
Free Chlorine (mg/L Cl2)
# of
Inst
ance
s
Figure 5-2. Difference in free chlorine residual between the UNCOV and COV sides
(UNCOV-COV) separated into concentration ranges.
The difference in the free chlorine residual of the UNCOV and COV basin sides
was plotted versus the difference in temperature between the sides (Figure 5-3). Six of
the nine points were in the fourth quadrant, showing that in most cases the UNCOV side
of the basin had a higher effluent temperature and a lower effluent free chlorine residual
than the COV side. Using the paired t-test method, with the Pearson product momentum
correlation coefficient, there was no significant linear correlation between the difference
in effluent free chlorine concentration and the difference in temperature.
∆
89
-1.20
-1.00
-0.80
-0.60
-0.40
-0.20
0.00-0.5 0.0 0.5 1.0
Temperature (°C)
Free
Chl
orin
e (m
g/L
Cl2
)
Figure 5-3. Free chlorine difference of the UNCOV and COV basin sides plotted versus the difference in temperature.
A greater difference in effluent temperature was observed in the pilot study than in
the full-scale study. There are two explanations for this phenomenon. First, the larger
quantity of water used in the full-scale study over the pilot-study helped to reduce the
temperature increase caused by solar radiation exposure. Second, only the first chlorine
contact basin, in the series of two basins, was observed in the full-scale study thus the
contact time of the solar radiation and the wastewater, the HRT, was less in the full-scale
study than the pilot study.
Total Chlorine
The effluent total chlorine residual data for the UNCOV and COV sides are
partitioned into range increments for comparison (Figure 5-4). The samples were in the
3.25 to 3.50 mg/L Cl2 residual range increment for the UNCOV side. The COV side did
not have a large number of samples in one incremental range but rather had two samples
∆
∆
90
in the 0.25 to 3.50 mg/L Cl2 residual range, four samples in the 3.75 to 4.00 mg/L Cl2
residual range, and three samples in the >4.00 mg/L Cl2 residual range. It was also
apparent that the COV side produced more samples in the higher concentration ranges
than the UNCOV side. As stated before, since the total chlorine residual is composed
mostly of free chlorine the results were similar to those shown for free chlorine residual.
01234
5678
3.0-3.25 3.25-3.5 3.5-3.75 3.75-4.0 >4.0Total Chlorine (mg/L Cl2)
# of
Insta
nces
UNCOV Total Cl2 COV Total Cl2
Figure 5-4. Total chlorine residual of the UNCOV and COV side effluents separated into concentration ranges.
The difference in the total chlorine residual of the UNCOV and COV basin sides
was plotted versus the difference in temperature between the sides (Figure 5-5). Seven of
the nine points were in the fourth quadrant, showing that in most cases the UNCOV side
of the basin had a higher effluent temperature and a lower effluent total chlorine residual
than the COV side. Using the paired t-test method, with the Pearson product momentum
correlation coefficient, there was no significant linear correlation between the difference
in effluent total chlorine concentration and the difference in temperature.
91
-1.00
-0.80
-0.60
-0.40
-0.20
0.00-0.5 0.0 0.5 1.0
Temperature (°C)
Tota
l Chl
orin
e R
esid
ual (
mg/
L C
l2)
Figure 5-5. Total chlorine difference of the UNCOV and COV basin sides plotted versus the difference in temperature.
Disinfection By-Products
Trihalomethane
As stated previously, the TTHM concentration of an effluent sample is the summed
values of the chloroform, bromodichloromethane, dibromochloromethane, and
bromoform concentrations calculated for the said sample using the GC/MS equipment.
The THM speciation for each of the sampling full-scale runs can be seen in Appendix F.
The TTHM effluent mass concentrations were separated into range increments and
plotted in a histogram (Figure 5-6). The concentrations are raw values in that they were
not normalized to pH, temperature, and chlorine effluent concentration. The COV side
had the most numerous samples in the 25-50 µg/L TTHM concentration range with four
samples. Also, the COV side TTHM effluent concentrations had three samples in the 75-
100 µg/L range. The UNCOV side of the basin had equal number of samples, three, in
the 25-50 µg/L and 50-75 µg/L TTHM effluent concentration ranges. In the highest
∆
∆
92
range increment, >100 µg/L, the UNCOV side had two samples and the COV side only
had one sample. It appears that the effluent TTHM concentrations for the full-scale study
were only slightly higher than what was seen in the pilot study. However, in the
full-scale plant the wastewater would flow through a second chlorine contact basin, prior
to discharge or reuse, adding additional time for DBP formation.
0
1
2
3
4
5
6
<25 25-50 50-75 75-100 >100TTHM ( g/L)
# of
Inst
ance
s
UNCOV TTHM COV TTHM
Figure 5-6. The TTHM effluent mass concentrations for the UNCOV and COV sides are shown in range increments.
The TTHM effluent molar concentrations were separated into range increments and
plotted in a histogram (Figure 5-7). The UNCOV and COV sides both had the most
numerous samples in the 0.25-0.50 µmoles/L TTHM concentration range with five
samples each. In the second highest range increment, 0.75-1.00 µmoles/L, the UNCOV
side had two samples and the COV side had three samples.
µ
93
0
1
2
3
4
5
6
<0.25 0.25-0.50 0.50-0.75 0.75-1.0 >1.0
TTHM ( moles/L)
# of
Inst
ance
s
UNCOV TTHM COV TTHM
Figure 5-7. The TTHM effluent molar concentrations for the UNCOV and COV sides are shown in range increments.
The difference in the UNCOV and COV TTHM mass and molar effluent
concentrations for all of the full-scale basin experimental runs is shown as a histogram
(Figure 4-14 and 4-15), respectively. The differences in TTHM concentrations were the
actual concentrations in the effluent sample; the concentrations were not normalized for
the differences in chlorine residual, temperature or pH. There were five sampling sets of
a total of nine experimental sampling sets where the COV basin side had a higher TTHM
concentration than the UNCOV side. In the rest of the nine sampling sets the UNCOV
side effluent concentration was higher than that of the COV side. The average difference
of effluent TTHM mass concentration between the UNCOV and COV sides for the
full-scale sampling sets was -2.24 µg/L with a standard deviation of 9.5 µg/L. The
average difference of effluent TTHM molar concentration between the UNCOV and
COV sides for the full-scale sampling sets was –0.02 µmoles/L with a standard deviation
µ
94
of 0.08 µmoles/L. According to the paired t-test, using the Pearson product momentum
correlation coefficient, there was no significant difference between the TTHM effluent
concentration of the UNCOV and COV sides, mass or molar.
0
1
2
3
4
5
6
<0 0-8 8-16 >16
TTHM ( g/L)
# of
Insta
nces
Figure 5-8. Difference in TTHM concentration between the UNCOV and COV sides (UNCOV-COV) separated into mass concentration ranges.
0
1
2
3
4
5
6
<0 0-0.07 0.07-0.14 >0.14
TTHM ( moles/L)
# of
Insta
nces
Figure 5-9. Difference in TTHM concentration between the UNCOV and COV sides (UNCOV-COV) separated into molar concentration ranges.
∆ µ
∆ µ
95
The difference in the UNCOV and COV TTHM mass and molar effluent
concentrations for all of the full-scale experimental runs was plotted versus the difference
in free chlorine residual (Figure 5-10 and Figure 5-11), respectively. The COV side
effluent TTHM concentration was higher than the UNCOV side effluent concentration in
five sampling sets out of the nine. Of these five sampling sets, four occurred when the
effluent free chlorine residual difference between the sides was larger than the average
residual difference of –0.71 mg/L. The average difference in the TTHM effluent
concentrations between the UNCOV and COV sides was –2.24 µg/L with a standard
deviation of 9.5 µg/L. The average difference in the TTHM effluent concentrations
between the UNCOV and COV sides was –0.02 µmoles/L with a standard deviation of
0.08 µmoles/L. According to the paired t-test, with the Pearson product momentum
correlation coefficient, there was no significant correlation between the difference in
TTHM, mass or molar, effluent concentrations and the difference in free chlorine
residual.
-20-15-10
-505
101520
-1.50 -1.00 -0.50 0.00Free Chlorine (mg/L)
TTH
M (
g/L
)
Figure 5-10. Difference in the TTHM effluent mass concentration between the UNCOV and COV sides (UCOV-COV) plotted versus the difference in free chlorine residual of the UNCOV and COV sides (UCOV-COV).
∆
µ∆
96
-0.15
-0.10
-0.05
0.00
0.05
0.10
0.15
-1.50 -1.00 -0.50 0.00
∆Free Chlorine (mg/L)
∆TT
HM
( µm
oles
/L)
Figure 5-11. Difference in the TTHM effluent molar concentration between the UNCOV and COV sides (UCOV-COV) plotted versus the difference in free chlorine residual of the UNCOV and COV sides (UCOV-COV).
The THM formation for all of the sampling runs for both the UNCOV and COV
sides were, for the most part, as the chloroform molecule. Chloroform made up at least
70%, by mass, of the TTHM formed for both sides of the basin during each of the
sampling runs of the full-scale study (Figure 5-12).
84%
16%
0%
0%
Chloroform BromodichloromethaneDibromochloromethane Bromoform
Figure 5-12. Speciation of the TTHM formed in the UNCOV side sampled at 9 am on August 25, 2004.
97
The average, minimum, and maximum values of the normalization factors used to
normalize the COV effluent TTHM concentrations to the UNCOV effluent TTHM
concentrations are shown in (Table 5-1). The normalized TTHM concentrations will be
denoted as TTHM’. All TTHM normalized data can be found in Appendix D. The
difference in temperature of the two sides did not exceed 1.0 °C and thus temperature did
not have as great an effect on TTHM concentration differences as it did in the pilot basin
study. As in the pilot study, the COV side of the basin maintained higher effluent free
chlorine residuals, as much as 1.05 mg/L Cl2 higher than the UNCOV side, and thus had
a greater effect on TTHM concentration differences. The relative effect of parameters on
the TTHM concentration differences is reflected in the normalization factors, the more
the factors deviate from 1.0 the greater the effect that parameter had on the TTHM
concentration difference.
The free chlorine residual normalization factor deviates the most from 1.0, with a
value of 0.85, and thus was the determining factor in the difference of the TTHM
concentration between the two sides. The chlorine residual having the greatest effect on
the TTHM concentration difference of the two sides was important in that in all of the
sampling sets the COV side had a higher effluent free chlorine residual than the UNCOV
side.
Table 5-1. Normalization factors used to normalize COV TTHM effluent concentrations to UNCOV TTHM effluent concentrations.
pH Normalization
Factor
Temperature Normalization
Factor
Chlorine Residual
Normalization Factor
COV COV COV Average 1.00 1.01 0.85
Maximum 1.04 1.03 0.94 Minimum 0.99 0.99 0.74
98
The effluent TTHM’ mass concentration data for the UNCOV and COV sides are
partitioned into range increments for comparison (Figure 5-13). The most TTHM’
concentration samples for the COV side effluent were in the 25-50 µg/L TTHM range
increment, with four samples. The UNCOV side effluent had the most numerous
samples in the both the 25-50 µg/L and the 50-75 µg/L TTHM range increments, both
with three samples. It is also worth noting that at the UNCOV side of the basin had two
samples where the TTHM concentration was greater than 100 µg/L.
0
1
2
3
4
5
6
<25 25-50 50-75 75-100 >100TTHM' ( g/L)
# of
Inst
ance
s
UNCOV TTHM' COV TTHM'
Figure 5-13. The TTHM’ mass concentration instances separated into concentration ranges for the UNCOV and COV side.
The effluent TTHM’ molar concentrations for the UNCOV and COV sides are
partitioned into range increments for comparison (Figure 5-14). Most TTHM’
concentration samples for the UNCOV and COV side effluents were in the 0.25 to 0.50
µmoles/L TTHM range increment, with 5 and 6 samples, respectively. It is also worth
µ
99
noting that at the highest concentration increment the UNCOV side had two samples
while the COV side had only one.
0
1
2
3
4
5
6
7
<0.25 0.25-0.50 0.50-0.75 0.75-1.0 >1.0
TTHM' ( moles/L)
# of
Inst
ance
s
UNCOV TTHM' COV TTHM'
Figure 5-14. The TTHM’ molar concentration instances separated into concentration ranges for the UNCOV and COV side.
The difference in the effluent TTHM’ concentrations between the UNCOV and
COV sides was separated into mass concentration ranges (Figure 5-15). The histogram
shows that in only two sampling sets, out of a total of nine sampling sets, did the COV
side have a higher TTHM’ concentration than the UNCOV side. Most differences in the
effluent TTHM’ mass concentrations were in the 8 to 16 µg/L range. The average
difference of normalized TTHM’ mass concentration between the UNCOV and COV
sides for the full-scale study was 7.48 µg/L with a standard deviation of 9.17 µg/L.
Using the paired t-test method there was a 95% confidence level that there was a
difference between the UNCOV side effluent TTHM’ concentrations and the COV side
effluent TTHM’ concentrations. Thus, when the effluent TTHM concentrations are
µ
100
normalized to account for the difference in TTHM forming parameters between the two
basin side streams the difference can be shown to be significant.
00.5
11.5
22.5
33.5
44.5
5
<0 0-8 8-16 >16TTHM' ( g/L)
# of
Inst
ance
s
Figure 5-15. Difference in TTHM’ concentration between the UNCOV and COV sides (UNCOV-COV) separated into mass concentration ranges.
The difference in the effluent TTHM’ concentrations were separated into molar
concentration ranges (Figure 5-16). The histogram shows that in only two sampling sets,
out of a total of nine sampling sets, did the COV side have a higher TTHM’
concentration than the UNCOV side. Most sampling sets of the TTHM’ molar
concentration difference were in the 0.07 to 0.14 µmoles/L range. The average
difference of normalized TTHM’ concentration between the UNCOV and COV sides for
the full-scale study was 0.06 µmoles/L with a standard deviation of 0.07 µmoles/L.
Using the paired t-test method there was a 95% confidence level that there was a
difference between the UNCOV side effluent TTHM’ molar concentrations and the COV
side effluent TTHM’ concentrations.
µ∆
101
0
1
2
3
4
5
<0 0-0.07 0.07-0.14 >0.14
TTHM' ( moles/L)
# of
Inst
ance
s
Figure 5-16. Difference in TTHM’ concentration between the UNCOV and COV sides (UNCOV-COV) separated into molar concentration ranges.
Through the normalization of the effluent TTHM concentration the number of
sampling sets where the COV side had a higher TTHM concentration than the UNCOV
side was reduced from five to only two, mostly resulting from the difference in free
chlorine residual. Thus, in the majority of the sampling sets the UNCOV, UV radiation
irradiated, side had a higher TTHM’ effluent concentration. The TTHM’ effluent
concentrations demonstrate and support the findings of the 2002 IPPD team2, that UV
radiation, and more simply covering the chlorination process, not only provides the
benefit of a higher free chlorine residual but also the tendency toward a lower TTHM
effluent concentration.
Haloacetic Acid
As stated previously, the HAA(5) concentration of an effluent sample is the
summed values of the monochloroacetic acid (MCAA), monobromoacetic acid (MBAA),
dichloroacetic acid (DCAA), dibromoacetic acid (DBAA), and trichloroacetic acid
(TCAA) concentrations calculated for the said sample using the GC/ECD. The THM
speciation for each of the sampling full-scale runs can be seen in Appendix F.
µ∆
102
The HAA(5) effluent mass concentrations for the UNCOV and COV sides were
separated into range increments and plotted in a histogram (Figure 5-17). The
concentrations are raw values in that they were not normalized to temperature or chlorine
residual. Most of the effluent HAA(5) concentrations fell within the greater than
100 µg/L range for the UNCOV and COV sides, with seven and six samples respectively.
The HAA(5) effluent molar concentrations were separated into range increments and
plotted in a histogram (Figure 5-18). Most of the effluent HAA(5) concentrations fell
within the 0.75 to1.0 µmoles/L range for the UNCOV side while the most instances for
the COV side occurred in the 0.50 to 0.75 and the 0.75 to1.0 µmoles/L range, both with
four samples. The UNCOV side effluent sample for HAA(5) concentration for August
25, 2004 at 9 am was lost so it was not included in the histograms. It is good to note that
the majority of the UNCOV and COV side HAA(5) effluent concentrations fall in the
range that is greater the proposed EPA standard. The HAA(5) effluent concentrations
were greater than those found in the pilot study and since the chlorine disinfection basins
are in series the wastewater will pass through a second basin prior to discharge, or reuse,
adding more time for DBP formation.
01234567
<25 25-50 50-75 75-100 >100HAA ( g/L)
# of
Inst
ance
s
UNCOV HAA COV HAA
Figure 5-17. The HAA(5) effluent mass concentrations for the UNCOV and COV sides are shown in range increments.
µ
103
0
1
2
3
4
5
6
<0.25 0.25-0.50 0.50-0.75 0.75-1.0 >1.0HAA ( moles/L)
# of
Inst
ance
s
UNCOV HAA COV HAA
Figure 5-18. The HAA(5) effluent molar concentrations for the UNCOV and COV sides are shown in range increments.
The difference in the HAA(5) concentrations (∆HAA(5)) were separated into mass
and molar concentration ranges in (Figure 5-19 and 5-20), respectively. The UNCOV
side effluent sample for HAA(5) concentration for August 25, 2004 at 9 am was lost so it
was not included in the histograms. In eight of the nine sampling sets the UNCOV side
effluent HAA(5) mass concentration was higher than the COV side effluent
concentration, one sampling set was not used in the analysis since the UNCOV side
sample was lost. In the HAA(5) mass concentration difference histogram the most values
were in the greater than 16 µg/L range, with four sampling sets. The average difference
in HAA(5) effluent mass concentration was 39.5 µg/L with a standard deviation of 35.2
µg/L. In six of the nine sampling sets the UNCOV side effluent HAA(5) molar
concentration was higher than the COV side effluent concentration. In the histogram of
the differences in HAA(5) effluent molar concentration the values were spread evenly
across the concentration ranges. The average difference in HAA(5) effluent molar
µ
104
concentration was 0.16 µmole/L with a standard deviation of 0.25 µmoles/L. Using the
paired t-test method it was determined that there was a 99% confidence that the
difference between the UNCOV and COV side effluent HAA(5) mass concentrations
were significant. There was a 95% confidence that there was a significant difference in
the HAA(5) effluent molar concentrations.
01234567
<0 0-8 8-16 >16HAA ( g/L)
# of
Inst
ance
s
Figure 5-19. Difference in HAA(5) concentration between the UNCOV and COV sides (UNCOV-COV) separated into mass concentration ranges.
0
1
2
3
4
<0 0-0.07 0.07-0.14 >0.14
HAA ( moles/L)
# of
Inst
ance
s
Figure 5-20. Difference in HAA(5) concentration between the UNCOV and COV sides (UNCOV-COV) separated into molar concentration ranges.
µ∆
µ∆
105
The difference in HAA(5) effluent mass concentrations of the UNCOV and COV
sides was plotted versus the difference in free chlorine residual of the UNCOV and COV
sides (Figure 5-21). As stated previously, in eight of the nine sampling sets the UNCOV
side HAA(5) effluent mass concentrations were higher than those of the COV side.
Using the paired t-test method, with the Pearson product momentum correlation
coefficient, it was determined that there was no significant correlation between the
difference in effluent HAA(5) mass concentration and the difference in free chlorine
residual. Even though there does not appear to be a linear correlation between the
difference in effluent HAA(5) concentration and the difference in effluent free chlorine
residual the largest difference in effluent HAA(5) concentration does corresponds with
the largest difference in effluent free chlorine residual.
020406080
100120
0.00 1.00 2.00 3.00 4.00
Free Chlorine (mg/L Cl2)
HA
A (
g/L
)
Figure 5-21. Difference in HAA(5) effluent mass concentration of the UNCOV and COV sides versus the difference in free chlorine residual of the UNCOV and COV sides.
The difference in HAA(5) effluent molar concentrations of the UNCOV and COV
sides was plotted versus the difference in free chlorine residual of the UNCOV and COV
sides (Figure 5-22). Similar to the mass concentration, using the paired t-test method,
∆
µ∆
106
with the Pearson product momentum correlation coefficient, it was determined that there
was no significant linear correlation between the difference in effluent HAA(5) molar
concentration and the difference in free chlorine residual. Again, it was observed that
though there was no significant linear relationship between the difference in HAA(5) and
the difference in free chlorine residual, the largest difference in effluent HAA(5)
concentration corresponds with the largest difference in effluent free chlorine residual.
-0.100.000.100.200.300.400.500.600.700.80
0.00 1.00 2.00 3.00 4.00
Free Chlorine (mg/L Cl2)
HA
A (
mol
e/L)
Figure 5-22. Difference in HAA(5) effluent molar concentration of the UNCOV and COV sides versus the difference in free chlorine residual of the UNCOV and COV sides.
The HAA(5) speciation for the sampling runs for both the UNCOV and COV sides
is shown in Appendix F No single species made up the majority of the HAA(5)
concentration in all of the sampling sets though it did appear that DCAA made up the
highest percentage for the greatest number of sets compared with the other HAA(5)
species. The speciation of the HAA(5) effluent concentration in the COV side on August
25, 2004 taken at 12 pm is shown with species percentage (Figure 5-23). In this case,
DCAA made up 59% of the HAA(5) mass concentration. In this sample there was no
measurable MCAA or DBAA present.
∆µ
∆
107
0% 8%
59%0%
33%
MCAA MBAA DCAA DBAA TCAA
Figure 5-23. Speciation of the HAA(5) formation in the COV effluent on a mass basis sampled at 12 pm on August 25, 2004.
Like THM formation, HAA(5) formation is affected by environmental conditions,
such as, temperature and free chlorine residual. In order to compensate for the
differences between these parameters in the North basin effluents the HAA(5)
concentrations were normalized like in the pilot study. All HAA(5) normalized data can
be found in Appendix D. Though DCAA did not make up the highest percentage in all
sampling sets it did make up the highest percentage of the HAA(5) concentrations in
most cases and thus the formation equation coefficients for DCAA was used in the
normalization of the COV side effluent HAA(5) concentration to the UNCOV side
effluent HAA(5) concentration.
The average, minimum, and maximum values of the normalization factors used to
normalize the COV effluent HAA(5) concentrations to the UNCOV effluent HAA(5)
concentrations are shown in (Table 5-2). The average values give an idea of how much
the difference in the parameter affects the HAA(5)concentration of the two sides. As
stated previously, the farther the normalization factor is from 1.0 the greater the
parameter contributes to the HAA(5) concentration difference between the two sides.
108
The free chlorine residual normalization factor deviates the most from 1.0, with a value
of 0.87, and thus was the determining factor in the difference of the HAA(5)
concentration between the two sides according to the model. The chlorine residual
having the greatest effect on the HAA(5) concentration difference of the two sides was
important since in all cases the COV side had a higher free chlorine residual effluent than
the UNCOV side, and in all but two sampling sets the UNCOV side had a higher HAA(5)
effluent concentration than the COV side.
Table 5-2. Normalization factors used to normalize COV HAA(5) effluent concentrations to UNCOV HAA(5) effluent concentrations.
Temperature (°C)
Normalization Factor
Chlorine Residual
Normalization Factor
COV COV Average 1.01 0.87
Maximum 1.02 0.95 Minimum 0.99 0.78
The HAA(5)’ effluent mass concentrations were separated into range increments
and plotted in a histogram (Figure 5-24). The UNCOV side effluent sample for HAA(5)
concentration for August 25, 2004 at 9 am was lost so it was not included in the
histograms. Similar to the raw HAA(5) histogram, most of the effluent HAA(5)’
concentrations fell within the greater than 100 µg/L range for the UNCOV side, with
seven samples. However, for the COV side most values fell within the 75 to 100 µg/L
HAA(5)’ effluent concentration range, with four samples. The HAA(5)’ effluent molar
concentrations were separated into range increments and plotted in a histogram
(Figure 5-25). Most of the effluent HAA(5)’ molar concentrations fell within the 0.75 to
100 µmoles/L range for the UNCOV side, with five samples. The COV side HAA(5)’
109
effluent concentrations fell mostly in the 0.50 to 0.75 µmoles/L range, with seven
samples. It is significant to note that the UNCOV side had more concentration values fall
within the greater than 100 µg/L than the COV side. Also, the UNCOV side had one
sample in the greater than 1.0 µmoles/L range where the COV side had none and the
UNCOV side had more values in the second to highest range, 0.75 to 1.0 µmoles/L range,
than the COV side, with five and one samples respectively.
0
2
4
6
8
<25 25-50 50-75 75-100 >100
HAA' (µg/L)
# of
Inst
ance
s
UNCOV HAA' COV HAA'
Figure 5-24. The HAA(5)’ effluent mass concentrations for the UNCOV and COV basin sides are shown in range increments.
0
2
4
6
8
<0.25 0.25-0.50 0.50-0.75 0.75-1.0 >1.0
HAA' (µmoles/L)
# of
Inst
ance
s
UNCOV HAA' COV HAA'
Figure 5-25. The HAA(5)’ effluent molar concentrations for the UNCOV and COV basin sides are shown in range increments.
110
The difference in the HAA(5)’ concentrations (∆HAA(5)’) were separated into
mass and molar concentration ranges (Figure 5-26 and 5-27), respectively. In all of the
nine sampling sets the UNCOV side effluent HAA(5)’ mass and molar concentration
were higher than the COV side effluent concentration. In the HAA(5)’ mass
concentration difference histogram the six sampling sets were in the greater than 24 µg/L
range. The average difference in HAA(5)’ effluent mass concentration was 38.96 µg/L
with a standard deviation of 35.15 µg/L. Most instances in HAA(5)’ molar concentration
difference histogram were in the greater than 0.14 µmole/L range, with five sampling
sets. The average difference in HAA(5)’ effluent molar concentration was 0.24 µmole/L
with a standard deviation of 0.23 µmoles/L. Using the paired t-test method it was
determined that there was a 99% confidence that there was a difference between the
UNCOV and COV side effluent HAA(5)’ concentrations, mass and molar.
0
1
2
3
4
5
6
7
<0 0-8 8-16 >16HAA' ( g/L)
# of
Inst
ance
s
Figure 5-26. Difference in HAA(5)’ concentration between the UNCOV and COV sides (UNCOV-COV) separated into mass concentration ranges.
∆ µ
111
01234567
<0 0-0.07 0.07-0.14 >0.14
HAA' ( moles/L)
# of
Inst
ance
s
Figure 5-27. Difference in HAA(5)’ concentration between the UNCOV and COV sides (UNCOV-COV) separated into molar concentration ranges.
In all of the nine sampling sets for the non-normalized and normalized, to
temperature and free chlorine residual, HAA(5) concentrations the UNCOV side had a
higher HAA(5) mass concentration than the COV side. Also, all of the average HAA(5)
concentrations, normalized and non-normalized, there was at least a 95% confidence that
the difference was significant, for mass concentrations the confidence was 99%. Thus,
preventing the UV radiation exposure of wastewater during chlorine disinfection could
result in lower HAA(5) formation than in the exposed chlorination process.
∆ µ
112
CHAPTER 6 DISCUSSION: MEASURED PARAMETERS
Other water quality parameters, such as, total coliform, total suspended solids
(TSS), pH, conductivity, temperature, and dissolved oxygen were measured during the
pilot and full-scale studies. Measurement of these water quality parameters made it
possible to determine the extent of the difference between the conventional process of
allowing the chlorine disinfection stage of the wastewater treatment process to be
exposed to solar radiation, ultraviolet and global radiation, versus covering the basin thus
preventing the exposure of the wastewater during the disinfection process.
Temperature
The temperature did not appear to have a great influence on the chlorine residual or
on the difference in the TTHM or HAA(5) formation between the UV radiation exposed
and UV limited wastewater effluents. The temperature parameter does not appear in the
model equation for MCAA and the TTHM average normalization factor for temperature
was 1.01 for the pilot system and 1.05 for the full-scale system. The temperature values
for the pilot and full-scale studies can be viewed in the Appendix E and F, for the pilot
and full-scale studies respectively.
Total Coliform
In almost all cases in both the pilot and full-scale studies the total coliform counts
were less than the detectable limit, 1/100 mL, for both the UV radiation exposed and UV
limited wastewater effluents. The total coliform values for the pilot and full-scale studies
for the following water quality parameters can be viewed in the Appendix E and F,
113
respectively. An example of typical total coliform values is shown in (Figure 6-1), the
values are samples taken from July 14, 2004. The facts that in all sampling cases effluent
total coliform counts were less than the detectable limit demonstrates that both systems,
the solar radiation exposed and protected, produce adequate disinfection.
0.00
0.02
0.04
0.06
0.08
0.10
0.12
9:00 12:00 14:00Time of Day (hr:min)
Tota
l Col
iform
(#
/100
mL)
25
27
29
31
33
Tem
pera
ture
(°C
)
TRANS TC OPAQ TCTRANS Temp OPAQ Temp
Figure 6-1. Total coliform and temperature plotted against sampling time on July 14, 2004.
Total Suspended Solids
In almost all cases in both the pilot and full-scale studies the total suspended solids
concentrations were less than the detectable limit, 1 mg/L TSS, for both the UV radiation
exposed and limited wastewater effluents. The TSS values for the pilot and full-scale
studies can be viewed in the Appendix E and F, respectively. An example of typical TSS
values is shown in (Figure 6-2), the values are samples taken from July 14, 2004. Both
the solar radiation exposed and protected wastewater chlorine disinfection systems had
less than detectable effluent TSS concentrations demonstrating that both systems would
perform adequately with respect to TSS effluent concentration.
114
0.000.200.400.600.801.001.20
9:00 12:00 14:00Time of Day (hr:min)
TSS
(mg/
L)25
27
29
31
33
Tem
pera
ture
(°C
)
INT TSS TRANS TSS OPAQ TSSTRANS Temp OPAQ Temp
Figure 6-2. Total suspended solids and temperature plotted against sampling time on July 14, 2004.
pH
The pH did not appear to have a great influence on the difference in the TTHM or
HAA(5) formation between the solar radiation exposed and protected wastewater
effluents, since for both DBPs the average normalization factor was 1.00. The pH values
for the pilot and full-scale studies can be viewed in the Appendix E and F, for the pilot
and full-scale studies respectively. An example of typical pH values is shown in (Figure
6-3), the values are samples taken from July 14, 2004.
6.5
6.8
7.0
7.3
7.5
9:00 12:00 15:00Time of Day (hr:min)
pH
25
27
29
31
33
Tem
pera
ture
(°C
)
INT pH TRANS pH OPAQ pHTRANS Temp OPAQ Temp
Figure 6-3. pH and temperature plotted against sampling time on July 14, 2004.
115
Conductivity
The conductivity did not appear to have a great influence on the chlorine residual or
on the difference in the TTHM or HAA(5) formation between the UV radiation exposed
and UV limited wastewater effluents. The conductivity values for the pilot and full-scale
studies can be viewed in the Appendix E and F, for the pilot and full-scale studies
respectively. An example of typcal conductivity values is shown in (Figure 6-4), the
values are samples taken from July 14, 2004.
550
600
650
700
750
800
9:00 12:00 15:00Time of Day (hr:min)
Con
duct
ivity
s (
mho
s/cm
)
25
27
29
31
33
Tem
pera
ture
(°C
)
INT Cond TRANS CondOPAQ Cond TRANS TempOPAQ Temp
Figure 6-4. Conductivity and temperature plotted against sampling time on July 14, 2004.
Dissolved Oxygen
The dissolved oxygen did not appear to have a great influence on the chlorine
residual or on the difference in the TTHM or HAA(5) formation between the UV
radiation exposed and UV limited wastewater effluents. The dissolved oxygen values for
the pilot and full-scale studies can be viewed in the Appendix E and F, for the pilot and
full-scale studies respectively. An example of typical dissolved oxygen values is shown
in (Figure 6-5), the values are samples taken from July 14, 2004. The DO effluent
µ
116
concentrations did not vary greatly between the solar radiation exposed and protected
systems.
0.00.51.01.52.02.53.03.54.04.5
9:00 12:00 15:00Time of Day (hr:min)
Dis
solv
ed O
xyge
n(m
g/L
O2)
25262728293031323334
Tem
pera
ture
(°C
)
INT DO TRANS DO OPAQ DOTRANS Temp OPAQ Temp
Figure 6-5. Dissolved oxygen and temperature plotted against sampling time on July 14, 2004.
117
CHAPTER 7 CONCLUSIONS
The KWRF is mandated to maintain no less than 1 mg/L chlorine residual as the
wastewater exits the chlorine disinfection basins. While in the chlorine contact basins the
wastewater is left exposed to ultraviolet radiation, which catalyzes the reduction of free
chlorine to the chloride ion. In order, to compensate for the loss in chlorine through this
mechanism additional chlorine must be added to ensure sufficient disinfection and
effluent chlorine residual. In pilot and full-scale studies, the significance of shielding the
wastewater during chlorine disinfection was tested. In one process stream, the
wastewater was left exposed; whereas in the second process stream an opaque cover was
used to shield the wastewater during chlorine disinfection from ultraviolet radiation. It
was found that the wastewater effluent from the opaquely covered chlorination process
had higher total and free chlorine residuals. Using the paired t-test method for statistical
data analysis, there was a 99% confidence that the effluent chlorine residuals of the two
process streams were different, for both the pilot and full-scale study. Preventing
ultraviolet radiation exposure of wastewater during chlorine disinfection provides for
higher chlorine residual and reduces the need for chlorine compensation caused by
exposure.
In order to ascertain the cause of the difference in effluent chlorine residuals linear
correlations were tested for temperature and ultraviolet radiation, for the pilot study. The
Pearson product momentum correlation coefficient with the paired t-test analysis was
used to determine the confidence of the correlation. There was a 95% confidence that the
118
difference in free chlorine residual correlated linearly with the difference in effluent
temperature. There was no confidence that there was a linear correlation between the
difference in total chlorine residual and the difference in effluent temperature. There was
a 95% confidence that there was a linear correlation between both the difference in free
and total chlorine residual with the difference in average ultraviolet radiation exposure.
Also found, was a 99% confidence in a linear correlation between the effluent
temperature of the exposed and non-exposed pilot basins with the average ultraviolet
radiation exposure. As ultraviolet radiation intensity increased during the day the
difference in effluent temperature would increase and the difference in chlorine, total and
free, would also increase. The extent of residual difference depends on the hydraulic
retention time of wastewater in the basin, the initial chlorine dosage, and the amount of
ultraviolet radiation that the water will be exposed to while in the basin.
Since ultraviolet radiation exposure of microorganism result in a degree of
inactivation, preventing the ultraviolet radiation exposure of wastewater during
chlorination becomes a concern over adequate disinfection. During the pilot and full-
scale studies effluent samples were tested for total coliforms. In all sampling sets, both
the ultraviolet radiation exposed and non-exposed process streams provided adequate
disinfection. Thus, preventing ultraviolet radiation exposure of wastewater does not
compromise disinfection.
Disinfection by-product formation is becoming an ever-increasing concern and
future regulations for stricter discharge concentrations have only yet to be implemented.
Since chlorine disinfection leads to DBP formation, the DBP formation of the exposed
and non-exposed chlorination streams in the pilot and full-scale studies were also
119
analyzed. Total trihalomethanes (TTHMs) and the regulated five haloacetic acids
HAA(5)s were measured to evaluate DBP formation for the pilot and full-scale studies.
Both in the pilot and full-scale studies there was found no significant difference in the
raw effluent TTHM concentrations between the UV exposed and non-exposed chlorine
disinfection processes. However, the normalized TTHM effluent concentrations were
statistically higher in the exposed chlorine disinfection process than the non-exposed
process. Though there was no significant difference in the raw TTHM concentrations
there was a 99% and a 95% confidence that the mass and molar TTHM effluent
concentrations were different for the pilot and full-scale studies, respectively. Showing
that there is significant evidence that shielding the chlorine disinfection process not only
results in a higher chlorine residual but also a lower TTHM concentration.
In the pilot study for the raw and normalized HAA(5) concentrations their appeared
to be no significant difference between the exposed and non-exposed processes.
Although the non-exposed process provided for a higher chlorine residual it did not result
in a higher HAA(5) concentration which is desired if the process were to be implemented
at the KWRF. However, for the full-scale study the HAA(5) effluent concentration was
statistically higher in the exposed process over the non-exposed process. Statistical
analysis showed a 99% and a 95% confidence that the raw effluent HAA(5) mass and
molar concentrations, respectively, were different; providing support that the non-
exposed wastewater not only provided higher chlorine residual but also less HAA(5)
formation. Statistical analysis showed a 99% confidence that the normalized HAA(5)
mass and molar concentrations were also different. It is important to note that the full-
scale study was performed on only the first portion of the KWRF chlorine disinfection
120
process, the first of two chlorine contact basins in series. Thus, the difference in pilot and
full-scale data is not unexpected since the hydraulic retention used in the pilot study was
not available during the full-scale study. If the complete KWRF chlorine disinfection
process were to be analyzed in future studies it would be expected that the data would be
more comparable to the data collected during the pilot study.
The data provided during the pilot and full-scale study have positively determined
the following:
1. Preventing ultraviolet radiation exposure of wastewater during chlorine disinfection results in a higher effluent free and total chlorine residual
2. Preventing ultraviolet radiation exposure of wastewater significantly reduces the
TTHM formation during chlorine disinfection 3. Preventing ultraviolet radiation exposure of wastewater does not result in an
increase in HAA(5) formation 4. Preventing ultraviolet radiation exposure of wastewater during chlorine disinfection
does not adversely affect microorganism inactivation.
Because the findings of these studies provide evidence against the more common
theory behind DBP formation with respect to chlorine residual it is recommended that
future studies concerning UV radiation exposure and DBP formation be performed.
121
APPENDIX A PILOT-SCALE BASIN DESIGN
Table A-1. South chlorine contact basin Elevation Feet Side View: Outer Wall/Baffle 79.82Inlet Weir 71.50Effluent Weir 73.80Bottom 64.57Outer Wall/Baffle 15.25Inlet Weir 6.93Effluent Weir 9.23Top View: Length w/o Thickness 93.00Length w/ Thickness 95.67Width w/o Thickness 77.33Width w/ Thickness 80.00Width of Channel 9.00No. of channels 8.00Area 7653 ft2
Volume 116712 ft3
Table A-2. North chlorine contact basin Actual Height (Feet) Side View: Outer Wall/Baffle 11.00Inlet Weir 7.00Effluent Weir 7.92Top View: Length w/o Thickness 56.00Length w/ Thickness 58.00Width w/o Thickness 56.33Width w/ Thickness 58.33Width of Channels 5.00No.of Channels 10.00Area 3383 ft2
Volume 37216 ft3
Table A-3. Pilot basin. Basin (Scaled) Feet Length 4.000 Width 3.653 Height 0.693 No. Channels 9.000 Channel Width 0.362 Channel Width 4.344 in Area 14.610 ft2 Volume 10.123 ft3
122
APPENDIX B FLUOROSCEIN TRACER ANALYSIS
Table B-1. Fluoroscein tracer at KWRF pilot basin, clear top. Time sample collection Time Reading Fluoroscein Time/HRT
h min min mg/L 4 0 0 0.5 0.0096 03 54 6 0.5 0.0096 0.0563 48 12 0.5 0.0096 0.1123 42 18 0.5 0.0096 0.1683 36 24 0.5 0.0096 0.2243 30 30 0.4 0.00768 0.283 24 36 0.5 0.0096 0.3363 18 42 0.5 0.0096 0.3923 12 48 0.5 0.0096 0.4483 6 54 0.5 0.0096 0.5043 0 60 0.5 0.0096 0.562 56 64 0.8 0.01536 0.5973332 52 68 1.4 0.02688 0.6346672 48 72 1.7 0.03264 0.6722 44 76 2.1 0.04032 0.7093332 40 80 2.6 0.04992 0.7466672 36 84 3.4 0.06528 0.7842 32 88 3.8 0.07296 0.8213332 28 92 4.1 0.07872 0.8586672 24 96 4.8 0.09216 0.8962 20 100 4.8 0.09216 0.9333332 16 104 5.2 0.09984 0.9706672 12 108 5.1 0.09792 1.0082 8 112 5.3 0.10176 1.0453332 4 116 5.6 0.10752 1.0826672 0 120 5.6 0.10752 1.121 56 124 5.5 0.1056 1.1573331 52 128 5.9 0.11328 1.1946671 48 132 5.8 0.11136 1.2321 44 136 5.8 0.11136 1.2693331 40 140 5.6 0.10752 1.3066671 36 144 5.7 0.10944 1.3441 32 148 6 0.1152 1.3813331 28 152 5.9 0.11328 1.418667
123
Table B-1. Continued.
Time sample collection Time Reading Fluoroscein Time/HRT h min min mg/L
1 24 156 5.7 0.10944 1.4561 20 160 5.9 0.11328 1.4933331 16 164 5.7 0.10944 1.5306671 12 168 5.6 0.10752 1.5681 8 172 5.8 0.11136 1.6053331 4 176 5.5 0.1056 1.6426671 0 180 5.7 0.10944 1.680 54 186 6 0.1152 1.7360 48 192 6.1 0.11712 1.7920 42 198 5.8 0.11136 1.8480 36 204 5.9 0.11328 1.9040 30 210 5.8 0.11136 1.960 24 216 5.7 0.10944 2.0160 18 222 5.5 0.1056 2.0720 12 228 5.5 0.1056 2.1280 6 234 5.4 0.10368 2.1840 0 240 5.2 0.09984 2.24
Table B-2. Conditions during tracer analysis. Basin one
Reactor 75Gal Flow Rate 42GPH HRT 1.79h Wastewater Flow Rate 84.0GPH Flow Rate 5.30L/min Flow Rate 0.451mg/L Fluoroscein Flow Rate 21.7mL/minFlow Rate 0.0217L/min Conc. 110.1455mg/L Conc. 0.110146g/L Pump 7
124
0.000.020.040.060.080.100.120.14
0 0.5 1 1.5 2 2.5
Time of Sample (min) / HRT(min)Fl
uoro
scei
n (m
g/L)
Figure B-1. Fluoroscein versus sampling time.
Table B-3. Flouroscein F curve calculation. Time (min) [ ] mg/L F
Time (min) [ ] mg/L F
0 0.0096 0.087157 116 0.10752 0.9761636 0.0096 0.087157 120 0.10752 0.976163
12 0.0096 0.087157 124 0.1056 0.95873218 0.0096 0.087157 128 0.11328 1.02845824 0.0096 0.087157 132 0.11136 1.01102630 0.00768 0.069726 136 0.11136 1.01102636 0.0096 0.087157 140 0.10752 0.97616342 0.0096 0.087157 144 0.10944 0.99359548 0.0096 0.087157 148 0.1152 1.04588954 0.0096 0.087157 152 0.11328 1.02845860 0.0096 0.087157 156 0.10944 0.99359564 0.01536 0.139452 160 0.11328 1.02845868 0.02688 0.244041 164 0.10944 0.99359572 0.03264 0.296335 168 0.10752 0.97616376 0.04032 0.366061 172 0.11136 1.01102680 0.04992 0.453219 176 0.1056 0.95873284 0.06528 0.592671 180 0.10944 0.99359588 0.07296 0.662397 198 0.11136 1.01102692 0.07872 0.714691 204 0.11328 1.02845896 0.09216 0.836711 210 0.11136 1.011026
100 0.09216 0.836711 216 0.10944 0.993595104 0.09984 0.906437 222 0.1056 0.958732108 0.09792 0.889006 234 0.10368 0.9413112 0.10176 0.923869
125
Table B-4. The F curve values. tm = 113 Min tm
2= 12822 σ2 = 313 σ = 18 n = 41 CMFRs in Seriest10= 61 Min
-0.20
0.20.40.60.8
11.2
0 20 40 60Time (min)
F
Figure B-2. The F curve.
126
APPENDIX C CHLORINE DOSING CALCULATIONS
Table C-1. Chlorine dosing during pilot-scale study. Date Qr Qw Cw Cr
M/DD/YR GPH mL/min mg/L Cl2 mg/L Cl2
6/23/2004 56 21 1350 8.03 6/30/2004 56 21 1350 8.03 7/7/2004 52 21 1253 8.02
7/13/2004 56 19.5 1350 7.45 7/26/2004 56 18.25 1350 6.97 7/28/2004 56 18.25 1350 6.97 8/2/2004 40 17 1350 9.09 8/4/2004 40 21 1401 11.66 8/9/2004 56 21 1153 6.85
8/16/2004 40 24 1716 16.32 Qr=Flow Rate of Wastewater to Reactors, Qw=Flow Rate of Chlorine Solution, Cw=Concnetration of Chlorine Solution, Cr=Concentration of Chlorine going to Reactors Table C-2. Acid and base addition during pilot-scale study. Chemical Date Qr Qw Cw Cr
Added M/DD/YR GPH mL/min Normal Normal H2SO4 7/26/2004 56 19.6 0.2 4.75E-04NaOH 7/28/2004 56 19.6 0.2 4.75E-04
127
APPENDIX D COMPILED DATA
Table D-1. Pilot-scale study compiled and calculated parameter data.
Time Time pH
TRANSpH
OPAQTemperature
TRANS Temperature
OPAQ M/DD/Yr hr:min (°C) (°C) 6/23/2004 9:00 6.85 6.86 27.2 27.0 6/23/2004 12:00 6.83 6.85 29.0 27.6 6/23/2004 14:00 6.87 6.78 30.3 29.2 6/30/2004 9:00 7.34 7.2 28.4 27.5 6/30/2004 12:00 7.3 7.37 30.4 29.6 6/30/2004 14:00 7.36 7.39 33.5 29.8 7/7/2004 9:00 7.29 7.23 28.3 28.1 7/7/2004 12:00 7.27 7.33 31.7 29.9 7/7/2004 14:00 7.33 7.35 33 29.8
7/14/2004 9:00 7.25 7.24 27.9 27.4 7/14/2004 12:00 7.22 7.27 31.2 28.5 7/14/2004 14:00 7.23 7.27 33.3 29.6 7/26/2004 9:00 6.63 6.64 28.1 27.9 7/26/2004 12:00 6.3 6.22 31.3 29.2 7/26/2004 14:00 6.07 6.5 33.5 29.9 7/28/2004 9:00 9.61 9.48 28.1 27.8 7/28/2004 12:00 9.3 8.92 31.0 30.0 7/28/2004 14:00 8.4 8.73 29.9 29.1 8/2/2004 9:00 7.2 7.2 28.1 28.0 8/2/2004 12:00 7.35 7.45 31.3 29.3 8/2/2004 14:00 7.53 7.53 33.0 29.8 8/4/2004 9:00 7.3 7.31 28.3 27.8 8/4/2004 12:00 7.08 7.1 31.2 29.4 8/4/2004 14:00 7.26 7.16 33.5 32.1
8/11/2004 9:00 7.05 7.04 27.4 27.4 8/11/2004 12:00 7.34 7.2 29.2 28.2 8/11/2004 14:00 7.59 7.24 30.6 28.9 8/16/2004 9:00 7.12 7.14 27.1 27.0 8/16/2004 12:00 7.26 7.48 30.4 28.3 8/16/2004 14:00 7.36 7.45 32.6 29.2
128
Table D-2. Pilot-scale study compiled chlorine data and differences.
Time Time
Free Chlorine Residual TRANS
Free Chlorine Residual OPAQ
Total Cl2 Residual TRANS
Total Cl2 Residual OPAQ
Free Chlorine Residual (TRANS-OPAQ)
Total Chlorine Residual (TRANS-OPAQ)
M/DD/Yr hr:min mg/L Cl2 mg/L Cl2 mg/L mg/L mg/L mg/L 6/23/2004 9:00 1.05 1.30 3.05 3.25 -0.25 -0.20 6/23/2004 12:00 0.75 2.1 1.85 2.65 -1.35 -0.80 6/23/2004 14:00 0.25 1 1.4 2.1 -0.75 -0.70 6/30/2004 9:00 1.15 1.25 2.5 2.9 -0.10 -0.40 6/30/2004 12:00 1.00 1.55 2.45 2.8 -0.55 -0.35 6/30/2004 14:00 1.50 1.90 2.15 2.65 -0.40 -0.50 7/7/2004 9:00 4.10 4.90 5.2 5.75 -0.80 -0.55 7/7/2004 12:00 3.00 3.75 3.45 5.45 -0.75 -2.00 7/7/2004 14:00 2.85 4.3 3.85 5.1 -1.45 -1.25
7/14/2004 9:00 3.85 2.7 4.5 3.7 1.15 0.80 7/14/2004 12:00 1.9 2.25 2.8 2.35 -0.35 0.45 7/14/2004 14:00 1.1 1.85 1.55 2.5 -0.75 -0.95 7/26/2004 9:00 0.25 0.30 2.9 3 -0.05 -0.10 7/26/2004 12:00 0.35 0.55 1.05 1.3 -0.20 -0.25 7/26/2004 14:00 0.95 1.1 1.65 1.75 -0.15 -0.10 7/28/2004 9:00 1.6 1.9 1.95 2.2 -0.30 -0.25 7/28/2004 12:00 1.1 1.6 1.9 2.25 -0.50 -0.35 7/28/2004 14:00 0.85 1.1 1.95 2.15 -0.25 -0.20 8/2/2004 9:00 1.65 2.20 2.25 2.95 -0.55 -0.70 8/2/2004 12:00 0.56 0.71 1.1 1.26 -0.15 -0.16 8/2/2004 14:00 0.12 0.21 0.37 0.59 -0.09 -0.22 8/4/2004 9:00 4.1 2.95 3.75 3.45 1.15 0.30 8/4/2004 12:00 1.3 0.68 1.48 1.05 0.62 0.43 8/4/2004 14:00 0.1 0.29 0.37 0.64 -0.19 -0.27
8/11/2004 9:00 1.4 1.82 1.85 2.4 -0.42 -0.55 8/11/2004 12:00 0.59 1.44 0.97 1.91 -0.85 -0.94 8/11/2004 14:00 0.22 0.72 0.73 1.27 -0.50 -0.54 8/16/2004 9:00 9.90 10.00 11 11.67 -0.10 -0.67 8/16/2004 12:00 5.50 7.55 7.33 9.83 -2.05 -2.50 8/16/2004 14:00 4.70 7.10 6.75 8.17 -2.40 -1.42
129
Table D-3. Pilot-scale study compiled TTHM data and differences.
Time Time TTHM TRANS
TTHM OPAQ
TTHM TRANS
TTHM OPAQ
Difference in TTHM
(TRANS-OPAQ)
Difference in TTHM
(TRANS-OPAQ)
M/DD/Yr hr:min µmole/L µmole/L µg/L µg/L µmole/L µg/L 6/23/2004 9:00 1.077 0.999 139.6 131.4 0.08 8.2 6/23/2004 12:00 1.26 1.007 164.1 131.7 0.25 32.4 6/23/2004 14:00 1.033 1.008 134.3 132.1 0.02 2.2 6/30/2004 9:00 1.874 1.615 233.8 201.3 0.26 32.5 6/30/2004 12:00 2.068 2.295 258.4 286 -0.23 -27.6 6/30/2004 14:00 2.026 1.895 253.7 236.6 0.13 17.1 7/7/2004 9:00 0.865 0.742 113.3 96.9 0.12 16.4 7/7/2004 12:00 0.960 1.058 126.0 138.2 -0.10 -12.2 7/7/2004 14:00 0.946 0.877 124.6 114.9 0.07 9.7
7/14/2004 9:00 0.812 0.817 111.0 111.2 0.00 -0.2 7/14/2004 12:00 0.931 0.828 127.9 113.2 0.10 14.7 7/14/2004 14:00 0.819 0 112.8 0.0 0.82 112.8 7/26/2004 9:00 0.134 0.126 17.1 16.3 0.01 0.8 7/26/2004 12:00 0.207 0.145 26.6 19.3 0.06 7.3 7/26/2004 14:00 0.348 0.312 44.1 40.2 0.04 3.9 7/28/2004 9:00 0.740 0.945 93.7 119.4 -0.20 -25.7 7/28/2004 12:00 0.550 0.759 72.8 97.5 -0.21 -24.7 7/28/2004 14:00 0.740 0.845 95.4 108.0 -0.10 -12.6 8/2/2004 9:00 0.404 0.443 52.2 57.0 -0.04 -4.8 8/2/2004 12:00 0.006 0.453 0.9 57.8 -0.45 -56.9 8/2/2004 14:00 0.313 0.454 41.3 59.0 -0.14 -17.7 8/4/2004 9:00 0.438 0.389 55.6 49.5 0.05 6.1 8/4/2004 12:00 0.724 0.427 91.9 54.6 0.30 37.3 8/4/2004 14:00 0.267 0.416 34.1 53.3 -0.15 -19.2
8/11/2004 9:00 0.41 0.369 53.1 47.5 0.04 5.6 8/11/2004 12:00 0.476 0.321 61.7 41.6 0.16 20.1 8/11/2004 14:00 0.411 0.322 53.5 41.9 0.09 11.6 8/16/2004 9:00 0.519 0.396 65.1 49.8 0.12 15.3 8/16/2004 12:00 0.742 0.47 92.3 59.1 0.27 33.2 8/16/2004 14:00 0.587 0.409 73.4 52.0 0.18 21.4
130
Table D-4. Pilot-scale study compiled TTHM and normalization factors.
Time Time
pH Normalization
Factor
Temperature Normalization
Factor
Chlorine Residual
Normalization Factor
Multiplication of
Normalization Factors
M/DD/Yr hr:min 6/23/2004 9:00 1.00 1.01 0.89 0.89 6/23/2004 12:00 1.00 1.05 0.56 0.59 6/23/2004 14:00 1.02 1.04 0.46 0.48 6/30/2004 9:00 1.02 1.03 0.95 1.01 6/30/2004 12:00 0.99 1.03 0.78 0.79 6/30/2004 14:00 1.00 1.13 0.88 0.98 7/7/2004 9:00 1.01 1.01 0.90 0.92 7/7/2004 12:00 0.99 1.06 0.88 0.93 7/7/2004 14:00 1.00 1.11 0.79 0.88
7/14/2004 9:00 1.00 1.02 1.22 1.24 7/14/2004 12:00 0.99 1.10 0.91 0.99 7/14/2004 14:00 0.99 1.13 0.75 0.84 7/26/2004 9:00 1.00 1.01 0.90 0.91 7/26/2004 12:00 1.01 1.07 0.78 0.85 7/26/2004 14:00 0.92 1.12 0.92 0.96 7/28/2004 9:00 1.02 1.01 0.91 0.93 7/28/2004 12:00 1.05 1.03 0.81 0.88 7/28/2004 14:00 0.96 1.03 0.87 0.85 8/2/2004 9:00 1.00 1.00 0.85 0.85 8/2/2004 12:00 0.98 1.07 0.88 0.92 8/2/2004 14:00 1.00 1.11 0.73 0.81 8/4/2004 9:00 1.00 1.02 1.20 1.22 8/4/2004 12:00 1.00 1.06 1.44 1.52 8/4/2004 14:00 1.02 1.04 0.55 0.58
8/11/2004 9:00 1.00 1.00 0.86 0.86 8/11/2004 12:00 1.02 1.04 0.61 0.64 8/11/2004 14:00 1.06 1.06 0.51 0.58 8/16/2004 9:00 1.00 1.00 0.99 0.99 8/16/2004 12:00 0.97 1.08 0.84 0.87 8/16/2004 14:00 0.99 1.12 0.79 0.88
131
Table D-5. Pilot-scale study compiled normalized TTHM’ data and differences.
Time Time TTHM' TRANS
TTHM' OPAQ
Difference TTHM'
(TRANS-OPAQ)
TTHM' TRANS
TTHM' OPAQ
Difference TTHM'
(TRANS-OPAQ)
M/DD/Yr hr:min µmole/L µmole/L µmole/L µg/L µg/L µg/L 6/23/2004 9:00 1.077 0.891 0.186 139.6 117.2 22.4 6/23/2004 12:00 1.26 0.592 0.668 164.1 77.5 86.6 6/23/2004 14:00 1.033 0.488 0.545 134.3 64.0 70.3 6/30/2004 9:00 1.874 1.629 0.245 233.8 203.0 30.8 6/30/2004 12:00 2.068 1.824 0.244 258.4 227.3 31.1 6/30/2004 14:00 2.026 1.861 0.165 253.7 232.3 21.4 7/7/2004 9:00 0.865 0.683 0.182 113.3 89.2 24.1 7/7/2004 12:00 0.960 0.981 -0.021 126.0 128.2 -2.2 7/7/2004 14:00 0.946 0.770 0.176 124.6 100.9 23.7
7/14/2004 9:00 0.812 1.017 -0.205 111.0 138.4 -27.4 7/14/2004 12:00 0.931 0.819 0.112 127.9 112.0 15.9 7/14/2004 14:00 0.819 0.000 0.819 112.8 0.0 112.8 7/26/2004 9:00 0.134 0.114 0.019 17.1 14.8 2.3 7/26/2004 12:00 0.207 0.122 0.085 26.6 16.3 10.3 7/26/2004 14:00 0.348 0.298 0.050 44.1 38.4 5.7 7/28/2004 9:00 0.740 0.881 -0.141 93.7 111.4 -17.7 7/28/2004 12:00 0.550 0.667 -0.117 72.8 85.8 -13.0 7/28/2004 14:00 0.740 0.719 0.021 95.4 91.9 3.5 8/2/2004 9:00 0.404 0.378 0.026 52.2 48.7 3.5 8/2/2004 12:00 0.006 0.417 -0.411 0.9 53.3 -52.4 8/2/2004 14:00 0.313 0.368 -0.055 41.3 47.8 -6.5 8/4/2004 9:00 0.438 0.476 -0.038 55.6 60.5 -4.9 8/4/2004 12:00 0.724 0.650 0.074 91.9 83.2 8.7 8/4/2004 14:00 0.267 0.243 0.024 34.1 31.1 3.0
8/11/2004 9:00 0.41 0.319 0.091 53.1 41.1 12.0 8/11/2004 12:00 0.476 0.206 0.270 61.7 26.7 35.0 8/11/2004 14:00 0.411 0.185 0.226 53.5 24.1 29.4 8/16/2004 9:00 0.519 0.394 0.125 65.1 49.5 15.6 8/16/2004 12:00 0.742 0.409 0.333 92.3 51.4 40.9 8/16/2004 14:00 0.587 0.358 0.229 73.4 45.5 27.9
132
Table D-6. Pilot-scale study compiled HAA(5) data.
Time Time HAA(5) TRANS
HAA(5) OPAQ
HAA(5) TRANS
HAA(5) OPAQ
M/DD/Yr hr:min µg/L µg/L µmoles/L µmoles/L6/23/2004 9:00 36.19 NA 0.25 NA 6/23/2004 12:00 21.98 12.43 0.15 0.08 6/23/2004 14:00 23.46 6.78 0.17 0.04 6/30/2004 9:00 13.91 20.74 0.10 0.15 6/30/2004 12:00 24.55 8.64 0.17 0.06 6/30/2004 14:00 13.60 26.58 0.10 0.19 7/7/2004 9:00 64.88 51.71 0.46 0.36 7/7/2004 12:00 4.65 56.93 0.03 0.40 7/7/2004 14:00 60.58 33.08 0.43 1.06
7/14/2004 9:00 29.32 29.09 0.26 0.26 7/14/2004 12:00 29.53 24.79 0.26 0.22 7/14/2004 14:00 NA 95.29 NA 0.87 7/26/2004 9:00 NA 0.00 NA 0.00 7/26/2004 12:00 19.96 24.18 0.14 0.17 7/26/2004 14:00 27.69 14.55 0.20 0.10 7/28/2004 9:00 29.72 18.89 0.22 0.14 7/28/2004 12:00 38.91 31.36 0.29 0.23 7/28/2004 14:00 0.00 33.59 0.00 0.25 8/2/2004 9:00 41.11 12.13 0.29 0.07 8/2/2004 12:00 86.41 9.87 0.61 0.06 8/2/2004 14:00 40.07 15.02 0.29 0.11 8/4/2004 9:00 63.95 38.42 0.44 0.26 8/4/2004 12:00 45.64 24.29 0.31 0.16 8/4/2004 14:00 6.17 20.16 0.04 0.14
8/11/2004 9:00 61.32 7.76 0.44 0.05 8/11/2004 12:00 7.81 22.41 0.05 0.16 8/11/2004 14:00 5.78 6.12 0.04 0.04 8/16/2004 9:00 31.74 115.33 0.22 0.81 8/16/2004 12:00 94.59 33.81 0.66 0.23 8/16/2004 14:00 85.86 79.52 0.60 0.55
133
Table D-7. Pilot-scale study compiled normalized HAA(5) data.
Time Time
HAA Chlorine Residual
Normalization Factor
HAA Temp Normalization
Factor HAA'
TRANSHAA' OPAQ
HAA' TRANS
HAA' OPAQ
M/DD/Yr hr:min OPAQ OPAQ µg/L µg/L µmoles/L µmoles/L6/23/2004 9:00 0.90 1.005 36.19 NA 0.25 NA 6/23/2004 12:00 0.61 1.033 21.98 7.84 0.15 0.05 6/23/2004 14:00 0.51 1.025 23.46 3.57 0.17 0.02 6/30/2004 9:00 0.96 1.022 13.91 20.36 0.10 0.14 6/30/2004 12:00 0.81 1.018 24.55 7.13 0.17 0.05 6/30/2004 14:00 0.89 1.081 13.6 25.65 0.10 0.18 7/7/2004 9:00 0.92 1.005 64.88 47.69 0.46 0.33 7/7/2004 12:00 0.90 1.040 4.65 53.17 0.03 0.37 7/7/2004 14:00 0.82 1.070 60.58 29.06 0.43 0.93
7/14/2004 9:00 1.19 1.012 29.32 34.91 0.26 0.31 7/14/2004 12:00 0.92 1.062 29.53 24.28 0.26 0.21 7/14/2004 14:00 0.78 1.081 NA 80.30 NA 0.74 7/26/2004 9:00 0.92 1.005 NA 0.00 NA 0.00 7/26/2004 12:00 0.80 1.047 19.96 20.38 0.14 0.15 7/26/2004 14:00 0.93 1.079 27.689 14.63 0.20 0.10 7/28/2004 9:00 0.92 1.007 29.72 17.52 0.22 0.13 7/28/2004 12:00 0.84 1.022 38.91 26.78 0.29 0.20 7/28/2004 14:00 0.88 1.018 0 30.22 0.00 0.22 8/2/2004 9:00 0.87 1.002 41.114 10.59 0.29 0.06 8/2/2004 12:00 0.89 1.045 86.41 9.20 0.61 0.06 8/2/2004 14:00 0.76 1.070 40.07 12.29 0.29 0.09 8/4/2004 9:00 1.17 1.012 63.95 45.53 0.44 0.31 8/4/2004 12:00 1.36 1.040 45.64 34.49 0.31 0.23 8/4/2004 14:00 0.60 1.029 6.17 12.44 0.04 0.08
8/11/2004 9:00 0.88 1.000 61.32 6.84 0.44 0.04 8/11/2004 12:00 0.65 1.023 7.81 14.95 0.05 0.10 8/11/2004 14:00 0.57 1.039 5.78 3.60 0.04 0.02 8/16/2004 9:00 1.00 1.002 31.74 115.06 0.22 0.80 8/16/2004 12:00 0.86 1.049 94.59 30.46 0.66 0.21 8/16/2004 14:00 0.82 1.076 85.86 70.19 0.60 0.49
134
Table D-8. Pilot-scale study compiled differences in HAA(5) and HAA(5)’ data.
Time Time
Difference HAA'
TRANS-OPAQ
Difference in HAA
(TRANS-OPAQ)
Difference in HAA
(TRANS-OPAQ)
Difference in HAA'
(TRANS-OPAQ)
M/DD/Yr hr:min µg/L µg/L µmoles/L µmoles/L 6/23/2004 9:00 NA NA NA NA 6/23/2004 12:00 14.1 9.55 0.07 0.10 6/23/2004 14:00 19.9 16.68 0.13 0.14 6/30/2004 9:00 -6.4 -6.83 -0.05 -0.05 6/30/2004 12:00 17.4 15.91 0.12 0.13 6/30/2004 14:00 -12.0 -12.98 -0.09 -0.09 7/7/2004 9:00 17.2 13.17 0.10 0.13 7/7/2004 12:00 -48.5 -52.28 -0.37 -0.35 7/7/2004 14:00 31.5 27.5 -0.63 -0.50
7/14/2004 9:00 -5.6 0.23 0.00 -0.05 7/14/2004 12:00 5.3 4.74 0.04 0.05 7/14/2004 14:00 NA NA NA NA 7/26/2004 9:00 NA NA NA NA 7/26/2004 12:00 -0.4 -4.22 -0.03 0.00 7/26/2004 14:00 13.1 13.139 0.10 0.10 7/28/2004 9:00 12.2 10.83 0.08 0.09 7/28/2004 12:00 12.1 7.55 0.06 0.09 7/28/2004 14:00 -30.2 -33.59 -0.25 -0.22 8/2/2004 9:00 30.5 28.98 0.21 0.22 8/2/2004 12:00 77.2 76.54 0.55 0.55 8/2/2004 14:00 27.8 25.046 0.18 0.20 8/4/2004 9:00 18.4 25.53 0.18 0.13 8/4/2004 12:00 11.2 21.35 0.15 0.08 8/4/2004 14:00 -6.3 -13.99 -0.10 -0.05
8/11/2004 9:00 54.5 53.56 0.39 0.39 8/11/2004 12:00 -7.1 -14.6 -0.11 -0.06 8/11/2004 14:00 2.2 -0.34 0.00 0.01 8/16/2004 9:00 -83.3 -83.59 -0.59 -0.59 8/16/2004 12:00 64.1 60.78 0.43 0.45 8/16/2004 14:00 15.7 6.34 0.05 0.11
135
Table D-9. Full-scale study compiled and calculated parameter data.
Time Time pH
UNCOVpH
COV UNCOV
TemperatureCOV
Temperature
Difference in Temperature (UNCOV-
COV) M/DD/Yr hr:min (°C) (°C) (°C) 8/19/2004 9:00 6.8 6.7 28.2 28.3 -0.1 8/19/2004 12:00 6.6 6.6 29.3 29.6 -0.3 8/19/2004 14:00 6.6 6.6 30.1 29.6 0.5 8/24/2004 9:00 6.90 6.90 28.0 27.8 0.2 8/24/2004 12:00 6.92 6.87 28.9 29.0 -0.1 8/24/2004 14:00 6.87 6.87 29.7 29.6 0.1 8/25/2004 9:00 6.72 6.51 28.5 28.1 0.4 8/25/2004 12:00 6.80 6.85 29.9 29.2 0.7 8/25/2004 14:00 6.89 6.95 29.7 28.8 0.9 Table D-10. Full-scale study compiled chlorine data and differences.
Time Time
Free Cl2 Residual UNCOV
Free Cl2Residual
COV
Free Cl2 Residual
(UNCOV-COV)
Total Cl2 Residual UNCOV
Total Cl2 Residual
COV
Total Cl2 Residual
(UNCOV-COV)
M/DD/Yr hr:min mg/L mg/L mg/L mg/L mg/L mg/L 8/19/2004 9:00 2.45 2.75 -0.30 3.3 3.8 -0.50 8/19/2004 12:00 1.90 2.75 -0.85 3.15 3.8 -0.65 8/19/2004 14:00 2.90 3.55 -0.65 3.9 4.5 -0.60 8/24/2004 9:00 1.5 2.55 -1.05 3.35 3.45 -0.10 8/24/2004 12:00 2.4 2.85 -0.45 3.35 3.85 -0.50 8/24/2004 14:00 2.75 3.55 -0.80 3.4 4.25 -0.85 8/25/2004 9:00 1.50 2.55 -1.05 3.35 3.45 -0.10 8/25/2004 12:00 2.40 2.85 -0.45 3.35 3.85 -0.50 8/25/2004 14:00 2.75 3.55 -0.80 3.4 4.25 -0.85
136
Table D-11. Full-scale study compiled TTHM data and differences.
Time Time TTHM
UNCOVTTHM COV
TTHM UNCOV
TTHM COV
Difference in TTHM (TRANS-OPAQ)
Difference TTHM
(UNCOV-COV)
M/DD/Yr hr:min µmole/L µmole/L µg/L µg/L µmole/L µg/L 8/19/2004 9:00 0.291 0.370 37 47 -0.08 -10 8/19/2004 12:00 0.542 0.597 68.6 75.4 -0.06 -6.8 8/19/2004 14:00 0.485 0.465 60.8 58.8 0.02 2 8/24/2004 9:00 0.655 0.768 80.5 94.2 -0.11 -13.7 8/24/2004 12:00 0.910 0.779 111.7 95.3 0.13 16.4 8/24/2004 14:00 0.867 0.916 106.1 112 -0.05 -5.9 8/25/2004 9:00 0.350 0.345 43.8 43.1 0.01 0.7 8/25/2004 12:00 0.410 0.361 51.3 45.1 0.05 6.2 8/25/2004 14:00 0.297 0.374 37.6 46.7 -0.08 -9.1 Table D-12. Full-scale study compiled TTHM and normalization factors.
Time Time
pH Normalization
Factor
Temperature Normalization
Factor
Chlorine Residual
Normalization Factor
Multiplication of
Normalization Factors
M/DD/Yr hr:min COV COV COV COV 8/19/2004 9:00 1.02 1.00 0.94 0.95 8/19/2004 12:00 1.00 0.99 0.81 0.80 8/19/2004 14:00 1.00 1.02 0.89 0.91 8/24/2004 9:00 1.00 1.01 0.74 0.75 8/24/2004 12:00 1.01 1.00 0.91 0.91 8/24/2004 14:00 1.00 1.00 0.87 0.87 8/25/2004 9:00 1.04 1.01 0.74 0.78 8/25/2004 12:00 0.99 1.02 0.91 0.92 8/25/2004 14:00 0.99 1.03 0.87 0.89
137
Table D-13. Full-scale study compiled normalized TTHM’ data and differences.
Time Time TTHM'
UNCOVTTHM' COV
TTHM' UNCOV
TTHM' COV
Difference TTHM'
(UNCOV-COV)
Difference TTHM'
(UNCOV-COV)
M/DD/Yr hr:min µmole/L µmole/L µg/L µg/L µmole/L µg/L 8/19/2004 9:00 0.291 0.352 37 44.65 -0.061 -7.65 8/19/2004 12:00 0.542 0.480 68.6 60.64 0.062 7.96 8/19/2004 14:00 0.485 0.422 60.8 53.40 0.063 7.40 8/24/2004 9:00 0.655 0.575 80.5 70.46 0.081 10.04 8/24/2004 12:00 0.910 0.711 111.7 86.97 0.200 24.73 8/24/2004 14:00 0.867 0.796 106.1 97.39 0.071 8.71 8/25/2004 9:00 0.350 0.269 43.8 33.69 0.081 10.11 8/25/2004 12:00 0.410 0.333 51.3 41.60 0.077 9.70 8/25/2004 14:00 0.297 0.331 37.6 41.34 -0.034 -3.74
Table D-14. Full-scale study compiled HAA(5) data.
Time Time HAA(5) UNCOV
HAA(5) COV
HAA(5) UNCOV
HAA(5) COV
HAA Temp Normalization
Factor
HAA Chlorine Residual
Normalization Factor
M/DD/Yr hr:min µg/L µg/L µmoles/L µmoles/L COV COV 8/19/2004 9:00 96.00 98.67 0.61 0.64 0.998 0.946 8/19/2004 12:00 118.67 105.33 0.77 0.68 0.993 0.837 8/19/2004 14:00 122.67 18.67 0.81 0.11 1.011 0.907 8/24/2004 9:00 109.33 89.33 0.71 0.64 1.005 0.775 8/24/2004 12:00 122.67 122.67 0.81 0.81 0.998 0.921 8/24/2004 14:00 136.00 125.33 0.90 0.83 1.002 0.885 8/25/2004 9:00 NA 101.33 NA 0.73 1.009 0.775 8/25/2004 12:00 142.67 130.67 0.94 0.94 1.016 0.921 8/25/2004 14:00 176.00 109.33 1.16 0.79 1.021 0.885
138
Table D-15. Pilot-scale study compiled normalized HAA(5) data.
Time Time HAA'
UNCOV HAA' COV
HAA' UNCOV
HAA' COV
M/DD/Yr Hr:min µg/L µg/L µmoles/L µmoles/L 8/19/2004 9:00 96.00 93.13 0.61 0.60 8/19/2004 12:00 118.67 87.61 0.77 0.57 8/19/2004 14:00 122.67 17.13 0.81 0.10 8/24/2004 9:00 109.33 69.58 0.71 0.50 8/24/2004 12:00 122.67 112.70 0.81 0.74 8/24/2004 14:00 136.00 111.12 0.90 0.73 8/25/2004 9:00 NA 79.29 NA 0.57 8/25/2004 12:00 142.67 122.23 0.94 0.88 8/25/2004 14:00 176.00 98.72 1.16 0.71
Table D-16. Full-scale study compiled differences in HAA(5) and HAA(5)’ data.
Time Time
Difference HAA'
UNCOV-COV
Difference HAA
UNCOV-COV
Difference HAA
UNCOV-COV
Difference HAA'
UNCOV-COV
M/DD/Yr hr:min µg/L µg/L µmole/L µmole/L 8/19/2004 9:00 3 3 -0.03 0.01 8/19/2004 12:00 31 32 0.09 0.21 8/19/2004 14:00 106 106 0.70 0.71 8/24/2004 9:00 40 40 0.07 0.21 8/24/2004 12:00 10 10 0.00 0.07 8/24/2004 14:00 25 26 0.08 0.17 8/25/2004 9:00 na na NA NA 8/25/2004 12:00 20 21 0.00 0.06 8/25/2004 14:00 77 78 0.38 0.45
139
APPENDIX E PILOT-SCALE DATA
5INT: Pilot Basin Feed Water, prior to chlorination
5TRU: TRANS Basin Effluent, exposed to UV radiation
5TRC: OPAQ Basin Effluent, not exposed to UV radiation
Table E-1. Trihalomethane mass concentrations in the pilot-scale study. Trihalomethane (µg/L)
Date Time Location Chloroform
Bromodi-chloro-
Methane
Dibromo- chloro- methane Bromoform
Total THM
6/23/2004 9:00 5TRU 102.9 31.2 5 0.5 139.606/23/2004 9:00 5TRC 91.1 33.4 6.3 0.6 131.406/23/2004 12:00 5TRU 118.2 39.1 6.3 0.5 164.106/23/2004 12:00 5TRC 93.4 32 5.8 0.5 131.706/23/2004 14:00 5TRU 97.7 31 5.1 0.5 134.306/23/2004 14:00 5TRC 92.9 32.7 6 0.5 132.106/23/2004Blank1 Blank 1 1.3 1.3 1.4 2.5 6.506/30/2004 9:00 5TRU 201.2 26 6.2 0.4 233.806/30/2004 9:00 5TRC 174.3 21.3 5.3 0.4 201.306/30/2004 12:00 5TRU 221.1 30.1 6.8 0.4 258.406/30/2004 12:00 5TRC 246.8 32.2 6.6 0.4 286.006/30/2004 14:00 5TRU 215.5 30.9 6.9 0.4 253.706/30/2004 14:00 5TRC 203.2 26.9 6.1 0.4 236.606/30/2004Blank1 Blank 1 1.3 0.5 0.6 0.4 2.80
7/7/2004 9:00 5TRU 80.7 26 6.2 0.4 113.307/7/2004 9:00 5TRC 69.9 21.3 5.3 0.4 96.907/7/2004 12:00 5TRU 88.7 30.1 6.8 0.4 126.007/7/2004 12:00 5TRC 99 32.2 6.6 0.4 138.207/7/2004 14:00 5TRU 86.4 30.9 6.9 0.4 124.607/7/2004 14:00 5TRC 81.5 26.9 6.1 0.4 114.907/7/2004Blank1 Blank 1 0.5 0.5 0.6 0.9 2.50
7/14/2004 9:00 5TRU 64.4 38.1 8.5ND (5.0) 111.007/14/2004 9:00 5TRC 65.8 37.2 8.2ND (5.0) 111.207/14/2004 12:00 5TRU 72.8 44.3 10.8ND (5.0) 127.907/14/2004 12:00 5TRC 65.7 38.5 9ND (5.0) 113.20
140
Table E-1. Continued. Trihalomethane (µg/L)
Date Time Location Chloroform
Bromodi-chloro-
Methane
Dibromo- chloro- methane Bromoform
Total THM
7/14/2004 14:00 5TRU 63.3 39.5 10 ND (5.0) 112.807/14/2004 14:00 5TRC ND (5.0) ND (5.0) ND (5.0) ND (5.0) 0.007/14/2004Blank1 Blank 1 ND (5.0) ND (5.0) ND (5.0) ND (5.0) 0.007/26/2004 9:00 5TRU 13.3 3.2 0.5 0.1 17.107/26/2004 9:00 5TRC 12 3.7 0.5 0.1 16.307/26/2004 12:00 5TRU 20.4 5.2 0.9 0.1 26.607/26/2004 12:00 5TRC 12.5 5.7 1 0.1 19.307/26/2004 14:00 5TRU 35.7 7.1 1.2 0.1 44.107/26/2004 14:00 5TRC 30.4 8.2 1.5 0.1 40.207/26/2004Blank1 Blank 1 0.4 0.2 0.2 0.1 0.907/28/2004 9:00 5TRU 76 15 2.6 0.1 93.707/28/2004 9:00 5TRC 97.6 18.2 3.4 0.2 119.407/28/2004 12:00 5TRU 49.5 18.8 4.3 0.2 72.807/28/2004 12:00 5TRC 74.9 18.3 4.1 0.2 97.507/28/2004 14:00 5TRU 72.3 18.9 4 0.2 95.407/28/2004 14:00 5TRC 85 18.2 4.5 0.3 108.007/28/2004Blank1 Blank 1 ND (5.0) ND (5.0) ND (5.0) ND (5.0) 0.00
8/2/2004 9:00 5TRU 39.1 11 1.9 0.2 52.28/2/2004 9:00 5TRC 43.3 11.4 2.1 0.2 57.08/2/2004 12:00 5TRU 0.4 0.2 0.2 0.1 0.908/2/2004 12:00 5TRC 44 11.3 2.3 0.2 57.808/2/2004 14:00 5TRU 28.2 11.1 1.8 0.2 41.308/2/2004 14:00 5TRC 43.3 12.9 2.6 0.2 59.008/2/2004Blank1 Blank 1 ND (5.0) ND (5.0) ND (5.0) ND (5.0) 0.008/4/2004 9:00 5TRU 44.4 9.7 1.4 0.1 55.608/4/2004 9:00 5TRC 39.1 9 1.3 0.1 49.508/4/2004 12:00 5TRU 73.4 16.2 2.2 0.1 91.908/4/2004 12:00 5TRC 42.4 10.5 1.6 0.1 54.608/4/2004 14:00 5TRU 26.8 6.3 0.9 0.1 34.108/4/2004 14:00 5TRC 41.2 10.4 1.6 0.1 53.308/4/2004Blank1 Blank 1 ND (5.0) ND (5.0) ND (5.0) ND (5.0) 0.00
8/11/2004 9:00 5TRU 39.3 11.7 2 0.1 53.108/11/2004 9:00 5TRC 35.9 9.8 1.7 0.1 47.508/11/2004 12:00 5TRU 45.4 13.9 2.3 0.1 61.708/11/2004 12:00 5TRC 30.8 9.1 1.6 0.1 41.608/11/2004 14:00 5TRU 38.6 12.6 2.2 0.1 53.508/11/2004 14:00 5TRC 30.4 9.7 1.7 0.1 41.908/11/2004Blank1 Blank 1 0.2ND (5.0) ND (5.0) ND (5.0) 0.208/16/2004 9:00 5TRU 54.5 9.4 1.1 0.1 65.10
141
Table E-1. Continued. Trihalomethane (µg/L)
Date Time Location Chloroform
Bromodi-chloro-
Methane
Dibromo- chloro- methane Bromoform
Total THM
8/16/2004 9:00 5TRC 41.2 7.7 0.9 0 49.808/16/2004 12:00 5TRU 79.5 11.6 1.2 0 92.308/16/2004 12:00 5TRC 48.7 9.4 1.0 0 59.108/16/2004 14:00 5TRU 61.9 10.3 1.2 0 73.408/16/2004 14:00 5TRC 41.3 9.5 1.1 0.1 52.008/16/2004Blank1 Blank 1 0.2ND (5.0) ND (5.0) ND (5.0) 0.2
142
Table E-2. Trihalomethane molar concentrations in the pilot-scale study. Trihalomethane (µmoles/L)
Date
Time Location Chloroform
Bromodi-chloro-
Methane
Dibromo- chloro- methane Bromoform
Total THM
6/23/2004 9:00 5TRU 0.861 0.190 0.024 0.002 1.0776/23/2004 9:00 5TRC 0.762 0.204 0.030 0.002 0.9996/23/2004 12:00 5TRU 0.989 0.238 0.030 0.002 1.2606/23/2004 12:00 5TRC 0.782 0.195 0.028 0.002 1.0076/23/2004 14:00 5TRU 0.818 0.189 0.024 0.002 1.0336/23/2004 14:00 5TRC 0.777 0.199 0.029 0.002 1.0086/23/2004Blank1 Blank 1 0.011 0.008 0.007 0.010 0.0356/30/2004 9:00 5TRU 1.684 0.159 0.030 0.002 1.8746/30/2004 9:00 5TRC 1.459 0.130 0.025 0.002 1.6156/30/2004 12:00 5TRU 1.850 0.184 0.033 0.002 2.0686/30/2004 12:00 5TRC 2.065 0.196 0.032 0.002 2.2956/30/2004 14:00 5TRU 1.803 0.188 0.033 0.002 2.0266/30/2004 14:00 5TRC 1.700 0.164 0.029 0.002 1.8956/30/2004Blank1 Blank 1 0.011 0.003 0.003 0.002 0.018
7/7/2004 9:00 5TRU 0.675 0.159 0.030 0.002 0.8657/7/2004 9:00 5TRC 0.585 0.130 0.025 0.002 0.7427/7/2004 12:00 5TRU 0.742 0.184 0.033 0.002 0.9607/7/2004 12:00 5TRC 0.828 0.196 0.032 0.002 1.0587/7/2004 14:00 5TRU 0.723 0.188 0.033 0.002 0.9467/7/2004 14:00 5TRC 0.682 0.164 0.029 0.002 0.8777/7/2004Blank1 Blank 1 0.004 0.003 0.003 0.004 0.014
7/14/2004 9:00 5TRU 0.539 0.232 0.041ND (5.0) 0.8127/14/2004 9:00 5TRC 0.551 0.227 0.039ND (5.0) 0.8177/14/2004 12:00 5TRU 0.609 0.270 0.052ND (5.0) 0.9317/14/2004 12:00 5TRC 0.550 0.235 0.043ND (5.0) 0.8287/14/2004 14:00 5TRU 0.530 0.241 0.048ND (5.0) 0.8197/14/2004 14:00 5TRC ND (5.0) ND (5.0) ND (5.0) ND (5.0) 0.0007/14/2004Blank1 Blank 1 ND (5.0) ND (5.0) ND (5.0) ND (5.0) 0.0007/26/2004 9:00 5TRU 0.111 0.020 0.002 0.0004 0.1347/26/2004 9:00 5TRC 0.100 0.023 0.002 0.0004 0.1267/26/2004 12:00 5TRU 0.171 0.032 0.004 0.0004 0.2077/26/2004 12:00 5TRC 0.105 0.035 0.005 0.0004 0.1457/26/2004 14:00 5TRU 0.299 0.043 0.006 0.0004 0.3487/26/2004 14:00 5TRC 0.254 0.050 0.007 0.0004 0.3127/26/2004Blank1 Blank 1 ND (5.0) ND (5.0) ND (5.0) ND (5.0) 0.0007/28/2004 9:00 5TRU 0.636 0.091 0.012 0.000 0.7407/28/2004 9:00 5TRC 0.817 0.111 0.016 0.001 0.9457/28/2004 12:00 5TRU 0.414 0.115 0.021 0.001 0.5507/28/2004 12:00 5TRC 0.627 0.112 0.020 0.001 0.759
143
Table E-2. Continued. Trihalomethane (µmoles/L)
Date
Time Location Chloroform
Bromodi-chloro-
Methane
Dibromo- chloro- methane Bromoform
Total THM
7/28/2004 14:00 5TRU 0.605 0.115 0.019 0.001 0.7407/28/2004 14:00 5TRC 0.711 0.111 0.022 0.001 0.8457/28/2004Blank1 Blank 1 ND (5.0) ND (5.0) ND (5.0) ND (5.0) 0.000
8/2/2004 9:00 5TRU 0.327 0.067 0.009 0.001 0.4048/2/2004 9:00 5TRC 0.362 0.070 0.010 0.001 0.4438/2/2004 12:00 5TRU 0.003 0.001 0.001 0.000 0.0068/2/2004 12:00 5TRC 0.362 0.079 0.011 0.001 0.4538/2/2004 14:00 5TRU 0.236 0.068 0.009 0.001 0.3138/2/2004 14:00 5TRC 0.362 0.079 0.012 0.001 0.4548/2/2004Blank1 Blank 1 ND (5.0) ND (5.0) ND (5.0) ND (5.0) 0.0008/4/2004 9:00 5TRU 0.372 0.059 0.007 0.0004 0.4388/4/2004 9:00 5TRC 0.327 0.055 0.006 0.0004 0.3898/4/2004 12:00 5TRU 0.614 0.099 0.011 0.0004 0.7248/4/2004 12:00 5TRC 0.355 0.064 0.008 0.0004 0.4278/4/2004 14:00 5TRU 0.224 0.038 0.004 0.0004 0.2678/4/2004 14:00 5TRC 0.345 0.063 0.008 0.0004 0.4168/4/2004Blank1 Blank 1 ND (5.0) ND (5.0) ND (5.0) ND (5.0) 0.000
8/11/2004 9:00 5TRU 0.329 0.071 0.010 0.0004 0.4108/11/2004 9:00 5TRC 0.300 0.060 0.008 0.0004 0.3698/11/2004 12:00 5TRU 0.380 0.085 0.011 0.0004 0.4768/11/2004 12:00 5TRC 0.258 0.055 0.008 0.0004 0.3218/11/2004 14:00 5TRU 0.323 0.077 0.011 0.0004 0.4118/11/2004 14:00 5TRC 0.254 0.059 0.008 0.0004 0.3228/11/2004Blank1 Blank 1 0.002ND (5.0) ND (5.0) ND (5.0) 0.0028/16/2004 9:00 5TRU 0.456 0.057 0.005 0.0004 0.5198/16/2004 9:00 5TRC 0.345 0.047 0.004 0 0.3968/16/2004 12:00 5TRU 0.665 0.071 0.006 0 0.7428/16/2004 12:00 5TRC 0.408 0.057 0.005 0 0.4708/16/2004 14:00 5TRU 0.518 0.063 0.006 0 0.5878/16/2004 14:00 5TRC 0.346 0.058 0.005 0.0004 0.4098/16/2004Blank1 Blank 1 0.002ND (5.0) ND (5.0) ND (5.0) 0.002
144
Table E-3. Haloacetic acid mass concentrations in the pilot-scale study. Haloacetic Acid (µg/L) Date Time Location MCAA MBAA DCAA DBAA TCAA
Total HAA
6/23/2004 9:00 5TRU ND(13.30) ND(4.0) 18.86ND(2.7) 17.33 36.196/23/2004 9:00 5TRC NA NA NA NA NA 06/23/2004 12:00 5TRU ND(13.30) ND(4.0) 11.14ND(2.7) 10.84 21.986/23/2004 12:00 5TRC ND(13.30) ND(4.0) 4ND(2.7) 8.43 12.436/23/2004 14:00 5TRU ND(13.30) ND(4.0) 13.91ND(2.7) 9.55 23.466/23/2004 14:00 5TRC ND(13.30) ND(4.0) ND(6.7) ND(2.7) 6.78 6.786/23/2004Blank Blank ND(13.30) ND(4.0) ND(6.7) ND(2.7) ND(2.7) 06/30/2004 9:00 5TRU ND(13.30) ND(4.0) 6.77ND(2.7) 7.14 13.916/30/2004 9:00 5TRC ND(13.30) ND(4.0) 11.24ND(2.7) 9.5 20.746/30/2004 12:00 5TRU ND(13.30) ND(4.0) 14.22ND(2.7) 10.33 24.556/30/2004 12:00 5TRC ND(13.30) ND(4.0) 2.61ND(2.7) 6.03 8.646/30/2004 14:00 5TRU ND(13.30) ND(4.0) 7.09ND(2.7) 6.51 13.66/30/2004 14:00 5TRC ND(13.30) ND(4.0) 14.9ND(2.7) 11.68 26.586/30/2004Blank Blank ND(13.30) ND(4.0) ND(6.7) ND(2.7) ND(2.7) 0
7/7/2004 9:00 5TRU ND(13.30) ND(4.0) 37.76ND(2.7) 27.12 64.887/7/2004 9:00 5TRC ND(13.30) ND(4.0) 27.21ND(2.7) 24.5 51.717/7/2004 12:00 5TRU ND(13.30) ND(4.0) ND(6.7) ND(2.7) 4.65 4.657/7/2004 12:00 5TRC ND(13.30) ND(4.0) 32.37ND(2.7) 24.56 56.937/7/2004 14:00 5TRU ND(13.30) ND(4.0) 35.24ND(2.7) 25.34 60.587/7/2004 14:00 5TRC ND(13.30) ND(4.0) 21.96ND(2.7) 11.12 33.087/7/2004Blank Blank ND(13.30) ND(4.0) ND(6.7) ND(2.7) ND(2.7) 0
7/14/2004 9:00 5TRU ND(13.30) ND(4.0) 17.42ND(2.7) 11.9 29.327/14/2004 9:00 5TRC ND(13.30) ND(4.0) 17.92ND(2.7) 11.17 29.097/14/2004 12:00 5TRU ND(13.30) ND(4.0) 17.87ND(2.7) 11.66 29.537/14/2004 12:00 5TRC ND(13.30) ND(4.0) 14.76ND(2.7) 10.03 24.797/14/2004 14:00 5TRU NA NA NA NA NA NA 7/14/2004 14:00 5TRC ND(13.30) ND(4.0) 65.19ND(2.7) 30.1 95.297/14/2004Blank Blank ND(13.30) ND(4.0) ND(6.7) ND(2.7) ND(2.7) 07/26/2004 9:00 5TRU NA NA NA NA NA NA 7/26/2004 9:00 5TRC ND(13.30) ND(4.0) ND(6.7) ND(2.7) ND(2.7) 07/26/2004 12:00 5TRU ND(13.30) ND(4.0) 13.76ND(2.7) 6.2 19.967/26/2004 12:00 5TRC ND(13.30) ND(4.0) 15.88ND(2.7) 8.3 24.187/26/2004 14:00 5TRU ND(13.30) ND(4.0) 18.62ND(2.7) 9.069 27.6897/26/2004 14:00 5TRC ND(13.30) ND(4.0) 8.12ND(2.7) 6.43 14.557/26/2004Blank Blank ND(13.30) ND(4.0) ND(6.7) ND(2.7) ND(2.7) 07/28/2004 9:00 5TRU ND(13.30) ND(4.0) 23.7ND(2.7) 6.02 29.727/28/2004 9:00 5TRC ND(13.30) ND(4.0) 13.49ND(2.7) 5.4 18.897/28/2004 12:00 5TRU ND(13.30) ND(4.0) 29.44ND(2.7) 9.47 38.917/28/2004 12:00 5TRC ND(13.30) ND(4.0) 23.13ND(2.7) 8.23 31.36
145
Table E-3. Continued.
7/28/2004 14:005TRU ND(13.30) ND(4.0) ND(6.7) ND(2.7) ND(2.7) 0.007/28/2004 14:005TRC ND(13.30) ND(4.0) 25.14ND(2.7) 8.45 33.597/28/2004Blank Blank ND(13.30) ND(4.0) ND(6.7) ND(2.7) ND(2.7) 0.00
8/2/2004 9:005TRU ND(13.30) ND(4.0) 21.17ND(2.7) 19.94 41.118/2/2004 9:005TRC ND(13.30) ND(4.0) ND(6.7) ND(2.7) 12.13 12.138/2/2004 12:005TRU ND(13.30) ND(4.0) 47.99ND(2.7) 38.42 86.418/2/2004 12:005TRC ND(13.30) ND(4.0) ND(6.7) ND(2.7) 9.87 9.878/2/2004 14:005TRU ND(13.30) ND(4.0) 26.13ND(2.7) 13.94 40.078/2/2004 14:005TRC ND(13.30) ND(4.0) 10.59ND(2.7) 4.43 15.028/2/2004Blank Blank ND(13.30) ND(4.0) ND(6.7) ND(2.7) ND(2.7) 0.008/4/2004 9:005TRU ND(13.30) ND(4.0) 30.58ND(2.7) 33.37 63.958/4/2004 9:005TRC ND(13.30) ND(4.0) 17.52ND(2.7) 20.9 38.428/4/2004 12:005TRU ND(13.30) ND(4.0) 21.56ND(2.7) 24.08 45.648/4/2004 12:005TRC ND(13.30) ND(4.0) 9.97ND(2.7) 14.32 24.298/4/2004 14:005TRU ND(13.30) ND(4.0) ND(6.7) ND(2.7) 6.17 6.178/4/2004 14:005TRC ND(13.30) ND(4.0) 7.95ND(2.7) 12.21 20.168/4/2004Blank Blank ND(13.30) ND(4.0) ND(6.7) ND(2.7) ND(2.7) 0.00
8/11/2004 9:005TRU ND(13.30) ND(4.0) 37ND(2.7) 24.32 61.328/11/2004 9:005TRC ND(13.30) ND(4.0) ND(6.7) ND(2.7) 7.76 7.768/11/2004 12:005TRU ND(13.30) ND(4.0) ND(6.7) ND(2.7) 7.81 7.818/11/2004 12:005TRC ND(13.30) ND(4.0) 11.35ND(2.7) 11.06 22.418/11/2004 14:005TRU ND(13.30) ND(4.0) ND(6.7) ND(2.7) 5.78 5.788/11/2004 14:005TRC ND(13.30) ND(4.0) ND(6.7) ND(2.7) 6.12 6.128/11/2004Blank Blank ND(13.30) ND(4.0) ND(6.7) ND(2.7) ND(2.7) 0.008/16/2004 9:005TRU ND(13.30) ND(4.0) 12.99ND(2.7) 18.75 31.748/16/2004 9:005TRC ND(13.30) ND(4.0) 60.95ND(2.7) 54.38 115.338/16/2004 12:005TRU ND(13.30) ND(4.0) 49.58ND(2.7) 45.01 94.598/16/2004 12:005TRC ND(13.30) ND(4.0) 14.22ND(2.7) 19.59 33.818/16/2004 14:005TRU ND(13.30) ND(4.0) 44.55ND(2.7) 41.31 85.868/16/2004 14:005TRC ND(13.30) ND(4.0) 39.18ND(2.7) 40.34 79.528/16/2004Blank Blank ND(13.30) ND(4.0) ND(6.7) ND(2.7) ND(2.7) 0.00
Haloacetic Acid (µg/L) Date Time Location MCAA MBAA DCAA DBAA TCAA
Total HAA
146
Table E-4. Haloacetic acid molar concentrations in the pilot-scale study. Haloacetic Acid (µmole/L) Date Time Location MCAA MBAA DCAA DBAA TCAA
Total HAA
6/23/2004 9:005TRU ND(5.0) ND(0.33) 0.146202ND(0.08) 0.106 0.2526/23/2004 9:005TRC NA NA NA NA NA 0.0006/23/2004 12:005TRU ND(5.0) ND(0.33) 0.086357ND(0.08) 0.0663 0.1536/23/2004 12:005TRC ND(5.0) ND(0.33) 0.031008ND(0.08) 0.0516 0.0836/23/2004 14:005TRU ND(5.0) ND(0.33) 0.107829ND(0.08) 0.0584 0.1666/23/2004 14:005TRC ND(5.0) ND(0.33) ND(0.25) ND(0.08) 0.0415 0.0416/23/2004 Blank Blank ND(5.0) ND(0.33) ND(0.25) ND(0.08) ND(0.83) 0.0006/30/2004 9:005TRU ND(5.0) ND(0.33) 0.052ND(0.08) 0.044 0.0966/30/2004 9:005TRC ND(5.0) ND(0.33) 0.087ND(0.08) 0.058 0.1456/30/2004 12:005TRU ND(5.0) ND(0.33) 0.110ND(0.08) 0.063 0.1736/30/2004 12:005TRC ND(5.0) ND(0.33) 0.020ND(0.08) 0.037 0.0576/30/2004 14:005TRU ND(5.0) ND(0.33) 0.055ND(0.08) 0.040 0.0956/30/2004 14:005TRC ND(5.0) ND(0.33) 0.116ND(0.08) 0.071 0.1876/30/2004 Blank Blank ND(5.0) ND(0.33) ND(0.25) ND(0.08) ND(0.83) 0.000
7/7/2004 9:005TRU ND(5.0) ND(0.33) 0.052ND(0.08) 0.044 0.0967/7/2004 9:005TRC ND(5.0) ND(0.33) 0.087ND(0.08) 0.058 0.1457/7/2004 12:005TRU ND(5.0) ND(0.33) 0.110ND(0.08) 0.063 0.1737/7/2004 12:005TRC ND(5.0) ND(0.33) 0.020ND(0.08) 0.037 0.0577/7/2004 14:005TRU ND(5.0) ND(0.33) 0.055ND(0.08) 0.040 0.0957/7/2004 14:005TRC ND(5.0) ND(0.33) 0.116ND(0.08) 0.071 0.1877/7/2004 Blank Blank ND(5.0) ND(0.33) ND(0.25) ND(0.08) ND(0.83) 0.000
7/14/2004 9:005TRU ND(5.0) ND(0.33) 0.135ND(0.08) 0.0728 0.2087/14/2004 9:005TRC ND(5.0) ND(0.33) 0.139ND(0.08) 0.0683 0.2077/14/2004 12:005TRU ND(5.0) ND(0.33) 0.139ND(0.08) 0.0713 0.2107/14/2004 12:005TRC ND(5.0) ND(0.33) 0.114ND(0.08) 0.0613 0.1767/14/2004 14:005TRU ND(5.0) NA NA NA NA NA 7/14/2004 14:005TRC ND(5.0) ND(0.33) 0.505ND(0.08) 0.1841 0.6897/14/2004 Blank Blank ND(5.0) ND(0.33) ND(0.25) ND(0.08) ND(0.83) 0.0007/26/2004 9:005TRU NA NA NA NA NA NA 7/26/2004 9:005TRC ND(5.0) ND(0.33) ND(0.25) ND(0.08) ND(0.83) 0.0007/26/2004 12:005TRU ND(5.0) ND(0.33) 0.107ND(0.08) 0.0379 0.1457/26/2004 12:005TRC ND(5.0) ND(0.33) 0.123ND(0.08) 0.0508 0.1747/26/2004 14:005TRU ND(5.0) ND(0.33) 0.144ND(0.08) 0.0555 0.2007/26/2004 14:005TRC ND(5.0) ND(0.33) 0.063ND(0.08) 0.0393 0.1027/26/2004 Blank Blank ND(5.0) ND(0.33) ND(0.25) ND(0.08) ND(0.83) 0.0007/28/2004 9:005TRU ND(5.0) ND(0.33) 0.184ND(0.08) 0.0368 0.2217/28/2004 9:005TRC ND(5.0) ND(0.33) 0.105ND(0.08) 0.033 0.1387/28/2004 12:005TRU ND(5.0) ND(0.33) 0.228ND(0.08) 0.0579 0.2867/28/2004 12:005TRC ND(5.0) ND(0.33) 0.179ND(0.08) 0.0503 0.2307/28/2004 14:005TRU ND(5.0) ND(0.33) ND(0.25) ND(0.08) ND(0.83) 0.000
147
Table E-4. Continued. Haloacetic Acid (µmole/L) Date Time Location MCAA MBAA DCAA DBAA TCAA
Total HAA
7/28/2004 14:005TRC ND(5.0) ND(0.33) 0.195ND(0.08) 0.0517 0.2477/28/2004 Blank Blank ND(5.0) ND(0.33)ND(0.25) ND(0.08) ND(0.83) 0.000
8/2/2004 9:005TRU ND(5.0) ND(0.33) 0.164ND(0.08) 0.122 0.2868/2/2004 9:005TRC ND(5.0) ND(0.33)ND(0.25) ND(0.08) 0.0742 0.0748/2/2004 12:005TRU ND(5.0) ND(0.33) 0.372ND(0.08) 0.235 0.6078/2/2004 12:005TRC ND(5.0) ND(0.33)ND(0.25) ND(0.08) 0.0604 0.0608/2/2004 14:005TRU ND(5.0) ND(0.33) 0.203ND(0.08) 0.0853 0.2888/2/2004 14:005TRC ND(5.0) ND(0.33) 0.082093ND(0.08) 0.0271 0.1098/2/2004 Blank Blank ND(5.0) ND(0.33)ND(0.25) ND(0.08) ND(0.83) 0.0008/4/2004 9:005TRU ND(5.0) ND(0.33) 0.237ND(0.08) 0.2041 0.4418/4/2004 9:005TRC ND(5.0) ND(0.33) 0.136ND(0.08) 0.1278 0.2648/4/2004 12:005TRU ND(5.0) ND(0.33) 0.167ND(0.08) 0.1473 0.3148/4/2004 12:005TRC ND(5.0) ND(0.33) 0.077ND(0.08) 0.0876 0.1658/4/2004 14:005TRU ND(5.0) ND(0.33)ND(0.25) ND(0.08) 0.0377 0.0388/4/2004 14:005TRC ND(5.0) ND(0.33) 0.062ND(0.08) 0.0747 0.1368/4/2004 Blank Blank ND(5.0) ND(0.33)ND(0.25) ND(0.08) ND(0.83) 0.000
8/11/2004 9:005TRU ND(5.0) ND(0.33) 0.287ND(0.08) 0.1487 0.4368/11/2004 9:005TRC ND(5.0) ND(0.33)ND(0.25) ND(0.08) 0.0475 0.0478/11/2004 12:005TRU ND(5.0) ND(0.33)ND(0.25) ND(0.08) 0.0478 0.0488/11/2004 12:005TRC ND(5.0) ND(0.33) 0.088ND(0.08) 0.0676 0.1568/11/2004 14:005TRU ND(5.0) ND(0.33)ND(0.25) ND(0.08) 0.0354 0.0358/11/2004 14:005TRC ND(5.0) ND(0.33)ND(0.25) ND(0.08) 0.0374 0.0378/11/2004 Blank Blank ND(5.0) ND(0.33)ND(0.25) ND(0.08) ND(0.83) 0.0008/16/2004 9:005TRU ND(5.0) ND(0.33) 0.101ND(0.08) 0.1147 0.2158/16/2004 9:005TRC ND(5.0) ND(0.33) 0.472ND(0.08) 0.3326 0.8058/16/2004 12:005TRU ND(5.0) ND(0.33) 0.384ND(0.08) 0.2753 0.6608/16/2004 12:005TRC ND(5.0) ND(0.33) 0.110ND(0.08) 0.1198 0.2308/16/2004 14:005TRU ND(5.0) ND(0.33) 0.345ND(0.08) 0.2527 0.5988/16/2004 14:005TRC ND(5.0) ND(0.33) 0.304ND(0.08) 0.2467 0.5508/16/2004 Blank Blank ND(5.0) ND(0.33)ND(0.25) ND(0.08) ND(0.83) 0.000
148
Table E-5. Pilot-scale study chlorine effluent concentrations.
Date Time Location Free Cl2
(mg/L Cl2) Total Cl2
(mg/L Cl2) 6/23/2004 9:005TRU 1.05 3.05 6/23/2004 9:005TRC 1.30 3.25 6/23/2004 12:005INT 0.05 0.11 6/23/2004 12:005TRU 0.75 1.85 6/23/2004 12:005TRC 2.10 2.65 6/23/2004 14:005INT 0.09 0.20 6/23/2004 14:005TRU 0.25 1.40 6/23/2004 14:005TRC 1.00 2.10 6/30/2004 9:005INT 0.11 0.18 6/30/2004 9:005TRU 1.15 2.50 6/30/2004 9:005TRC 1.25 2.90 6/30/2004 12:005INT 0.12 0.25 6/30/2004 12:005TRU 1.00 2.45 6/30/2004 12:005TRC 1.55 2.80 6/30/2004 14:005INT 0.12 0.26 6/30/2004 14:005TRU 1.50 2.15 6/30/2004 14:005TRC 1.90 2.65
7/7/2004 9:005INT 0.09 0.13 7/7/2004 9:005TRU 4.10 5.20 7/7/2004 9:005TRC 4.90 5.75 7/7/2004 12:005INT 0.07 0.13 7/7/2004 12:005TRU 3.00 3.45 7/7/2004 12:005TRC 3.75 5.45 7/7/2004 14:005INT 0.09 0.14 7/7/2004 14:005TRU 2.85 3.85 7/7/2004 14:005TRC 4.30 5.10
7/14/2004 9:005INT 0.07 0.10 7/14/2004 9:005TRU 3.85 4.50 7/14/2004 9:005TRC 2.70 3.70 7/14/2004 12:005INT 0.12 0.23 7/14/2004 12:005TRU 1.90 2.80 7/14/2004 12:005TRC 2.25 2.35 7/14/2004 14:005INT 0.10 0.24 7/14/2004 14:005TRU 1.10 1.55 7/14/2004 14:005TRC 1.85 2.50 7/26/2004 9:005INT 0.04 0.09 7/26/2004 9:005TRU 0.25 2.90 7/26/2004 9:005TRC 0.30 3.00 7/26/2004 12:005INT 0.11 0.20
149
Table E-5. Continued.
Date Time LocationFree Cl2
(mg/L Cl2) Total Cl2
(mg/L Cl2) 7/26/2004 12:005TRU 0.35 1.05 7/26/2004 12:005TRC 0.55 1.30 7/26/2004 14:005INT 0.14 0.13 7/26/2004 14:005TRU 0.95 1.65 7/26/2004 14:005TRC 1.10 1.75 7/28/2004 9:005INT 0.05 0.07 7/28/2004 9:005TRU 1.60 1.95 7/28/2004 9:005TRC 1.90 2.20 7/28/2004 12:005INT 0.10 0.17 7/28/2004 12:005TRU 1.10 1.90 7/28/2004 12:005TRC 1.60 2.25 7/28/2004 14:005INT 0.05 0.11 7/28/2004 14:005TRU 0.85 1.95 7/28/2004 14:005TRC 1.10 2.15
8/2/2004 9:005INT 0.04 0.09 8/2/2004 9:005TRU 1.65 2.25 8/2/2004 9:005TRC 2.20 2.95 8/2/2004 12:005INT 0.11 0.27 8/2/2004 12:005TRU 0.56 1.1 8/2/2004 12:005TRC 0.71 1.26 8/2/2004 14:005INT 0.12 0.19 8/2/2004 14:005TRU 0.12 0.37 8/2/2004 14:005TRC 0.21 0.59 8/4/2004 9:005INT 0.11 0.17 8/4/2004 9:005TRU 4.10 3.75 8/4/2004 9:005TRC 2.95 3.45 8/4/2004 12:005INT 0.10 0.23 8/4/2004 12:005TRU 1.30 1.48 8/4/2004 12:005TRC 0.68 1.05 8/4/2004 14:005INT 0.21 0.26 8/4/2004 14:005TRU 0.10 0.37 8/4/2004 14:005TRC 0.29 0.64
8/11/2004 9:005INT 0.04 0.09 8/11/2004 9:005TRU 1.40 1.85 8/11/2004 9:005TRC 1.82 2.4 8/11/2004 12:005INT 0.07 0.14 8/11/2004 12:005TRU 0.59 0.97 8/11/2004 12:005TRC 1.44 1.91 8/11/2004 14:005INT 0.14 0.25 8/11/2004 14:005TRU 0.22 0.73 8/11/2004 14:005TRC 0.72 1.27
150
Table E-5. Continued.
Date Time LocationFree Cl2
(mg/L Cl2) Total Cl2
(mg/L Cl2) 8/16/2004 9:005INT 0.07 0.10 8/16/2004 9:005TRU 9.90 11.00 8/16/2004 9:005TRC 10.00 11.67 8/16/2004 12:005INT 0.13 0.20 8/16/2004 12:005TRU 5.50 7.33 8/16/2004 12:005TRC 7.55 9.83 8/16/2004 14:005INT 0.06 0.16 8/16/2004 14:005TRU 4.70 6.75 8/16/2004 14:005TRC 7.10 8.17
151
Table E-6. Pilot-scale probe parameter data.
Date Time Location pH Temperature
(ºC) Conductivity (µmhos/cm)
Dissolved Oxygen
(mg/L O2) 6/23/2004 9:005INT 6.88 27.4 702 NA 6/23/2004 9:005TRU 6.85 27.2 745 NA 6/23/2004 9:005TRC 6.86 27.0 740 NA 6/23/2004 12:005INT 6.89 27.6 733 NA 6/23/2004 12:005TRU 6.83 29.0 768 NA 6/23/2004 12:005TRC 6.85 27.6 758 NA 6/23/2004 14:005INT 6.97 28.9 714 NA 6/23/2004 14:005TRU 6.87 30.3 742 NA 6/23/2004 14:005TRC 6.78 29.2 744 NA 6/30/2004 9:005INT 7.44 28.4 594 4.25 6/30/2004 9:005TRU 7.34 28.4 632 2.40 6/30/2004 9:005TRC 7.2 27.5 628 2.75 6/30/2004 12:005INT 7.38 28.8 622 2.75 6/30/2004 12:005TRU 7.3 30.4 646 3.25 6/30/2004 12:005TRC 7.37 29.6 637 3.25 6/30/2004 14:005INT 7.39 29.2 648 3.75 6/30/2004 14:005TRU 7.36 33.5 648 3.15 6/30/2004 14:005TRC 7.39 29.8 642 3.25
7/7/2004 9:005INT 7.27 29.2 624 4.30 7/7/2004 9:005TRU 7.29 28.3 637 2.50 7/7/2004 9:005TRC 7.23 28.1 640 2.50 7/7/2004 12:005INT 7.31 29.9 658 4.30 7/7/2004 12:005TRU 7.27 31.7 672 3.25 7/7/2004 12:005TRC 7.33 29.9 658 4.00 7/7/2004 14:005INT 7.4 30.1 657 3.55 7/7/2004 14:005TRU 7.33 33.0 765 3.10 7/7/2004 14:005TRC 7.35 29.8 704 2.95
7/14/2004 9:005INT 7.13 28.5 658 3.50 7/14/2004 9:005TRU 7.25 27.9 703 2.50 7/14/2004 9:005TRC 7.24 27.4 698 3.00 7/14/2004 12:005INT 7.23 30.0 749 3.95 7/14/2004 12:005TRU 7.22 31.2 734 3.30 7/14/2004 12:005TRC 7.27 28.5 719 3.05 7/14/2004 14:005INT 7.36 30.6 684 4.25 7/14/2004 14:005TRU 7.23 33.3 698 3.30 7/14/2004 14:005TRC 7.27 29.6 704 3.60 7/26/2004 9:005INT 7.04 28.3 668 1.75 7/26/2004 9:005TRU 6.63 28.1 704 1.30 7/26/2004 9:005TRC 6.64 27.9 708 1.15
152
Table E-6. Continued.
Date Time Location pH Temperature
(ºC) Conductivity (µmhos/cm)
Dissolved Oxygen
(mg/L O2) 7/26/2004 12:005INT 7.21 30.5 640 3.40 7/26/2004 12:005TRU 6.3 31.3 666 1.45 7/26/2004 12:005TRC 6.22 29.2 640 1.50 7/26/2004 14:005INT 7.29 31.1 673 3.40 7/26/2004 14:005TRU 6.07 33.5 730 2.70 7/26/2004 14:005TRC 6.5 29.9 751 2.40 7/28/2004 9:005INT 7.26 28.6 760 3.15 7/28/2004 9:005TRU 9.61 28.1 819 3.00 7/28/2004 9:005TRC 9.48 27.8 950 3.10 7/28/2004 12:005INT 7.31 30.0 731 4.20 7/28/2004 12:005TRU 9.3 31.0 813 3.25 7/28/2004 12:005TRC 8.92 30.0 796 3.00 7/28/2004 14:005INT 7.32 28.5 768 3.40 7/28/2004 14:005TRU 8.4 29.9 792 3.40 7/28/2004 14:005TRC 8.73 29.1 772 3.65
8/2/2004 9:005INT 7.11 28.5 513 1.45 8/2/2004 9:005TRU 7.2 28.1 530 2.60 8/2/2004 9:005TRC 7.2 28.0 534 2.90 8/2/2004 12:005INT 7.37 30.5 508 3.75 8/2/2004 12:005TRU 7.35 31.3 510 3.30 8/2/2004 12:005TRC 7.45 29.3 521 3.50 8/2/2004 14:005INT 7.58 30.4 515 4.20 8/2/2004 14:005TRU 7.53 33.0 529 3.10 8/2/2004 14:005TRC 7.53 29.8 523 3.30 8/4/2004 9:005INT 7.38 29.1 505 3.25 8/4/2004 9:005TRU 7.3 28.3 513 3.30 8/4/2004 9:005TRC 7.31 27.8 514 2.95 8/4/2004 12:005INT 7.28 30.7 499 3.65 8/4/2004 12:005TRU 7.08 31.2 518 3.40 8/4/2004 12:005TRC 7.1 29.4 511 3.20 8/4/2004 14:005INT 7.37 31.1 503 4.35 8/4/2004 14:005TRU 7.26 33.5 510 3.90 8/4/2004 14:005TRC 7.16 32.1 510 3.25
8/11/2004 9:005INT 7.18 27.7 491 3.75 8/11/2004 9:005TRU 7.05 27.4 502 3.05 8/11/2004 9:005TRC 7.04 27.4 506 2.85 8/11/2004 12:005INT 7.38 29.1 493 3.80 8/11/2004 12:005TRU 7.34 29.2 505 4.85 8/11/2004 12:005TRC 7.2 28.2 508 3.45 8/11/2004 14:005INT 7.42 30.5 486 4.25 8/11/2004 14:005TRU 7.59 30.6 509 6.10
153
Table E-6. Continued.
Date Time Location pH Temperature
(ºC) Conductivity (µmhos/cm)
Dissolved Oxygen
(mg/L O2) 8/11/2004 14:005TRC 7.24 28.9 489 3.80 8/16/2004 9:005INT 6.82 28.0 507 3.20 8/16/2004 9:005TRU 7.12 27.1 559 2.50 8/16/2004 9:005TRC 7.14 27.0 555 2.15 8/16/2004 12:005INT 7.26 29.7 525 3.75 8/16/2004 12:005TRU 7.26 30.4 564 2.00 8/16/2004 12:005TRC 7.48 28.3 550 2.40 8/16/2004 14:005INT 7.24 30.2 511 3.30 8/16/2004 14:005TRU 7.36 32.6 563 3.15 8/16/2004 14:005TRC 7.45 29.2 544 2.65
154
Table E-7. Pilot-scale data provided by GRU laboratory.
Date Time Location TSS
(mg/L)
Total Coliform
(# /100 mL) 6/23/2004 9:005INT 0.9 4100 6/23/2004 9:005TRU 0.6 0.5 6/23/2004 9:005TRC 0.4 0.5 6/23/2004 12:005INT 1.3 6400 6/23/2004 12:005TRU 0.5 0.5 6/23/2004 12:005TRC 0.3 0.5 6/23/2004 14:005INT 0.4 5200 6/23/2004 14:005TRU 0.4 1.0 6/23/2004 14:005TRC 0.2 0.5 6/30/2004 9:005INT 0.2 5500 6/30/2004 9:005TRU 0.2 0.2 6/30/2004 9:005TRC 0.1 0.2 6/30/2004 12:005INT 0.3 3650 6/30/2004 12:005TRU 0.2 0.2 6/30/2004 12:005TRC 0.2 0.2 6/30/2004 14:005INT 0.2 4750 6/30/2004 14:005TRU 0.1 0.2 6/30/2004 14:005TRC 0.2 0.2
7/7/2004 9:005INT 0.4 16000 7/7/2004 9:005TRU 0.2 0.4 7/7/2004 9:005TRC 0.2 0.1 7/7/2004 12:005INT 0.4 16000 7/7/2004 12:005TRU 0.3 0.1 7/7/2004 12:005TRC 0.2 0.1 7/7/2004 14:005INT 0.4 16000 7/7/2004 14:005TRU 0.2 2.5 7/7/2004 14:005TRC 0.2 0.1
7/14/2004 9:005INT 3.0 7200 7/14/2004 9:005TRU 0.3 0.1 7/14/2004 9:005TRC 0.2 0.1 7/14/2004 12:005INT 0.6 8600 7/14/2004 12:005TRU 0.1 0.1 7/14/2004 12:005TRC 0.1 0.1 7/14/2004 14:005INT 0.2 5600 7/14/2004 14:005TRU 0.2 0.1 7/14/2004 14:005TRC 0.1 0.1 7/26/2004 9:005INT 0.6 3800 7/26/2004 9:005TRU 0.4 0.1 7/26/2004 9:005TRC 0.3 0.1 7/26/2004 12:005INT 1.0 5400
155
Table E-7. Continued.
Date Time Location TSS
(mg/L)
Total Coliform (# /100 mL)
7/26/2004 12:005TRU 0.4 0.1 7/26/2004 12:005TRC 0.2 0.1 7/26/2004 14:005INT 0.6 1800 7/26/2004 14:005TRU 0.3 0.1 7/26/2004 14:005TRC 0.2 0.1 7/28/2004 9:005INT 1.5 1600 7/28/2004 9:005TRU 5.7 0.1 7/28/2004 9:005TRC 5.4 0.2 7/28/2004 12:005INT 2.7 2300 7/28/2004 12:005TRU 0.7 0.1 7/28/2004 12:005TRC 1.6 0.1 7/28/2004 14:005INT 0.4 3200 7/28/2004 14:005TRU 0.5 0.1 7/28/2004 14:005TRC 0.5 0.1
8/2/2004 9:005INT 0.7 3900 8/2/2004 9:005TRU 0.1 0.2 8/2/2004 9:005TRC 0.1 0.2 8/2/2004 12:005INT 2.1 1900 8/2/2004 12:005TRU 0.1 0.2 8/2/2004 12:005TRC 0.1 0.2 8/2/2004 14:005INT 3.8 1600 8/2/2004 14:005TRU 0.1 0.1 8/2/2004 14:005TRC 0.1 0.1 8/4/2004 9:005INT 1.3 2800 8/4/2004 9:005TRU 0.1 0.1 8/4/2004 9:005TRC 0.1 0.4 8/4/2004 12:005INT 1.8 4100 8/4/2004 12:005TRU 0.1 0.1 8/4/2004 12:005TRC 0.1 0.3 8/4/2004 14:005INT 0.2 2700 8/4/2004 14:005TRU 0.2 0.1 8/4/2004 14:005TRC 0.1 0.3
8/11/2004 9:005INT 2.7 4000 8/11/2004 9:005TRU 0.1 0.1 8/11/2004 9:005TRC 0.0 0.1 8/11/2004 12:005INT 0.6 2700 8/11/2004 12:005TRU 0.6 0.1 8/11/2004 12:005TRC 0.2 0.1 8/11/2004 14:005INT 0.7 2600 8/11/2004 14:005TRU 0.7 0.1 8/11/2004 14:005TRU 0.3 0.1
156
Table E-7. Continued.
Date Time Location TSS
(mg/L)
Total Coliform
(# /100 mL) 8/16/2004 9:005INT 0.3 1900 8/16/2004 9:005TRU 0.2 0.1 8/16/2004 9:005TRC 0.4 0.1 8/16/2004 12:005INT 3.0 2400 8/16/2004 12:005TRU 1.4 0.1 8/16/2004 12:005TRC 0.3 0.1 8/16/2004 14:005INT 0.5 3000 8/16/2004 14:005TRU 0.4 0.1 8/16/2004 14:005TRU 0.3 0.1
157
APPENDIX F FULL-SCALE DATA
5PA: Post-Aeration Basin Effluent
58S: Inlet of the North Chlorine Contact Basin
53S: Uncovered Side Effluent (UNCOV) of the North Chlorine Contact Basin
53N: Covered Side Effluent (COV) of the North Chlorine Contact Basin
Table F-1. Trihalomethane mass concentrations in the full-scale study. Trihalomethane (µg/L)
Date
Time Location Chloroform
Bromodi-chloro-
Methane
Dibromo- chloro- methane Bromoform
Total THM
8/19/2004 9:00 58S Inf 43.1 10.3ND (5.0) ND (5.0) 53.48/19/2004 9:00 53S 28.7 8.3ND (5.0) ND (5.0) 378/19/2004 9:00 53N 36.8 10.2ND (5.0) ND (5.0) 478/19/2004 12:00 58S Inf 32.8 8.7ND (5.0) ND (5.0) 41.58/19/2004 12:00 53S 54.4 14.2ND (5.0) ND (5.0) 68.68/19/2004 12:00 53N 60.4 15ND (5.0) ND (5.0) 75.48/19/2004 14:00 58S Inf 43.8 10.7ND (5.0) ND (5.0) 54.58/19/2004 14:00 53S 50.4 10.4ND (5.0) ND (5.0) 60.88/19/2004 14:00 53N 46.9 11.9ND (5.0) ND (5.0) 58.88/19/2004Blank1 Blank 1 ND (5.0) ND (5.0) ND (5.0) ND (5.0) 08/24/2004 9:00 58S1 Inf 52.6ND (5.0) ND (5.0) ND (5.0) 52.68/24/2004 9:00 58S2 Inf 71.1 9.3ND (5.0) ND (5.0) 80.48/24/2004 9:00 53S 72.4 8.1ND (5.0) ND (5.0) 80.58/24/2004 9:00 53N 85.4 8.8ND (5.0) ND (5.0) 94.28/24/2004 12:00 58S1 Inf 73.1 10ND (5.0) ND (5.0) 83.18/24/2004 12:00 58S2 Inf 61.1 7.3ND (5.0) ND (5.0) 68.48/24/2004 12:00 53S 101 10.7ND (5.0) ND (5.0) 111.78/24/2004 12:00 53N 87 8.3ND (5.0) ND (5.0) 95.38/24/2004 14:00 58S1 Inf 64.2 8.1ND (5.0) ND (5.0) 72.38/24/2004 14:00 58S2 Inf 75.7 7.8ND (5.0) ND (5.0) 83.58/24/2004 14:00 53S 96.8 9.3ND (5.0) ND (5.0) 106.18/24/2004 14:00 53N 102.5 9.5ND (5.0) ND (5.0) 1128/24/2004Blank1 Blank 1 ND (5.0) ND (5.0) ND (5.0) ND (5.0) 08/25/2004 9:00 58S1 Inf 25ND (5.0) ND (5.0) ND (5.0) 25
158
Table F-1. Continued. Trihalomethane (µg/L)
Date
Time Location Chloroform
Bromodi-chloro-
Methane
Dibromo- chloro- methane Bromoform
Total THM
8/25/2004 9:00 58S2 Inf 24.1ND (5.0) ND (5.0) ND (5.0) 24.18/25/2004 9:00 53S 36.6 7.2ND (5.0) ND (5.0) 43.88/25/2004 9:00 53N 36.1 7ND (5.0) ND (5.0) 43.18/25/2004 12:00 58S1 Inf 32.2 5.1ND (5.0) ND (5.0) 37.38/25/2004 12:00 58S2 Inf 31 5.7ND (5.0) ND (5.0) 36.78/25/2004 12:00 53S 43 8.3ND (5.0) ND (5.0) 51.38/25/2004 12:00 53N 37.9 7.2ND (5.0) ND (5.0) 45.18/25/2004 14:00 58S1 Inf 35.2 7ND (5.0) ND (5.0) 42.28/25/2004 14:00 58S2 Inf 34.5 6.5ND (5.0) ND (5.0) 418/25/2004 14:00 53S 30 7.6ND (5.0) ND (5.0) 37.68/25/2004 14:00 53N 39.3 7.4ND (5.0) ND (5.0) 46.78/25/2004Blank1 Blank 1 ND (5.0) ND (5.0) ND (5.0) ND (5.0) 0
159
Table F-2. Trihalomethane molar concentrations in the full-scale study. Trihalomethane (µmoles/L)
Date
Time Location Chloroform
Bromodi-chloro-
Methane
Dibromo- chloro- methane Bromoform
Total THM
8/19/2004 9:00 58S Inf 0.361 0.063ND (5.0) ND (5.0) 0.4238/19/2004 9:00 53S 0.240 0.051ND (5.0) ND (5.0) 0.2918/19/2004 9:00 53N 0.308 0.062ND (5.0) ND (5.0) 0.3708/19/2004 12:00 58S Inf 0.274 0.053ND (5.0) ND (5.0) 0.3288/19/2004 12:00 53S 0.455 0.087ND (5.0) ND (5.0) 0.5428/19/2004 12:00 53N 0.505 0.091ND (5.0) ND (5.0) 0.5978/19/2004 14:00 58S Inf 0.367 0.065ND (5.0) ND (5.0) 0.4328/19/2004 14:00 53S 0.422 0.063ND (5.0) ND (5.0) 0.4858/19/2004 14:00 53N 0.392 0.073ND (5.0) ND (5.0) 0.4658/19/2004Blank1 Blank 1 ND (5.0) ND (5.0) ND (5.0) ND (5.0) 0.0008/24/2004 9:00 58S1 Inf 0.440ND (5.0) ND (5.0) ND (5.0) 0.4408/24/2004 9:00 58S2 Inf 0.595 0.057ND (5.0) ND (5.0) 0.6528/24/2004 9:00 53S 0.606 0.049ND (5.0) ND (5.0) 0.6558/24/2004 9:00 53N 0.715 0.054ND (5.0) ND (5.0) 0.7688/24/2004 12:00 58S1 Inf 0.612 0.061ND (5.0) ND (5.0) 0.6738/24/2004 12:00 58S2 Inf 0.511 0.045ND (5.0) ND (5.0) 0.5568/24/2004 12:00 53S 0.845 0.065ND (5.0) ND (5.0) 0.9108/24/2004 12:00 53N 0.728 0.051ND (5.0) ND (5.0) 0.7798/24/2004 14:00 58S1 Inf 0.537 0.049ND (5.0) ND (5.0) 0.5878/24/2004 14:00 58S2 Inf 0.633 0.048ND (5.0) ND (5.0) 0.6818/24/2004 14:00 53S 0.810 0.057ND (5.0) ND (5.0) 0.8678/24/2004 14:00 53N 0.858 0.058ND (5.0) ND (5.0) 0.9168/24/2004Blank1 Blank 1 ND (5.0) ND (5.0) ND (5.0) ND (5.0) 0.0008/25/2004 9:00 58S1 Inf 0.209ND (5.0) ND (5.0) ND (5.0) 0.2098/25/2004 9:00 58S2 Inf 0.202ND (5.0) ND (5.0) ND (5.0) 0.2028/25/2004 9:00 53S 0.306 0.044ND (5.0) ND (5.0) 0.3508/25/2004 9:00 53N 0.302 0.043ND (5.0) ND (5.0) 0.3458/25/2004 12:00 58S1 Inf 0.269 0.031ND (5.0) ND (5.0) 0.3018/25/2004 12:00 58S2 Inf 0.259 0.035ND (5.0) ND (5.0) 0.2948/25/2004 12:00 53S 0.360 0.051ND (5.0) ND (5.0) 0.4108/25/2004 12:00 53N 0.317 0.044ND (5.0) ND (5.0) 0.3618/25/2004 14:00 58S1 Inf 0.295 0.043ND (5.0) ND (5.0) 0.3378/25/2004 14:00 58S2 Inf 0.289 0.040ND (5.0) ND (5.0) 0.3288/25/2004 14:00 53S 0.251 0.046ND (5.0) ND (5.0) 0.2978/25/2004 14:00 53N 0.329 0.045ND (5.0) ND (5.0) 0.3748/25/2004Blank1 Blank 1 ND (5.0) ND (5.0) ND (5.0) ND (5.0) 0.000
160
Table F-3. Haloacetic acid mass concentrations in the full-scale study. Haloacetic Acid (µg/L) Date Time Location MCAA MBAA DCAA DBAA TCAA
Total HAA
8/19/2004 9:0058S Inf 968.47ND(0.33) 52.14ND(0.08) 18.9 1039.518/19/2004 9:0053S 118.04ND(0.33) 58.61ND(0.08) 25.23 201.888/19/2004 9:0053N 970.44ND(0.33) 60.12ND(0.08) 27.75 1058.318/19/2004 12:0058S Inf 968.71ND(0.33) 53.92ND(0.08) 18.46 1041.098/19/2004 12:0053S 932.87ND(0.33) 74.91ND(0.08) 31.58 1039.368/19/2004 12:0053N 187.35ND(0.33) 66.87ND(0.08) 26.22 280.448/19/2004 14:0058S Inf 466.44ND(0.33) 65.99ND(0.08) 24.71 557.148/19/2004 14:0053S 188.45ND(0.33) 77.16ND(0.08) 34.49 300.18/19/2004 14:0053N 163.13ND(0.33)ND(0.25) ND(0.08) 19.26 182.398/19/2004 Blank1 Blank 1 ND(0.17) ND(0.33)ND(0.25) ND(0.08) ND(0.83) 08/24/2004 9:0058S Inf 276.13ND(0.33) 59.54ND(0.08) 29.57 365.248/24/2004 9:0053S 305.07ND(0.33) 64.49ND(0.08) 34.78 404.348/24/2004 9:0053N 365.60ND(0.33) 58.21ND(0.08) 30.82 454.638/24/2004 12:0058S Inf 290.32ND(0.33) 70.93ND(0.08) 31.77 393.028/24/2004 12:0053S 585.61ND(0.33) 76.89ND(0.08) 34.91 697.418/24/2004 12:0053N 464.72ND(0.33) 74.37ND(0.08) 17.74 556.838/24/2004 14:0058S Inf 340.13ND(0.33) 64.38ND(0.08) 30.10 434.618/24/2004 14:0053S 411.33ND(0.33) 84.59ND(0.08) 41.94 537.868/24/2004 14:0053N 470.44ND(0.33) 75.93ND(0.08) 38.84 585.218/24/2004 Blank1 Blank 1 ND (0.17) ND(0.33)ND(0.25) ND(0.08) ND(0.83) 08/25/2004 9:0058S Inf 339.40ND(0.33) 59.32ND(0.08) 30.025 428.748/25/2004 9:0053S NA ND(0.33)NA ND(0.08) NA 08/25/2004 9:0053N 526.11ND(0.33) 66.60ND(0.08) 34.11 626.828/25/2004 12:0058S Inf 393.74ND(0.33) 70.88ND(0.08) 33.78 498.48/25/2004 12:0053S 396.91ND(0.33) 83.61ND(0.08) 47.3 527.828/25/2004 12:0053N 289.31ND(0.33) 84.00ND(0.08) 46.41 419.728/25/2004 14:0058S Inf 320.71ND(0.33) 71.92ND(0.08) 32.43 425.068/25/2004 14:0053S 1000.00ND(0.33) 102.81ND(0.08) 59.57 1162.388/25/2004 14:0053N 26.79ND(0.33) 72.25ND(0.08) 36.88 135.928/25/2004 Blank1 Blank 1 ND (0.17) ND(0.33)ND(0.25) ND(0.08) ND(0.83) 0
161
Table F-4. Haloacetic acid molar concentrations in the full-scale study. Haloacetic Acid (µmole/L) Date Time Location MCAA MBAA DCAA DBAA TCAA
Total HAA
8/19/2004 9:0058S Inf 10.25ND(0.33) 0.40ND(0.08) 0.12 10.778/19/2004 9:0053S 1.25ND(0.33) 0.45ND(0.08) 0.15 1.868/19/2004 9:0053N 10.27ND(0.33) 0.47ND(0.08) 0.17 10.918/19/2004 12:0058S Inf 10.25ND(0.33) 0.42ND(0.08) 0.11 10.788/19/2004 12:0053S 9.87ND(0.33) 0.58ND(0.08) 0.19 10.658/19/2004 12:0053N 1.98ND(0.33) 0.52ND(0.08) 0.16 2.668/19/2004 14:0058S Inf 4.94ND(0.33) 0.51ND(0.08) 0.15 5.608/19/2004 14:0053S 1.99ND(0.33) 0.60ND(0.08) 0.21 2.808/19/2004 14:0053N 1.73ND(0.33)ND(0.25) ND(0.08) 0.12 1.848/19/2004 Blank1 Blank 1 NA NA NA ND(0.08) NA 0.008/24/2004 9:0058S Inf 2.92ND(0.33) 0.46ND(0.08) 0.18 3.568/24/2004 9:0053S 3.23ND(0.33) 0.50ND(0.08) 0.21 3.948/24/2004 9:0053N 3.87ND(0.33) 0.45ND(0.08) 0.19 4.518/24/2004 12:0058S Inf 3.07ND(0.33) 0.55ND(0.08) 0.19 3.828/24/2004 12:0053S 6.20ND(0.33) 0.60ND(0.08) 0.21 7.018/24/2004 12:0053N 4.92ND(0.33) 0.58ND(0.08) 0.11 5.608/24/2004 14:0058S Inf 3.60ND(0.33) 0.50ND(0.08) 0.18 4.288/24/2004 14:0053S 4.35ND(0.33) 0.66ND(0.08) 0.26 5.278/24/2004 14:0053N 4.98ND(0.33) 0.59ND(0.08) 0.24 5.808/24/2004 Blank1 Blank 1 NA NA NA ND(0.08) NA 0.008/25/2004 9:0058S Inf 3.59ND(0.33) 0.46ND(0.08) 0.18 4.248/25/2004 9:0053S NA ND(0.33)NA ND(0.08) NA 0.008/25/2004 9:0053N 5.57ND(0.33) 0.52ND(0.08) 0.21 6.298/25/2004 12:0058S Inf 4.17ND(0.33) 0.55ND(0.08) 0.21 4.928/25/2004 12:0053S 4.20ND(0.33) 0.65ND(0.08) 0.29 5.148/25/2004 12:0053N 3.06ND(0.33) 0.65ND(0.08) 0.28 4.008/25/2004 14:0058S Inf 3.39ND(0.33) 0.56ND(0.08) 0.20 4.158/25/2004 14:0053S 10.58ND(0.33) 0.80ND(0.08) 0.36 11.748/25/2004 14:0053N 0.28ND(0.33) 0.56ND(0.08) 0.23 1.078/25/2004 Blank1 Blank 1 NA NA NA ND(0.08) NA 0.00
162
Table F-5. Full-scale study chlorine effluent concentrations.
Date Time LocationFree Cl2
(mg/L Cl2) Total Cl2
(mg/L Cl2) 8/19/2004 9:005PA 0.09 0.12 8/19/2004 9:0058S 3.75 4.60 8/19/2004 9:0053S 2.45 3.30 8/19/2004 9:0053N 2.75 3.80 8/19/2004 12:005PA 0.06 0.13 8/19/2004 12:0058S 3.30 4.25 8/19/2004 12:0053S 1.90 3.15 8/19/2004 12:0053N 2.75 3.80 8/19/2004 14:005PA 0.07 0.11 8/19/2004 14:0058S 4.65 5.20 8/19/2004 14:0053S 2.90 3.90 8/19/2004 14:0053N 3.55 4.50 8/24/2004 9:005PA 0.04 0.09 8/24/2004 9:0058S 3.05 4.45 8/24/2004 9:0053S 1.50 3.35 8/24/2004 9:0053N 2.55 3.45 8/24/2004 12:005PA 0.05 0.23 8/24/2004 12:0058S 4.05 4.70 8/24/2004 12:0053S 2.40 3.35 8/24/2004 12:0053N 2.85 3.85 8/24/2004 14:005PA 0.07 0.23 8/24/2004 14:0058S 4.05 4.85 8/24/2004 14:0053S 2.75 3.40 8/24/2004 14:0053N 3.55 4.25 8/25/2004 9:005PA 0.04 0.09 8/25/2004 9:0058S 3.05 4.45 8/25/2004 9:0053S 1.50 3.35 8/25/2004 9:0053N 2.55 3.45 8/25/2004 12:005PA 0.05 0.23 8/25/2004 12:0058S 4.05 4.70 8/25/2004 12:0053S 2.40 3.35 8/25/2004 12:0053N 2.85 3.85 8/25/2004 14:005PA 0.07 0.23 8/25/2004 14:0058S 4.05 4.85 8/25/2004 14:0053S 2.75 3.40 8/25/2004 14:0053N 3.55 4.25
163
Table F-6. Full-scale probe parameter data.
Date Time Location pH Temperature
(ºC) Conductivity (µmhos/cm)
Dissolved Oxygen
(mg/L O2) 8/19/2004 9:005PA 7.0 27.9 497 3.15 8/19/2004 9:0058S 6.6 27.5 490 2.90 8/19/2004 9:0053S 6.8 28.2 489 2.95 8/19/2004 9:0053N 6.7 28.3 481 2.85 8/19/2004 12:005PA 7.0 29.8 493 3.60 8/19/2004 12:0058S 6.6 29.1 488 3.50 8/19/2004 12:0053S 6.6 29.3 492 3.60 8/19/2004 12:0053N 6.6 29.6 494 3.70 8/19/2004 14:005PA 7.0 30.2 480 3.80 8/19/2004 14:0058S 6.6 29.9 594 3.75 8/19/2004 14:0053S 6.6 30.1 533 3.60 8/19/2004 14:0053N 6.6 29.6 800 3.65 8/24/2004 9:005PA 7.10 27.9 495 3.25 8/24/2004 9:0058S 6.91 27.9 493 3.75 8/24/2004 9:0053S 6.90 28.0 494 3.50 8/24/2004 9:0053N 6.90 27.8 497 3.50 8/24/2004 12:005PA 7.20 28.8 492 3.00 8/24/2004 12:0058S 6.92 28.9 492 3.20 8/24/2004 12:0053S 6.92 28.9 489 3.60 8/24/2004 12:0053N 6.87 29.0 484 3.20 8/24/2004 14:005PA 7.11 29.6 483 3.55 8/24/2004 14:0058S 6.91 29.3 477 3.50 8/24/2004 14:0053S 6.87 29.7 480 3.45 8/24/2004 14:0053N 6.87 29.6 483 3.75 8/25/2004 9:005PA 7.14 28.3 513 3.25 8/25/2004 9:0058S 6.83 28.5 508 3.00 8/25/2004 9:0053S 6.72 28.5 507 4.15 8/25/2004 9:0053N 6.51 28.1 658 3.20 8/25/2004 12:005PA 7.23 29.1 477 3.50 8/25/2004 12:0058S 6.93 29.2 472 3.65 8/25/2004 12:0053S 6.80 29.9 467 3.50 8/25/2004 12:0053N 6.85 29.2 474 3.65 8/25/2004 14:005PA 7.18 29.2 494 3.45 8/25/2004 14:0058S 6.90 29.7 476 3.50 8/25/2004 14:0053S 6.89 29.7 470 3.40 8/25/2004 14:0053N 6.95 28.8 490 3.40
164
Table F-7. Full-scale data provided by GRU.
Date Time Location
TSS (mg/L)
Total Coliform
(# /100 mL) 8/19/2004 9:005PA 0.3 3800 8/19/2004 9:0058S 0.4 0.2 8/19/2004 9:0053S 0.2 0.1 8/19/2004 9:0053N 0.4 0.3 8/19/2004 12:005PA 0.5 1100 8/19/2004 12:0058S 0.3 0.6 8/19/2004 12:0053S 0.5 0.3 8/19/2004 12:0053N 0.6 0.1 8/19/2004 14:005PA 0.6 1900 8/19/2004 14:0058S 0.8 1 8/19/2004 14:0053S 0.5 0.1 8/19/2004 14:0053N 0.4 0.1 8/24/2004 9:005PA 0.4 2400 8/24/2004 9:0058S 0.5 1.4 8/24/2004 9:0053S 0.3 0.2 8/24/2004 9:0053N 0.4 0.2 8/24/2004 12:005PA 0.6 1600 8/24/2004 12:0058S 0.2 0.7 8/24/2004 12:0053S 0.3 0.4 8/24/2004 12:0053N 0.3 0.3 8/24/2004 14:005PA 0.5 1100 8/24/2004 14:0058S 0.5 0.4 8/24/2004 14:0053S 0.5 0.1 8/24/2004 14:0053N 0.3 0.2 8/25/2004 9:005PA 0.3 3900 8/25/2004 9:0058S 0.2 3.9 8/25/2004 9:0053S 0.4 0.2 8/25/2004 9:0053N 0.3 0.2 8/25/2004 12:005PA 0.5 1800 8/25/2004 12:0058S 0.3 0.3 8/25/2004 12:0053S 0.4 0.3 8/25/2004 12:0053N 0.3 0.3 8/25/2004 14:005PA 0.4 2700 8/25/2004 14:0058S 0.3 0.2 8/25/2004 14:0053S 0.2 0.1 8/25/2004 14:0053N 0.2 0.1
165
APPENDIX G GAS CHROMATOGRAPHY INFORMATION
RT: 1.00 - 18.09
2 4 6 8 10 12 14 16 18Time (min)
0
5
10
15
20
25
30
35
40
45
50
55
60
65
70
75
80
85
90
95
100
Rel
ativ
e A
bund
ance
13.66
6.86
11.2011.39
12.02 14.1711.10
14.31
9.22 13.23
9.766.75
14.768.947.45
9.9517.1114.928.076.30
5.733.43
4.335.202.652.33 16.10
NL:7.38E6TIC MS 08060402
Figure G-1. Trihalomethane GC for spiked sample.
166
RT: 0.98 - 18.10
2 4 6 8 10 12 14 16 18Time (min)
0
5
10
15
20
25
30
35
40
45
50
55
60
65
70
75
80
85
90
95
100
Rel
ativ
e A
bund
ance
9.17
11.127.26
12.76
6.926.32 14.34
2.00 11.3913.709.772.83 7.45 12.045.21 17.593.43 17.1014.95
NL:2.38E6TIC MS 08060403
Figure G-2. Trihalomethane GC for blank sample.
167
RT: 0.98 - 18.10
2 4 6 8 10 12 14 16 18Time (min)
0
5
10
15
20
25
30
35
40
45
50
55
60
65
70
75
80
85
90
95
100
Rel
ativ
e A
bund
ance
6.10
9.187.28
11.12
8.18
12.786.3114.34
10.161.97 2.13 4.17 13.71 17.5912.424.32 16.8714.91
NL:4.57E6TIC MS 08060404
Figure G-3. Trihalomethane GC for field sample.
168
THM Analysis Conditions:Tekmar 3100 Purge-and-Trap Concentrator attached to a Finnigan Trace 2000 GC/MS Tekmar Conditions: Type K Trap Sample purged for 10 minutes at 40 ml/min with helium 2 minute dry purge desorb preheat 245C desorb 250C for 4 minutes bake 260C for 10 minutes
GC/MS Conditions: GC:Restek Rtx-VMS capillary column, 30m x 0.32 mm i.d., 1.8 um film thickness 35C to 180C at 10C/min, initial hold at 35C for 4 minutes 180C to 200C at 25C/min MS: Electron Ionization, 34 amu to 280 amu in 0.4 seconds Source temp 200C, transfer line temp 200C, 150uA emission current
169
Figure G-4. Haloacetic acid GC for spiked sample.
170
Figure G-5. Haloacetic acid GC for blank sample.
Figure G-6. Haloacetic acid GC for field sample.
171
53N 8/19 9am
HAA Conditions:
Hewlett-Packard 5890 Series II GC/ECD
Restek DB5MS Capillary Column, 30m x 0.25 mm i.d., 0.25 um film thickness
12 psi head pressure
35C to 70C at 2.5C/min, 10 minute initial hold at 35C
70C to 210C at 5C/min
Injector = 150C
172
APPENDIX H T-TEST AND PEARSON COEFFICIENT TABLES
Table H-1. Pilot-scale t-test values. Pilot Scale (n=30)
t* t*(0.05)Statistical Difference t*(0.01)
Statistical Difference
Free Cl2 mg/L 3.28 1.699 y 2.462 y Total Cl2 mg/L 4.03 1.699 y 2.462 y TTHM µg/L 1.30 1.699 n 2.462 n TTHM µmoles/L 1.27 1.699 n 2.462 n TTHM' µg/L 2.92 1.699 y 2.462 y TTHM' µmoles/L 2.93 1.699 y 2.462 y HAA µg/L 1.23 1.699 n 2.462 n HAA µmoles/L 0.46 1.699 n 2.462 n HAA' µg/L 1.55 1.699 n 2.462 n HAA' µmoles/L 0.83 1.699 n 2.462 n Free Cl2 bl mg/L 3.01 1.860 y 2.896 y Temperature °C 6.84 1.699 y 2.462 y y = yes, n = no
Table H-2. Full-scale t-test values. Full Scale (n=9)
t* t*(0.05)Statistical Difference t*(0.01)
Statistical Difference
Free Cl2 mg/L 7.97 1.860 y 2.896 y Total Cl2 mg/L 5.68 1.860 y 2.896 y TTHM µg/L 0.71 1.860 n 2.896 n TTHM µmoles/L 0.72 1.860 n 2.896 n TTHM' µg/L 2.45 1.860 y 2.896 n TTHM' µmoles/L 2.42 1.860 y 2.896 n HAA µg/L 3.37 1.860 y 2.896 y HAA µmoles/L 1.93 1.860 y 2.896 n HAA' µg/L 3.33 1.860 y 2.896 y HAA' µmoles/L 3.02 1.860 y 2.896 y y = yes, n = no
173
Table H-3. Pilot-scale Pearson coefficient and linear correlation values.
Pilot-Scale Study r t* t*(0.05)Statistical Difference t*(0.01)
Statistical Difference
∆TTHM (µg/L) vs ∆Free Cl2 (mg/L) -0.219 1.187 1.701 n 2.467 n ∆TTHM (µmole/L) vs ∆Free Cl2 (mg/L) -0.225 1.222 1.701 n 2.467 n ∆TTHM' (µg/L) vs Avg UV Rad (mW/cm2) 0.299 1.656 1.701 n 2.467 n ∆TTHM' (µmole/L) vs Avg UV Rad (mW/cm2) 0.289 1.600 1.701 n 2.467 n ∆HAA (µg/L) vs ∆Free Cl2 (mg/L) -0.119 0.636 1.701 n 2.467 n ∆HAA (µmole/L) vs ∆Free Cl2 (mg/L) 0.049 0.258 1.701 n 2.467 n ∆HAA' (µg/L) vs Avg UV Rad (mW/cm2) -0.046 0.246 1.701 n 2.467 n ∆HAA' (µmole/L) vs Avg UV Rad (mW/cm2) -0.097 0.516 1.701 n 2.467 n ∆Free Cl2 (mg/L) vs Temp (°C) -0.344 1.941 1.701 y 2.467 n ∆Total Cl2 (mg/L) vs Temp (°C) -0.227 1.233 1.701 n 2.467 n ∆Total Cl2 (mg/L) vs Avg UV Rad (mW/cm2) -0.281 1.548 1.701 n 2.467 n ∆Free Cl2 (mg/L) vs Avg UV Rad (mW/cm2) -0.405 2.342 1.701 y 2.467 n Avg Global Rad vs Avg UV Rad (mW/cm2) 0.996 61.643 1.701 y 2.467 y ∆Temp (°C) vs Avg UV Rad (mW/cm2) 0.884 9.993 1.701 y 2.467 y ∆Free Cl2 (mg/L) vs Avg UV Rad (mW/cm2) bl -0.574 3.708 1.895 y 2.998 y ∆TTHM (µg/L) vs ∆Free Cl2 (mg/L) bl -0.289 1.595 1.895 y 2.998 n ∆Free Cl2 (mg/L) vs Temp (°C) bl -0.319 1.781 1.895 n 2.998 n Temp (°C) (OPAQ) vs Avg UV Rad (mW/cm2) 0.786 6.732 1.701 y 2.467 y Temp (°C) (TRANS) vs Avg UV Rad (mW/cm2) 0.934 13.820 1.701 y 2.467 Y y = yes, n = no
174
Table H-4. Full-scale pearsons coefficient and linear correlation values.
Full-Scale Study (n=9) r t* t*(0.05)
Statistical Difference t*(0.01)
Statistical Difference
∆TTHM (µg/L) vs ∆Free Cl2 (mg/L) 0.423 1.237 1.895 n 2.998 n ∆TTHM (µmole/L) vs ∆Free Cl2 (mg/L) 0.431 1.264 1.895 n 2.998 n ∆TTHM' (µg/L) vs Temp (°C) -0.246 0.672 1.895 n 2.998 n ∆TTHM' (µmole/L) vs Temp (°C) -0.250 0.682 1.895 n 2.998 n ∆HAA (µg/L) vs ∆Free Cl2 (mg/L) -0.394 1.134 1.895 n 2.998 n ∆HAA (µmole/L) vs ∆Free Cl2 (mg/L) -0.221 0.599 1.895 n 2.998 n ∆Free Cl2 (mg/L) vs Temp (°C) -0.122 0.325 1.895 n 2.998 n ∆Total Cl2 (mg/L) vs Temp (°C) -0.088 0.233 1.895 n 2.998 n y = yes, n = no
175
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178
BIOGRAPHICAL SKETCH
Heather Fitzpatrick was born March 26, 1980. She and her father and two sisters
moved to Florida when she was 7 years old. She attended the Center for Advanced
Technologies, a magnet high school in St. Petersburg, Florida. After graduating high
school, she went on to receive a bachelor’s degree in Environmental Engineering at the
University of Florida (UF; Gainesville) in 2002. She stayed at UF to pursue a Master of
Engineering degree, also in environmental engineering, giving her the opportunity to
work on this study with Dr. Paul A. Chadik and Gainesville Regional Utilities (GRU).
While pursuing her master’s degree, she married Anthony J. Manganiello, III, in May
2004.