AWWA Chloro Organic Changes Due To WT Pract

AWWA RESEARCH
FOUNDATION
6666 West Quincy Avenue
Denver, Colorado 80235
RESEARCH REPORT
SUBJECT AREA: Water Treatment and Operations
LIBRARY
COPY
PLEASE
RETURN
CHLORO-ORGANIC WATER QUALITY CHANGES
RESULTING FROM MODIFICATION OF
WATER TREATMENT PRACTICES
FINAL REPORT
SEPTEMBER 1986
Prepared for AWWARF by:
Stephen A. Hubbs and G.C. Holdren

Louisville Water Company Water Resources Laboratory
435 South Third Street University of Louisville
Louisville, Kentucky 40202 Louisville, Kentucky 40292
Published by American Water Works Association

DISCLAIMER
This study was funded by the American Water Works Association

Research Foundation (AWWARF). AWWARF assumes no responsibil
ity for the content of the research study reported in this
publication, or for the opinions or statements of fact
expressed in the report. The mention of tradenames for
commercial products does not represent or imply the approval
or endorsement of AWWARF. This report is presented solely
for informational purposes.
Although the research described in this document has been
funded in part by the United States Environmental Protection
Agency through a Cooperative Agreement, CR-811335-01, to
AWWARF, it has not been subjected to Agency review and
therefore does not necessarily reflect the views of the
Agency and no official endorsement should be inferred.
Copyright 1987
by
American Water Works Association Research Foundation
American Water Works Association
Printed in U.S.
ISBN 0-89867-391-7
ii
TABLE OF CONTENTS
List of Tables v
List of Figures ix
Acknowledgements xiii
Preface xiv
CHAPTER I Introduction 1
CHAPTER II Literature Survey 3
CHAPTER III Methods 15
CHAPTER IV Six Cities Survey 25
CHAPTER V TOX and THM Formation Rates 43
CHAPTER VI Pilot Plant Studies 66
CHAPTER VII Conclusions 142
Literature Cited 147

Appendix A: Six Cities Descriptions 152
Appendix B: Reaction Curve Data 169
Appendix C: Operational Data, Pilot Plant 175
iii
LIST OF TABLES PAGE
Table III-l Comparison of observed and expected THM concentrations 19

for EPA quality control standards.
Table IV-1. Six Cities Survey: Water Treatment Techniques. 26
Table IV-2. TOX, TOG, and TTHM Ratios, Annual Averages, Six Cities. 36
Table IV-3. Analysis of TOX, TTHM, TOC and Temperature 39

Correlations, City D.
Table V-l. TOX Temperature Dependence Reaction Model: 51

TOX=(a)+(b) LOG(time).
Table VI-1. Determination of retention times for the contact chambers 73

using fluoride as a tracer.
Table VI-2. Schedule of pilot plant runs 13 to 50. 75
Table VI-3. Influent and effluent temp, for pilot plant Runs 13-55. 86
Table VI-4. Pilot plant turbidity levels. 88
Table VI-5. Pilot plant pH levels. 89
Table VI-6. Pilot plant bacteriological results, SPC. 91
Table VI-7. Pilot plant bacteriological results, total coliforms. 92
Table VI-8. Chlorine residuals in the effluent from the pilot plants 93
and the chlorine dosages.
Table VI-9. Chlorine dioxide dosages and residuals. 95
Table VI-10. Pilot plant TOC concentrations. 97
Table VI-11. Influent TTHM levels for pilot plant runs 13 to 50. 103
Table VI-12. Influent TOX levels for pilot plant 1 Runs 13 to 50. 104
Table VI-13. Two-sample T-test statistical analysis of TTHM data for 106
from Pilot Plant 2.
Table VI-14. Two-sample T-test statistical analysis of TOX data for 107
the effluent from Pilot Plant 2.
Table VI-15. Two-way analysis of variance data for Pilot Plant 2 108
effluents at low temperatures.
Table VI-16. Analysis of variance for changes in TTHM levels 109

(effluent-influent) as a function of
temperature and primary disinfectant.
LIST OF TABLES (continued) PAGE
Table VI-17. Analysis of variance for changes in TOX levels 110

Table VI-18. Analysis of variance for changes in TOC levels 111

Table VI-19. Summary of treatment effects on THM and TOX concentra- 122
tions for the three primary disinfectants investigated.
Table VI-20. Treatment schemes for extended pilot plant Runs 51 to 56. 128
Table Vl-21. Run 51 organics data: PPl=chlorine, PP2=ozone/chlorine. 131
Table VI-22. Run 52 organics data: PP1 = chlorine dioxide, 133

PP2 = ozone/chloramine.

PP2 = ozone/chlorine dioxide.

PP2 = ozone/chlorine dioxide.
Table VI-25. Run 54 organics data: PPl = chloramine, 137

PP2 = chlorine dioxide.
Table VI-26. Run 56 organics data. 138
Table A-l. City A: Finished Water Temperature and pH 153
Table A-2. City A: Organics Data, Six Cities Survey 154
Table A-3. City B: Raw Water Quality 156
Table A-4 City B: Finished Water Temperature, pH, and Chlorine 156
Residual
Table A-5. City B: OrganicsData, Six Cities Survey 157
Table A-6. City C: Raw Water Quality 159
Table A-7. City C: Finished Water Temperature, pH, and Chlorine 159
Residual
Table A-8. City C: Organics Data 160
Table A-9 City D: Raw Water Quality 162
Table A-10 City D: Finished Water Temperature, pH, and Chlorine 162
Residual
vi
LIST OF TABLES ( continued) PAGE
Table A-ll. City D: Organics Data: Six Cities Survey 163
Table A-12. City E: Raw Water Quality 164
Table A-13. City E: Organics Data: Six Cities Survey 165
Table A-14. City F: Finished Water Temperature and pH Data 167
Table A-15. City E: Organics Data: Six Cities Survey 168
Table B-l. Reaction Curve Data: Curve #1 through #30 171
Table C-l. Run #51,. Operational Data 175

Table C-2. Run #52, Operational Data 176
vil
LIST OF FIGURES PAGE
Figure III-l, Value of TTHM standards (October, 1984 through 18

July, 1985.)
Figure III-2. Apparatus for Chlorine Dioxide Generation 21
Figure IV-1. Six Cities Survey, Raw Water TOX Values 28
Figure IV-2. Six Cities Survey, Raw Water TTHM Values 29
Figure IV-3. Six Cities Survey, Raw Water TOC Values 31
Figure IV-4. Six Cities Survey, Finished Water TOX Values 32
Figure IV-5. Six Cities Survey, Finished Water TTHM Values 33
Figure IV-6. Six Cities Survey, Finished Water TOC Values 35
Figure IV-7. Six Cities Survey, TOX vs TTHM, City D 40
Figure IV-8. Six Cities Survey, TOX vs Temperature, City D 41
Figure IV-9. Six Cities Survey, TTHM vs Temperature, City D 42
Figure V-l. TOX Reaction Curve #2: Free Chlorine 46
Figure V-2. TOX Reaction Curve #3, #4, #5: Free Chlorine, pH 7.2 - 7.4 47
Figure V-3. TOX Reaction Curves #14, #20, #26: Free Chlorine, pH 6.5 48
Figure V-4. TOX Reaction Curves #13, #19, #25: Free Chlorine, pH 8.5 49
Figure V-5. TOX Reaction Curves #13, #14, #19, #20, #25, #26, Semi-Log 50
Plot: Free Chlorine
Figure V-6. THM Reaction Curves #13, #14, #19, #20, #25, #26 Free 52
Chlorine
Figure V-7. TOX Reaction Curves #6, #7, #8: C102, pH 7.4 54
Figure V-8. TOX Reaction Curve #16, #22, #28: C102, pH 6.5 55
Figure V-9. TOX Reaction Curve #15, #21,#27: C102, pH 8.5 56
Figure V-10. TOX Reaction Curve #18, #24, #30: NH2C1, pH 6.5 58
Figure V-ll. TOX Reaction Curve #17, #23, #29: NH2C1, pH 8.5 59
Figure V-12. TOX Reaction Curves, Pre-Ozone, Free Chlorine, 63

Semi-Log Plot
ix
LIST OF FIGURES (continued) PAGE
Figure V-13. THM Reaction Curve, Pre-Ozone, Free Chlorine, 64

Semi-Log Plot
Figure VI-1. Layout of pilot plant system. 67
Figure VI-2. Mixing tank for pilot plant system. 68
Figure VI-3. Plate settler for pilot plant system. 70
Figure VI-4. Ozone contactor for pilot plant system. 71
Figure VI-5. Pilot plant configuration, Run 51. 76
Figure VI-11. Effluent TTHM levels for Pilot Plant 1. 99
Figure VI-12. Effluent TTHM levels for Pilot Plant 2. 100
Figure VI-13. Effluent TOX levels for Pilot Plant 1. 101
Figure VI-14. Effluent TOX levels for Pilot Plant 2. 102
Figure VI-15. Scatterplot showing the effects of temperature on 118

TTHM concentrations following disinfection with chlorine.
Figure VI-16. Scatterplot showing the effects of temperature on 119

TTHM concentrations following disinfection with chloramines.
Figure VI-17. Scatterplot showing the effects of temperature on TTHM 120

concentrations following disinfection with chlorine dioxide.
Figure VI-18. Scatterplot showing the effects of temperature on TOX 123

concentrations following disinfection with chlorine.

concentrations following disinfection with chloramines.
x
LIST OF FIGURES (continued) PAGE

concentrations following disinfection with chlorine
dioxide.
Figure VI-21. TOX values for extended pilot plant Runs 51, 52, 53, 55. 129
Figure VI-22. THM values for extended pilot plant Runs 51, 52, 53, 55. 130
Figure VI-23. TOX values for extended pilot plant Run 56. 139
Figure VI-24. THM values for extended pilot plant Run 56. 140
xi
FOREWORD
This report is part of the on-going research program of the AWWA Research
Foundation. The research described in the following pages was funded by
the Foundation in behalf of its members and subscribers in particular and
the water supply industry in general. Selected for funding by AWWARF's
Board of Trustees, the project was identified as a practical, priority need
of the industry. It is hoped that this publication will receive wide and
serious attention and that its findings, conclusions, and recommendations
will be applied in communities throughout the United States and Canada.
The Research Foundation was created by the water supply industry as its
center for cooperative research and development. The Foundation itself
does not conduct research; it functions as a planning and management
agency, awarding contracts to other institutions, such as water utilities,
universities, engineering firms, and other organizations. The scientific
and technical expertise of the staff is further enhanced by industry
volunteers who serve on Project Advisory Committees and on other standing
committees and councils." An extensive planning process involves many
hundreds of water professionals in the important task of keeping the
Foundation's program responsive to the practical, operational needs of
local utilities and to the general research and development needs of a
progressive industry.
All aspects of water supply are served by AWWARF's research agenda:
resources, treatment and operations, distribution and storage, water
quality and analysis, economics and management. The ultimate purpose of
this effort is to assist local water suppliers to provide the highest
possible quality of water, economically and reliably. The Foundation's
Trustees are pleased to offer this publication as contribution toward that
end.
The drinking water industry became aware of the presence of organic chlori-
nation by-products, including trihalomethanes in the mid-1970s. It was
generally believed that a reduction in the THM level would result in an
overall reduction in chloro-organic by-products and an associated improve
ment in water quality. This report presents the findings of a program that
was conducted to assess the actual full-scale implications of changing
water treatment processes to reduce THM levels. Information was collected
from a number of different plants and this evaluation will be of great
practical use to any utility considering similar process modifications.
*ome B. Gilbert Jarp£s F. Manwaring, P.E.

irman, Board of Trustees rxecutive Director
'AWWA Research Foundation AWWA Research Foundation
xli
ACKNOWLEDGEMENTS
This project was a cooperative effort between the Louisville Water Company
and the University of Louisville. A special acknowledgement is given to the
students who participated in this project: Matthew Alvey (pilot plant
operation), David Haas (oxidant work), Thomas Nolan (reaction curve work), and
James Smith (Ames Testing). Without their dedicated efforts this project could
not have been completed.
The five water utilities participating with the Louisville Water Company
in this project are also gratefully acknowledged for their cooperation in this
study: Bowling Green Municipal Utilities, Bowling Green, Kentucky; Cincinnati
Water Works, Cincinnati, Ohio; Seattle Water Department, Seattle, Washington;
Bay City Metro Water Treatment Plant, Bay City, Michigan; and Memphis Light,
Gas, and Water, Memphis, Tennessee.
The guidance of the Project Advisory Committee is acknowledged with
appreciation for the hours of review and assistance provided in producing
the final report: Michael McGuire, Alan Stevens, and Richard Valentine.
Financial support for this Project was provided by the American Water
Works Research Foundation, through a grant with EPA. The guidance and
patience of the Project Officer, Nancy McTigue, is sincerely appreciated.
xiii
PREFACE
This report addresses the topic of TOX and THM formation in water
treatment plants. Emphasis has been placed on performing this research under
real world conditions as might be expected in operating water treatment plants.
Chapters 1, 2, and 3 contain information which pertain to the entire project.
Chapter 4 details results of a survey of six cities for TOX and THM levels.
Chapter 5 includes research into reaction conditions affecting the formation of
TOX. Chapter 6 describes results from pilot plant experiments on selected
treatment techniques.
Not included in this report are the results of Ames Mutagenicity Testing
which was performed on the final experiments with the pilot plant. These data
may be found in the Masters of Engineering Thesis of James C. Smith, from the
University of Louisville, entitled "The Effect of Alternate Disinfectants On
Direct-Acting Mutagen Formation in the Preparation of Drinking Water" (1986).
This work was not included in the scope of work as defined in the funded
portion of the Project.
xiv
I. INTRODUCTION
The discovery of trihalomethanes (THM) in drinking water during the mid
1970"s awakened the drinking water industry to the problems of chlorinated
disinfection by-products. Efforts were focused on understanding the THM
reaction and developing treatment schemes for minimizing THM formation. These
efforts have been successful in identifying reaction conditions which affect
THM formation, and in executing THM control programs, which have significantly
reduced THM concentrations in finished water across the nation.
Previous research has indicated that THMs typically account for only 10%
to 20% of all chlorinated reaction products. The remaining by-products include
a large number of largely unidentified chlorinated organic compounds whose
health significance is unknown. These products are classified under a general
parameter known as Total Organic Halogen (TOX), which includes all carbon
absorbable halogenated organics.
The goal of this project was to define treatment techniques effective in
reducing both the level of TOX and THM in finished water delivered at the
customer's tap. The proiect was divided into three major tasks: 1) A survey of
six water utilities to determine typical TOX values expected across one year;
2) a study of reaction conditions affecting the THM and TOX levels generated by
various disinfectants; and 3) the development of treatment schemes effective in
reducing THM and TOX levels, using pilot plant data. Each task was conducted
simultaneously, with developing trends in each task utilized in later
experimentation.
The six cities survey focused on water supplies employing widely varying
water sources and treatment techniques. Samples were collected at a point
where the water entered the distribution system. The six cities were widely
1
distributed across the nation representing river supplies, groundwater
supplies, and mountain reservoir supplies. Samples were collected by personnel
from the participating utilities.
The research into reaction characteristics of the various oxidants with
naturally-occurring organics was conducted on Ohio River water receiving
various levels of treatment. This work was conducted over a period of 14
months, representing a wide range of water quality variations at one source.
Although this work was conducted in bench-scale batch investigations, efforts
were taken to utilize experimental conditions that would yield data
representative of real-world conditions.
Treatment techniques were tested in a pilot plant system involving two
identical treatment trains (Pilot Plant 1 and Pilot Plant 2). Throughout most
of the project, Pilot Plant 1 was utilized as a control, treating water with
conventional coagulation and free chlorination. Pilot Plant 2 was utilized as
the variable unit, evaluating alternate disinfectants (chlorine dioxide,
chloramine, and ozone) and variable reaction conditions (reaction times,
temperature, and pH.). As with the previous task, efforts were made to maintain
conditions as close as possible to real-world conditions.
This report has been divided into 7 chapters. Chapters I, II, and III
(Introduction, Literature Survey, and Analytical Methods) contain information
common to the entire project. Chapter IV contains information and data for the
six cities survey; Chapter V, the TOX/THM reaction study; and Chapter VI, the
pilot plant work on treatment schemes. Major conclusions of the project are
summarized in Chapter VII. Raw data for the six cities survey has been
included in Appendix A. Appendix B contains the raw data from research into
the reaction characteristics of the various oxidants. Raw data from the pilot
plant work is included in Appendix C.

II. LITERATURE SURVEY
A literature survey was conducted to evaluate previous investigations of
total organic halogens (TOX) in water supplies. The computer search facilities
at the University of Louisville were utilized for the survey. The following
data bases were examined and found to provide pertinent citations on the
formation and/or analysis of TOX: ENVIROLINE, 1970-1984 (EIC, Inc.), CA SEARCH,
1977-1979, 1982-1984 (American Chemical Society), and WATERNET, 1971-1984
(American Water Works Association). In addition, a manual search of Selected
Water Resources Abstracts and various water-related journals was made to obtain
more recent publications and information from sources not covered by the
computer search. Information in the literature has also been supplemented with
personal interviews with R. Kent Sorrell and other personnel familiar with TOX
at the U. S. Environmental Protection Agency in Cincinnati, Ohio.
Current information on TOX appears to be largely concerned with analytical
methodology, although there are a few notable exceptions. For this reason, some
information on the trihalomethanes (THM's), a ubiquitous and well-studied
fraction of TOX in chlorinated water supplies, has been included.
THM FORMATION
The National Organics Reconnaissance Survey (NORS) found that all water
supplies utilizing chlorine as a disinfectant contained THM's (Arguello et al.,
1979). The four THM's that predominate when water containing organic precursors
is chlorinated are chloroform (CHC1 ), dichlorobromoraethane (CHC1 Br),
dibromochloromethane (CHBr Cl), and bromoforra (CHBr~) (Blanck, 1979).
The types and quantities of organic precursors in water influence the
amount of THM's produced (Arguello et al., 1979). It has been demonstrated that
trihaloraethane precursors include humic and fulvic materials and nitrogenous

organic compounds (Rook, 1976; Hoehn et al., 1979; Sacks, 1984). Hoehn et al.
(1979) found that extracellular products produced from green and blue-green
algae yield, upon chlorination, as much chloroform per unit organic carbon as
humic and fulvic acids. Other THM precursors include phenols and aromatic
amines, when pH is high, and some aliphatic carbonyl compounds (Arguello et al.,
1979). Arguello et al. (1979) listed THM production rates for a number of
different organic compounds.
Observations of seasonal trends indicate THM production increases at higher
temperatures (Arguello et al., 1979; Brett and Calverly, 1979; Young and Singer,
1979; Oliver and Visser, 1980; Veenstra and Schnoor, 1980; Otson et al., 1981,
and Singer et al., 1981). Lower THM production during the winter months was
attributed to lower precursor concentrations in the raw water (Young and Singer,
1979; and Singer et al., 1981). Singer et al. (1981) also attribute the lower
THM concentrations during the winter months to slower reaction kinetics. Higher
THM concentrations at warmer temperatures were attributed to higher THM
precursor concentrations in the raw waters (Veenstra and Schoor, 1980).
Kavanaugh et al. (1980) developed a model that indicated the rate constant for
THM formation doubled for every 10 C increase in temperature over the
range of 10 to 30 C.
An increase in THM production with increasing pH has been noted by
numerous investigators (Rook, 1976; Stevens et al., 1976; Oliver and Lawrence,
1979; Kavanaugh et al., 1980; Oliver and Schindler, 1980; Peters et al., 1980).
The THM formation model developed by Kavanaugh et al. (1980) predicted that the
rate constant for THM formation would triple for each unit pH increase over the
pH range of 6 to 9.
Urano et al. (1983) examined the effects of humic acid concentrations,
chlorine dose, pH, and temperature on THM formation. Concentrations of THM's
increased rapidly in the initial few hours after chlorination and continued to
increase slowly for least 100 hr. Concentrations of THM's also increased with
increases in humic acid concentrations, chlorine dose, pH, and temperature. An
empirical equation predicting THM concentrations as a function of these various
factors was presented.
THM REDUCTION
Alterations in water treatment processes have been proposed to control or
reduce THM concentrations in drinking water. These alternatives include
pretreatment of raw water to reduce the amount of THM precursors, removal of
THM's after their formation, and the use of alternative disinfectants that would
not generate THM's. Alternative disinfectants examined for this purpose have
included inorganic chloramine compounds, chlorine dioxide, and ozone (Ward et
al., 1984). Changing the point of chlorination in the treatment system has been
found effective in reducing THM's (Blanck, 1979). Stevens et al. (1985)
conducted an extensive survey on the effects of different disinfectants on THM
formation. They found that the use of chloramines reduced THM formation by more
than 95% compared to disinfection using chlorine, and the use of chlorine
dioxide as a disinfectant completely eliminated THM formation.
Reed (1983) compared the effects of pre-disinfection by free chlorine to
pre-disinfection by chloramines by operating two pilot plants, each with a
capacity of 2.5 gpm, in parallel as continuous-flow systems. The pilot plants
provided alum coagulation, sedimentation, filtration, and carbon adsorption.
Results indicated THM levels (less than 2 ug/L) in the pilot plant
prechlorinated with chloramine were much lower than THM levels (approximately
10-50 ug/L) in the unit prechlorinated with free chlorine. Prechlorination with
chloramine was more consistent in controlling bacterial levels, as indicated by
standard plate counts, while the two treatments were equally effective in
removing THMP's.
TOX FORMATION
Recent evidence indicates other halogenated organics, in addition to THM's,
are present in water supplies and are of potential concern. Christman et al.
(1983) found trichloroacetic acid levels exceeded CHC1- levels in samples
prepared from humic and fulvic acids isolated from Black Lake, North Carolina.
Although CHC1 is the primary constituent of THM's (U. S. EPA, 1978), it may
represent only a small fraction of the total amount of chlorinated organic
compounds formed during water treatment processes (Fleischacker and Randtke,
1983). The analysis of TOX provides water plant chemists with a surrogate
measurement to evaluate the importance of halogenated organics in drinking water
(Dressman and Stevens, 1983).
Sources of TOX in finished drinking water include both naturally occurring
and man-made TOX in the raw water source and TOX formed from chlorination during
the purification process. By analogy to THM, it is assumed that TOX formation
can be influenced by pH, temperature, precursor concentration and composition,
and by the method of disinfection. Temperature and type of precursor affect TOX
formation but are largely determined by the choice of raw water, although
riverbank infiltration or similar treatment processes may have some beneficial
effects (Sontheimer, 1979a).
CONTROL OF TOX
Fleischacker and Randtke (1983) found that process modifications leading to
THM reductions did not always lead to reduction in Total Organic Chloride (TOC1)
and Non-Purgeable Organic Chloride (NPOC1), indicating that both THM and TOX
must be monitored to have an optimal treatment scheme. In contrast to THM
formation, a decrease in pH was found to increase NPOC1 concentrations in
samples dosed with free chlorine or with combined chlorine (Fleischacker and
Randtke, 1983). The NPOC1 concentration in a peat fulvic acid sample dosed with
free chlorine increased from about 400 to 1400 ug Cl/L as the pH was decreased
from 11 to 3. Dosage with combined chlorine resulted in an increase from 0 to
about 400 ug/L over the same pH range. Stevens et al. (1985) also studied
relationships between non-purgeable organic halides (NPOX) and pH. They found
that NPOX levels decreased with an increase in pH over the range of pH 4.7 to
11.5. A decrease was also noted when C10? or chloramine was used as the
disinfectant. Amounts of CHC1 increased at all pH levels when temperature
was increased, and NPOX increased with temperature at low pH. At levels higher
than pH 7, no increase in NPOX with temperature was noted. This pH dependence
may present particular problems for water treatment plant operators because of
the previously noted increase in THM with pH.
Fleischacker and Randtke (1983) reported that NPOC1 concentrations
increased with temperature. NPOC1 levels ranged from 513 ug Cl /L at 3
C to 665 ug C1~/L at 20 C. Fleischacker and Randtke also
noted a linear relationship between NPOC1 production and precursor (total
organic carbon) concentrations. Changes in the rate of TOX formation with
temperature were also noted by Dressman and Stevens (1983). Stevens et al.
(1985) found that NPOX levels increased with temperature at low pH but, at pH
greater than 7, the increase in NPOX with temperature was not evident. In
contrast, chloroform amounts increased at all pH values when temperature was
increased. Wachter and Andelman (1984) found that decreases in temperature and
contact time decreased the generation of purgeable (POX), nonpurgeable (NPOX),
and total (TOX) organic halide during chlorination of algal extracellular
products. Decreases in pH increased NPOX levels, but reduced POX and CHC1,
formation.
The precursor source and chlorine dosage, either free or combined, were
shown to affect concentrations of both CHC1 and NPOC1 (Fleischacker and

Randtke, 1983). The formation of CHC1- and NPOC1 were not linear functions
of chlorine dosage; however, chlorine dosage may strongly influence the yield of
one precursor source relative to another.
ALTERNATIVE DISINFECTANTS
The method of disinfection has been reported to have major effects on THM
and TOX formation. Chlorination is the most widely-used method of disinfection
because it has been proven to be effective in killing pathogens in drinking
water. Unfortunately, free chlorine residuals also contribute to the formation
of THM's.
Ozone, chlorine dioxide, and chloramines have also been used as
disinfectants and are currently being examined in an attempt to reduce the
formation of THM's and TOX. Stevens et al. (1985) studied the effects of
chlorine, chloramine, and CIO- on TOX formation. They found that NPOX
formation was reduced by 85% when using chloramine as the disinfectant instead
of chlorine, and reductions with C10_ were even greater. TOX formation
decreased with an increase in pH when chloramines or chlorine dioxide were used
as disinfectants.
Ozone
Some advantages and disadvantages of using ozone were discussed by Gulp and
Gulp (1974) and Sontheimer (1979b). Ozone has a high germicidal effectiveness,
even against resistant organisms, and the time required for disinfection is
short. Ozone is able to ameliorate many problems of odor, taste, and color in
water supplies, without requiring additional commercial chemicals for treatment.
Upon decomposition, the only residual of the oxidant is dissolved oxygen,
although other organic by-products may be formed as a result of the partial
oxidation of the organic matter in the raw water. Other advantages of ozone
8
treatment include the transformation of resistant substances into biodegradable
substances (Sontheimer, 1979b), and the fact that the potency of ozone is
unaffected by ammonia content (Gulp and Gulp, 1974).
Some disadvantages are encountered when ozone is used as a disinfectant
(Gulp and Gulp, 1974; Sontheimer, 1979b). Because ozone is produced
electrically as it is needed, it cannot be stored and there are additional
investment and operating costs involved with its use. The presence of organic
substances in water results in a high consumption of ozone, making it difficult
to adjust treatment to variations in load. Another problem encountered with the
use of ozone as a disinfectant is increased germ formation in the distribution
network because ozone leaves no residual. In addition, a recent study by Hoigne
et al. (1985) indicated that ozone reacts with a number of inorganic molecules,
including chlorine, chlorine dioxide, and chloramines, and these reactions may
present difficulties when ozone is used in conjunction with other disinfectants.
For most cases, an ozone residual of 0.1 mg/L for 5 minutes is adequate to
disinfect a water low in organics and free of suspended material (Hann, 1956).
Ozone concentrations of 0.5 to 4.0 mg/L are usually used in water disinfection
applications (Rosen, 1972).
In a study using ozone and ultraviolet radiation as alternatives to
chlorine for disinfection in small community water systems, Witherell et al.
(1979) found that both ozone and ultraviolet light were inferior to chlorination
from the standpoint of operation and maintenance requirements and maintaining
disinfection in the distribution system.
Robertson and Oda (1983) investigated the application of ozone as the
primary disinfectant to reduce elevated levels of THM's in Ontario water
supplies containing high concentrations of dissolved organic carbon. Their
pilot plant studies showed that pre-ozonation, coupled with controlled use of
post-chlorination, led to significant reductions in both THM's and non-purgeable

organo-halogenated (NPOX) compounds.
Reckhow and Singer (1983) examined the removal of organic halide precursors
by pre-ozonation and by alum coagulation. Ozonation with natural bicarbonate
levels at pH 7 removed THM's, TOX, trichloroacetic acid, and dichloro-
acetonitrile precursors. Love et al. (1976) treated tap water containing THM's
with ozone for 4 to 5 minutes at ozone concentrations as high as 25 mg/L and
found that this treatment did not oxidize the THM's present.
Neukrug et al. (1983) presented results from a 3 year pilot-scale
investigation of advanced water treatment systems conducted on Delaware River
water in Philadelphia. Ozonation affected organic levels in drinking water
through mechanisms of oxidation and volatilization. As a pretreatment to GAC,
Ozonation decreased organic loads applied to the GAC bed, increased organic
biodegradability, and provided for viral and bacterial disinfection without
producing chlorinated by-products. Their findings also indicated that the cost
of preozonation was not sufficiently offset by lower GAC operating costs when
removal of volatile halogenated organic compounds is the criterion controlling
GAC service life.
Hoigne and Bader (1983a; 1983b) and Hoigne et al. (1985) performed
extensive studies on reactions of ozone with organic and inorganic compounds in
water. All direct reactions of dissolved ozone with test solutes were found to
be first order in both ozone and solute concentrations. Most non-dissociating
solutes, such as aliphatic alcohols, olefins, chlorosubstituted ethylenes,
substituted benzenes and carbohydrates, were found to be either highly reactive
or highly inert to ozone at concentrations practical for water treatment
Ozonation (Hoigne and Bader, 1983a). Ozonation rates of organic acids and bases
increased with the degree of dissociation of the protonated species, indicating
pH is in important factor in the ozonation of these species (Hoigne and Bader,
1983b).
10
Rice and Miller (1985) also studied the reactions of ozone with organic
compounds in water. They found that the oxidation of individual organic
compounds in water usually produced new compounds with a lower molecular weight
and higher oxygen content than the original compounds present. These oxidation
products usually react more slowly with other disinfectants than the original
organic compounds.
Chlorine Dioxide
Chlorine dioxide is being investigated as an alternate disinfectant for
drinking water, primarily because it produces significantly lower levels of
chlorinated by-products, both volatile and non-volatile, than chlorine.
Chlorine dioxide is a more efficient disinfectant than chlorine, especially
against viruses, and preserves a high residual in the distribution system.
Disinfection is not dependent on pH because chlorine dioxide does not react with
water (Rav-Acha, 1984). Chlorine dioxide has the potential for reducing the
need for chlorination, oxidizing organic compounds, and eliminating bacteria
(Masschelein, 1979b).
Chlorine dioxide can explode in the presence of bright light or subsequent
shocks. It can also be explosive by reacting with rubber, cork, other organic
products, sulfur or mercury (Masschelein, 1979a). Thus, care must be taken
during its generation and application. Although taste and odor problems are
usually reduced with chlorine dioxide, the maximum residual concentration
releasing no objectionable taste or odor is 0.4 to 0.5 mg/L (Masschelein,
1979a). One of the major weaknesses of chlorine dioxide is that about 50% of it
is converted to chlorite, an undesirable by-product, upon reaction with aquatic
organics (Rav-Acha, 1984). Other undesireable by-products, including chlorite
and hypochlorite, may also be produced (Gordon and Ikeda, 1984).
In a laboratory study on the use of chlorine dioxide for use as a
11
wastewater disinfectant, Roberts et al. (1981) found that, for a given contact
time, the residual required to achieve a given fractional kill of coliforms was
2 to 70 times lower for chlorine dioxide than for chlorine. Chlorine dioxide
was found to be 2 to 5 times as expensive as chlorine for disinfection, but it
formed much lower quanities of halogenated by-products and was more effective in
inactivation of viruses than chlorine. Studies carried out with municipal
secondary effluent (Aieta et al., 1979) indicated that chlorine dioxide is also
a promising candidate to replace chlorine in wastewater disinfection.
A study carried out at the Louisville Water Company, Louisville, Kentucky
(Hubbs et al., 1980), compared the effectiveness of a chlorine-chloramine
process with a chlorine dioxide-chloramination and found a decrease in THM
concentrations in the finished water with the use of the chlorine
dioxide-chloramination process. This process also produced acceptable
finished-water bacterial quality, but it showed an increase in Standard Plate
Counts.
Most studies have indicated chlorine dioxide produces lower levels of THM's
than chlorine, but a recent report by Lin et al. (1984) showed increased THM
production for some model compounds, primarily substituted benzoic acids. They
found that 2,4- and 3,5-dihydroxybenzoic acids, 2,4,6-trihydroxybenzoic acid,
and 3,5-dimethoxybenzoic acid produced higher levels of THM's when treated with
chlorine dioxide. The enhancement was postulated to be the result of a chlorine
dioxide-mediated decarboxylation and subsequent degradation pathway. Chlorine
dioxide was also found to react with several heterocyclic compounds found in the
environment, but produced predominantly oxygenation products (Lin and Carlson,
1984). In contrast chlorination resulted in products incorporating both
chlorine and oxygen into the molecule, while chloramines were largely unreactive
at pH's greater than 5.
12
Chloramines
Chlorine in the presence of ammonia or other nitrogenous material produces
a mixture of chloramines. They exist in various proportions depending on the
relative rates of formation of monochloramine and dichloramine, which change
with the relative concentrations of chlorine and ammonia, as well as with pH and
temperature. Above pH 9.0, chloramines exist almost exclusively as
monochioramine; at pH 6.5 there are equal amounts of monochloramine and
dichloramine; dichloramines are predominant below pH 6.5; and trichloramines
exist below pH 4.5 (Culp and Gulp, 1974).
Wolfe et al. (1984) reviewed the use of chloramines in the disinfection of
drinking water. Chloramination was first suggested as a disinfectant for water
supplies in the early 1900's and reached wide-spread popularity in the 1930's.
There is currently a renewed interest in chloramination because chloramines
appear to produce fewer chlorinated by-products than chlorine, produce stable
residuals in distribution systes, and reduce some of the odor problems caused by
chlorine.
There are several disadvantages involved with the use of chloramines,
including reductions in disinfection caused by the preferential reactions of
chlorine and certain nitrogenous organics. Chloramines are less effective than
chlorine for inactivating bacteria, viruses, and protozoans, with inactivation
highly dependent on solution pH, temperature, and contact time (Wolfe et al.,
1984). In addition, low levels of chloramines are acutely toxic to some aquatic
organisms, are weakly mutagenic, and have been shown to produce raethemoglobin in
hemodialysis patients. It should be noted that treatment of a water supply with
chloramines resulted in less mutagenic activity, as determined by the Ames
Salmonella test, than treatment with chlorine (Cheh et al., 1980).
In Huron, South Dakota, chloramines were found to maintain the water
quality and reduce THM levels while improving the taste and odor characteristics
13
of the water. Chloramines offered a relatively inexpensive method for
alternative disinfection to the use of free chlorine (Norman et al., 1980).
In an investigation using a pilot plant system by the Metropolitan Water
District of Southern California, Means et al. (1983) found that the point of
application of chlorine and ammonia affected the extent of THM formation. The
application point did not appear to affect the occurrence of coliform bacteria
in the effluent from the pilot plant; the coliforms were uniformly absent.
Means et al. concluded that chloramination significantly reduced THM's and, with
long contact times, provided disinfection equivalent to that observed with free
chlorine.
Engelbrecht and Severin (1982) discussed the use of alternative
disinfectants and concluded that hypochlorite ion and chloramines are the least
effective against viruses. The use of chloramine to provide a residual
following pre-ozonation virtually eliminated the formation of THM's and NPOX
(Robertson and Oda, 1983).
14
III. METHODS
ANALYTICAL PROCEDURES
TOC, THM, and bacteriological samples were analyzed by trained personnel
at the Louisville Water Company. TOX samples and all routine analyses,
including turbidity, pH, and temperature, were performed by project personnel.
The influent to the pilot plants was analyzed for TOX, TOC, pH,
temperature, and turbidity once per day. Bacteriological results for the
influent were obtained by using the results for the daily settled water sample
taken at the Crescent Hill Filter Plant. THM levels in the influent to the
pilot plants was estimated to be that of the previous day's raw water sample
taken at the Crescent Hill Filter Plant.
The effluent from each pilot plant was analyzed for the disinfectant
concentration, in addition to THM, TOC, TOX, duplicate bacteriological samples,
pH, and turbidity for every run. Bacteriological samples were taken from PP1
only once per day since the disinfectant feed remained constant and the chlorine
demand was not expected to vary much over the day. Temperature of the effluent
of the two plants was taken once per day. All samples were collected by the
graduate assistants involved with this project. Bacteriological samples were
analyzed by certified bacteriologists for the following parameters according the
procedures listed in Standard Methods (1981): Heterotrophic Plate Count
(formerly known as Standard Plate Count), Method Number 907, and MFT (membrane
filter technique) total coliform, Method Number 909A, using M-Endo broth and
M-Endo agar L.E.S. (Lawrence Experimental Station).
The levels of THM's in the samples taken frpm the effluent were measured by
liquid-liquid extraction gas chromatography (U. S. EPA, 1978; 1979). Analyses
were made on a Hewlett Packard Model 5710A gas chromatograph equipped with a six
foot squalene column (isothermal, 70 "C) and an electron capture detector.
The THM's were generally low in the influent samples. For these values, the
15
purge and trap technique (Bellar and Lichtenberg, 1974; U. S. EPA, 1978; 1979)
was used. A Hewlett Packard Model 5840A gas chromatograph equipped with a
twelve foot carbowax column was used in conjunction with a Tekmar Purge and Trap
Concentrator LSC-3 for these analyses. The LSC-3 was temperature programmed as
follows: the sample was purged for 16 minutes onto a Tenax trap; the trap was
heated to 180 C for 4 minutes; following desorption onto the column, the
temperature was set for 4 minutes at 60 C; an increase in temperature of
6 "C/minute followed until the final temperature of 160 C was
reached; and the final temperature was maintained for 20 minutes at 160
C. A Coulson detector was used.
Quality control on the gas chromatograph (Model 5710A) was achieved
through: (1) checking a commercial standard (Supelco Reference Standard for
Trihalomethanes) prepared by the GC operator daily, (2) running a duplicate on
the Crescent Hill finished water daily, and (3) checking the percent recovery of
a spike. In all cases an upper and lower control limit was set by the following
equations:
UCL = P + 3(SD) (1)
LCL = P - 3(SD) (2)
where, UCL = upper control limit
LCL = lower control limit
P = mean value
SD = standard deviation.
The standard contained six compounds, including the four trihalomethanes of
interest.. The mean TTHM value for the 153 runs for the reference TTHM standard
anlayzed for this project was 37.94 +_ 3.29 ug/L (relative standard deviation =
8.7%), compared to the listed value of 37.00 ug/L. The standard value as a
16
function of time is shown in Figure III-l, and shows no discernible changes
occurred in TTHM analyses over the course of the project.
In addition, the quality control included a quarterly analysis of the four
THM's of interest. Blanks were spiked with various known concentrations of the
THM's. The actual value obtained was plotted versus the expected value and a
best fit line was obtained using a linear regression analysis. The correlation
coefficients for the data obtained were always greater than 0.99, indicating the
response of the GC was linear over the range of concentrations (17 to 240 ug/L)
tested.
Weekly quality assurance analyses were performed for the purge and trap gas
chromatographic method using a prepared standard consisting of 17 different
compounds, including the four THM's of interest. Quality control samples

obtained from the U. S. EPA, Cincinnati, Ohio, were used as an additional check
on the accuracy of the standardization procedure at low TTHM concentrations, and
on the reproducibility of results between analysts. Results obtained for
chloroform, the only THM present in most of the samples analyzed, agreed with
expected values to within 1 ug/L for each of the THM's analyzed at low
concentrations, and to within 8 ug/L at higher concentrations (Table III-l).
TOC measurements were made with a Dohrmann analyzer (Model DC 50/54). This
instrument was standardized daily with a spiked carbon sample and operated
according to procedures outlined by Dohrmann Envirotech (1978). Results should

be accurate within 2% or 0.01 mg TOC/L (Dohrmann Envirotech, 1978).
TOX measurements were made with a Xertex/Dohrmann Model MC-1 DX-20 Total
Organic Halide Analyzer following methods outlined by Dohrman Division, Xertex
Corporation (1984). Samples (500 mL) were collected for analysis and
pre-treated with 0.5 mL of 0.1 bl sodium sulfite and 1 mL of reagent grade nitric
acid. Samples were passed through columns packed with Calgon Type F400 granular
activated carbon (GAG) that had been prepared by grinding in a mortar and pestal
17
FIGURE m-1. VALUE OF TTHM STANDARDS
(OCTOBBR 1964 - AUGUST 1986)
60
70 -
50 -
f 40 -
30 -
20 -
10 -
" IIIIIMIIIIII!
OCT84 MAY 66 AUG66

DATE
18
Table III-l. Comparison of observed and expected THM concentrations
for ERA quality control standards.
Sample Number Parameter Experimental Value True Value
ug/L
WS016 Chloroform 7.44 7.55
41.46 45.3
Bromodichloromethane 11.49 12.5

61.46 53.2
43.74 38.6
Dibromochl orome thane 14.72 12.9
Bromoform 15.65 16.9

69.50 67.5
Total trihalomethane 78.32 75.55

187.1 178.9
WS879 Chloroform 5.21 4.29
Bromodichloromethane 1.21 1.78
Dibromochl oromethane 2.51 2.52
Bromoform 4.35 4.85
Total trihalomethane 13.29 13.44
19
and seived to retain the 100 to 200 mesh fraction. Each column was packed with
approximately 40 mg of carbon. A 100-mL aliquot of the pre-treated water sample
was passed through two consecutive packed columns under 20 psi of pressure
provided by the adsorption module. Each sample was then washed with 2 mL of a
5000 mg/L potassium nitrate (KN03) solution under 5 psi of pressure. The carbon
from each column was transferred immediately after the nitrate wash into the
analyzer chamber. Total organic halide concentrations were then measured using
the microcouloraetric analyzer. A TOX standard containg 500 ng Cl~/uL was
prepared from 2,4,6-trichlorophenol and used to confirm recovery of TOX. A
correction for the reagent blank was made by measuring the TOX content of blank
GAC columns washed with 2 mL of nitrate solution along with each set of samples.
Duplicate samples were analyzed from each sample bottle and the mean of these
values was used as the TOX value in the statistical analyses. Analyses usually
varied by less than 5 ug/L from the mean.
Turbidity was measured using a Hach Turbidimeter (Model 2100A) with
prepared Hach standards. Sample pH was analyzed with an Orion digital
ionanalyzer (Model 801A) with a Ross combination pH electrode (Orion Model
81-55). The pH meter was standardized with two buffers (pH 7.00 and 10.00)
daily. Temperature was measured using a mercury thermometer with readings in
degrees Celsius (0.2 degree increments).
PRODUCTION AND ANALYSIS OF OXIDANTS
Chlorine dioxide (ClO^) was generated by the procedure given in
Standard Methods (1981). Compressed air was passed through glass wool into a
Oxiclear filter, through more glass wool, and then bubbled into 300 mL of
distilled water in an Erlenmeyer flask (1000 mL), labeled A in Figure 1II-2, via
tygon tubing. This air stream was conducted by way of glass tubing into the gas
generating bottle (1 liter, round-bottom, two-neck flask), labeled B in Figure
20
* Bottle C was replaced with a drying column
packed with flaked NaClO2 .
FIGURE HI-2 Chlorine Dioxide Generation & Absorption System
21
III-2, containing 10 g NaCIO- dissolved in 750 mL distilled water. The
glass tubing ended within 5 mm of the bottom of the generating bottle. The
evolved gas was then conducted into a solution containing 37% by volume of
NaCIO (bottle labeled C in Figure III-2). The purpose of this solution was
to convert any free chlorine into CIO,,. The gas was then conducted into a
500-mL borosilicate glass collecting bottle, labeled D in Figure HI-2, filled
with distilled water. A frit was used to produce smaller bubbles to enhance
absorption. An outlet was provided on the gas collecting bottle for the escape
of air. Ground-glass stoppers were used for the two-necked generating flask,
the gas washing bottle, and the collecting bottle. When two pieces of glass
tubing were connected, the two pieces were butted against each other and joined
with a small piece of tygon tubing to minimize exposure to the tubing. Air was
passed through the system to transport the chlorine dioxide. Sulfuric acid
(10%) was added in 5-mL increments to the generating bottle every five minutes
until a total of 20 mL of the acid had been added. The air flow continued for
30 minutes after the last addition of acid. The stock solution of C102 was
stored in a glass-stoppered, foil-wrapped bottle.
Low yields of chlorine dioxide (approximately 500 mg/L) prompted changing to
the use of a drying column (approximately 4" long by 5/8" i.d.) packed with
flaked NaC10 2 . Since the solution of NaCIO used prior to this was not
saturated, it is most likely that chlorine dioxide gas was absorbed in this
bottle. In addition, the following adjustments were made to increase the
concentraion yield of C10 2 (Marco Aieta, Rio Linda Chemical Company,
personal communication): (1) the NaC10 2 concentration in the generating
bottle was increased from 10 g to 20 g per 750 mL of distilled water, (2) the
concentration of the H2 S04 that was added to the generating bottle was
increased from 10% to 20%, (3) approximately 2 g of NaCl were added to the
generating bottle, (4) the collecting bottle's distilled water was chilled, (5)
22
approximately 1 drop of HC1 was added to the collecting bottle, and (6) the
entire generating system was foil wrapped to prevent light contact. The water
in the collecting bottle was chilled and the HC1 was added to this bottle to
help increase the solubility of the C10_ gas. The concentration of the
stock solution and of the residual in the effluent from the contact chamber was
determined by titration with 0.025 _N sodium thiosulfate according to the
procedure listed in Standard Methods (1981). Yields of approximately 1200 mg/L
were achieved by this altered format.
The chlorine that was fed into the pilot plant system was obtained by using
Clorox bleach (5.25% sodium hypochlorite). Chloramines were obtained by adding
NH^Cl prior to the addition of the Clorox bleach. In both cases the DPD
method for the measurement of free chlorine, monochloramine, and dichloramine
was followed (Standard Methods, 1981). Chlorine was fed continuously to
the pilot plants when runs were not being performed in an effort to control the
bacteria growth in the contact chambers.
Ozone was produced by a Welsbach Laboratory Ozonator (Model T-816). Ozone
residuals were determined by titration with 0.005 _N sodium thiosulfate according
to the procedure listed in Standard Methods (1981). The ozone was fed into a
column at the effluent from the plate settlers and prior to the addition of the
disinfectant with countercurrent flow. When ozone was added in addition to one
of the oxidants it was fed as a pre-oxidant.
The amount of ozone absorbed by the process water was determined by
measuring the difference between ozone entering and leaving the column. Ozone
entering the adsorption column was determined by taking an ozone sample directly
from the ozonator sample port. The ozone sample was then diffused through a
30-mm fine frit (the same size as the frit used in the contact chamber) into a
2% (w/v) potassium iodide (KI) solution contained in a 1000-mL graduated
cylinder for a measured amount of time. The solution was acidified with 1 _N
23
sulfuric acid and titrated with a 0.005 N_ sodium thiosulfate solution. The
ozone feed was then calculated from the ratio of the gas flowrates from the
sample port and the adsorption column. Excess ozone was suctioned from the top
of the adsorption column and passed into 2% KI solution through a fine frit, and
the amount of ozone coming from the top of the column was then determined. The
amount of ozone transferred was then calculated by subtracting the ozone
concentration of the gas leaving the top of the adsorption column from the
influent dosage.
Direct measurements of ozone residuals were measured by collecting samples
directly from the ozone contact chamber in a 1000-raL cylinder containing 30 mL
of a 2% KI solution. Sulfuric acid (1 _N) was added immediately and the
sample was then titrated with 0.005 _N sodium thiosulfate. Blanks were analyzed
to check for interferences.
24
IV. SIX CITIES SURVEY
Water utilities from five cities were invited to participate with LWC in a
ten-month sampling program in conjunction with this Project. A cross section
of various raw water sources and treatment techniques were selected in an
attempt to gain knowledge on differing plant-scale operations. Descriptions of
the six water supplies are included in Table IV-1 and in Appendix A.
METHODS
Two 500 mL samples (one raw water, one finished water) were collected each
month from each city from October, 1984 through July, 1985. Amber glass sample
bottles with teflon liners were cleaned with chromic acid, triple rinsed with
distilled water, and then heated to 260 degrees C. After cooling, the bottles
were labeled with the appropriate utility name and water type and then shipped
via UPS.
The individual utilities were instructed by written communication not to
rinse the sample bottles because 5 milligrams of sodium sulfite had been added
to the bottles prior to sampling. Concentrated nitric acid (0.5 mL) was added
after sampling. (Shipping regulations prohibit the transport of concentrated
nitric acid in aircraft.) Samples were returned to Louisville Water Company via
UPS in a styrofoam cooler with freezer packs. The utilities provided
temperature and pH data for each sample.
Upon receipt, the sample containers were placed in storage at 4 degrees C.
At the time of analysis for TOX, the sample bottle was opened and two 75 mL
amber glass vials were immediately filled with the sample and sealed for TOG
and TTHM analysis. TOX analysis was begun immediately in accordance with the
manufacturer's operating procedures. Sample pH and chlorine levels were
25
TABLE IV-1. SURVEY: TREATMENT TECHNIQUES
CITY SOURCE TREATMENT OXIDANT CONTACT TIME

PRIOR TO SAMPLING
surface bay water, pre-ozone,coag/floe/sedimentation, 28 hours after ozonation

influenced by river chlorination,filtration 24 hours after chlorination
surface water, ore-C102,coag/floe/sedimentation 5 hours after pre-C102

small river chlorination,filtration,post 3 hours after chlorination
chlorination
S3
surface water, coag/floe/sedimentation 5 hours after free chlorination
large river chlorination,filtration
D surface water, coag/floe/sedimentation 20 min of free chlorine

large river chlorination/chloramination 8 to 12 hours after chloramination
filtration
groundwater supply coke tray areation, lime 4 to 24 hours after free chlorination
chlorination, filtration
mountain reservoir chlorination, pH control 1 to 7 days after free chlorination

analyzed to insure that the samples had been properly acidified and
dechlorinated. TOX, TOC, and TTHM analyses were performed within three weeks
of sampling.
SIX CITIES RESULTS AND DISCUSSIONS
The results of this survey are graphically displayed in Figures IV-1
through IV-6 and are tabulated in Appendix A. Data that were not appropriate
for comparison were the October finished water samples from cities A, B, and E
(samples not quenched), and the November sample from city C (sample not taken
at the routine sample location). These data points are not displayed in the
Figures but are included in Appendix A.
RAW WATER DATA
Raw water TOX values for the six cities varied from a high of about 30
ugCl-/L to a low of below the detection limit of 5 ugCl-/L (Figure VI-1). The
groundwater supply typically showed no measurable levels of TOX in the raw
water, and the highest raw water TOX values were found in the two large river
water sources of cities C and D. These two cities also showed a seasonal trend
in raw water TOX values directly associated with temperature. Lake supply city
A showed a slight seasonal trend. The small river supply and the mountain
reservoir showed no discernable seasonal trends in raw water TOX levels. Many
of the raw water samples collected during this survey had TOX values at or
below the defined minimum detection level of 5 ugCl-/L TOX, but are included in
the figures for illustrative purposes.
Raw water TTHM values for the six cities were usually below the detection
limit of 0.5 ug/L (Figure VI-2). Detections were sporadic across the entire
database and showed no apparent trends.
27
FIGURE IV-1. SIX CITIES SURVEY
RAW WATER TOX, Oct-Jul 1984-85
32
30 - f
' \
28 _ / V,
7
x S,
26
/ ^ y
24 - /\ '
s ', 7
X /
? 22
' S , / , /\
_ '\ ' ' ' f\
20 t> /\
s / /
' S /\ ' s /\
18 V /\ / / /\
i2h
'S /\ / / fs
0 / X f
16 ' S / \ / V / \ t> V
/ V /X \ ' /\ V /X
3o s/\
14 ~" ~ f
V /\ / \ /• V V f \ V
s /s / s /s \ s / s s /
00 ^
Sf /^ /\ 7 / y
12 k /V / \ / \ X \ s / V /s
/ s, s * /s/s •» ' /\ 's x ' •« s *s ' /s s/s
*
O 10 - V /s / •; /\ / \ X "7 s /\ / s f\ 5;
H ' S /s / s /V / s X s /s /s X / s X
/s X /s /V / - r r X t s
— / ^
/ s i>
8 / V /\ /\ X / s X \ /\ / \ x /\ X
/ X
' S s, X /\ ' /s X / \ X / /V X / /s x •v / s
/ V / \ / \ l_l / s /> V
~
_ V / s X /\ /\ X / V _ K /\ R s N / \ X /s X
6 t V s ^ X / V /s X / X X /\ X s \ / s X /s K
"" /
<\ X /• s / /s / /• / X /s /\ X X /\ ~ X
_ / V S X V X / •v x /s X / S / s X /s
4 V X /\
<\ VX /s/ s, X /V V X /s f^ / V X / / V, X n / V, / X X / \ / V X ' /sXX / V / V. xx
s / s X s x / s -I / V X / V. K /X X / V / s, X / s X
2 V / V X S X /\ 1 / s, X / V X / V. X / V / s, X /\ X
s\ X /\ / s M /s / X f\ X / S X / X /s X
'\ j ^ x S X ;^ ] /^ x y\ x S s. x. /^ /^ x s^ x
0
Oct Nov Dec Jan'85 Feb Mar Apr May Jun Jul
CITIES
r~7i A r\~i E
RAW WATER TTHM, Oct-Jul 1984-85
10
8 -
7 -
6 -
X
5 -
9
v^1
a 4 -
3 -
2 -
CITIES
Raw water TOG levels for the six cities varied irregularly throughout the
year, ranging from 7 mg/L TOC to below 0.5 mg/L TOG (Figure VI-3). No
correlation could be found between raw water TOC values and raw water TOX
values. No seasonal trends for raw water TOC were apparent for any of the
supplies. A significant increase in raw water TOC was observed in the
groundwater supply (city E) in the last two months of the survey. The source
of the high TOC from city E for June and July was undetermined.
FINISHED WATER DATA
All finished water data collected during this survey were taken before the
water was discharged to the distribution systems. Since chlorine contact time
significantly affects the TOX and TTHM levels in finished water, the contact
time between the initial point of chlorination and the finished water sample
point was of great significance in interpreting the results of this survey.
Contact times varied from 3 to 4 hours (Cities B and E) to as long as 168 hours
(City F), as shown in Table IV-1. Data for specific cities should be
interpreted with respect to the chlorine contact time for the finished water
samples. Any comparisons between cities should likewise recognize the
influence of the sample locations on chlorine contact times for each city.
Data for finished water TOX, THM, and TOC from the six cities survey are
found in Figures VI-4, VI-5, and VI-6. Finished water TOX values ranged from
below detection limits (chlorinated groundwater supply) to above 360 ug C1-/L
(large river supply). Typically, values ranged between 50 and 250 ug C1-/L.
Seasonal trends were observed for cities B, C, and D (river supplies), with no
trends observed for cities A, E, and F.
Finished water TTHM data for the six cities indicated a higher degree of
seasonal influence than did any of the other raw and finished water parameters.
30
RAW WATER TOC, Oct-Jul 1984-85
o —
-
7 -
-
6 ~ / \
s
^ ,
s
s
/'
5 - , X
/ s
' ' X /X ' X ^
II ""
, s /\ 7
/ N /s /
4 -/ / / / X \
/ s / V / -
-!> 0 ' i - ' ' s f /s ^ ' X /\ X
u> ~
V ^ , V /V /
_ s s / s /s / \
' ' '- ' /• /X X / \ K
3 -' 7s s , s V \ \
' /X/ / \ \X
' ' /s ^ ' ' /s s ' /s s
, ^s X
/s /X ,_, s /\ _v / \ __ s, /\ \
/x /s /\ /s / s s, \ /s \
/\ / \ /• \ s fX / s / / X X /\ X
2 - /s /X s /\ /N / \ \ \ sV \
/ x / s, /\ / V /s V / X
/\ / >\ / s ' / K\ S \ / s, / X X / \ X X
~
/s K ^/* X s /\ /s X* /\ K X /X X X
s, X
X
ss. /X X
/V s K /\ /s / s *, s
/s / \ X / s *^ /X / V /X /s X /\ X
1 H / s, X /\ /s X /V X S s, /X X X
M /V/V X /V/V X V X / V /XX X s\ X X
- / s, // sV / V, / V X X /V s /X/\
/ V M /s X s /\ /s X /V K \ s /X X X
/ V /X X s /\ /X X /s X S V /X X X
fs x /S X /\ 3 /X / s X /s X /s X / \ X
0 - ——X| X, K X s. s. /^ 1 / s. /^ / X, X
Oct Nov Dec Jan'85 Feb Mar Apr May Jim Jul
CITIES
r~7i A C k^xNl D
FINISHED WATER TOX, Oct-Jul 1984-85
400
7
350 -
300 -i
'
? 250 H
X
« ' X
2 / K X X
' » * X X
•§ 200 H \
, K X X , X ;
A ' _ II K X X 7 ' X \' K
O
/V K X X X / X / X
/s X X X X / X f X
/ \
150 H /s K X X X X /\ X / X
/s * X X X X • -, ' /s X 7\ / ^ X
/V K X _ X X X rq /\ X /s X
/S X ^ X X X X s / s X f s X
/ / / — / \ / *, / s
100 - /s K \ X X X \ X 7\ „\ /s x /\ X
/S X rT s, X ' \ X ' - X s * ' / V / s/\ /\/s X /\ ss X
/S X X X - ^ s, X - s•v X /\ /s /s X /s X
s. S X s X ^ f^ X X f / s, X /V X
/ •s f\ / / ^ •v / /s / s /\ / s
50 - /s X y X s X /\ / X /N X /\ / \ /\ X l> s X
fV * / S, \ X f\ s X /^/\ /V/\ X ' •X / \ X /s/\ /\/\ /\/\ X /\/ V X
/V X s, X v X /\ /V X /s X / s /\ / S X / s X
/\ N s X s X /s /\ X /s X /\ /\ /\ X / \ X
/S " /\ fs /s / \ / \ /s /\ /s -x
/^ X is X ^ _K s s, 1 /i X î X /^ /si /i X / ^
Oct Nov Dec Jan'85 Feb Mar Jun Jul

CITIES
B
FINISHED WATER TTHM, Oct-Jul 1984-85
1OO
90
80
70
X
X
F \
60 X
•rt
i-< ' X \
X
X
50 f \
«^^> x _^ r.
TTHM
I ' X \ /\
/ X \
/ X \ ^
40 "•
f / / /\
/ X ^ /\ \
' ' - - - X ' s ' /\ /s s
30 \ / X X v /\ v
\ / X x s /s s
f / / / / - /s
\ / X X / Jx /\ /\ X
' \ / ' X X ' ' X ' /\ /^/V X /\ *>•\
™
20 /\ a, s X _ X -/ /\ / s X s
r- /
'\ X \ s X X \ X ><^ /\ /V X s,
/ \ / r ~/ J /\ /\ /\ /\
/\ X s X s X X \ X / x /\ /\ X "•>•\
'\ / \ X /s N x ' s X ' /\ X /_ s X /\ / X f s/\ / s, / \ X /\
10
/\ X s X s X X X , V / V / s X s
/\ m
\ X /
X
s\ /\
/\ X X s /\ 1 rr^ X X /\ X s
's /s / /_ /V / /\ /\ /s
/\ X / V, x s^ ^ / \ r-, li/k! K s. X \r X / ^ —1 /^ X ^
0 1 |
CITIES
r~7\ A
Seasonal trends for finished water TTHM were observed in cities A, B, C, and D.
The groundwater supply (city E) consistently had very low TTHM values. TTHM
data for the entire six city database ranged from below detection limits (1.0
ug/L) to 70 ug/L. For comparison, the EPA THM compliance data for the six
cities is also included in Appendix A.
Finished water TOG values ranged between 0.4 mg/L to greater than 5 mg/L
TOG (Figure VI-6). No seasonal trends for finished water TOG were evident. A
general reduction of TOG levels was observed between raw and finished samples.
The unusually high TOG values found in the raw water of city E in June and July
did not result in a high level of TOG in the finished water. The compounds
responsible for the high raw water TOG were apparently removed by treatment,
which included coke-tray aeration.
An analysis of the finished water TTHM and TOX data indicated that the
TTHM concentration might be expected to account for 15% of the TOX
concentration when all values were compared on a mole to mole basis (Table
VI-2). There was no apparent seasonal trend in the finished water TTHM/TOX
ratio for any of the cities, and survey averages of this ratio ranged from
0.10% to 0.18%.
The ratios of finished water TOX and TTHM to finished water TOG for each
city was evaluated to determine the impact of TOG levels on TOX and TTHM
formation. Finished water TOG was selected for analysis instead of raw water
TOG because the sediment-carried TOG was typically removed in coagulation
processes prior to disinfection. Utilizing the finished water TOG value for
all cities provided a more consistent database for the evaluation of
oxidant/organic reactions than did raw water TOG.
The ratios of finished water TOX/TOC and TTHM/TOC values were highest for
the mountain reservoir supply and lowest for the groundwater supply. (The long
retention time for free chlorine contact prior to sampling in the mountain
34
FINISHED WATER TOC, Oct-Jul 1984-85
8
K
5 - K 7-
K X x
K x x
4 -
K / x
X r ' - X x
OJ
"§
l
M 0)
3 - it , , / / ,
^^ 0 [-] K f ' ' / x x
_
' -, f
/ -.
, X , f x
X V \ \, —
/ s
f X ' ' /X
/ s \K - f X s X s ^ s
2 - -
X \ s xT X \ X
R \ - \
X s, s X \ X s .. \ X _^ ^ S X s s
X _ X K xS / / / - /S x\
X s, * N K s K /S S y \ K \ \ y\ \
/ s, X V K / »> ^ xX fs s X f _ XS ' /X V X V x V X ^ ^ X\ x s X ^ ^
X \ K ^ S x ^ X /s ~X s X x \ X V S /\ \
1 - / V K X s X s X X V X s X x s X \ \ /\ s
X V /s K x\ / V /\ /\ X s ^ / s
X s, l< X \ x s X /S /S x / \ X •s s /\ s,
X \ X •s K X \ X s K X fV s X X V X\ x V, X \ X X s x \ K s. \ X \/ s X X V, N
X s X V X s X X s x\ X x \ /V s
X s K X V X X X V X \, X x V X s \ X \ s,
X s, * X s X f s K X s / s K /\ K X s K X s
X ^ X X i X X. X^ 1 xi X i x X s f]
CITIES
r~y\A
TABLE IV-2: TOX, TOC, AND TTHM RATIOS, SURVEY AVERAGES, SIX CITIES
BASED ON MOLAR RATIOS OF TOX AND TTHM, uMOLES HALOGEN/LITER
AND TOC, uMOLES CARBON/LITER.
SURVEY AVERAGES (umoles/liter) RATIO RATIO RATIO

CITY TOC * TTHM ** TOX ** TTHM/TOX TOX/TOC TTHM/TOC
A 283.33 0.587 3.35 0.18 0.012 0.0021

B 133.33 0.401 2.56 0.16 0.019 0.0030
C 150.00 0.669 4.45 0.15 0.030 0.0045
D 166.67 0.536 3.27 0.16 0.020 0.0032
E 91.67 0.022 0.20 0.11 0.002 0.0002
F 133.33 0.732 5.77 0.13 0.043 0.0055
AVERAGE 0.15 0.021 0.0031
* umole Carbon/liter
** umole halogen/liter
TABLE IV-2a: TOX, TOC, AND TTHM RATIOS, SURVEY AVERAGES, SIX CITIES
BASED ON TTHM EXPRESSED AS uGRAM/LITER, TOX AS uGRAM C1-/L
AND TOC AS uGRAM CARBON/LITER.
SURVEY AVERAGES (ug/1) RATIOS*

CITY TOC TTHM TOX TTHM/TOX TOX/TOC TTHM/TOC
A 3400 29 119 0.24 0.035 0.009

B 1600 19 91 0.21 0.057 0.012
C 1800 32 158 0.20 0.088 0.018
D 2000 26 116 0.22 0.058 0.013
E 1100 1 7 0.14 0.006 0.001
F 1600 27 205 0.13 0.128 0.017
AVERAGE 0.19 0.062 0.011
* Ratio of TTHM and TOC in ug/1, compared to the TOX level in ug C1-/1.
36
reservoir supply undoubtedly influenced this observation.) The ozonated surface
water supply (City A) produced the second lowest yield of THM and TOX per
milligram TOG, followed by the pre-chlorine dioxide/free chlorine surface
supply (City B), the free chlorine/chloraminated surface supply(City D), and
the free chlorine surface supply (City C). It is interesting to note that the
order of ranking was the same for both the TOX/TOC ratio and the TTHM/TOC
ratio.
These data indicate the wide range of yields of TOX and THM that may be
expected for varying treatment techniques and source waters. Cities E and F
are high quality supplies requiring minimal treatment. Both utilize free
chlorine, but the yields of TOX and THM per milligram TOC were dramatically
different indicating a major difference in the precursor susceptibility to
chlorination and the impact of chlorine contact time. The major difference in
these two cities was the source of supply; groundwater for city E and mountain
reservoir for city F. The groundwater supply yielded TOX and THM formation
rates per milligram of TOC of less than one-tenth those for the mountain
reservoir. The October, 1984 sample for City E was inadvertently rinsed of the
quenching agent, resulting in a chlorine contact time of 10 days. The TOX from
this sample (groundwater, City E) of 11 ug C1-/L compares to the approximate 1
to 7 day contact time value from City F (mountain reservoir) TOX value of 224
ug C1-/L.
Similar comparisons can be made between Cities C and D, which are surface
water supplies treating similar sources by conventional treatment. The major
difference between these two cities is the use of short-term free chlorination
followed by chloramination in City D, compared to free chlorination alone at
City C. Raw and finished water TOC values were similar for these two supplies,
while the yields of THM and TOX per milligram of TOC were significantly higher
for City C which utilizes free chlorine only.
37
Cities A and B varied greatly in source of supply and type of treatment
utilized. The TOG concentration of the source of supply for City A was
approximately twice that of City B; however, the yield of both TOX and THM per
milligram of TOC for City A was approximately one-third lower than City B,
despite a chlorine contact time of 24 hours for City A compared to 3 to 5 hours
for City B. City A utilized ozone as a pre-oxidant, followed by chlorination,
while City B utilized chlorine dioxide as a pre-oxidant, followed by
chlorination. Because of the differences in TOC levels and composition, it is
difficult to hypothesize the relationship between type of pre-oxidant and
resulting yields of TOX and THM; it is observed, however, that the pre-ozonated
supply resulted in lower yields of TOX and THM as compared to the supply using
chlorine dioxide as a pre-oxidant. (The impact of pre-ozonation on subsequent
free chlorine TOX and THM production was demonstrated in the bench scale and
pilot-scale work done under this project and is described in Chapters 5 and 6).
(The data in Table-IV 2 have also been presented in Table IV-2a in units
common to the industry (mass per unit volume). The ratios computed in this
table should not be interpreted rigorously, as the units are not directly
comparable. These data are provided in this format to allow the reader to
review the information in common units of measure.)
Three of the six cities provided samples in October, 1984 that contained
measureable levels of free chlorine at the time of analysis. (This apparently
was the result of the absence of a quenching agent at the time of sampling.)
The resulting contact times were 9 days, 14 days, and 10 days respectively for
Cities A, B, and E. Resulting TOX levels were 250 ug C1-/L (City A), 220 ug
C1-/L (City B)., and 34 ug C1-/L (City E). These values may be compared to the
October TOX value of 224 u'g C1-/L for City F (1 to 7 day contact time) and a
special sample (not dechlorinated) from City C in June of 1985, which had a TOX
value of 417 ug C1-/L (contact time 14 days). TOX rate studies for free
38
chlorine performed at City D (no chloramination used during this experiment)
yielded TOX values of 295 ug C1-/L after 24 hours (June 1985). Although none
of these data points were intentionally taken to indicate the TOX levels
expected after long contact times, they do provide some insight into the
highest TOX levels that might occur in the distribution systems.
An extensive analysis of the ten-month database was made for City D
(Louisville). Correlation coefficients were calculated for TTHM vs TOC, TOX vs
TOC, THM vs TOX, THM vs temperature, TOX vs temperature, and TOC vs temperature
(See Table VI-3). No strong correlation was found between THM and TOC or TOX
and TOC; however, there was a correlation found between THM and TOX, THM and
temperature, TOX and temperature, and a weak correlation between TOC and
temperature. The influence of temperature was statistically removed from the
TOX and THM data by partial correlation techniques, resulting in nonsignificant
correlations between TTHM versus TOX (P > 0.501) and TOX versus TOC (P > 0.20).
It thus appears that these data show an association between TOX and temperature
and THM and temperature, but no significant association between TOX and THM
when the influence of temperature is removed. Data for these statistical
analysis are presented graphically in Figures VI-7, VI-8, and VI-9.
TABLE IV-3. Analysis of TOX, TTHM, TOC, and Temperature

Correlations , City D
A B CORR COEF SIGNIFICANCE LEVEL
TEMP TOX 0.86 P <0.01

TEMP TTHM 0.94 P <0.01
TEMP TOC 0.73 P <0.02
TOX TTHM 0.79 P <0.01
TOX TOC 0.59 P <0.05
TTHM TOC 0.44 P <0.20
39
FIGURE IV-7. TOX vs TTHM
Six Cities Survey: CITY D
au —
a
45 -
40 - a
a
35 -
L,
a
| 30 -
I
25 -
2
a
1 20 - D D
D
15 -
a
10 -
5 - i i
i ^ i i i i i i i i
60 80 100 120 140 160 180
TOTAL ORGANIC HALOGEN, ug Cl/liter
FIGURE IV-8. TOX vs TEMPERATURE
Six Cities Survey, CITY D
i»*u —
D
180 -
170 -
160 -
? 150 - D
a 140 - D
•0
"JJ
130 -
0
D
2u 120 -
D
9
^** 110 -
D
X D
o 100 -
D
90 -
80 i1
70 -
D
60 - I 1 1 I 1 I I I
35 45 55 65 75
TEMP, degrees Farenheit

FIGURE IV-9. TTHM vs TEMPERATURE
Six Cities Survey: CITY D
so
45 -
40 - D
D
35 -
30
ro 25 -
20 -
15 -
10 -
5 -Eh I I I
35 45 55 65 75
TEMP, degrees Farenheit

V. TOX AND THM FORMATION RATES
INTRODUCTION
It is recognized that the THM and TOX reactions are affected by the choice
of disinfectant, pH, temperature, reaction time, and variations in the source
water. Of these variables, a given water supplier can typically alter reaction
pH, reaction time, and choice of disinfectant, while temperature and source
water are usually uncontrollable variables. To obtain a better understanding
of how the THM and TOX reaction kinetics might be exploited to reduce the final
concentration of THM and TOX, a series of experiments were performed
investigating THM and TOX formation as a function of reaction time. The goal
of these experiments was to obtain information that would lead to promising
treatment schemes for implementation in the pilot plant, and to support and
expand results from the pilot plant.
The results of these experiments have been plotted as a series of graphs
referred to as reaction curves. Initial tests investigated reaction kinetics
of the single oxidants (chorine, chloramine, and chlorine dioxide) by
themselves. Subsequent tests investigated the effects of oxidants used
sequentially (free chlorine followed by chloramine, and others), and the effect
of pre-ozonation on the reaction kinetics of the singular oxidants. A final
set of experiments was run to support pilot plant data on a treatment scheme
involving pre-ozonation, free chlorination for 15 minutes, followed by
chloramination.
METHODS
The reaction curve experiments were conducted as batch studies. Source
waters were LWC settled water and LWC pilot plant water for investigations on
water treated by pre-ozonation. The experiments were conducted using a 5
43
gallon glass reaction vessel and a laboratory stirrer. No attempt was made to
prevent atmospheric losses of volatile reaction products. Mixing was complete
but not vigorous.
Solution pH was varied using nitric acid or sodium hydroxide. Stock
solutions for chlorine and chloramine were prepared as described in Chapter
III. Chloramine solutions were generated by adding ammonium chloride to the
reaction vessel and mixing for 30 minutes prior to chlorine addition.
Temperature was not varied directly: temperature variations were observed and
recorded over the ten month study period. The source water (Ohio River at
Louisville) experienced a wide range of variations throughout the course of the
experiment. (Refer to Appendix A, System Description, City D.)
Each reaction curve was generated from a single batch experiment, with the
only independent variable within the batch being reaction time. A 12 liter
volume was used in each experiment, with samples being removed by a siphon.
Samples were quenched with sodium sulfite at the time of collection to
terminate the oxidant reaction, preserved with nitric acid, and stored at 4
degrees C. Temperature was monitored at the beginning and end of the 60 minute
reaction experiments, and the average temperature was recorded. An unpreserved
sample was analyzed for oxidant residual at 60 minutes. TOX samples were
analyzed within 24 hours of collection; THM and TOG samples were analyzed
within three weeks.
RESULTS AND DISCUSSION
Chlorine Reaction Curves
Data for a total of eleven free chlorine reaction curves were collected
over an eight month period, encompassing a wide range of water quality and
temperature conditions. Data for these reaction curves are listed in Appendix
44
B and presented graphically in Figures V-l through V-6. Reaction times
typically spanned 60 minutes, although shorter and longer timeframes were
utilized in selected instances to better define segments of the reaction curve.
Reaction pH values for these curves were ambient (ranging from pH 7.1 to 7.4)
for curves #1 through #5 (Appendix B and Figure V-2), controlled at pH 6.5 for
curves #14, #20, and #26 (Figure V-3), and controlled at pH 8.5 for curves #13,
#19, and #25 (Figure V-4).
All of the reaction curves displayed typical first order reaction kinetics
with respect to time, with the exception of curve #2 (Figure V-l), which
displayed zero order kinetics over a 5 minute reaction time. Figure V-2
displays the data from curves #3, #4, and #5, for ambient pH (7.4) and room
temperature conditions. A direct association between pH and TOX levels was
indicated by these data, although the experiments were not conducted to display
pH effects and the range of pH was rather narrow.
Three sets of curves were run at controlled pH values of 6.5 and 8.5..
These data are graphically displayed in Figures V-3 (pH 6.5 )and V-4 (pH 8.5).
The curves analyzed at 13 degrees C showed very little variation of TOX
associated with pH; however, an inverse association between pH values and TOX
levels was observed for those curves analyzed at 17 degrees C and 22 degrees C
(Figure V-5). This observation is supported by documentation in the
literature. An analysis of the data indicates that a direct association
between temperature and TOX levels existed at pH 6.5, while a weak, inverse
association was observed at pH 8.5. Noting that the temperature differences
were not dramatic, and the raw water quality varied throughout the sampling
period, these contrasting relationships are not considered significant.
The TOX data from curves #3, #4, #5, #13, #14, #19, #20, #25, and #26
(Figures V-l and V-5) were modeled by first order reaction kinetics, linearized
by log 10 Time (Table V-l). The data showed a good fit for first order
45
FIGURE V-1. TOX REACTION CURVE #2
FREE CHLORINE, pH=7.4, Temp=18 C
u
9
0.00 2.00 4.00
Reaction Time, MINUTES

FIGURE V-2. TOX REACTION CURVES #3,4,5
FREE CHLORINE, pH=7.2 to 7.4, Temp =19 C
5
A
U
gH
0.00 20.00 40.00 60.00

D RUN *3 + RUN *4 O RUN «5
FIGURE V-3. TOX RCs #14, #20, #26
FREE CHLORINE, pH=6.5
a
>5
•d
•^4
S
i-«
-p-
00
g
0.00 20.00 40.00 60.00

D RUN *14: 13 C RUN *20: 17 C RUN *26: 22 C
FIGURE V-4. TOX RCs #13, #19, #25
FREE CHLORINE, pH=B.5
I—I
1
A
u
g
H
0.00 20.00 40.00 60.00

O RUN *13: 13 C + RUN *19: 17 C O RUN *25: 21 C
FIGURE V-5. TOX REACTION CURVES
FREE CHLORINE, Semi-Log Plot
u
Ui
o
1.00 1.58 2.51 3.98 6.31 10.00 15.85 25.12 39.81 63.10
Reaction Time, MINUTES (log scale)

D *13 *14 O *19 A *20 X *25
pH=8.5 pH=6.5 pH=8.5 pH=6.5 pH=8 .5 pH=6.5
T=13°c T=14°c T=17°c T=17°c T=21°c T=22°c
TABLE V-l. TOX TEMPERATURE DEPENDENCE REACTION MODEL:
TOX=(a)+(b)LOG(TIME)
REACTION TEMP. CORRELATION

CURVE # pH C (a) (b) COEFFICIENT
14 6.5 14 43 40 0.994
20 6.5 17 58 42 0.979
26 6.5 22 57 56 0.992
3 7.4 16 55 40 0.999
4 7.3 19 47 38 0.991
5 7.15 20 33 42 0.977
13 8.5 13 32 45 0.995
19 8.5 17 41 42 0.998
25 8.5 21 34 36 0.995
reaction kinetics. Slopes varied from 38 to 56; intercepts varied from 33 to
57. The background data were inadequate to explain the variations in slopes
and intercepts.
TTHM data for free chlorine reaction curves are presented in Figure V-6.
A direct association between pH and THM was observed from these data, as has
been found in the literature. As with the TOX data, the effect of temperature
is not clearly established with the TTHM data. The effect of using a
non-constant, uncontrolled natural source of water undoubtedly limited the
ability to make inter-batch comparisons with these data.
Chlorine Dioxide Reaction Curves
Data for a total of nine chlorine dioxide reaction curves were collected
over a six month period from December, 1984 through May, 1985. Initial
reactions were run at ambient pH (7.4) at room temperature (curves #6, #7, and
#8)(Figure V-7). Reaction curves #16, #22, and #28 (Figure V-8) were
controlled at pH 6.5, while reactions #15, #21, and #27 (Figure V-9) were
conducted at pH 8.5. Data for these reaction curves are listed in Appendix B.
The reaction times for all data were standardized at 0.5, 1, 2.5, 5, 30, and 60
minutes.
51
FIGURE V-6. TTHM REACTION CURVES
FREE CHLORINE
Ul
N>
I
a
0.00 20.00 40.00 60.00
Reaction Time. MINUTES

*13 O *19 A 020 > »26
pH=8.5 pH=6.5 pH=8.5 pH=6.5 pH=8.5 pH=6.5
T=13°c T=14.°c T=17°c T=17°c T=21°c T=22°c
The reaction kinetics for the chlorine dioxide experiments were quite
variable, apparently the result of variable raw water conditions. Figure V-7
presents data run at ambient pH conditions and room temperature. The trend of
peaking TOX levels after 5 minutes of reaction time for reaction curves #7 and
#8 indicated somewhat complicated reaction kinetics, suggestive of continued
oxidation of chloro-organic intermediates to non-chlorinated reaction products.
Reaction curve #6 indicated a possible organic-reactant (precursor) limited
reaction, noting that an excess of oxidant of greater than 2.0 mg/L was
maintained after 60 minutes. These data were collected under highly variable
raw water conditions.
Chlorine dioxide reactions #16, #22, and #28 (Figure V-8) were controlled
at pH 6.5 and run at the ambient raw water temperature. Data from these runs
did not display simple reaction kinetics, although the data were not as
variable as were the data at ambient pH levels (pH 7.4). The reaction kinetics
during the first five minutes of reaction were quite unpredictable, while the
remainder of each run was somewhat constant. The rapid initial TOX formation,
followed by little subsequent formation has been observed in the literature
(Stevens, 1984).
The reaction pH for curves #15, #21, and #27 (Figure V-9) were maintained
at pH 8.5. As with previously discussed data for chlorine dioxide, the
reaction kinetics did not indicate classical conditions. Again, reaction
kinetics during the first five minutes were erratic, followed by simple but
unpredictable trends.
The experimental design for reaction curves #15, #16, #21, #22, #27, and
#28 (Figures V-8 and V-9) was established to allow for parametric analysis of
three batches of data at two pH values (6.5 and 8.5). This design assumes that
the changes in raw water quality between the paired curves were minimal and
would not significantly affect TOX levels. Parametric analysis of the 60
53
FIGURE V-7. TOX RCs #6. #7, #8
CHLORINE DIOXIDE, pH=7.4, Ts= 20 C
100
A
u
0.00 20.00 40.00 60.00

O RUN *6 + RUN #7 O RUN *8
FIGURE V-8. TOX RCs #16, #22, #28
CHLORINE DIOXIDE, pH=6.5
1OO
90
80 -
70
$
§ 60
•0
s
2 50
t_n u
3 40
gH 3O -
20 -
10 -
0.00 20.00 40.00 60.00

*16 + *22 0 *2B
FIGURE V-9. TOX RCs #15, #21, #27
CHLORINE DIOXIDE, pH=8.5
1OO
90 -
80 -
70
60
FN
I 50
g
40
g 30
H
20
10 -
0.00 20.00 40.00 60.00

D RUN *15 + RUN *21 O RUN *27
minute reaction time data indicated an inverse association between reaction pH
and TOX levels. An unexpected inverse association between water temperature
and TOX levels was also observed; however, due to the long time periods between
sample collection and the variable water quality conditions experienced, it is
expected that this trend is spurious and is more an affect of raw water quality
condition.
Trihalomethane data were collected for runs #15, #16, #21, #27, and #28
(Appendix B). TTHM formation was very low in all cases, making any further
interpretation of the data insignificant.
Chloramine Reaction Curves
Six reaction curves were run for chloramine over the three month period of
April, 1985, through June, 1985. Ambient water temperatures were employed,
while pH was controlled at 6.5 for curves #18, #24, and #30 (Figure V-10) and
at pH 8.5 for curves #17, #23, and #29 (Figure V-ll). Data for these reaction
curves are listed in Appendix B. The reaction times for all six curves were
standardized at 0.5, 1, 2.5, 5, 30, and 60 minutes.
Analysis of the data indicated that unlike the chlorine data, classical
reaction kinetics were not displayed. At pH 6.5, the initial 0.5 minute
reaction point was associated with a significant initial increase in TOX
levels, which might be attributed to the back reaction of monochloramine to
hypochlorous acid at lower pH values. Beyond the 0.5 minute reaction point,
the reaction was unpredictable, and apparently varied with raw water
conditions. Reaction curve #24 (Figure V-10) showed an apparent decrease in
TOX levels following the initial increase at 0.5 minutes.
The reaction kinetics for chloramines at pH 8.5 displayed less erratic
trends than at pH 6.5, perhaps as a function of the higher stability of the
monochloramine residual at pH 8.5. Data for curves #17 and #29 (Figure V-ll)
57
TOX (u« Chloride/Liter)
N U i^ W 0» -J OB O o
o o O O O O O O O O o
o I I___I___1___1_____I___I _l___I
I
T
c
in
I^
K O
1 *
CA
*«•
s 5 OD
O
§
G
2!
is
&
O Co
0)
o
FIGURE V-11. TOX RCs #17, #23, #29
CHLORAMINES, pH=8.5
1OO
90 -
80 -
70 -
a 60 -
*•o
t0
••« 50 -
£
U
40 -
gH 30 -
20 -
10 -
0
0.00 20.00 40.00 60.00

D RUN *17 + RUN #23 o RUN *29
exhibit approximate first-order reaction kinetics. Data for curve #23 (Figure
V-ll), however, displayed a trend similar to that observed for curve #24
(Figure V-10), which was under similar raw water conditions, but controlled at
pH 6.5. This indicates that the TOX concentration peaks observed at 0.5
minutes for reaction curves #23 and #24 were likely caused by raw water
conditions at the time of sampling.
No trends were apparent for pH and temperature effects for the chloramine
data, other than the initial 0.5 minute peak observed at pH 6.5. The final TOX
levels were typically below 40 ug C1-/L. These relatively low TOX levels make
the detection of slight trends difficult, particularly when the source water is
not controlled.
Trihalomethane data were collected for each of the chloramine reaction
curve runs. THM concentrations were typically below 1.0 ug/L, and showed no
obvious trends for reaction time, pH, or temperature. These data are presented
in Appendix B.
Sequential Oxidant Addition
Disinfection/oxidation schemes may be designed around the use of multiple
oxidants, used sequentially. To determine the impact of sequential oxidant
addition on TOX formation, a series of batch experiments were designed. For
uniformity, a primary oxidant was added to the reaction solution followed
twenty minutes later by a second oxidant. For these experiments, coagulated
process water was utilized at ambient pH (7.4) and temperature. TOX levels
were measured at time zero, 20 minutes, 25 minutes (5 minutes after the second
oxidant was added), and 40 minutes (20 minutes after the second oxidant was
added). Data from these experiments are listed in Appendix B.
An analysis of data for chlorine as a primary oxidant and chloramine and
chlorine dioxide as secondary oxidants indicated that the TOX reaction was
60
terminated upon addition of either of the secondary oxidants (reaction curve
#9, Appendix B). In the case of chloramine, the free chlorine residual was
reduced to monochloramine by the addition of ammonia. The termination of the
TOX reaction might be expected under these conditions, if it is assumed that
the free chlorine TOX reaction had oxidized those organic compounds that would
have been precursors to the chloramine TOX reaction. The termination of the
TOX reaction after chlorine dioxide addition is unexplained, unless the
chlorine dioxide solution was effective in reducing the free chlorine to a less
reactive species. No attempt was made to segregate the residual oxidant
species in these experiments.
A second series of experiments was conducted using chlorine dioxide as the
primary disinfectant followed by free chlorine or chloramines (reaction curve
#10, Appendix B). These data indicate that the chlorine dioxide treatment
contributed no substantial increase in TOX levels; however, subsequent addition
of free chlorine resulted in a significant increase in TOX levels. An increase
in TOX levels was also observed for subsequent addition of chloramines,
although the increase was not as great as with free chlorine. In both cases,
the final TOX levels were considerably lower than levels experienced with free
chlorine alone.
A final sequential experiment was run using chloramine as the primary
oxidant, followed by free chlorine or chlorine dioxide (reaction curve #11,
Appendix B). An analysis of the data for subsequent chlorine dioxide addition
indicates an increase in TOX levels beyond levels for either chloramine or
chlorine dioxide. This might be explained by inter-oxidant reactions,
producing reactive oxidant products (HOC1) which resulted in higher TOX levels.
Data for subsequent chlorine addition to a chloramine solution could not be
interpreted because of inadequate data to define the residuals.
61
Pre-ozone/Chlorine Reaction Curves
The effect of pre-ozonation on the free chlorine TOX and TTHM reaction was
investigated in a series of reaction curves. The source water was Pilot Plant
2 ozonated water (non-ozonated water for the zero dosage). Ozone dosages were
zero, 0.7 mg/L (low dose), 1.2 mg/L (medium dose), and 3.4 mg/L (high dose).
Ambient pH (7.6) and temperature (21 degrees C) conditions were employed.
Chlorine was applied at 3.0 mg/L 15 minutes after ozonation. Reaction times
were set at zero (initial conditions before chlorination), 0.25 hours, 2.0
hours, and 192 hours (8 days). Chlorine residuals were 2.4 mg/L after 15
minutes, 1.8 mg/L after two hours, and detectable traces (less than 0.1 mg/L)
after 8 days. Data for these experiments are found in Appendix B.
Data for these experiments are graphically presented in Figure V-12, and
Figure V-13, using a logarithmic x-axis. These data indicate that
pre-ozonation reduced the level of THM and TOX in the free chlorine reaction.
The reduction was most pronounced at the 15-minute reaction point, with TOX and
THM levels being at least half of the comparable non-ozonated level. This
reduction is likely the result of ozone-oxidation of easily chlorinated
oxidation sites, and subsequent formation of less reactive, oxygenated
compounds that are more resistant to chlorine oxidation.(Rice and Miller, 1985)
The effect of pre-ozone dosage was not clearly established by the data
obtained. The lowest pre-ozone dosage consistently produced the highest TOX
and THM levels of all pre-ozonated samples. The medium ozone dosage, however,
produced lower levels of TOX and THM at the 2-hour and 8-day sample points,
than did the high ozone dose. The failure of pre-ozonation to display a dose
response is unexplained at this time.
The impact of pre-ozonation on the reaction rate of free chlorine within
the first 15 minutes of reaction is significant, particularly if the free
chlorine reaction is terminated (by chloramination) within this timeframe.
62
FIGURE V-12. TOX REACTION CURVES
PRE-OZONE, FREE CHLORINE (semi-log)
250
240 -
230 -
220 -
210 -
200 -
190 -
180 -
170 -
160 -
U 150 -
ON no pre-ozon
OJ 140 -
130 -
120.
110
100
90 medium
BO
70
60
50
xigh ozone dose
40 i i i i
0.16 0.40 1.00 2.51 6.31 15.85 39.81 100.00 251.19
Reaction Time, HOURS

FIGURE V-13. TTHM REACTION CURVES
PRE-OZONE, FREE CHLORINE (semi-log)
120
110 -
100 -
90 -
80 -
70 -
60 -
I
3 50 -
40 -
no pre ozon
30 -
20 -
medium
10 -
igh ozone dose
\ I
0.16 0.40 1.00 2.51 6.31 15.85 39.81 100.00 251.19
Reaction Time, HOURS (Log Scale)

D LOW + MEDIUM O HIGH A NO OZONE
This aspect of the pre-ozone, free chlorine reaction was further investigated
at the pilot plant.
65
VI. PILOT PLANT STUDIES
PILOT PLANT CONFIGURATION AND OPERATION
Two identical pilot plants were used for this investigation to permit
direct comparisons between various sets of operating conditions. The pilot
plants were developed at the Louisville Water Company (LWC) and were designed
and built to operate in a manner similar to the operation of the LWC's Crescent
Hill Filter Plant (CHFP). The operational flow for the plants was 3 or 4
gallons per minute (gpm), with a maximum design flow rate of 8 gpm. A flow of 4
gpm was used for the initial tests, but a 3 gpm flow was used for the extended
runs required for the Ames testing because it was easier to maintain equal flow
rates in the two plants at the lower flow. The pilot plant system included
mixing systems, clarifiers, post-oxidant contact chambers, and an ozone contact
chamber for Pilot Plant 2 (Figure VI-1). The feedpoint for the oxidants used in
this study was at the effluent from the plate settlers.
Raw water from the Ohio River was typically retained in the reservoir for
24 hours before the settled water entered the pilot plants. The influent line
to the pilot plants was connected to the front side of a venturi between the
settled water reservoir and coagulation basin at the CHFP. The line was used as
an alum taxi water line before 1982, and is now used as a back-up system for the
liquid alum system. The line was rinsed thoroughly with settled water before it
was put into service for the pilot plants.
Each pilot plant contained one mixing tank, 2 ft wide by 2 ft deep by 8 ft
long, made of 304 stainless steel (Figure VI-2). The mixing tank was separated
into three equally-spaced sections, each with a retention time of 20 minutes.
The sections were separated by redwood baffles, placed so that water flowing
through the plant went over the first, under the second, and over the third
66
iop
PLATG
;^
_£____f___r___r___f.
MIXING
I I
FIGURE VI-1. Layout of Pilot Plant System

o - 100 "'
TT
MCCH&N15M nl
)=( N
CO
view
FIGURE VI-2. Mixing Tank for Pilot Plant System

baffle. A single horizontal shaft was used to turn the paddles in all three
sections. The mixing intensity in the three sections decreased from the
influent to the effluent. The mixing intensities were G = 100 seconds in
the influent section, G = 50 seconds in the middle section, and G = 25
seconds in the effluent section.
Clarification of the coagulated water was accomplished with plate settlers
(Figure VI-3). There was one plate settler for each pilot plant system. The
plate settlers were 1 ft wide by 4 ft deep by 4 ft long, with a bottom shaped
like an inverted pyramid. The tank was made of 304 stainless steel, with 28
plexiglass plates situated at 60 degree angles in each plate settler. Water
flowed upward through the plates while the coagulated particles settled out onto
the plates. The sludge from the plates slid down into the inverted pyramid at
the bottom of the settler, where the sludge could be withdrawn for disposal.
The surface overflow rate for the plate settlers was 260 gpd/ft2 at a flow rate
of 4 gpm.
The ozone contactor was located on Pilot Plant 2 between the plate settler
and the post—oxidant contactor. The ozone contactor had a 3.5-inch o.d., was 4
ft tall, and was packed with 1.5-in burl saddles. Ozone gas was introduced into
the bottom of the contactor through a 30-mm fine frit, and bubbled up through
the burl saddles counter-current to the flow of the process water. Ozone
transfers of up to 90 per cent were typical. Excess ozone gas was suctioned off
the top of the column into a column of activated carbon (Figure VI-4).
The post-oxidant contact chambers were made from 20-ft lengths of 8-in i.d.
PVC pipe. The retention time in the chambers, as measured by a fluoride tracer
study, was 12 minutes at a flow rate of 4 gpm. Standpipes on the end of the
chambers were used to keep pressure on the system.
Jars were added to the post-oxidant contact chambers to extend the reaction
time for the runs used for some studies. They consisted of one 250-mL
69
4' -H
OOOOOOOOO
t I M t t t 1 1
////////////////////////B
CF FLUENT
4'
G'4- 11
M 1 t t I t T
:Q_ST° ooooo o o"
FIGURE VI-3. Plate Settler for Pilot Plant System
70
ACTIVATCD
CAP>!50N
COLUMW
K-Q
ozoê
PORT
CONTACTOR
OZOMO
D-
OZONC
MV\PL
POP.T
PO^T
CONTACT
GWAMfbCF.
FIGURE VI-4. Ozone contactor for pilot plant system
71
Erlenmeyer flask, one 4.3-L jar, and three 2-L jars on each pilot plant,
although not all of the jars were used for each extended run. At a flow rate of
290 mLs/min, the retention times in the Erlenmeyer flasks, 4.3-L jars, and 2-L
jars were one minute, 15 minutes, and 100 minutes, respectively.
The disinfectant concentration in the effluent from the contact chambers
was initially checked 20 to 30 minutes after feeding began. Adjustments of the
disinfectant residual were made by increasing or decreasing the feed rate of the
particular disinfectant. Once the effluents disinfectant concentration had
stabilized at an acceptable value, as defined by typical values found in the
literature, final samples were taken. Ample time was given between runs on a
given day to assure that the pilot plants had stabilized and that the previous
run would have no effect on the succeeding run.
To determine the minimum time that could be allowed between runs on a given
day, a fluoride trace study was conducted. Ten mL of hydrofluorosilic acid
(24.8%) were added at the point of disinfectant application. Samples were taken
from the effluent of each of the contact chambers at various time intervals and
analyzed for fluoride ion using an ion selective electrode (Standard
Methods, 1981). The results are listed in Table VI-1. They show that, for
the given flow rate, the pilot plants' contact chamber was not affected by the
previous run after about an hour; the fluoride concentration had returned to
less than its original concentration. The lower values of fluoride
concentration were attributed to a drift in electrode response during the
analysis period. In all cases, 2 hours were allotted between runs on a given
day to build in a safety factor. All bottles were marked and prepared in
advance of sample collection. As the samples were taken, the location was
double-checked to assure that the location matched the bottle label.
The pilot plants were used to examine the effects of primary disinfectant,
pre-ozonation, pH, and temperature on concentrations of THM's, TOG, and TOX in
72
Table VI-1. Determination of retention times for the contact chambers
using fluoride as a tracer.
Contact Chamber #1* Contact Chamber #2**

Time (min) Fluoride Cone, (ppm) Time (min) Fluoride Cone, (ppm)
0 0.180 0 0.189
5 0.149 5 0.159
10 14.4 10 12.9
11 20.7 11 20.6
12 19.9 12 21 .9
13 17.6 13 18.7
16 7.25 14 14.7
19 3.75 16 8.85
22 2.04 18 5.26
25 1 .46 21 2.43
30 0.776 24 1 .35
40 0.382 30 0.62
55 0.240 40 0.318
70 0.180 55 0.192
78 0.155 70 0.142
78 0.131
*Total flowrate through PPI = 3.995 SP'm; Flowrate through contact cham
ber #1 =3.65 gpm.
**Total flowrate through PPII = 3.963 gpm; Flowrate through contact cham
ber #2 = 3.62 gpm.
73
the finished water. Additional runs were made to provide samples for Ames
testing and to further evaluate the alternate disinfectants.
Twelve preliminary runs were made to adjust operating conditions and
optimize the operation of the pilot plants. Runs 13 to 50 were used primarily
to evaluate disinfectant, ozonation, pH, and temperature effects. Pilot Plant 1
(PP1) served as a control and received Cl as a disinfectant for each of these

2
runs, while conditions were varied in Pilot Plant 2 (PP2). The flow rates of
the two pilot plants were checked each morning before starting to make the
initial run. They were adjusted to obtain as equal of a flow between the two
plants as was possible. The runs made for the purpose of these studies are
shown in Table VI-2.
General operation of the pilot plants for the extended runs, Runs 51
through 56, included a coagulant (alum) feed to the influent of the mixing and
coagulation chambers, followed by clarification and sufficient contact time for
oxidant reaction. The contact chambers included post-oxidant contact chambers
and a variety of jars to increase the reaction time of the oxidants.
Samples for the analysis of organics were collected three times from the
influent of the pilot plants and the effluent of the contact chambers during
each extended run. The organics analyzed were THM's, TOG, and TOX. Operations
data, including turbidity, pH, pre-oxidant concentration (when used), and

i
post-oxidant concentration, were taken and analyzed daily, or more frequently if
necessary, during each run. Water temperatures were taken at the beginning of
each run.
Run 51 utilized a chlorine feed to the effluent of the PP1 plate settler,
while PP2 had an ozone feed immediately before the addition of chlorine (Figure
VI-5). After the oxidant was fed to both pilot plants, water flowed through the
post-oxidant contact chambers with a retention time of 12 minutes. Effluent
from the contact chambers was pumped at a rate of 290 mLs/min to two 4.3-L
74
Table VI-2. Schedule of pilot plant runs 13 to 50.
Treatment
Date Run No. PP1 PP2

2-26-85 13 Chlorine Chlorine
14 Chlorine Chlorine + post-coag. 0 3 (5.84 mg/L)
15 Chlorine (pH=7.10) Chlorine (pH=8.35)
3-4-85 16 Chlorine Chloramines
17 Chlorine Chloramines + post-coag. 0 3 (5.30 mg/L)
18 Chlorine (pH=7-lO) Chloramines (pH=8.29)
3-6-85 19 Chlorine Chlorine dioxide
20 Chlorine Chlorine dioxide + post-coag. 0 3 (2.75 mg/L)
21 Chlorine (pH=7.17) Chlorine dioxide (pH=8.38)
24 Chlorine (pH=6.92) Chloramines (pH=8.04)
27 Chlorine Chlorine + post-coag. 0 3 (4.13 mg/L)
29 Chlorine (pH=7-34) Chlorine dioxide (pH-8.22)
30 Chlorine Chlorine dioxide + post-coag. 0 3 (4.96 mg/L)
34 Chlorine (pH=7.17 Chloramines (pH=8.22)
3-19-85 35 Chlorine Chlorine + post-coag. 0 3 (1.04 mg/L)
38 Chlorine (pH=7.12) Chlorine dioxide (pH=7.82)
39- Chlorine Chlorine dioxide + post-coag. 0 3 (1.43 mg/L)
41 Chlorine Chloramines
43 Chlorine Chloramines
44 Chlorine Chlorine dioxide
»
dioxide
48 Chlorine Chlorine dioxide
75
P P II
PPI u* PPH
WA'bTG
L_
UJFl.
COLUMNS
FIGURE VI-5: Jar Set Up for Run #51

opaque jars, each with a retention time of approximately 15 minutes. Effluent
from the jars was split, with 230 mLs/min going to waste and 60 mLs/min pumped
to the Ames test resin columns. Samples for the analysis of organics were taken
at the effluent of post-oxidant contact chambers and the 4.3-L jars.
Run 52 was similar to Run 51, except that an ammonium chloride solution was
added before the chlorine. Sand filters were added to the effluent of the 4.3-L
jars to reduce the frequency of changing the glass fiber filters on the influent
to the resin columns. The samples for organic analyses were collected at the
effluent of the post-contact chambers and the sand filters (Figure VI-6).
Chlorine dioxide was fed after the plate settlers in PP1 and after the
ozone contact chamber (Figure VI-7) for Run 53. The post-oxidant contact
chambers for both pilot plants were bypassed, and the plate settler effluents
were pumped directly to the 4.3-L jars at a rate of 290 mLs/min. Sixty mLs/min
of the effluent were fed by gravity through three 2-L jars placed in series.
The extra 6-L volume increased the reaction time to a total of 115 minutes. The
effluent from the three 2-L jars was pumped through sand filters before going to
the Ames test resin columns. Samples for analysis of organics were collected at
the effluent of the 4.3-L jars and the sand filters.
Only PP1 was required for Run 54. Effluent water (580 mLs/min) from the
post-oxidant contact chamber was split into two streams and pumped into two 250
mL Erlenmeyer flasks. One flask was dosed with ammonium chloride followed by
chlorine, and the other was dosed with chlorine dioxide. Effluents from the
dosing flasks went to the corresponding 4.3-L jars. Effluents from the jars
were split, with 230 mLs/min wasted and 60 mLs/min fed by gravity through the
three 2-L jars and then pumped through the sand filters. The samples for
analysis of organics were collected from the effluent of the 4.3-L jars and the
effluent of the sand filters (Figure VI-8).
Chlorine dioxide was fed into the 250 mL Erlenmeyer flasks, along with 290
77
P P II
MHzC\
PPI V PPE
W/VbTG
r COLUMN
00
SAMPLE
03
NH40I -
012-

PP
CIO2
PPI PPH W&'bTC
5AM PLC
COLUMN
VO
WASTC
03-
cio-z

PP i
ClOl
CIO? or 5&MPLC
WW4CI *• C12.
C
/IN /\ SAMPLC
COLUMN!
co
o
FIGURE VI-8: Jar Set Up for Run #54 ;

mL/min of water from the post-oxidant contact chambers for Run 55. Effluent
water from the Erlenmeyer flask entered a 4.3-L opaque jar. As in Run 54, 230
mLs/min were wasted and 60 mLs/min flowed by gravity through three 2-L jars and
were then pumped through a sand filter before going onto the Ames test resin
columns (Figure VI-9). Pilot Plant 2 had the same flow pattern as Pilot Plant
1, but ozone was added to the pre-oxidant contact column 15 minutes before the
chlorine dioxide was added. Samples for analysis of organics were collected
from the effluents of the 4.3-L jar, the three 2-L jars, and the sand filters,
with the exception of the first sampling period when samples were collected only
from the effluents of the 4.3-L and 2-L jars.
Chlorine was added at the influent to the 250-mL Erlenmeyer flasks,
downstream from the post-oxidant contact chambers for both pilot plants for Run
56. Ozone was fed at the pre-oxidant contact chamber on PP2, 15 minutes before
the chlorine was added, and ammonium chloride was added after the 4.3-L jars.
The flow rate through each Erlenmeyer flask and the 4.3-L jars was 290 mLs/min,
with 230 mLs/min of the effluent wasted and 60 mLs/min fed to the three 2-L
jars. Effluent from the 2-L jars was pumped through the sand filters before
going to the resin columns (Figure VI-10). Samples for analysis of organics
were collected from the effluents of the 4.3-L jars and the sand filters. An
additional set of samples for analysis of organics was collected from the sand
filters, but not quenched for 8 days to determine long-term effects.
RESULTS AND DISCUSSION
Pilot Plant Runs 13 to 39, made at low effluent temperatures, examined the
various treatments used in the pilot plants. Runs 40 to 50 were made at higher
effluent temperatures to examine temperature effects on pilot plant operation,
and additional data from extended Runs 51 to 55 was also used for this purpose.
Three different primary disinfectants, free chlorine, chlorine dioxide, and
81
pp tt
CIO? 03 + ClOz
PPI PPTI
(T
COLUMKI
00
NJ
WA5TC
03-
C102.———»-

PPH
O2>1-
pp i vs PPH
012
~M I CT
SAMPLC
AMC-b
00 COLUMN
NH4.CI
03-

chloramines, were evaluated. Each disinfectant with no additional treatment,
with increased pH, and with ozone used as a pre-oxidant was tested at low
temperatures, but time did not permit the complete examination of pH and ozone
effects at the higher temperatures. Triplicate runs for each set of conditions
tested were made to substantiate the statistical significance, if any, of the
various parameters examined. Experimental conditions were varied in Pilot Plant
2 only; Pilot Plant 1 was run with chlorine as the disinfectant and no
additional treatment to allow the data to be normalized and remove the effects
of changes in raw water characteristics from the statistical analysis.
Three runs for a given disinfectant were completed each day, in most cases.
The pilot plants stabilized more quickly with the primary disinfectant alone
than the pilot plants with other adjustments, and treatment with either
increased pH or pre-ozonation required additional preparation time. Therefore,
the disinfectant with no adjustments was always run first to make the most
efficient use of time. The order in which the runs with the remaining
adjustments, pre-ozonation or increased pH, were made was varied where practical
in order to achieve a random sampling. The order in which the disinfectants
were tested was also randomized where practical, although chlorine dioxide was
always the last of the three disinfectants to be tested because of the time
required to generate the large quantities needed for testing. For two
consecutive days, involving one test with chlorine and one test with
chloramines, only the primary disinfectant alone and the disinfectant with
increased pH were tested because of problems with the ozonator. The following
day, these omitted ozone runs were made up; chlorine with pre-ozonation was
tested followed by chloramines with pre-ozonation. Extended Runs 51 to 56 were
made to more fully evaluate specific treatment schemes and operating conditions
for these runs are discussed separately.
84
OPERATING CONDITIONS
The temperature of the influent remained low (5.5 to 8.9 °C)
throughout the testing period for Runs 13 to 39. The lowest influent temperature
was recorded on the first two sampling days (5.5 °C); a temperature of 7.0
°C was recorded from the influent on the third day; and days 4 through 10
had influent temperatures ranging from 8.0 to 8.9 °C. The temperature of
the effluent from the contact chambers usually varied by less than 1 °C
from the influent temperature, with the exception of the second day, when an
increase of 2.1 °C occurred. The temperature of pilot plant effluents
ranged from 6.1 to 9.3 °C for Runs 13 to 39. Temperatures were taken once
each day, generally between 2:00 PM and 4:00 PM, a time when the daily maximum
temperature might be expected. Because of the low temperatures, concentrations
of THM, TOX, and TOG were near minimum annual levels. As a result, changes in
effluent THM and TOX concentrations resulting from the various treatment
processes examined were minimized and reduced the significance of any
differences observed.
Influent temperatures ranged from 19.5 to 21 °C for Runs 40 to 50,
and from 22.5 to 25.0 °C for Runs 51 to 55. The pilot plant effluents had
the same temperatures as the influents during these higher temperature runs.
Influent and effluent temperatures for the pilot plants are summarized in Table
VI—3. The temperature range for this study was only slightly narrower than the
annual expected range of 0 to 28 °C for the raw water supply at the
Louisville Water Company.
The turbidity of the influent ranged from 6.6 to 62 NTU for Runs 13 to 50,
with the lowest values occurring during the warmer months. The pilot plants
were controlled so that the turbidities in the effluent remained at a level
considered acceptable the Louisville Water Company, which is a turbidity of less
than 2 to 5 NTU in the coagulated water and a turbidity of less than 0.20 NTU
85
Table VI-3. Influent and effluent temperatures for pilot plant Runs 13-55.
Temperature (°C)
Date Runs Influent Effluent (PP1 ) Effluent (PP2)
26 Feb 1985 13-15 5.5 6.1 6.1

4 Mar 1985 16-18 5.5 7.6 7.6
6 Mar 1985 19-21 7.0 7.3 7.3
11 Mar 1985 • 22-24 8.0 8.8 8.8
13 Mar 1985 25-27 8.1 8.9 8.9
15 Mar 1985 28-30 8.9 9.3 9.3
17 Mar 1985 - 31-32 8.5 9.1 9.1
18 Mar 1985 33-34 8.2 8.8 8.8
19 Mar 1985 35-36 8.3 • 9.0 9.0
20 Mar 1985 37-39 8.6 9.1 9.1
21 May 1985 40-42 20.5 20.5 20.5
22 May 1985 43-44 20.5 20.5 20.5
23 May 1985 45 20.0 20.0 20.0
24 May 1985 46 19.5 19.5 19.5
29 May 1985 47-48 20.5
12-18 Jun 1985 51 — 22.5 22.5
20-25 Jun 1985 52 — 22.5 22.5
7-13 Jul 1985 54 — 25.0 25.0
23-27 Jul 1985 55 __ 25.0 25.0
86
following filtration. These conditions were achieved in the pilot plants by
controlling the quantity of alum being dosed to the system. Although the goal
of the pilot plant operation was to keep the two effluents at the same
steady-state turbidity value, this was not always accomplished, as shown by a
review of the turbidity data in Table Vl-4. Alum was dosed to the two plants at
their individual influent points for Runs 13 through 21 using a peristaltic pump
with two heads, and unequal feeding by the two heads was most likely the cause
of the observed differences in turbidity between the two pilot plants. For the
remaining runs, the alum feed point was moved to the main Influent line, prior
to being split to the two pilot plants, and was fed using a peristaltic pump
with a single head. Incomplete mixing of the alum before splitting to the two
plants was probably the cause of any significant dosage differences to the two
plants after this modification was made. Each pilot plant on a given day showed
a consistent turbidity In its effluent, Indicating that steady state conditions
were reached, with the exception of Day 1 when runs 2 and 3 were consistent, but
run 1 was higher. The alum dosages ranged from 150 to 300 ///MG during the
sampling period, and the higher alum doses lowered the pH of the effluent by up
to 0.3 of a pH unit. No polymers were used to aid coagulation.
The pH values for the influent to the pilot plants and for the effluents
from the contact chambers of the pilot plants are given in Table VI-5. The
effluent pH, measured after the addition of all chemicals, ranged from 7.5 to
7.78. The effluent from Pilot Plant 2 had a pH ranging from 6.92 to 7.6 after
the addition of the primary disinfectant when no additional adjustments were
made. The variation in pH values for effluents from pilot plants receiving the
same treatment can be explained by differences In alum dose on different days.
An increase in pH ranging from 0.61 to 1.25 pH units occurred for the runs where
the pH was deliberately increased by the addition of NaOH.
87
Table VI-A. Pilot plant turbidity levels.
Turbidity (NTU)
Run No. Influent PP1 Effluent* PP2 Effluent PP2 Treatment
13 62' 4.6 3.8 01 2

14 62 2.2 2.3 C1 2 + 0 3
15 62 1.9 2.0 C1 2 + NaOH
16 36 1 .6 2.05 NH 2 C1
17 36 1 .6 2.2 NH 2 C1 + 0 3
18 36 1 .6 1.9 NH 2 C1 + NaOH
19 35 1 .6 2.6 C10 2
20 35 1.7 2.3 C10 2 + 0 3
21 35 1 .6 2.4 C10 2 + NaOH
22 22 2.0 1.7 NH 2 C1
23 22 2.2 1.9 NH 2 C1 + 0 3
24 22 2.1 2.4 NH 2 C1 + NaOH
25 24 1.5 2.0 C1 2
26 24 1.3 1.7 C1 2 + NaOH
27 24 1 .4 2.0 C1 2 + 0 3
28 33 1.9 2.7 C10 2
29 33 2.0 2.5 C10 2 + NaOH
30 33 2.0 2.9 C10 2 + 0 3
31 31 2.4 2.55 C1 2
32 31 2.6 1.9 Cl z + NaOH
33 42 3.1 3.2 NH 2 C1
34 42 3.1 3.0 NH 2 C1 + NaOH
35 44 5.2** 2.5 C1 2 + 0 3
36 44 1.9 2.1 NH 2 C1 + °3
37 37 1.9 2.9 C10 2
38 37 1.9 2.6 C10 2 + NaOH
39 37 1 .8 2.7 C10 2 + 0 3
40 6.6 3.4 2.9 C1 2
41 6.6 3.6 2.9 NH 2 C1
42 7.8 2.9 2.8 01 2
43 7.8 4.0 5.6 NH 2 C1
44 7.8 1 .3 1 .3 C10 2
45 6.7 1 .6 1.5 C10 2
46 6.1 1 .7 1 .5 C10 2
47 14 2.1 1 .6 C1 2
48 14 2.6 2.0 C10 2
49 13 1 .2 1.2 NH 2 C1
50 17 1 -9 1 .8 NH 2 C1
*Disinfectant to PP1 was always C1 2 with no additional adjustments.
**Sample probably not representative; before contact turbidity = 2.3.
88
Table VI-5. Pilot plant pH levels.
pH
13 7.78 7.1 7.1 C1 2

14 7.06 6.98** C1 2 + 0 3
15 7.1 8.35 C1 2 + NaOH
16 7.59 7.12 7.10 NH 2 C1
17 7.05 7.01 NH 2 C1 + 0 3
18 7.10 8.29 NH 2 C1 + NaOH
19 7.55 7.15 7.18 C10 2
20 7.13 6.97 C102 + 0 3
21 7.17 8.38 C10 2 + NaOH
22 7.63 6.94 6.92 NH 2 C1
23 7.02 6.95 NH 2 C1 + 0 3
24 6.92 8.04 NH 2 C1 + NaOH
25 7-76 7.37 7.32 C1 2
26 7.35 8.37 C1 2 + NaOH
27 7.28 7.22 C1 2 + 0 3
28 7.73 7.34 7.28 C10 2
29 7.34 8.22 C10 2 + NaOH
30 7.29 7.21 C10 2 + 0 3
31 7.64 7.32 7.28 C1 2
32 7.32 8.08 C1 2 + NaOH
- 33 7.65 7.26 7.29 NH 2 C1
34 7.17 8.22 NH 2 C1 + NaOH
35 7.65 7.21 7.24 C1 2 + 0 3
36 7.07 6.97 NH 2 C1 + 0 3
37 7.61 7.15 7.21 C10 2
38 7.12 7.82 C102 + NaOH
39 7.12 7.10 C10 2 + 0 3
40 7.5 7.6 7.6 C1 2
41 7.7 7.6 7.6 NH 2 C1
42 7.7 7.7 7.6 C1 2
43 7.7 7.7 7.7 NH 2 C1
44 7.7 7.5 7.4 C10 2
45 7.7 7.6 7.5 C10 2
46 7.6 7.6 7.5 C10 2
47 7.6 7.5 7.5 C1 2
48 7.6 7.5 7.5 C10 2
49 7.6 7.4
'7.4 7.4 NH 2 C1
50 7.5 7.3 NH 2 C1
*Dlsinfectant to PP1 was always C1 2 with no additional adjustments.

**pH reading was very unstable.
89
Duplicate bacteriological samples were taken from the effluent of the PP2
contact chamber every run and from the effluent of the PP1 contact chamber once
each day. The bacteriological results are summarized in Table VI-6 and Table
VI-7. An estimate of the influent's bacteriological quality was determined by
looking at the dally settled water sample taken in the laboratory. The Standard
Plate Count for the pilot plant Influent ranged from 180 to 3700 colonies per
100 mL and the fecal coliform count ranged from <1 to 7400 colonies per 100 mL.
Pilot Plant 1, which served as a control and received only chlorine as a
disinfectant, had a SPC maximum of 56 colonies per 100 mL In the effluent. The
fecal coliform count was less than one per 100 mL in the effluent for all runs,
but a non-sheen growth was present in some of the analyses. The use of ozone
with any of the disinfectants apparently eliminated any non-sheen growth and
reduced the number of colonies present. The Louisville Water Company's general
goal in bacteriological quality is to keep the Standard Plate Count of the
finished water at less than 10 colonies per 100 mL and the total coliform count
at less than 1 per 100 mL, but this goal was not met for all of the pilot plant
runs.
Chlorine dosages to the pilot plants ranged from 2.0 to 3.8 mg/L during the
sampling period. The approximate chlorine dosages and effluent chlorine
concentrations for the pilot plants treated with chlorine or chloramines are
listed in Table VI-8. Ammonium chloride was added to produce a 6:1 C^ to
NH_ ratio at the start of each day when chloramines were used as the primary
disinfectant. The feed rate of the NH.C1 was adjusted as necessary to obtain
mostly monochloramine and virtually eliminate the free chlorine. The relative
amounts of free chlorine, monochloramine, and dichloramine in the effluent of
the contact chambers are also listed in Table VI-8. Chlorine dioxide dosages
ranged from 0.51 to 1.57 mg CIO . Chlorine dioxide dosages and residuals in the
effluent from PP2 are listed in Table VI-9 for the days when chlorine dioxide
90
Table VI-6. Pilot plant bacteriological results, SPC.
Standard Plate Count (colonies/100 mD*
Run No. Influent PP1 Effluent** PP2 Effluent PP2 Treatment
13 330+ 24/12+ 17/10+ C1 2

14 1/4 C1 2 + 0 3
15 4+/13 C1 2 + NaOH
16 1170 5/8 6/11 NH 2 C1
17 <1 /<1 NH 2 C1 + 0 3
18 8/17 NH 2 C1 + NaOH
19 1140 7/15 8+/13 C102
20 2/1 C10 2 + 0 3
21 7/17 C10 2 + NaOH
22 540 12+/4+ 9+/8+ NH 2 C1
23 3/<1 NH 2 C1 + 0 3
24 21/23 NH 2 C1 + NaOH
25 190+ 3+/3+ 3+/3+ C1 2
26 24/18 C1 2 + NaOH
27 <1 /<1 C1 2 + 0 3
28 3700 11/13 9+/12 C10 2
29 15/7+ C10 2 + NaOH
30 5/<1 C10 2 + 0 3
31 1600 14/7+ 7/7+ C1 2
32 9/9+ C1 2 + NaOH
33 2200 10/15 14/8+ NH 2 C1
34 24/12+ NH 2 C1 + NaOH
35 400+ 5/13 5/3 C1 2 + 0 3
36 2/4 NH 2 C1 + 0 3
37 1300 4+/4 13/19 C10 2
38 23/25+ C10 2 + NaOH
39 1/4 C10 2 + 0 3
40 1330 38/23+ 20/20 C1 2
41 1330 —— 100/82 NH 2 C1
42 1400 56/55 50/60 C1 2
43 1400 —— 120/79 NH 2 C1
44 1400 —— 26+/39+ C102
45 820 22+/155+ 13+/22+ C10 2
46 610+ —— —— C10 2
47 380+ 16+/19+ 14+/13+ C1 2
48 380+ —— 16/20+ C10 2
49 180+ 6/4 10/14 NH 2 C1
50 330+ NH 2 C1
*Duplicate counts were taken from the effluents of PP1 and PP2.
**Sample was taken with the first run of the day.
+Spreader
91
Table Vl-7. Pilot plant bacteriological results, total coliforms.
Total Conforms* (counts per 100 mL)

Run No. Influent PP1 Effluent PP2 Effluent PP2 Treatment
13 2500 <-|**/<1** <1**/<1** C1 2

14 <1 /<1 C1 2 + 0 3
15 <1 **/<1 ** C1 2 + NaOH
16 2200 <1/<1*** <1 /<!*** NH 2 C1
17 <1 /<!*** NH 2 C1 + 0 3
18 <1 /<1 *** NH 2 C1 + NaOH
19 7400 <i/<i*«* <1/<1*** C10 2
20 <1 /<1 C10 2 + °3
21 <1 /<1 C10 2 + NaOH
22 1100 <1**/<1*#* <1 **/<i **# NH 2 C1
23 <1 /<!*** NH 2 C1 + 0 3
24 <1 /<1 *** NH 2 C1 4- NaOH
25 500 <1 /<1 <1 /<1 C1 2
26 <1 /<!*** C1 2 + NaOH
27 <1/<1*** C1 2 -H 0 3
28 3800 <1/<1*** <1**/<1*«* C10 2

29 <1**/<1*** C10 2 + NaOH
30 <1 **/<-) *** C10 2 + 0 3
31 1700 <1**/<1*** <! **/<!*** 01 2
32 <•) **/<!*** C1 2 + NaOH
33 3950 <]**/<-]*** <1 **/<T *** NH 2 C1
34 <1 *#/<i *** NH 2 C1 + NaOH
35 2650 <1 **/<i *** <1/<1*** C1 2 + 0 3
36 <1 /<1*** NH2 C1 + 0 3
37 5150 <1/<1 *** <1 /<1*** C10 2
38 <1/<1*** C10 2 + NaOH
39 <1/<1*«* C102 + 0 3
40 <1** —— <1 /<1*** C1 2
41 <1** <1 /<1*** <1/<1** s NH 2 C1
42 ' 164 <1/<1*** <1 /<1*** C1 2
43 164 —— <1 /<1 *** NH 2 C1
44 164 —— <1 **/<T *** C10 2
45 148 <1**/<1** <1**/<1** C10 2
46 . 88 —— —— C10 2
47 900 <1**/<1** <1 *#/<T »* C1 2
48 900 —— <!**/<]** C102
49 160 <1**/<1** <1 **/<1 ** NH 2 C1
50 140 ._. ... NH 2 C1
*Duplicate counts were taken from the effluents of PP1 and PP2.
**Non-sheen growth was present.
***M-Endo Agar L.E.S.
92
Table VI-3. Chlorine residuals in the effluent from the pilot plants and the chlorine dosages.
Effluent from PP1 Effluent from PP2
Run Approximate C1 2 Dosage Free Mono- Di- Free Mono- Di- Treatment
No. to PP1/PP2 (mg/L) Chlorine chloramine chloramine Chlorine chloramine chloramine for PP2
13 3.8 1 .62 0.17 0.20 1 .98 0.14 0.20 C1 2

14 3.8 1 .97 0.14 0.30 1 .25 0.15 0.11 C1 2
15 3.8 1 .80 0.15 0.35 1 .82 0.13 0.12 C1 2
16 2.5 1 .40 0.15 0.21 0.02 3.02 0.37 NH 2 C1
17 2.5 1 .22 0.14 0.27 0.22 2.22 0.05 NH 2 C1
18 2.5 0.99 0.14 0.31 0.17 2.88 0.06 NH 2 C1
19 2.4 1 .17 0.24 0.24 ——— ——— ——— C10 2
20 2.4 1.43 0.20 0.27 ——— ——— ——— C10 2
21 2.4 1 .50 0.14 0.18 ——— ——— ——— C10 2
22 2.7 1 .27 0.26 0.20 <0.01 2.55 0.30 NH 2 C1
23 2.7 1.47 0.09 0.39 0.19 1 .90 0.11 NH 2 C1
24 2.7 1 .25 0.11 0.28 <0.01 2.77 0.07 NH 2 C1
25 2.4 1.53 0.07 0.21 1 .52 0.14 0.16 C1 2
26 2.4 1 .49 0.10 0.17 1 .69 0.11 0.11 C1 2
27 2.4 1 .20 0.24 0.20 0.67 0.12 0.14 C1 2
28 2.4 1 .16 0.12 0.21 ——— ——— ——— C10 2
29 2.4 1.17 0.04 0.15 ——— ——— ——— C10 2
30 2.4 1 .25 0.04 0.21 ——— ——— ——— C10 2
31 2.4 0.89 0.23 0.25 1 .15 0.14 0.20 C1 2
32 2.4 1 .42 0.05 0.20 1 .61 0.05 0.07 C1 2
33 2.0 0.92 0.14 0.15 <0.01 1.99 0.13 NH 2 C1
34 2.0 0.95 0.19 0.11 <0.01 2.03 0.04 NH 2 C1
35 2.4 1 .41 0.30 0.08 1 .29 0.13 0.14 C1 2
36 2.4 1 .62 0.16 0.11 0.27 1 .83 0.24 NH 2 C1
37 2.2 1 .42 0.10 0.24 ——— ——— ——— C10 2
38 2.2 1 .49 0.10 0.18 ——— ——— ——— C10 2
39 2.2 1 .64 0.09 0.15 ——— ——— ——— C10 2
40 3.4 1 .49 0.18 0.11 1 .55 0.11 0.14 C1 2
41 3.4 1 .57 0.24 0.12 <0.01 2.84 0.03 NH 2 C1
42 3.4 1 .77 0.13 0.12 1 .02 0.12 0.13 C1 2
Table VI-8 (continued)
Effluent from PP1 Effluent from PP2

Run Approximate C1 2 Dosage Free Mono- Di- Free Mono- Di- Treatment
No. to PP1/PP2 (mg/L) Chlorine chloramine chloramine Chlorine chloramine chloramine for PP2
A3 3.4 1 .98 0.18 0.14 <0.01 3.24 0.04 NH 2 C1

44 3.4 2.92 0.14 0.09 ——— ——— ——— C10 2
45 3.6 2.07 0.16 0.05 ——— ——— ——— C10 2
46 3.6 1 .83 0.19 0.11 ——— —' — ——— C10 2
47 3.2 2.44 0.14 0.12 ' 2.61 0.18 0.07 C1 2
48 3.2 2.08 0 .21 ____ ——— —— C102
49 3.2 2.69 0.12 0.18 <0.01 3.45 0.09 NH 2 C1
50 3.2 1 .92 0.24 0.14 <0.01 3.12 0.10 NH 2 C1
Table VI-9. Chlorine dioxide dosages and residuals.
Approximate Dosage to PP2 Effluent from PP2
Run No. (mg ClOj/L) (mg C10 2 /L)
19 1.17 0.67
20 1 .17 0.24
21 1 .17 0.12
28 1 .14 0.67
29 1 .14 0.67
30 1 .14 0.20
37 1 .57 0.47
38 1 .57 0.23
39 1.57 0.17
44 0.62 0.49
45 0.62 0.46
46 0.62 0.44
48 0.51 0.40
95
was used as the primary disinfectant. The chlorine was fed by a peristaltic
pump with two heads. Slight differences in the flow rates of the two pilot
plants and differences in the feedrates of the chlorine by using two heads on
one pump likely explain the variations in chlorine residuals between PP1 and
PP2.
Concentrations of TOC in the raw water were used as an indication of the
level of organic precursors. The TOC level was sampled in each pilot plant
after coagulation and prior to the addition of the primary disinfectant. Table
VI-10 summarizes the values of TOC in the influent to the pilot plants and in
the effluent from the two pilot plants for each of the sampling dates.
Influent TOC concentrations at the Louisville Water Company averaged 3.54
mg/L during 1984, with a range of 2.26 to 7.01 mg/L. Concentrations during this
study ranged from 2.19 to 3.67 mg/L (Table VI-10), with no distinct trends which
could be attributed to temperature. For the low-temperature runs, Runs 13 to
39, effluent TOC levels ranged from 47% to 65% of the initial influent
concentration. Effluent TOC concentations for the high-temperature runs, Runs
40 to 50, ranged from 76% to 95% of the influent concentrations. The average
decrease in influent TOC was 44% for the low-temperature runs and 18% for the
high-temperature runs, with no significant differences between treatments or
disinfectants.
The values of TOC obtained from the effluent of the contact chambers showed
an additional removal of less than 13% of the influent value. This confirmed
that coagulation and removal of the colloidal particles were responsible for the
majority of TOC removal. There was little additional TOC reduction after
application of the disinfectant, regardless of the disinfectant used.
The THM level in the raw water was generally less than the minimum
detection limit (MDL). The MDL's using the purge and trap method were 0.05 ug/L
for CHC1 3 , 0.1 ug/L for CHCl2 Br and CHBr2 Cl, and 0.5 ug/L for CHBr3 -
96
Table VI-10. Pilot plant TOC concentrations.
TOC Concentration (mg/L)
13 3.43 1.42 1 .44 C1 2

14 3.43 1 .36 1 .31 C1 2 + 0 3
15 3.43 1 .38 1 .29 C1 2 + NaOH
16 2.58 1.28 1 .32 NH 2 C1
17 2.58 1 .29 1 .28 NH 2 C1 + Os
18 2.58 1 .24 1 .26 NH 2 C1 + NaOH
19 2.17 1 .42 1 .42 C10 2
20 2.71 1.46 1 .40 C10 2 + 0 3
21 2.71 1 .46 1.39 C10 2 + NaOH
22 2.44 1 .29 1 .31 NH 2 C1
23 2.44 1.31 1 .32 NH 2 C1 + 0 3
24 2.44 1.31 1.25 NH 2 C1 + NaOH
25 2.19 1 .48 1 .52 C1 2
26 2.19 1 .44 1 .54 C1 2 + NaOH
27 2.19 1.53 1 .55 C1 2 + 0 3
28 2.79 1 .79 1.79 C10 2
29 2.79 1.76 1.76 C10 2 + NaOH
30 2.79 1 .78 1 .70 C10 2 + 0 3
31 2.51 1.51 1 .54 C1 2
32 2.51 1.52 1 .58 C1 2 + NaOH
33 2.56 1 .61 1 .65 NH 2 C1
34 2.56 1 .62 1 .64 NH 2 C1 + NaOH
35 3.22 1.72 1 .60 C1 2 + 0 3
36 3.22 1.58 1.59 NH 2 C1 + 0 3
37 2.64 1.33 1 .38 C10 2
38 2.64 1 .33 1.37 C102 + NaOH
39 2.64 1 .31 1.39 C10 2 + o 3
40 3.27 2.84 2.70 C1 2
41 3.27 2.89 2.71 NH 2 C1
42 3.06 2.73 2.74 C1 2
43 3.06 2.70 2.92 NH 2 C1
44 3.06 2.40 2.42 C10 2
45 — 2.40 2.40 C10 2
46 2.67 2.24 2.16 C10 2
47 2.96 2.47 2.44 C1 2
48 2.96 2.30 2.20 C10 2
49 — 1 .87 1 .86 NH 2 C1
50 2.95 2.25 2.30 NH 2 C1
*Disinfectant to PP1 was always C1 2 with no additional adjustments.
97
When THM's were detected, they were present only in the form of
chloroform and always at levels less than 1 ug/L. The maximum Influent THM
concentration was 0.57 ug/L for the low-temperature runs; no THM's were detected
in the influent for the high-temperature runs. The THM values for the influent
to the pilot plants are listed in Table VI-11. Figure VI-11 shows the effluent
total THM (TTHM) levels from PP1 for each of the runs performed. The high data
point at run 28 may be the result of analytical error; the analyst reported
instrumental difficulties at that time. Otherwise, the relative consistency of

the TTHM values indicated good control of pilot plant operation throughout the
sampling period. Figure VI-12 shows the TTHM levels for the effluent from PP2.
The large increase beginning with Run 40 indicated the influence of temperature
on THM formation. For Runs 13, 25, 31, 40, and 47, both pilot plants were run
under identical conditions of free chlorine dosage to ensure that any observed
differences in THM and TOX formation were not attributable to differences in the
pilot plants. Since the Influent to the pilot plants contained such low
concentrations of TTHM's, any THM's in the effluent could be assumed to have
formed during the treatment process.
The influent TOX levels to the pilot plants ranged from 9 to 20 ug
C1~/L during the sampling period and are summarized In Table VI-12. Values
were relatively constant and demonstrated no seasonal variation. The TOX values
in the effluent from PP1 and PP2 are shown in Figures VI-13 and VI-14,
respectively. Figure VI-13 again demonstrates both the consistency of pilot
plant operation and a lack of seasonal variation in TOX levels.
STATISTICAL ANALYSIS OF PILOT PLANT DATA
Readily available statistical programs (Ryan et al., 1981; Madigan and
Lawrence, 1982) were used to examine the statistical significance of the results
obtained. Since there were three disinfectants used and three adjustments to
98
FIGURE VI-11. EFFLUENT THM LEVELS
PILOT PLANT 1, RUNS * 13 TO 50
35 -
30 - _-1
\
25 - \
\ \
\ \ ^ \
20 - \ \ \ \ \ \
\ \ \ \ \ \
n\ n\ - -
15 - \ \ \ \ \ \ \ \ \ \ \
\ \ \ \ S \ \ \ \ \ \
10 - \ \ \ \ \ \ \ \ \ \ \
\ \ \ \
n\
\ \ \ \ \ \ \
j-0
5 - \ \ \ \ \ \ \ \ \ \ \ \
•^ —
\^ \ n\ ^ \ \ \ \
n\ ^ \ \ \ \ \ \ \ \ \
înRs\ \ \ \ \ \ \ \ \ \ \ \ \
1 1 1 1
0 - i • • ' 1
RnRnnnpn
i i i i i i i i \ \1 1
RR R' • i i i i i i i i i i i
i
n \' \i 1 \* \ \ \1 fl
13 18 23 28 33 38 43 48
RUN
FIGURE VI-12. EFFLUENT THM LEVELS
35 -
-
30 -
25 -
\ \
N
o 20 - \ \
o
\ \ ^
15 _
- \ \ \
\ \ \
10 - \ \ \
r—| \ \ \
n \ N \ \ s
\ \ \ \ \ \
^ NRRrnnin n,nRN \ n \ \ RR n \ \ \ RRR
i
13 IB 23 28
P 33 38
nRn 43 48
RUN
FIGURE VI-13. EFFLUENT TOX LEVELS
140
130
120 \ \
110
\ \ \ \ -
100 \\\\ \s
\\\ \ \\\-
90
17 \ \ \ \ \ \ \ \ _. \
80 \ \ \ \ \ \ \ \ \ r—i \
1
« 70 \ \ \ \ \ \ \ \ \ \ \
——\ \\ \ \ \\\\\ \ \
K 60
's \ \ \ \ \ \ _, \ \- \ p. n \ \ \ \ \ \ \ \ \ \ \
e 50
\ •— ^ i-^ r-1 \\\\\\\\\^\\\- \\\ \\\\\\ \ \
n\ —
40
\ \ \ \ \ \ \ \ \ \ \ \
30 \ \ \ \ \ \ \
\ \ \ \ \ \
n\ \\ \\ \\ \\ \\ \\ S\ \\ \\ \\ \\ \\ \\ \\ \\ \s \\ \\ \\ \\ \\ \\ \\ \\
20 S \ \ \ \ \ \ \ \ \ \ \\\\\\\\\\\s\\\\\\\\\\\\\ \ \
\ \ \ \ \ \ \ \ \ \ \ \\\\\\\\\\\\\\\\\\\\\\\\\ \ \
10
\ \ \ \ \ \ \ \ \ \ \ \\\\\\\\\\\\\\\\\\\\\\\\\ \ \
0
13 18 23 28 33 38 43 48
RUN *
FIGURE VI-14. EFFLUENT TOX LEVELS
140
130
120 \
\
110
\ \
100 -%
\ \
90
\ \ \
80 \ \ \
70 \ \ \
\ \ \
60
\ "s \ \ "x \ \ \
I 50
\ \ \ \ \ \ \ \
40
N s \ \ \ \ \ \ S \ \ \
30 \ \ \\ \ \ \ \ \ \ \ \
20 \ \ \ \ \\ \ \ \ \ \ \ \ ^ \ \ \ \
\ \\ \ \\ \ ^ \ \ \ ^ \ \ \ \ \ \ \ \ \ \ \
10
\ \ \ rqNNnR \ \ \ \ \ \ \ \ \ \ \ \ \ \ \ \ \ \ \
1 i i r ' iiii 1 '
0 n • i i i i \ i R R B I Ri i i i (WRN
i i i | i • i i | i •H . 1 i i
13 18 23 28 33 38 43 48
RUN
Table VI-11. Influent TTHM levels for pilot plant runs 13-50.
Run No. TTHM (fig/L)»
13-15 <0.05
16-18 0.57
19-21 <0.05
22-25 <0.05
26-28 <0.05
29-30 <0.05
31-32 <0.05
33-34 <0.05
35-36 <0.05
37-39 <0.05
40-41 <0.05
42-44 <0.05
45 <0.05
46 <0.05
47-48 <0.05
49 <0.05
50 <0.05
* Chloroform was the only THM detected.
103
Table VI-12. Influent TOX levels for pilot plant Runs 13 to 50.
Run No. TOX (ng/L)
13-15 16
16-18 13
19-21 17
22-25 9
26-28 13
29-30 20
31-32 14
33-34 13
35-36 15
37-39 14
40-41 15
42-44 16
45 14
46 13
47-48 14
49 —
50 11
104
pilot plant operation made for the data collected at low temperatures, a two
sample t-test was performed to show the relative significance between any two of
the combinations performed. Results from the two sample t-tests on the TTHM and
TOX data for the low-temperature runs are summarized in Tables VI-13 and VI-rl4,
respectively.
A. two-way analysis of variance was used to compare the TTHM and TOX data
from all 27 of the low-temperature runs to the type of disinfectant used and to
the type of adjustment (Table Vl-15). The critical F values in the analysis of
variance for the various parameters considered were dependent on the number of
degrees of freedom assigned to both the treatment and error terms. Critical F
values for this data were found in Bulgren (1982). Computed F values greater
than the critical values are considered to be significant at the appropriate
level of significance.
It should be emphasized that the raw water temperatures observed during the
low-temperature runs had some effect on the interpretation of the data,
especially for THM's. The small changes between influent and effluent THM
levels minimized differences between treatments; in many cases the observed
differences were less than the expected analytical error. Although the low
results affected the statistical significance of the results observed, the
trends observed for the low-temperature runs are in agreement with results
reported in the literature and results obtained during runs at higher
temperatures during this study.
Unequal numbers of samples were collected for the three primary
disinfectants for the low- and high-temperature runs. Regression analyses and
analyses of variance were used to determine the significance of temperature
effects on the various parameters examined. Results of the analyses of variance
for the effects of temperature on TTHM, TOX, and TOG levels are presented in
Tables VI-16, VI-17, and VI-18, respectively.
105
Table VI-13. Two-sample T-test statistical analysis of TTHM data for the
effluent from Pilot Plant 2.
Mean TTHM Value

Comparison (u.g/L) Significance Level
C1 2 3.57
vs. NH 2 C1 2.00 0.10
C1 2 3.57
vs. C10 2 0.33 0.01
NH 2 C1 2.00
vs. C10 2 0.33 0.10
C1 2 + +pH 6.00
vs. NH 2 C1 + +pH 1 .33 0.10
NH 2 C1 + +pH 1 .33
vs. C10 2 + +pH 0.20 0.10
C1 2 + +pH 6.00
vs. C10 2 + +pH 0.20 0.05
C1 2 + 0 3 1 .80
vs. NH 2 C1 + 0 3 0.90 N.S.
C1 2 + 0 3 1 .80
vs. C10 2 + 0 3 2.70 N.S.
NH 2 C1 + 0 3 0.90
vs. C10 2 + 0 3 2.70 N.S.
C1 2 3.57
vs. C1 2 + tpH 6.00 N.S.
NH 2 C1 2.00
vs. NH 2 C1 + +pH 1 .33 N.S.
C10 2 0.33
vs. C10 2 + +pH 0.20 N.S.
C1 2 3.57
vs. C1 2 + 0 3 1 .80 N.S.
NH 2 C1 2.00
vs. NH 2 C1 + 0 3 0.90 N.S.
C10 2 0.33
vs. C10 2 + 0 3 2.70 N.S.
C1 2 + ^H 6.00
vs. C1 2 + 0 3 1 .80 0.10
NH 2 C1 + +pH 1 .33
vs. NH 2 C1 + 0 3 0.90 N.S.
C10 2 + ipH 0.20
vs. C10 2 + 0 3 2.70 N.S.
N.S. = not significant at the 0.10 level
106
Table VI-14. Two-sample T-test statistical analysis of TOX data for the
effluent from Pilot Plant 2.
Comparison Change in TOX* Significance Level

C1 2 3.93
vs. NH 2 C1 2.16 0.05
C1 2 3.93
vs. C10 2 0.81 0.01
NH 2 C1 2.16
vs. C10 2 0.81 0.10
C1 2 + +pH 3.69
vs. NH 2 C1 + +pH 1 .21 0.05
C1 2 + ipH 3.69
vs. C10 2 + tpH 0.62 0.05
NH 2 C1 + +pH 1 .21
vs. C10 2 + fpH 0.62 0.10
C1 2 + 0 3 0.88
vs. NH 2 C1 + 0 3 0.56 N.S.
C1 2 + 0 3 0.88
vs. C10 2 + 0 3 0.41 0.05
NH 2 C1 + 0 3 0.56
vs. C10 2 + 0 3 0.41 N.S.
C1 2 3.93
vs. C1 2 + ipH 3.69 N.S.
NH 2 C1 2.16
vs. NH 2 C1 + tpH 1.21 0.10
C10 2 0.81
vs. C10 2 + tpH 0.62 N.S.
C1 2 3.93
vs. C1 2 + 0 3 0.88 0.01
NH 2 C1 2.16
vs. NH 2 C1 + 0 3 0.56 0.05
C10 2 0.81
vs. C10 2 + 0 3 0.41 0.05
C1 2 + +pH 3.69
vs. C1 2 + 0 3 0.88 0.05
NH 2 C1 + tpH 1 .21
vs. NH 2 C1 + 0 3 0.56 0.10
C10 2 + t pH 0.62
vs. C10 2 + 0 3 0.41 N.S.
*Effluent TOX/Influent TOX
107
Table VI-15. Two-way analysis of variance data for Pilot Plant 2 ef
fluents at low temperatures.
Variables Computed F Critical F Significance Level
TUM
Disinfectant 6.85 6.01 0.01
Treatment 0.43 2.62 N.S.

Interaction 3.30 2.93 0.05
- TOY
Disinfectant 71.5 6.01 - 0.01
Treatment 42.02 6.01 0.01

Interaction 11.98 4.58 0.01
N.S. = not significant at the 0.10 level.
108
Table VI-16. Analysis of variance for changes in TTHM levels (effluent-
influent) as a function of temperature and primary disinfectant.
ATTHM
(|-ig/L)
Treatment (eff.-inf.) Variable Computed F Significance
Low-temperature Chlorine 3.86 Temperature 43.73 p<0.001

Low-temperature Chloramine 1.84
Low-temperature Chlorine dioxide 1.53
Disinfectant 92.14 p<0.001
High-temperature Chlorine 21 .38

High-temperature Chloramine 1 .41
High-temperature Chlorine dioxide 0.16 Interaction 60.27 p<0.001
109
Table VI-17. Analysis of variance for changes in TOX levels (effluent-
ATOX
Low-temperature Chlorine 37.2 Temperature 58.84 p<0.001

Low-temperature Chloramine 12.7
Low-temperature Chlorine dioxide -3.3
Disinfectant 114.85 p<0.001
High-temperature Chlorine 90.7

High-temperature Chloramine 18.8
High-temperature Chlorine dioxide 14.3 Interaction 17.95 p<0.001
110
Table VI-18. Analysis of variance for changes in TOC levels (effluent-
ATOC
(mg/L)
Low-temperature Chlorine -1 .22 Temperature 30.67 p<0.001

Low-temperature Chloramine -1.10
Low-temperature Chlorine dioxide -1.18
Disinfectant 0.24 N.S.
High-temperature Chlorine -0.54

High-temperature Chloramine -0.53
High-temperature Chlorine dioxide -0.62 Interaction 0.11 N.S.
111
Effect of Primary Disinfectant on TTHM and TOX Levels
Comparison of the three disinfectants, with no other modifications in the
treatment scheme for the low-temperature runs (Table VI-13), showed that the
free chlorine produced the highest mean level of TTHM's (3.57 ug/L), followed by
chloramines (2.00 ug/L), and then chlorine dioxide with the lowest mean TTHM
level (0.33 ug/L). Results from the two sample t-test indicated chlorine
produced significantly higher levels of TTHM's than either chloramine or
chlorine dioxide (p<0.0l), and that chloramines produced significantly higher
TTHM levels than chlorine dioxide at the 0.10 confidence level; however, the
differences between chloramines and chlorine dioxide are well within the
expected analytical error and may not, in reality, be significant. The mean THM
formation was reduced by 45% by using chloramines instead of free chlorine. The
observed reduction in TTHM levels at low temperature was not as great as the
value of 95% reported by Stevens et al. (1985), probably due to the low levels
of TTHM observed during the study period, and to the presence of some free
chlorine in the chloramine runs.
Chlorine dioxide had been reported to produce no THM's (Stevens et al.,
1985). The data in the pilot plant study tends to agree with those findings.
The mean value of TTHM's in the effluent from PP2 when CIO was used as the
disinfectant was only 0.33 ug/L and raw water TTHM's were also less than 1 ug/L.
The variation in the TTHM level in PP2 produced as a function of disinfectant
used was significant at the 0.01 level using the two way analysis of variance
test (Table VI-15), but the type of adjustment in pilot plant operation caused
no significant variation in TTHM levels in the PP2 effluent. The interaction
between type of disinfectant and type of adjustment was significant at the 0.05
level. This indicates that there were significant differences in the TTHM
values due to a combination of type of disinfectant and type of adjustment to
112
pilot plant operation.
Comparison of the three disinfectants, with no additional modifications to
pilot plant operation, showed that treatment with both chlorine and chloramines
caused an increase in TOX (Table VI-14). Chlorine produced a TOX value that was
3.6 to 4.2 times (mean = 3.93) that of the influent and chloramines yielded a
TOX level that was 1.6 to 2.8 times (mean = 2.16) that of the influent. In
contrast, TOX concentrations decreased following treatment with C102.

Effluent TOX values were only 0.65 to 0.93 times (mean = 0.81) that of the
influent.
Use of chloramine in place of chlorine reduced the mean value of TOX formed
by 45%. This reduction is not as great as the value of 85% reported by Stevens
et al. (1985) and, like the low TTHM reductions, may have been caused by the
relatively low levels of TOX observed during the study period and to the
presence of some free chlorine in the chloramine runs. The use of chlorine
dioxide in place of chlorine yielded an even lower TOX mean value than
chloramine, agreeing with the results of Stevens et al. (1985). The variation
in the TOX level in PP2 produced as a function of oxidant was significant at the
0.01 level for the two-way analysis of variance test (Table Vl-15). The TOX
value produced as a function of adjustment to pilot plant operation was also
significant at the 0.01 level in the analysis of variance test, as was the
interaction between type of disinfectant and type of adjustment.
A comparison of the oxidants, with no additional changes in pilot plant
operation, using the two-sample t-test indicated that chlorine produced
significantly higher levels of TOX than chloramine (p<0.05) and significantly
higher levels of TOX than chlorine dioxide (p<0.01). The mean TOX value for
chloramine was significantly higher than the mean TOX value for chlorine dioxide
at the 0.10 confidence level.
113
Effects of Increased pH on Pilot Plant Effluents
The mean value of the TTHM for chlorine with increased pH (6.00 ug/L) was
higher than that of chloramine with increased pH (2.00 ug/L) for the runs made
at low temperatures. The means for both chlorine and chloramines with increased
pH were higher than the mean for C102 with increased pH (0.20 ug/L). Analysis
of the THM data for the oxidants with increased pH in the two sample t-test
(Table VI-13) indicated that chlorine with increased pH produced
significantly higher TTHM levels than the chlorine dioxide at the 0.05 level.
The TTHM levels following treatment with chloramines at elevated pH levels were
significantly lower than those produced by treatment with chlorine at increased
pH, and were significantly higher than those produced by treatment with chlorine
dioxide at increased pH at the 0.10 level.
The increase in TTHM concentrations following treatment with chlorine at
increased pH, compared with chlorine with no additional changes in operating
conditions, was in agreement with previous studies (Rook, 1976; Stevens et al.,
1976; Oliver and Lawrence, 1979; Kavanaugh et al., 1980; Oliver and Schindler,
1980; and Peters et al., 1980). In contrast, treatment with either chlorine
dioxide and chloramines produced mean TTHM values that were slightly higher when
no adjustment was made than when NaOH was added to raise the pH. The mean
differences in TTHM concentrations, less than 1.0 ug/L when pH was raised and
either chloramines or chlorine dioxide were used as the primary disinfectant,
were too small to lead to any definite conclusions concerning the relative
benefits or liabilities of those two disinfectants. The two sample t-test
comparing the disinfectant alone to the disinfectant with increased pH indicated
no statistically significant differences in THM formation occurred as a function
of pH for any of the disinfectants examined.
Treatment using chlorine with NaOH added also resulted in the largest
increase in TOX of the three primary disinfectants. The effluent TOX levels
114
from the pilot plant treated with chlorine at increased pH were 3.7 times those
of the influent. Treatment with chloramines at increased pH produced a mean
effluent TOX 1.2 times higher than the influent. In contrast, treatment with
C1CL at elevated pH levels caused TOX concentrations to decrease to an average
of 60% of the influent levels. Comparisons of the TOX data for the
disinfectants with increased pH (Table VI-14) showed that treatment with
chloramines at increased pH produced significantly higher TOX values than
treatment with chlorine dioxide at increased pH (p<0.10) in the two sample
t-test. Both chloramine and chlorine dioxide produced significantly lower
effluent TOX concentrations than chlorine at elevated pH.
Comparison of the disinfectant, with and without pH adjustment, indicated
that mean TOX values tended to decrease when NaOH was added, although the
increases were not always statistically significant. Of the three primary
disinfectants, only treatment with chloramines resulted in significantly higher
mean TOX values at the lower pH at the 0.10 confidence level. The decrease in
TOX formation with increased pH observed in the pilot plant effluents agrees
with previous studies (Fleischacker and Randtke, 1983; Stevens et al., 1985).
Effects of Pre-ozonation on Pilot Plant Effluents
All values of TTHM were lowered by using ozone as a pre-oxidant at low
temperatures. Treatment using chloramines with pre-ozonation resulted in the
lowest mean TTHM value, 0.90 ug/L, of any of the treatments examined.
Chlorination in combination with pre-ozonation produced a mean TTHM value of
1.80 ug/L. The highest mean TTHM value of the group, 2.70 ug/L, was produced by
pre-ozonation in combination with C102, but one apparently bad data point may
have affected the results for this combination. Two TTHM concentrations were
less than 1.5 ug/L, but the third was 7.0 ug/L, over three times the other two
values. The third point may have been the result of analytical error because
115
the operator of the gas chromatograph reported trouble In obtaining a stable
baseline when the third sample was analyzed. Without inclusion of the high TTHM
value, average TTHM concentrations following treatment with C1CL and
pre-ozonation would have been as low as TTHM concentrations produced by
treatment using chloramines with pre-ozonation.
Although mean TTHM concentrations for each disinfectant with pre-ozonation
were lower than the concentrations of TTHM produced by the disinfectant alone,
differences in TTHM concentrations for the primary disinfectants with and
without pre-ozonation were not significant in the two sample t-test (Table
VI-13). All mean TTHM concentrations for the primary disinfectant with
pre-ozonation were low, and the expected analytical error was of approximately
the same magnitude as the results. Therefore, no significant differences could
be found. This emphasizes one of the weaknesses of the two sample t-test for
analyzing this data. The test is intended mainly for larger populations and,
with the triplicate samples run for this study, a large error in one point is
magnified in the statistical analysis.
Pre-ozonation in conjunction with each of the disinfectants examined
yielded a lower mean TTHM level than use of the disinfectant at increased pH,
except in the case of C1CL, which was probably affected by a bad data point.
Levels of THM's produced by chlorine with increased pH were significantly higher
than treatment with chlorine using ozone as a pre-ox.idant at the 0.10 level in
the two sample t-test. Treatments with chloramines at an increased pH versus
treatment with chloramines with ozone added as a pre-oxidant or treatment with
chlorine dioxide at an increased pH versus treatment with chlorine dioxide with
ozone were not significantly different.
The mean TOX values for the disinfectants with pre-ozonation were much
lower than the mean TOX values for the disinfectant only. The observed
reductions in TOX when ozone was used as a pre-oxidant were significant at the
116
0.05 level when chloramines or chlorine dioxide was used as the primary
disinfectant, and at the 0.01 level when chlorine was the primary disinfectant.
Both increased pH and pre-ozonation in conjunction with one of the
disinfectants reduced the mean TOX values in pilot plant effluents. Treatment
with chlorine at increased pH produced a significantly higher mean TOX level
than treatment with chlorine and ozone (Table VI-14). Significantly higher TOX
levels were produced by chloramines in combination with increased pH than by
chloramines in combination with ozone. Chlorine dioxide with increased pH was
not significantly different from chlorine dioxide with pre-ozonation, probably
because TOX levels were very low following TOX reductions with both treatments.
Effects of Temperature on Pilot Plant Effluents
Temperature effects on TOO, TOX, and THM concentrations were examined by
comparing data from pilot plant Runs 13 to 39 with data from Runs 40 to 55 for
each disinfectant. Because Pilot Plant 1 was not used as a control for extended
Runs 51 to 55, the statistical analysis of the data was altered for the
determination of temperature effects. All pilot plant runs using a given
disinfectant, including runs 13 to 39 for Pilot Plant 1 with chlorine as the
disinfectant, were combined for the analysis of temperature effects.
Temperature effects on treatment with the various disinfectants at elevated pH,
or in combination with pre-ozonation, were not examined because of time
constraints.
Temperature effects on concentrations of TTHM for each of the disinfectants
examined are readily apparent from scatterplots of increases (effluent levels
minus influent levels) in TTHM concentrations as a function of temperature for
each of the three primary disinfectants. Results for TTHM concentrations are
shown in Figures VI-15, VI-16, and Vl-17 for treatment with chlorine,
chloramines, and chlorine dioxide, respectively. The production of TTHM's
117
FIGURE VI-15. SCATTERPLOT
CHLORINE, TTHM VS TEMPERATURE
4.0
35 -
30 -
a
a
25 -
E
a
20 - a
oo
15 -
10 - D
5 -
l
9 11 13 15 17 19 21 23
TEMPERATURE C
CHLORAMINES, TTHM VS TEMPERATURE
« —
3 - D
2 -
° o
D
Z
*H _
w. 3
M A ~ D
31 D D
D
0 -
— 1 —
-2 - D
i i i i i i i i i i i i i i i i i i I i
<i 7 9 11 13 15 17 19 21 23 25
TEMPERATURE C
CHLORINE DIOXIDE, TTHM VS TEMPERATURE
a, —
a
3 -
2 -
^~» aa
fc
2
H-I <
1 * ~ a
D
6
————————————B———————————————————————————————B——B—————————————S——
§fc
-1 -
-2 -
a
_o _
O i i i i i i i i i i i i i i i i i i i i
»i 7 9 11 13 15 17 19 21 23 25
TEMPERATURE C
increased significantly with temperature when chlorine was used as the
disinfectant (Figure VI-15 and Table VI-16). Small decreases in TTHM production
with temperature were noted when either chloramines (Figure VI-16 and Table
VI-16) or chlorine dioxide (Figure VI-17 and Table VI-16) were used as the
disinfectant; however, differences between effluent and influent concentrations
were small, and were within expected analytical error. An analysis of variance
(Table VI-16) confirmed that both temperature and disinfectant, as well as the
interaction between the two, had significant (p>0.001) effects on TTHM
production. . A multiple regression analysis and a step-wise regression analysis,
using influent temperature, THM, TOX, and TOG levels as predictors, were
examined for the prediction of effluent THM and/or TOX levels, but results were
inconclusive, and temperature appeared to be the only significant predictor for
effluent THM or TOX concentrations for any of the disinfectants examined.
The use of chlorine as the primary disinfectant also led to a significant
(p>0.001) increase in the formation of effluent TOX with temperature (Figure
VI-18 and Table VI-17). The formation of TOX also increased with temperature
when either chloramines (Figure VI-19 and Table VI-17) or chlorine dioxide
(Figure VI-20 and Table VI-17) were used. As mentioned previously, differences
in THM and TOX production between chlorine and the other disinfectants at low
temperature were not as great as those reported in the literature (Stevens et
al., 1985); however, the observed differences at high temperatures did approach
these earlier studies.
Temperature also had significant effects on changes in TOC with all three
of the disinfectants examined. The type of disinfectant had little effect on
TOC concentrations, but a larger decrease in TOC concentrations was observed at
the lower treatment temperatures in all cases (Table VI-18). TOC levels had no
significant effects on either THM or TOX concentrations in the pilot plant
effluents but, as noted previously, coagulation was responsible for most of the
121
Table VI-19. Summary of treatment effects on THM and TOX concentrations
for the three primary disinfectants investigated.
Disinfectant Variable THM TOX
Chlorine pH N.S. N.S.

Pre-ozonation N.S. p<0.01
Temperature p<0.001 p<0.001
Chlorine pH N.S. P<0.10

Temperature N.S. N.S.
Chlorine dioxide pH N.S. N.S.

Temperature N.S. p<0.05
122
CHLORINE, TOX VS TEMPERATURE
J./CV —
a
110 - a
g
100 - D
D D
90 -
D D
80 - § a a
a D
70 -
a
U> 60 -
1£
X
g 50 -
P CD,-,
40 - a R nci
D gi
30 - 0 SB g°
20 -
a
10 -
0 - \]\}\]\\\\\\\\\\\
<S 7 9 11 13 15 17 19 21 2
TEMPERATURE C
CHLORAMINES, TOX VS TEMPERATURE
oa —
30 -
D
25 - D
D D
§ 20 -
NJ
D
15 -
siX
O a a a
D D
10 -
a
5 -
a
0 - 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 !
i>i 7 9 11 13 15 17 19 21 23 25
TEMPERATURE C
CHLORINE DIOXIDE, TOX VS TEMPERATURE
JiJ —
D
30 -
D
25 -
20 -
Z D
7 is -
NJ
fc
U D
*" 10 -
*o
H
D
5 -
D
D
0 -
D
D
-5 -
D
-10 - I 1 I 1 I I f I I I I 1 1 I I I 1 1 I 1
5 7 9 11 13 15 17 19 21 23 25
TEMPERATURE C
TOG removal during treatment, and only small changes in influent TOG
concentrations were observed during the pilot plant runs.
The effects of increased pH, pre-ozonation, and temperature on THM and TOX
concentrations for each of the three primary disinfectants are summarized in
Table VI-19. As noted previously, effects of increased pH and pre—ozonation
were examined only at low temperatures. Increases in treatment pH did not
result in significant changes in either THM or TOX concentrations for any of the
primary disinfectants. Pre-ozonation had no significant effects on THM's, but
there was a significant decrease in TOX levels when pre-ozonation was used in
combination with each of the three disinfectants. Both THM and TOX
concentrations increased with temperature when chlorine was used as the
disinfectant, while no significant effects on either THM or TOX were observed
when chloramines were used. There was no significant change in THM levels with
temperature when chlorine dioxide was used as the disinfectant, but TOX levels
increased.
EXTENDED PILOT PLANT RUNS
The experimental design for the first 50 pilot plant runs utilized Pilot
Plant 1, which was always treated with free chlorine, as a control unit. Data
from these runs indicated that treatment schemes other than free chlorine
greatly reduced the THM and TOX levels; however, the differences between the
various alternates was not firmly established. Data from these runs and
reaction curve work also indicated that pre-ozonation showed promise in reducing
the TOX and THM reaction, particularly in the first hour of reaction. To better
define the effectiveness of the alternate disinfectants and pre-ozonation in the
TOX and THM reactions, a final series of pilot plant runs, Runs 51 to 56, was
conducted. These runs were extended to allow longer contact times for the
reactants, and to allow appropriate samples to be collected for mutagenicity
126
testing. These runs did not utilize Pilot Plant 1 as a free chlorine control.
The treatment schemes used for the extended pilot plant runs are listed in Table
Vl-20 and operational data are listed in Appendix C.
Treatment with Ozone as a Pre-oxidant
The effect of ozonation after coagulation and before disinfection with
chlorinated oxidants on the THM and TOX reactions was investigated in Runs 51,
52, 53, and 55 (Figures VI-21 and VI-22). Ozone was fed to the effluent of
Pilot Plant 2 in each of these runs, followed by the chlorinated disinfectant.
The chlorinated disinfectant was fed immediately (approximately 15 seconds)
after ozone addition in Runs 51, 52, and 53. A review of the data and a recent
article on ozone/chlorine interactions (Hoigne, 1985) prompted the separation of
the ozone/chlorine process application points by a 15-minute reaction time. The
chlorine dioxide run, Run 53, was repeated in Run 55, with improved results.
The data from Runs 51, 52, 53, and 55 are presented in Tables VI-21, VI-22,
VI-23, and VI-24, respectively. In each case, pre-ozonation (Pilot Plant 2)
resulted in lower TOX and THM levels than those produced by the control
treatment (Pilot Plant 1), which the same chlorinated disinfectants without
pre-ozonation. The impact of pre-ozonation on the chlorine reactions is
illustrated by the data from Run 51 (Table VI-21). The decrease in THM
formation resulting from pre-ozonation, 18.8 ug/L versus 31 ug/L TTHM for the
control after 30 minutes, was expected from results with the reaction curve
data. The difference, 4.7 ug/L versus 20.4 ug/L, was even more pronounced for
the 12-minute reaction time, again indicating that pre-ozonation can effectively
limit THM formation in the early minutes of the reaction. Similar trends were
observed for TOX data, with pre-ozonation significantly reducing TOX levels
after both the 12-minute (28 versus 93 ug Cl /L) and 30-minute (57 versus
131 ug Cl /L) reaction times. Measureable chlorine residuals were
127
TABLE VI-20
TREATMENT SCHEMES FOR PILOT PLANT RUNS 51-56
Date Run No. PP1 PP2

6/12 to 6/18/85 51 Chlorine Ozone/Chlorine
6/20 to 6/25/85 52 Chloramine Ozone/Chlorarnine
6/27 to 7/04/85 53 Chlorine Dioxide Ozone/Chlorine Dioxide
7/07 to 7/13/85 54 Chloramine Chlorine Dioxide
7/22 to 7/27/85 55 Chlorine Dioxide Ozone/Chlorine Dioxide
12/20 to 12/24/85 56 Chlorine/Chloramine Ozone/Chlorine/Chloramine
128
FIGURE VI-21. TOX VALUES, EXTENDED RUNS
RUNS: * 51, 52, 54, AND 55
160
150
140
PP1
130 n
\
120
\
110
\
\
100
pr \
90
/\
/\
VO 80
/ \
/ \
gh 70 / \
/ \
60 PP2
/ \
/ \ \
50
PPI
/ \ \
/ \ \
s n 1 ^L
40 X\ \ rs PP1 /PP2 /PPl <fp2
/\ \ /S PP2 ~ ' r-i 'I
A r-, "1
A H
30 /\ \
/\ r\ /S P, 7 / / /
XX
20 /\ /\ / / r\// X
X
/\ /\
/s _. Ss
p,/S T/ X *s/ X
r\S/ XX
10 /S /\ /\_s / / / /
/V /\
\ s \x\x \x\x
S £ S /
\ /^/S.
0 f / i, / s,
1 r i i i i
RUN 51 RUN 52 RUN 54 RUN 55
INF (Z7! 12 MIN 30 MIN 115 MIN

FIGURE VI-22. THM VALUES, EXTENDED RUNS
RUNS: *51, 52, 54, AND 55
»u
35 -
PPl
^
30 - \
\
s
25 -
s
\
U)
o 20 - PP2
/ \V
/ •n
V
\
// V,X,
15 - / Vs \
/ \
s.
s,
// \s
10 - \
\
// \
V
// V.V
PPl
5 - Xs s
/s 7
/V /s Cv ra PP1 PP2
/y /\ f• i r .-—| T^f ?
0 - F / s, F /^ F" SJ R^R FdR

r r i j i i i i n ippl n i n i
RUN 51 RUN 52 RUN 54 RUN 55
r\~i INF 12 MIN k.N\l 30 MIN 115 MIN

TABLE # VI-21. ORGANICS DATA: RUN # 51, PPl=CHLORINE, PP2=OZONE/CHLORINE
TOX TTHM TOG

(ug/L) (ug/L) (mg/L)
SAMPLE PILOT INFLUENT 15 MIN 30 MIN INFLUENT 15 MIN 30 MIN INFLUENT 15 MIN 30 MIN
DATE PLANT
6/12/85 PP1 11 84 120 16.9 26.9 2.32 2.02 2.04

PP2 11 34 74 4.8 18.5 1.8 1.99
% RED. 59.5 38.3 71.6 31.2 10.9 2.5
6/15/85 PP1 12 97 128 2.4 22.3 34.4 2.9 2.51 2.3

PP2 12 21 41 4.6 19.1 2.4 2.35
% RED. 78.4 70 80.7 44.5 4.4 -2.2
6/18/85 PP1 18 99 146 22.1 36.1 2.9 2.34 •2.31

PP2 18 6 16 1.9 2.2 2.14 2.11
% RED. 93.9 89 91.4 93.9 9.3 9.5
RUN AVG. PPI 13.7 93.3 131.3 2.1 20.4 31.4 2.72 2.29 2.22
PP2 13.7 27.5 57.2 2.1 4.7 18.8 2.72 2.11 2.15
% RED. 70.5 56.2 77 40.1 8.5 3.2
maintained throughout the run, indicating that the ozone-chlorine reaction was
not depleting the chlorine residual.
The impact of pre—ozonation on the TOX and THM reactions with chloramine
was demonstrated by Run 52 (Table VI-22). The TTHM levels from both the pre-
ozonated and control (chloramine without pre-ozonation) treatment schemes were
very low; however, the pre—ozonation plus chloramine treatment consistently
displayed lower TTHM levels (3.1 ug/L versus 4.5 ug/L for the control after 30
minutes). TOX levels were also lower in the pre-ozonated pilot plant than in
the control after both the 12-minute (10 versus 39 ug Cl /L) and 30-minute
(26 versus 47 ug Cl /L) reaction times.
The interferences that can result from interactions between ozone and
chlorine dioxide were evident in results from Run 53. Chlorine dioxide
residuals could not be maintained beyond 15 minutes (Table VI-23).
Modifications to the pilot plants provided a 15-minute ozone contact time prior
to chlorine dioxide addition for Run 55. Data from Run 55 (Table VI-24)
indicated that pre-ozonation did not affect the TOX reaction, as both treatment
schemes, chlorine dioxide with and without pre-ozonation, contained nearly
equivalent TOX concentrations of 45 to 49 ug Cl /L after 12 minutes, and 34
to 36 ug Cl /L after the 30-minute reaction time. The decrease in TOX
levels between the 12-minute and 30-minute reaction times may be explained by
trends observed in the chlorine dioxide reaction curve work (Chapter V).
Negligible THM formation (less than 1.0 ug/L) was observed from both treatment
schemes.
Comparison of Chloramines and Chlorine Dioxide
The previous pilot plant runs and reaction curve data indicated the amounts
of TOX and THM formed by disinfection with chloramines and chlorine dioxide were
similar. Run 54 was designed to provide a direct comparison between these two
132
TABLE # VI-22. OGANICS DATA: RUN # 52, PPl=CHLORAMINE, PP2=OZONE/CHLORAMINE
TOX TTHM TOC

SAMPLE PILOT INFLUENT 15 MTN 30 MIN INFLUENT 15 MIN 30 MIN INFLUENT 15 MIN 30 MIN
DATE PLANT
6/20/85 PP1 15 48 65 2.1 3.8 6.4 2.93 2.62 2.57

PP2 15 *105 41 1.9 5.1 2.93 2.62 2.43
% RED. -118 36.9 50 20.3 0 5.4
u> 6/23/85 PP1 39 43 2 4.1 4.3 2.97 2.42 2.5
PP2 14 23 2 2 2.97 2.82 2.38
% RED. 64.1 46.5 51.2 53.5 -16.5 4.8
6/25/85 PP1 18 30 34 2 2.5 2.7 2.95 2.62 2.4
PP2 18 6 15 2.1 2.1 2.95 2.54 2.46
% RED. 80 55.9 16 22.2 3.1 -2.5
RUN AVG. PPI 16.5 39 47.3 2 3.5 4.5 2.95 2.55 2.49
PP2 16.5 10 26.3 2 2 3.1 2.95 2.66 2.42
% RED. 74 44.4 42.9 31.1 -4.3 2.8
* NOT FIGURED INTO AVERAGE SAMPLE HAD FREE C12
TABLE # VI-23, ORGANICS DATA: RUN # 53, PPl=CHLORINE DIOXIDE, PP2=OZONE/CHLORINE DIOXIDE
TOX TTHM TOG

i—• (ug/L) (ug/L) (mg/L)
u>
** SAMPLE PILOT INFLUENT 15 MIN 30 MIN INFLUENT 15 WIN 30 WIN INFLUENT 15 WIN 30 MIN
DATE PLANT
7/2/85 PP1 22 26 1.7 1.9 3.04 2.38

PP2 22 22 1.7 1.9 3.04 2.37
% RED. 15.4 0 0.4
TABLE #VI-24, ORGANICS DATA: RUN #55, PP1=CHLORINE DIOXIDE, PP2 = OZONE/CHLORINE DIOXIDE
!_____ i(JA VUg/ l_,y-------- _-__-___

SAMPLE PILOT
DATE PLANT INFLUENT 15 MIN 115 MIN INFLUENT 15 MIN 115 MIN INFLUENT 15 MIN 115 Mtt
7/22/85 PP1 21 45 34 1 °.5 °.5 2.57 2.33 2.0/
OJ
PP2 21 49 36 1 °.5 0.9 2.57 2.13 2.12
%RED. -8 -5 0 8 -2
7/25/85 PP1 56 32 0.7 0.9 0.9 2.12 2.57 2.6:
PP2 0.7
%RED.
7/25/85 PP1 0.85 0.6 0.6 3.11 2.8:

PP2 0.85
%RED.
RUN AVG. PP1 21 50.5 0.66 0.66 2.35 2.67 2.51

PP2 21 49 °.5 0.9 2.13 2.12
%RED. 24 16 20 U
disinfectants in a simple parametric experiment. Results from Run 54 (Table
VI-25) again indicated that differences in TOX and THM levels following
treatment with either chloramines or chlorine dioxide were indistinguishable
after the 115-minute reaction time. Effluent TOX levels were approximately 33
ug Cl /L for both disinfectants, and effluent TTHM levels were unchanged
from influent levels. The TOX levels after 12 minutes, however, were
significantly higher following treatment with chlorine dioxide than those
observed following treatment with chloramines (44 versus 28 ug Cl /L). This
trend was previously experienced and explained in the reaction curve work for
chlorine dioxide (Chapter V).
Treatment with Pre-ozonation, Short-term Free Chlorine, and Chloramines
The Louisville Water Company currently employs a treatment scheme for THM
control involving chlorination with free chlorine for 15 minutes, followed by
ammonia addition to form monochloramine. Data from the reaction curve work and
previous pilot plant runs indicated that pre-ozonation, followed by short-term
(15 minutes) free chlorine, and ammonia to form monochloramine, should produce
low levels of both THM's and TOX for extended reaction times. Run 56 was
designed to compare the existing LWC treatment scheme to pre-ozonation in
combination with the LWC treatment scheme, free chlorination, and free
chlorination with pre-ozonation. Results for this run are presented in Table
VI-26. It should be noted that TOX and THM formation potential was low because
this run was made under cold-weather conditions (4 °C). Treatment A
represents the existing LWC treatment; Treatment B, the existing treatment with
pre-ozonation and a 15-minute reaction prior to chlorination; Treatment C, free
chlorine only; and Treatment D, free chlorine with pre-ozonation. These data
(Figures VI-23 and VI-24) indicated that the pre-ozonation/free
chlorine/chloramine treatment scheme (Treatment B) produced low levels of TOX
136
TABLE # VI-25, ORGANICS DATA: RUN # 54, PPl=CHLORAMINE, PP2=CHLORINE DIOXIDE
TOX TTHM TOG

SAMPLE PILOT INFLUENT 15 MEN 115 MEN INFLUENT 15 MEN 115 MEN INFLUENT 15 MEN 115 MEN
DATE PLANT
7/23/85 PP1 17 29 32 1.5 2.1 2.3 3.67 2.62 2.62

PP2 17 49 39 1.5 1.6 1.7 3.67 2.58 2.52
% RED. -69 -21.8 23.6 26.1 1.5 3.8
7/25/85 PP1 22 26 31 2.1 2.2 2.5 2.92 2.3 2.35
PP2 22 51 30 2.1 2.6 2 2.92 2.45 2.31
% RED. -96.2 3.2 -18.2 20 -6.5 1.7
7/27/85 PPI 15 29 34 2.7 0.8 1.7 2.95 2.58 2.5

PP2 15 31 33 2.7 <0.5 3.2 2.95 2.56 2.57
% RED. -6.8 2.9 37.5 -88.2 0.7 -2.8
RUN AVG. PPI 18 28 32.3 2.1 1.7 2.2 3.18 2.5 2.49
PP2 18 43.6 34 2.1 1.6 2.3 3.18 2.53 2.49
% RED -55.7 -5.2 5.8 -4.5 -1.2 0
TABLE #VI-26, ORGANICS DATA: RUN #56
&/ *-•>-
-TOX (ug/L) TTHM (uUg/lj/
SAMPLE TREAT INFLUENT OZONE MIN 115 MIN 8 DAYS INFLUENT OZONE MIN 115 MIN 8 DAYS
DATE MENT @ 15 MIN @ 15 MIN
12/21/85 A 22.5 76.9 79.6 77.6 0.54 5.4 7.2
OJ B 22.5 9.5 18.6 9 37.8 0.54 0.32 0.92 0.92 0.82
oo
C 22.5 76.9 181 0.54 5.4 5.4
D 22.5 18.6 0.54 0.92
12/24/85 A 24 85.8 68.4 90 0.23 8.2 10.4 9.4
B 24 18.5 14.8 22.2 48.5 0.23 0.23 3.4 3.4 3.8
C 24 85.8 197.8 0.23 8.2 £
D 24 14.8 141.8 0.23 3.4 3.6
FIGURE VI-23. EXTENDED RUN #56
TOX VALUES
<cou —
240 -
220 -
200 -
V;
180 - ^
,-N 16° ~
^
bb 140 -
^ ^
X 120 -
O
H
100 -
80 -
^
^\ ^
60 -
t^ ^ ^
^^
40 - f\ ^
20 - f\ \ ^ \
^^
V\ / s,
^ \
7^
0 - \
t: A
n B
i i
C
^ i
D
TREATMENT SCHEME
r\~i INF EZ2 15 MIN R^vxl 8 DAYS
FIGURE VI-24. EXTENDED RUN #56
THM VALUES
10
9 -
8 -
7 -
ft —
5 -
4 -
3 -
2 -
1 -
0 I i
A B D
INF 15 MIN 8 DAYS

(48 ug C1~/L) and THM (3.8 ug/L) after 8 days of reaction. The same
treatment scheme without pre-ozonation (Treatment A) produced TOX and THM levels
(90 ug Cl /L and 9.4 ug/L, respectively) approximately twice as high as
treatment with pre-ozonation. The treatment scheme utilizing pre-ozonation with
free chlorine (Treatment D) produced TOX and THM values of 142 ug Cl /L and
3.6 ug/L, respectively. Treatment with free chlorine alone (Treatment C)
produced TOX and'THM values of 198 ug Cl /L and 8 ug/L, respectively, after
an 8-day reaction.
Operational data for Run 56 is presented in Appendix C. Chlorine residuals
were maintained at acceptable levels throughout the I15-minute reaction period,
and were above detectable trace levels after the 8-day reaction period. All
data were collected from a single batch of samples, eliminating any variation in
water quality.
141
VII. CONCLUSIONS
The goal of this project was to define disinfection treatment techniques
effective in reducing both THM and TOX levels. Major objectives included
establishing typical TOX and THM levels in various water supplies (Six Cities
Survey), defining the effect of variable reaction parameters (pH, time,
oxidant) on the TOX and THM reaction (reaction curve study), and testing
TOX/THM control schemes at the pilot plant level (pilot plant Runs 13 through
56). Each of these objectives was designed to strengthen the conclusions drawn
from each separate portion of the study.
SIX CITIES SURVEY
The Six Cities Survey indicated that TOX and THM levels could be expected
to vary widely from source to source and according to treatment techniques.
The 10-month survey average TOX level for the individual cities varied from
less than 7 to 161 ug C1-/L; THM values averaged from 1 to 33 ug/L . It was
observed that the TTHM concentration generally accounted for approximately 15%
of the TOX concentration, varying from 10% to 18%, when compared on a mole to
mole basis.
The protected groundwater supply yielded the lowest values of TOX and THM
of the six cities; the protected mountain watershed produced the highest
levels. Chlorine contact time prior to sample collection varied widely from
city to city, and likely accounted for a great deal of variation observed
between the cities. This variable contact time limited the utility of
comparisons of TOX and THM levels between the cities.
Data from City D were analyzed for correlations between TOX, TTHM, and
temperature. A temperature dependence was observed for TOX and THM. Other
142
associations (TOX to THM) proved to be the result of covariance with
temperature. These trends have been established in the literature and were
expected.
REACTION CURVE WORK
First order reaction kinetics were observed for all but one of the free
chlorine reaction curves. The rapid rate of reaction for TOX and THM in the
first 30 minutes was clearly established for free chlorine using source water
from City D. These data indicated that effective THM and TOX control could be
obtained by reducing the rate of reaction by pre-ozonation, and/or by
terminating the free chlorine reaction by ammonia addition to form chloramines.
The impact of pre-ozonation on both the TOX and THM free chlorine reactions was
significant, particularly in the first 30 minutes of reaction.
The chlorine dioxide TOX reaction curves were variable in shape from
experiment to experiment, presumably as a function of source water quality.
Two types of reaction curves were defined: one which showed a rapid increase in
the first minutes of reaction, followed by little or no further TOX increases,
and one which showed an increase to a peak within the first 5 minutes of
reaction, followed by a gradual decrease to near-initial TOX levels after
several hours. For waters displaying the latter type of reaction (with a
peak), the level of TOX observed could be affected by the length of time
between chlorine dioxide addition and sample collection, as well as by the
length of time -between chlorine dioxide addition and reaction termination (by
exhaustion of the oxidant or dechlorination).
Chlorine dioxide produced very low levels of THM when fed without free
chlorine. Pre-ozonation did reduce the level of TOX formed from chlorine
dioxide. In general, chlorine dioxide was very effective in reducing both THM
and TOX, as compared to free chlorine.
143
The TOX and THM reactions for chloramine (monochloramine) were
characterized by an initial rapid reaction within the first minutes, followed
by insignificant increases through several hours. First order kinetics were
not apparent. Pre-ozonation was effective in reducing TOX levels in the
chloramine TOX reaction. Chloramine, like chlorine dioxide, proved an
effective alternate to chlorine for TOX and THM reduction.
It is emphasized that the reaction curve work focused upon the impact of
various oxidants on the TOX and THM reactions only. The oxidant/disinfection
process also effects the bacterial quality of water and often the taste and
odor, and in these areas, free chlorination (or breakpoint chlorination)
occupies a firm position as being a proven process. Considerations towards
using alternate disinfectants for TOX and THM control should recognize the
entire role of the oxidant/disinfection process in water treatment.
PILOT PLANT RUNS 13 THROUGH 56
Data collected from the pilot plants confirmed the results obtained from
reaction curve studies: chlorine dioxide and chloramines were effective in
reducing TOX and THM levels when compared to free chlorine. Pre-ozonation was
effective in reducing TOX levels for all three of the chlorinated oxidants used
in this investigation.
Information compiled from pilot plant runs 13 through 55 and the reaction
curve work was developed into a final run, Run 56, which compared four separate
processes:
A) free chlorine, followed by chloramine,
B) pre-ozone, followed by free chlorine, followed by chloramine,
C) free chlorine alone, and
D) pre-ozone, followed by free chlorine.
144
Run 56 allowed the side-by-side comparison of several feasible treatment
processes. Each utilized free chlorine, in recognition of its role in
conventional water treatment processes and its multiple purposes in water
treatment. Of the four treatment processes evaluated, Process B exploited the
benefits of pre-ozonation in reducing the free chlorine TOX and THM reactions
and ammoniation in terminating the free chlorine TOX and THM reactions after 15
minutes. This process was effective in limiting TOX formation to under 50 ug
C1-/L and TTHM formation to under 5 ug/L after 8 days reaction, compared to
values of 200 ug C1-/L TOX and 8 ug/L TTHM for free chlorine (wintertime
conditions).
The data collected during the course of this project indicated that the
TOX and THM reactions could be manipulated to reduce organic by-product
formation without sacrificing the primary goals of the oxidant/disinfectant
processes. This work was performed using a natural source water (the Ohio
River) with a highly variable water quality. Certain observations, including
the lower production of TOX and THM following treatment with chloramines or
chlorine dioxide, are believed to be somewhat universal. The site specificity
of the chlorine dioxide reaction curve information (peaked reaction curve) to
water quality conditions experienced at Louisville requires interpretation with
caution. The impact of pre-ozonation in reducing chloro-organic reactions is
supported in the literature, and results of this project provide additional
data for one source.
Further research is warranted in the development of pre-ozonation for TOX
and THM control. Oxidant interactions, such as ozone with the hypochlorite
ion, might be further exploited to allow unimpeded disinfection with
hypochlorous acid while limiting hypochlorite-organic reactions. Long-term
operational data for the pre-ozone/short-term free chlorine/chloramine/ process
145
needs to be developed to determine seasonal variations and 12 month average
values that might be obtainable for TOX and THM. These developments may assist
utilities in meeting current and future limits for chloro-organic disinfection
by-products.
146
LITERATURE CITED
Aieta, E. M., B. Chow, and P. V. Roberts. 1979. Chlorine dioxide: Analytical

measurement and pilot plant evaluation, pp. 72-85 In A. D. Venosa (ed.).
Progress in Wastewater Disinfection Technology. Report EPA-600/9-79-018,
U. S. EPA, Cincinnati, OH.
Arguello, M. D., C. D. Chriswell, J. S. Fritz, L. D. Kissinger, K. W. Lee, J.

J. Richard, and H. J. Svec. 1979. Trihalomethanes in water: A report on
the occurrence, seasonal variation in concentrations, and precursors of
trlhalomethanes. Jour. AWWA 71:504-508.
Bellar, T. A. and J. J. Lichtenberg. 1974. Determining volatile organics at

microgram-per-litre levels by gas chromatography. Jour. AWWA 66:739-744.
Blanck, C. A. 1979. Trihalomethane reduction in operating water treatment

plants. Jour. AWWA 71:525-528.
Brett, R. W. and R. A. Calverley. 1979. A one-year survey of trlhalomethane

concentration changes within a distribution system. Jour. AWWA 71:515-520.
Cheh, A. M., J. Skochdopole, P. Koski, and L. Cole. 1980. Nonvolatile

mutagens in drinking water: Production by chlorination and destruction by
sulflte. Science 207:90-92.
Christman, R. F., D. L. Norwood, D. S. Millington, J. D. Johnson, and A. A.

Stevens. 1983. Identity and yields of major halogenated products of
aquatic fulvic acid chlorination. Environ. Sci. Technol. 17:625-628.
Gulp, Gordon L. and Russell L. Gulp. 1974. New Concepts in Water Purification.
Van Nostrand Reinhold Co., New York.
DeGreef, E., J. Hrubec, and J. C. Morris. 1979. Ozone and halogenated organic
compounds, pp. 309-326 In W. Kuhn and H. Sontheimer (eds.). Oxidation
Techniques in Drinking Water Treatment. Report No. EPA-570/9-79-020, U. S.
EPA, Washington D. C.
DeKam, J. A. 1983. Ozonation experiences at the Bay Metropolitan Water

Treatment Plant. Sixth Ozone World Congress Proc.
Dohrmann Envirotech. 1978. Dohrmann DC-54 Ultra Low Level Total Organic Carbon
Analyzer System. Equipment Manual. Dohrmann Division, Envirotech
Corporation, Santa Clara, CA.
Dohrmann Division, Xertex Corporation. 1984. DX-20 Total Organic Halide

Analyzer System. Equipment Manual. Dohrman Division, Xertex Corporation,
Santa Clara, CA.
Dressman, R. C., and A. A. Stevens. 1983. The analysis of organohalides in

water—an evaluation update. Jour. AWWA 75:431-434.
Engelbrecht, R. S. and B. F. Severin. 1982. Unconventional disinfection

alternatives, pp. 64-75 ^n_ Proceedings of the Twenty-fourth Annual Public
Water Supply Engineers' Conference.
147
Fleischacker, S. J. and S. J. Randtke. 1983. Formation of organic chlorine in
public water supplies. Jour. AWWA 75:132-138.
Gordon, G., and Y. Ikeda. 1984. Lower detection limits found for chlorine
dioxide contaminants. Jour. AWWA 76(7):98-101.
Hann, V. A. 1956. Disinfection of drinking water with ozone. Jour. AWWA

48:1316.
Hoehn, R. C., D. B. Barnes, B. C. Thompson, C. W. Randall, T. J. Grizzard, and

P. T. B. Shaffer. 1980. Algae as sources of trihalomethane precursors.
Jour. AWWA 72:344-350.
Hoigne, J., and H. Bader. 1983a. Rate constants of reactions of ozone with
organic and inorganic compounds in water—I. Non-dissociating organic
compounds. Water Res. 17:173-183.
Hoigne, J., and H. Bader. 1983b. Rate constants of reactions of ozone with
organic and inorganic compounds in water—II. Dissociating organic
compounds. Water Res. 17:185-194.
Hoigne, J., H. Bader, W. R. Haag, and J. Staehelin. 1985. Rate constants of

reactions of ozone with organic and inorganic compounds in water—III.
Inorganic compounds and radicals. Water Res. 19:993-1004.
Hubbs, S. A., M. Goers, and J. Siria. 1980. Pilot-scale examination and

control of a chlorine dioxide-chloramination process at the Louisville Water
Company, pp. 769-775 In R. L. Jolley, W. A. Brungs, and R. B. Gumming
(eds.), Water Chlorination: Environmental Impact and Health Effects, Vol.
3. Ann Arbor Science Publishers, Inc., Ann Arbor.
Kavanaugh, M. C., A. R. Trussell, J. Croraer, and R. R. Trussell. 1980. An

empirical kinetic model of trihalomethane formation: Applications to meet
the proposed THM standard. Jour. AWWA 72:578-582.
Lin, S., and R. M. Carlson. 1984. Susceptibility of environmentally important

heterocycles to chemical disinfection: Reactions with aqueous chlorine,
chlorine dioxide, and chloramine. Environ. Sci. Technol. 18:743-748.
Lin, S., R. J. Liukkonen, R. E. Thorn, J. G. Bastian, M. T. Lukasewycz, and R.

M. Carlson. 1984. Increased chloroform production from model components of
aquatic humus and mixtures of chlorine dioxide/chlorine. Environ. Sci.
Technol. 18:932-935.
Love, 0. T., Jr., J. K. Carswell, R. J. Miltner, and J. M. Symons. 1976.

Treatment for the prevention or removal of trihalomethanes in drinking
water. I_ri J. M. Symons (ed.), Interim Treatment Guide for Control of
Chloroform and Other Trihalomethanes, Appendix 3. EP1.8 C45, U. S. EPA
Municipal Environ. Res. Lab., Cincinnati, OH.
Masschelein, W. J. 1979a. Chlorine Dioxide, Chemistry and Environmental

Impact of Oxychlorine Compounds. Ann Arbor Science Publishers Inc., Ann
Arbor.
148
Masschelein, W. J. 1979b. Use of chlorine dioxide for the treatment of drinking
water, pp. 459-480 In W. Kuhn and H. Sontheimer (eds.), Oxidation
Techniques in Drinking Water Treatment. Report No. EPA-570/9-79-020, U. S.
EPA, Washington, D. C.
McCabe, L. J. 1979. Chlorine residual substitution—rationale, pp. 57-63,

It^ C. W. Hendricks (ed.). Evaluation of the Microbiology Standards for
Drinking Water. NTIS, Washington D. C.
Means, E. G., T. S. Tanaka, D. J. Otsuka, and M. J. McGuire. 1983. Impact of

chlorine and ammonia application points on bacterial efficiency of free
chlorine and chloramines in pilot—plant studies. Paper No. 30—3,
Proceedings AWWA 1983 Annual Conference, Las Vegas.
Neukrug, H. M., M. G. Smith, S. W. Maloney, and I. Suffet. 1984. Biological

activated carbon—At what cost? Jour. AWWA 76(4):158-167.
Norman, T. S., L. L. Harms, and Robert W. Looyenga. 1980. The use of

chloramines to prevent trihalomethane formation. Jour. AWWA 72:176-180.
Oliver, B. G., and J. Lawrence. 1979. Haloforms in drinking water: A study

of precursors and precursor removal. Jour. AWWA 71:161-163.
Oliver, B. G., and D. B. Schindler. 1980. Trihalomethanes from the

chlorination of aquatic algae. Environ. Sci. Technol. 14:1502-1505.
Oliver, B. G., and S. A. Visser. 1980. Chloroform production from the

chlorination of aquatic humic material: The effect of molecular weight,
environment, and season. Water Res. 14:1137-1141.
Otspn, R., D. T. Williams, P. D. Bothwell, and T. K. Quon. 1981. Comparison

of trihalomethane levels and other water quality parameters for three
treatment plants on the Ottawa River. Environ. Sci. Technol. 15:1075-1080.
Peters, C. J., R. J. Young, and R. Perry. 1980. Factors influencing the

formation of haloforms in the chlorination of humic materials. Environ.
Sci. Technol. 14:1391-1395.
Rav-Acha, C. 1984. The reactions of chlorine dioxide with aquatic organic

materials and their health effects. Water Res. 18:1329-1341.
Reckhow, D. A., and P. C. Singer. 1984. The removal of organic halide

precursors by preozonation and alum coagulation. Jour. AWWA 76(4):151-157.
Reed, G. D. 1983. Effects of prechlorination on THM formation and microbial

growth in pilot-plant units. Jour. AWWA 75:426-430.
Roberts, P. V., E. M. Aieta, J. D. Berg, and B. M. Chow. 1981. Project

Summary—Chlorine dioxide for wastewater disinfection: A feasibility
evaluation. Report No. EPA-600/52-81-092, U. S. EPA.
Robertson, J. L. and A. Oda. 1983. Combined application of ozone and chlorine

or chloramine to reduce production of chlorinated organics in drinking water
disinfection, pp. 79-93 _In Ozone: Science and Engineering. The Journal of
the International Ozone Association.
149
Rook, J. J. 1976. Haloforms in drinking water. Jour. AWWA 68:168-172.
Rosen, H. M. 1972. Ozone generation and its relationship to the environmental

application of ozone in wastewater treatment, pp. 101-143 In F. L. Evan III
(ed.), Ozone in Water and Wastewater Treatment. Ann Arbor Science
Publishers Inc., Ann Arbor.
Sacks, R. S. 1984. Ann Arbor controls trihalomethanes. Jour. AWWA 76(7):

105-108.
Singer, P. C., J. J. Barry, III, G. M. Palen, and A. E. Scrivner. 1981.

Trihalomethane formation in North Carolina drinking waters. Jour. AWWA 73:
392-401.
Sontheimer, H. 1979a. Applying oxidation and adsorption techniques: A

summary of progress. Jour. AWWA 71:612-617.
Sontheimer, H. 1979b. Development, problems, aims, and significance of the

oxidation process in the treatment of drinking water, pp. 13-67 In W. Kuhn
and H. Sontheimer (eds.). Oxidation Techniques in Drinking Water Treatment.
Report No. EPA-570/9-79-020, U. S. Environmental Protection Agency,
Washington D. C.
Standard Methods for the Examination of Water and Wastewater, 15th Edition.
1981. APHA, AWWA, WPCF, Washington, D. C.
Stevens A. A., C. J. Slocum, D. R. Seegar, and G. G. Robeck. 1976.

Chlorination of organics in drinking water. Jour. AWWA 68:615-620.
Stevens, A. A., R. C. Dressman, R. K. Sorrell, and H. J. Brass. 1985. Organic

halogen measurements: Current uses and future prospects. Jour. AWWA 77(4):
146-154.
Urano, K., H. Wada, and T. Takemasa. 1983. Empirical rate equation for
trihalomethane formation with chlorination of humic substances in water.
Water Res. 17:1797-1802.
U. S. EPA. 1978. Methods for Benzidine, Chlorinated Organic Compounds,

Pentachlorophenol and Pesticides in Water and Wastewater. EP1.8 W31. U. S.
EPA, Environmental Monitoring and Support Laboratory, Cincinnati, Ohio.
U. S. EPA. 1979. An EPA Manual for Organics Analysis Using Gas

Chromatography-Mass Spectroscopy. EP1.8 Or3-2. EPA 600/8-79-006. U. S.
EPA, Environmental Monitoring and Support Laboratory, Cincinnati, Ohio.
\
Veenstra, J. N. and J. L. Schnoor. 1980. Seasonal variations in
trihalomethane levels in an Iowa river water supply. Jour. AWWA 72:583-590.
Wachter, J. K. and J. B. Andelman. 1984. Organohalide formation on

chlorination of algal extracellular products. Environ. Sci. Technol.
18:811-817.
150
Ward, N. R., R. L. Wolfe, and B. H. Olson. 1984. Effect of pH, application
technique, and chlorine—to—nitrogen ratio on disinfectant activity of
inorganic chloramines with pure culture bacteria. Appl. Environ. Microbiol.
48:508-514.
Witherell, L. E., R. L. Solomon, and K. M. Stone. 1979. Ozone and ultraviolet

radiation disinfection for small community water systems. Report No.
EPA-600/2-79-060, U. S. EPA.
Wolfe, R. L., N. R. Ward, and B. H. Olson. 1984. Inorganic chloramines as

drinking water disinfectants: A review. Jour. AWWA 76(5)74-88.
Young, J. S., Jr. and P. C. Singer. 1979. Chloroform formation in public

water supplies: a case study. Jour. AWWA 71:87-95.
151
APPENDIX A: SIX CITIES DESCRIPTIONS
CITY A: DESCRIPTION
City A is served by a water supply that utilizes lake water. Water
quality is strongly influenced by a river (during high flow) that empties into
the lake near the point of water intake for the plant. The raw water annual
average for hardness and alkalinity are 131 mg/L as CaC03 and 96 mg/L as CaC03,
respectively. The ranges of pH, turbidity and temperature are 7.0 to 8.8 pH
units, 1.0 to 138 NTU, and 1.5 to 24.3 degrees C, respectively. The raw water
is first treated with ozone at a dose of 1.5 mg/L. The water is then treated
with lime in a primary clarification system to remove hardness, followed by a
secondary coagulation system where it is treated with ferric chloride.
Chlorine is added between the secondary clarifiers and filters. A trim dose of
chlorine can be added after the filters to maintain a residual of 1.5 to 2.0
mg/L chlorine. The plant treats 4.6 MGD during low demands and 14 MGD during
high demand periods. The sample point for city A is located at the effluent of
the reservoir, providing a 24 hour contact time after chlorine is added. The
pH at the point of chlorination is typically 8.1 to 8.4 . The monthly average
finished water pH and temperature are given in Table A-l. Data collected
during this survey for TOC, TOX, and THM are presented in Table A-2.
152
TABLE A-l: Finished water temperature, pH, and TTHM,
City A. (monthly average data)
DATE TEMP(C) pH *TTHM (quarterly data)
Sep'84 59
Oct'84 14.2 8.3
Nov'84 17.2 8.2 79
Dec'84 2.7 8.02
Jan'85 2.2 8.08
Feb'85 3.1 8.08
Mar'85 3.7 8.14 36
Apr'85 6.5 8.19
May'85 14.4 8.31 52
Jun'85 17.4 8.26
Jul'85 21.4 8.22
Aug'85 21.0 8.41
Sep'85 92
* TTHM data (micrograms per liter) for compliance with EPA regulations
153
TABLE A2: ORGANICS DATA, SIX CITIES SURVEY CITY A
(All values expressed as micrograms per liter)
TOTAL ORGANIC HALOGEN T 0 C

Month Raw 1 Raw 2 Raw Avg Fin 1 Fin 2 Fin Avg IM CHC13 CHC12Br CHClRr2 CHBr3 TTHM TOC TOC
RAW1 F I N I S H E D FIN RAW FIN
247 7.53 * 250 1 3 9 24 26 * 62 4420 2650

Oct 19 23 21
14 93 90 91.5 0 9 11 10 4 34 3204 2565
Nov 9 19
Dec 9 10 9.5 122 124 123 0 7 3 2 0 12 2355 1906
Jan'85 0 0 0 110 116 113 1 8 7 n 0 15 3672 3494
Ui Feb 9 10 9.5 72 77 74.5 1 7 6 3 0 16 6280 3484
Mar 8 9 8.5 71 77 74 0 6 6 4 1 17 4446 3442
Apr 10 15 12.5 130 132 131 0 14 13 7 0 34
May 8 9 8.5 134 140 137 n 21 15 8 0 44
Jun 13 21 17 189 189 189 0 13 16 15 1 45 4887 4920
Jul 6 7 6.5 138 146 142 0 20 16 11 1 48 3857 4723
AVERAGES ** 11 119 12 10 7 29 4140 3398

MAXIM1JMS ** 21 189 21 15 48 6280 4920
* Values preceded by a "*" indicate samples that were not dechlorinated at the time of sampling.
** The average values and maximum values do not include samples that were not dechlorinated at the time of sampling.
CITY B: DESCRIPTION
City B obtains its raw water from a small river. Raw water quality is
listed in Table A-3. The raw water is first dosed with aluminum sulphate,
polymer, chlorine dioxide, activated carbon and lime in a flash mix chamber
before coagulation. Activated carbon and lime are dosed only as needed.
Chlorine dioxide is dosed at a rate to maintain 0.3 mg/L as free chlorine in
the coagulation system. After leaving the coagulation system, the pH is
typically around 7.8. The retention time in the coagulation system is in the
range of 2 to 3 hours. Chlorine is added before rapid sand filtration to the
effluent of the coagulation system. The water leaving the filters enters a
reservoir before going on to the distribution system. The water treatment
plant treats a yearly average of 9.0 MGD, ranging from 7.5 to 13.4 MGD.
Raw water samples for this investigation were taken before any chemical
treatment. Finished water samples were taken at a point beyond the finished
water reservoir approximately 5 hours after chlorine dioxide was added, and 3
hours after chlorine was added. Monthly finished water averages for pH,
temperature and free chlorine residual during the sampling period are given in
Table A-4. TOX, THM, and TOC data collected during this survey are presented
in Table A-5.
155
TABLE A-3. CITY B: Raw Water Quality (Annual Data)
RANGE
Turbidity 12.9 to 19.9

(NTU)
pH'
7.85 to 8.01
Alkalinity 87.1 to 133.3
(as mg/1 CaC03)
Hardness 115.9 to 163.9
(as mg/1 CaC03)
TABLE A-4, CITY B: Finished Water Temperature, pH

chlorine residual, and TTHM data.
(Monthly averages)
FREE * TTHM
DATE TEMP(C) PH CHLORINE quarterly
RESIDUAL average
Sep'84 0.15
Oct'84 20.7 7.51 1.74
Nov'84 15.6 7.52 1.79 0.041
Dec'84 11.7 7.45 1.85
Jan'85 6.6 7.55 1.88
Feb'85 6.7 7.51 1.51 0.015
Mar'85 12.8 7.61 1.42
Apr'85 18.6 7.67 1.39
May'85 21.9 7.57 1.38
Jun'85 24.6 7.56 1.43 0.047
Jul'85 27.1 7.52 1.48
Aug'85 26.2 7.53 1.56
Sep'85 0.091
TTHM data (micrograms per liter) for compliance with EPA regulations
156
TABLE A5: ORGANICS DATA, SIX CITIES SURVEY CITY B
TOTAL ORGANIC HALOGEN TRIHALOMETHANES T O C

MONTH Raw 1 Raw 2 Raw Avg Fin 1 Fin 2 Fin AVR TTHM CHC13 CHC12Rr CHClBr2 CHBr3 TTHM TOC TOC
RAW FINISHED FIN RAW FIN
Oct 11 14 12.5 219 222 * 220.5 1 q 5 2 n * 16 2170 1560

Nov 19 17 18 87 96 91.5 0 7 4 1 n 12 2369 1454
Dec 9 13 11 65 66 65.5 0 5 2 1 0 8 2444 1778
Jan 0 0 0 44 45 44.5 1 i 0 0 0 1 2260 1278
Feb 0 7 3.5 59 61 60 1 5 2. 1 0 8 3045 1060
Mar 0 0 0 42 45 43.5 0 5 3 2 n 10 1612 1511
Apr 8 14 11 64 67 65.5 0 9 4 6 0 19
May 7 7 7 131 139 135 0 8 6 3 0 17
Jun 0 0 0 106 107 106.5 0 12 8 3 0 23 3500 2219
Jul 12 19 15.5 207 209 208 n 62 21 6 n 69 4957 1880
AVERAGES ** 8 91 10 6 19 2795 1593

MAXIM1IMS ** 18 208 42 21 69 4957 2219
CITY C: DESCRIPTION
City C takes its water supply from a large river, which experiences
extreme changes in water quality over short periods of time. Monthly average
and extreme values for selected raw water quality parameters during this survey
are given in Table A-6.
Raw water is pumped into a solids removal system utilizing alum and
polymer which then flows into offstream storage reservoirs. PAC is added prior
to the reservoirs as needed. From the storage reservoirs, water flows to a
secondary clarification system (ferric sulfate, lime, soda ash, chlorine),
followed by rapid sand filtration. Chlorine is typically added before
secondary clarification, and after filtration to maintain an acceptable
residual leaving the plant. A free chlorine residual of 1.4 to 2.5 (avg. 1.9)
mg/L is held at the finished water tap, with distribution system samples
averaging approximately 1.0 mg/L. The chlorine contact time between the
initial point of chlorination and the sample point before distribution is
approximately 8 hours. The October sample from City C was taken immediately
following filtration, providing a chlorine contact time of approximately 5
hours.
The monthly average pH at the point of chlorination ranged from 8.2 to
8.7. Alkalinities ranged from 44 to 64 mg/L as CaC03 (raw water) and 47 to 68
mg/L as CaC03 after chemical addition. Monthly average values for finished
water temperature, pH, and total chlorine are presented in Table A-7. TOX,
THM, and TOG data collected during this survey are presented in Table A-8.
158
TABLE A-6 CITY C: Raw Water Duality (Monthly Avg. Values, 1984)
RANGE AVERAGE
Turbidity (NTU) 8 to 96 43
pH 7.3 to 7.7 7.6
Alkalinity (as mg/1 CaC03) 42 to 58 44
Hardness (as mg/1 CaC03) 96 to 129 113
TABLE A-7. CITY C: Finished Water Temperature, pH, Chlorine Residual,

and TTHM. (monthly average, except where noted)
* TTHM
Chlorine (running (quarterly
MONTH pH Free Total average) average)
Aug'84 80 130
Sep'84
Oct'84 8.4 1.44 1.62
Nov'84 8.4 1.58 1.77 80 80
Dec'84
Jan'85 8.2 1.51 1.67
Feb'85 8.5 1.56 1.71 70 40
Mar'85 8.4 1.30 1.43
Apr'85 8.5 1.43 1.55
May'85 8.5 1.64 1.79 80 90
Jun'85 8.7 1.49 1.64
Jul'85 8.7 1.59 1.71
Aug'85 8.5 1.62 1.75 90 170
Sep'85 8.6 2.33 2.50
* TTHM data (micrograms per liter) for compliance with EPA regulations
159
TABLE A8: ORGANICS DATA, SIX CITIES SURVEY CITY C
(All values expressed ns microRrams per liter)
TOTAL ORGAN I C H A L 0 G E N TRIHALOMETHA N E S T 0 C

MONTH Raw 1 Rawr 2 Raw Avg Fin 1 Fin 2 Fin Avg TTHM CHC13 CHC12Br CHClBr2 CHBr3 TTHM TOC TOC
RAW F I N I S H E D FIN RAW FIN
Oct 30 31 30.5 364 359 361.5 0 19 16 10 0 45 2860 2690
Nov 22 26 24 53 49 * 51 0 2 1 1 0 * 4 3001 1114
Dec
Jan 10 18 14 86 92 89 0 9 3 2 0 14 7467 2037
Feb 10 13 11.5 78 79 78.5 0 3 3 2 0 8 2417 1701
Mar 57 27 42 65 66 65.5 0 3 3 2 0 8 4742 2270
APR 9 10 9.5 100 101 100.5 2 13 9 4 0 26
MAY 10 12 11 96 98 97 0 14 9 5 0 28
JUN 0 44 22 200 201 200.5 0 34 16 7 0 57 4358 2858
JUL 22 23 22.5 198 198 198
AUG 75 86 80.5 234 232 233 28 23 19 72
AVERAGES ** 26.63 158.17 0.25 15.38 10.25 6.38 0.25 32.25 3549.29 1810.00
MAXIMUMS ** 80.50 361.50 2.00 34.00 23.00 19.00 2.00 72.00 7467.00 2858.00
* Values preceded by a "*" indicate samples that were not taken from the routine sampling location.
** The average values and maximum values include only samples that were taken from the routine sample location.
CITY D: DESCRIPTION
City D takes water from a large river. Raw water quality is susceptible
to quick and extreme changes. Yearly average and extreme values for raw water
are given in Table A-9.
Raw water is pumped into a presettling teservoir from the river. At the
reservoir, activated carbon and copper sulphate are added only as required.
Raw water flows from the reservoir to a coagulation system, where aluminum
sulfate and polymer are added. Chlorine is added at the effluent of the
coagulation system. The pH at this point averages 7.2, ranging from 6.6 to
7.8. Ammonia is added 15 to 20 minutes after chlorination at softening basins
to form chloramines. Lime and/or soda ash are also added at this point to
control hardness and pH. If necessary, the pH can be readjusted with carbon
dioxide in the same system.
Rapid sand filtration is the last physical process that is used to treat
the water. After filtration, a trim dose of chlorine and air.monia is added to
obtain a chloramine residual between 1.5 and 2.0 mg/L as total chlorine. The
treated water flows into a reservoir that has an average retention time of 8
hours. The plant treats an average of 100 MGD with peak demands of 140 MGD and
low demands of 80 MGD.
The raw water samples for this investigation were taken before the water
reached the presettling reservoir. Finished water samples were taken from the
discharge of the clearwell. The chlorine contact time at the finished water
sample point ranged from 8 to 12 hours. Monthly averages for finished water
temperature, pH and total chlorine are given in Table A-10. TOX, THM, and TOC
data collected during this survey are presented in Table A-ll.
161
TABLE A-9. CITY D: Raw Water Quality
RANGE AVG.
Turbidity (NTU) 1.7 to 340 39
pH 6.9 to 8.0 7.5
Alkalinity (as mg/1 CaCOS) 44 to 94 65
Hardness (as mg/1 CaC03) 88 to 180 137
TABLE A-10. CITY D: Finished Water Temperature and pH (Monthly avg.)

** TTHM
TOTAL CHLORINE (quarterly
DATE TEMP(C) pH mg/1 as C12 * average)
Oct'84 68.4 8.6 1.89 39

Nov'84 55.7 8.0 1.73
Dec'84 46.6 8.5 1.73
Jan'85 40.7 8.6 1.72 16
Feb'85 35.8 8.4 1.80
Mar'85 45.9 8.5 1.67
Apr'85 55.2 8.5 1.79 29
May'85 66.9 8.6 1.83
Jun'85 72.0 8.6 2.02
Jul'85 78.0 8.5 2.06 51
Aug'85 78.8 8.6 2.00
Sep'85
Oct'85 28
* Primarily as monochloramine
** TTHM data (micrograms per liter) for compliance with EPA regulations
162
TABLE All: ORGANICS DATA, SIX CITIRS SURVEY CITY n
TOTAL ORGANIC HALOREN T O C

MONTH Raw 1 Raw 2 Raw Avg Fin 1 "in 2 Fin Avg tM CMC 13 CHC12Br CHClBr2 CHBr3 TTHM TOC TOC
RAWI F I N I SHED FIN RAW FJN
Oct 31 28 29.5 182 182 182 0 15 12 5 0 32 2720 2360

Nov 18 20 19 114 117 115.5 0 7 7 6 0 20 3692 2770
Dec 6 5 5.5 94 95 94.5 0 q 8 3 0 20 3436 1885
OJ Jan 10 10 10 64 68 66 1 6 4 2 0 12 2476 1843
Feb 13 15 14 78 80 79 0 2 2 1 0 5 6140 iqo4
Mar 12 21 16.5 101 104 102.5 0 q 7 3 0 19 4723 157Q
APR 13 14 13.5 106 108 107 0 12 8 3 0 23 2456 1755
MAY 14 16 15 122 126 124 1 18 13 6 0 37 3115 2270
JUN 13 19 16 149 150 149.5 0 26 16 6 0 4H 2915 1992
JUL 19 25 22 137 142 139.5 0 19 14 7 0 40 3268 2360
AVERAGES 16 116 12 9 26 34 P4 2022

MAXIMUMS 30 182 26 16 48 6140 2360
CITY E: DESCRIPTION
City E takes its raw water from a deep, protected aquifer 500 to 600 feet
below land surface. Water quality for groundwater stays relatively constant
throughout the year. Typical water quality is given in Table A-12.
The wells discharge to a coke tray aerator, where C02 and soluble iron are
removed. The pH after aeration increases from 6.5 to a range of 7.1 to 7.6.
(The variance in the pH is contributed to the efficiency of the aerator.) After
aeration, the water is chlorinated and filtered through rapid sand filters into
a clearwell. Between the filters and the clearwell, hydrofluosilicic acid and
a trim dose of chlorine are added. The chlorine residual going into the
clearwell is maintained at 0.5 mg/L. The plant treats 20 to 30 MGD.
The raw water sample for this investigation was taken between the point of
aeration and chlorination (raw water). The finished water sample was taken
beyond the clearwell at some point between 4 and 24 hours after chlorination.
Temperature and pH at the finished water sample point ranged between 18 and 19
degrees C and 7.1 to 7.5, respectively. TOX, THM, and TOC data collected
during this survey are presented in Table A-13. Compliance data for.THMs are
consistently below 5 ug/1, and are not included in tabular form.
TABLE A-12. CITY E: Raw Water Quality
Turbidity 0.15
(NTU)
PH 6.5
Alkalinity 48
(as mg/1 CaC03)
Hardness 40
(as mg/1 CaC03)
Temperature 18 C
164
TABLE AH: ORGANICS DATA, SIX CITIES SURVEY CITY E
(All values expressed as microRtams per liter)
TOTAL ORGANIC HALOGEN TRIHALOMETHANES TOC

MONTH Raw 1 Raw 2 Raw Avg Fin 1 Fin 2 Fin Avg TTHM CHC13 CHC12Br CHClRr2 CHBr3 TTHM TOC TOC
RAW FINISHED FIN RAW F1N
Oct 9 13 11 34 33 * 33.5 0 n 0.2 l n * 1.2 735 526

Nov 0 0 0 10 14 12 n 0 n n 0 0 5723 1386
Dec n 0 0 6 0 3 0 n n n 0 n 411 215
Jan 0 5 2.5 13 13 13 0 i 0 n 0 i 719 245
Feb 0 0 0 0 0 0 0 n n n 0 n 412 306
Mar 6 6 6 f> 9 7.5 0 3 n 0 n 3 738 535
APR 0 5 2.5 0 0 0 3 3 n n 0 3
MAY 10 11 10.5 8 11 9.5 0 0 0 i n i
JUN 6 8 7 6 7 6.5 0 1.3 0 n 0 1.3 5195 983
JUL 0 9 4.5 7 8 7.5 n 0 n n n 0 3785 422
AVERAGES ** 4 7 2215 577

MAXIMUMS ** 11 13 5723 1386
CITY F: DESCRIPTION
City F takes its water from a mountain watershed. Water collects in a
large reservoir via several creeks. The mineral content of the water is low,
as indicated by the low hardness and alkalinity in the water. Hardness and
alkalinity range between 8 to 10 mg/L as CaC03 and 4 to 6 mg/L as CaC03
respectively. Typical water quality values include turbidity of 0.5 to 1.0
NTU, pH of 6.4 to 6.8, and temperature of 1.0 to 18 degrees C. The annual water
consumption from the reservoir averages 40 MGD, ranging from 10 MGD to 100 MGD.
Water is discharged from the mountain reservoir to a pressure regulating
reservoir. The effluent of this reservoir is treated with hydrofluosilicic
acid and is dosed with 1.5 mg/L chlorine. Lime and soda ash are also added at
this point to adjust the pH and alkalinity to 8.2 and 13 to 14 mg/L CaC03,
respectively.
Following preliminary treatment, the water flows to an open air
distribution reservoir 20 miles away. In this reservoir, the pH drops to an

average of 7.6. The effluent of the reservoir can be channeled in two
directions: directly to the distribution system, or to a second reservoir and
then to the distribution system. Before leaving the second reservoir the
chlorine residual is raised to a range of 0.3 to 0.5 mg/L chlorine. Raw water
samples for this investigation were taken before chlorination at the pressure
regulating reservoir. Finished water samples were taken from the distribution
system one to seven days after chlorine was added. During the study the second
distribution reservoir was not used. The pH range for the finished water
organic samples was 7.41 to 7.90. The temperature for the samples at the time
of collection varied seasonally, ranging from 5 degrees C (February) to 20
degrees C (June). Typical data for the finished water samples are given in
Table A-14. TOX, THM, and TOC data collected from City F during this survey
are presented in Table A-15.
166
TABLE A-14. CITY F: Finished Water Temperature, pH
and TTHM data, (monthly avg.)
DATE TEMP(C) pH TTHM*
Oct'84 15 7.59 31
Nov'84 - 7.44
Dec'84 8 7.55 80
Jan'85
Feb'85 5 7.35
Mar'85 10 7.55 62
Apr'85
May'85 7.90
Jun'85 20 7.41 78
Jul'85
Aug'85 - 7.64
TTHM data (micrograms per liter) for compliance with EPA regulations
167
TABLE A15: ORGANICS DATA, SIX CITIES SURVEY CITY F
TOTAL ORGANIC HALOGEN T 0 C

MONTH 1 Raw 2 Raw Avg Fin 1 Fin 2 Fin Avg TTHM CHC13 CHC12Br CHClBr?. CHBr3 TTHM TOC TOC
RAW FINISHED FTN RAW F!«J
Oct 0 0 0 227 220 223.5 0 19 1 0 0 20 1530 1540

Nov 40 5 193 183 188 0 13 1 0 0 14 1362 1843
Dec a 6 7 210.5 207 208.75 0 17 1 0 0 18 1534
Jan
Feb 7 10 8.5 218 223 220.5 0 32 2 0 0 34 1409 1212
00
Mar 11 13 12 148 153 150.5 0 27 1 0 0 28 1909 1706
APR 5 7 6 171 171 * '171 0 66 2 0 0 68
MAY
JUN 8 11 9.5 255 262 258.5 0 26 1 0 0 27 1669
JUL 12 8 10 ISA 192 188 2.3 31 1 0 0 32
AVERAGES ** 6 205 29 27 1576 1567

MAXIMUMS ** 12 25 <) 66 68 1909 1843
APPENDIX B
REACTION CURVE DATA
169
REACTION CURVE 1 REACTION CURVE 2 REACTION CURVE 3
OCTOBER 16,1984 NOVEMBER 2,1984 NOVEMBER 15,1984

South Coag, pH= temp= 70F, Cl=5.0 mg/L South coag, pH=7.4, temp=18C South coag, pH=7.4, temp=16c
time toxl tox2 tox ave tim toxl tox2 tox ave
0 16.9 22.1 19.5 0 25 23 24 time tox tox2 tox ave
1 90.9 87 88.95 0. 89 90 89.5 0 25 25 25
5 134 133 133.5 1 98 86 92 1 78 83 80.5
12.5 131 108 119.5 2 101 99 100 2.5 91 102 96.5
150 140 145 3 108 105 106.5 5 *** 107 106
20
170 163 166.5 5 123 119 121 30 *** 141 138.5
30
202 189 195.5 60 *** 154 152.5
45
60 260 161 210.5
REACTION CURVE 4 REACTION CURVE 5 REACTION CURVE 6

CHLORINE DIOXIDE
NOVEMBER 30,1984 DECEMBER 7,1984 DECEMBER 12,1984
South coag, pH=7.3, temp=19 South coag, pH=7.15, temp=20C South Coag, pH=7.4, temp =20C
time toxl tox2 tox ave tim toxl tox2 tox ave time tox tox2 tox avg
0 20 20 20 0 18 21 19.5 0 14 19 16.5
1 70 72 71 1 58 60 59 1 75 77 76
2.5 77 81 79 2. 67 69 68 2.5
5 87 92 89.5 5 74 78 76 5 80 81 80.5
30 120 134 127 30 107 111 109 30 80 84 82
60 133 136 134.5 60 131 141 136 60 82 85 83.5
REACTION CURVE 7 8
CHLORINE DIOXIDE CHLORINE DIOXIDE
Jan. 25,1985 TOX REACTION CURVE Feb. 6, 1985 TOX REACTION CURVE
South Coag, pH =7.4, temp =20C South Coag, pH =7.4, temp =20C
time toxl tox2 tox avg time toxl tox2 tox avg
0 10 10 10 0 23 31 27
1 51 54 52.5 1 42 44 43
2.5 55 56 55.5 2.5 81 90 85.
5 60 62 61 5 87 91 89
30 23 25 24 30 46 48 47
60 13 13 13 60 24 29 26.
Dosed with 4.5 mg/1 C102 Dosed with 4.5 mg/1 C102
Residual after 1 hr . 2.1 mg/1 Residual after 1 hr . 2.1 mg/1
CURVE # 22: CHLORINE DIOXIDE CURVE #23: CHLORAMINE CURVE # 24: CHLORAMINE
DATE: 04-26-85 DATE: 04-29-85 DATE: 04-30-85
pH=6.5 temp=65 dose= pH=8.5 temp=66 dose= pH=6.5 temp=66 dose=
Water: Water: Water:
residual 3 2 residual 3 0.68 residual 3 0.5
T (min) TOX 1 TOX 2 TOX AVG TTHM T (min) TOX 1 TOX 2 TOX TTHM T (min) TOX 1 TOX 2
0 13 12 12.5 0.3 0 17 16 16. 0.2 0 17 16
1 23 21 22 0.4 1 20 22 21 0.7 1 31 32
2.5 25 22 23.5 0.6 2.5 20 19 19. 0.6 2.5 17 17
5 21 23 22 0.5 5 17 16 16. 0.3 5 17 17
30 29 27 28 0.3 30 15 15 15 0.5 30 31 34
60 29 30 29.5 0.3 60 20 20 20 0.9 60 34 30
STACKED CURVES
CURVE 9 (CL2 AS BASELINE)
CL2 CL2 +CL02

CL2 +NH2CL
time toxl tox2 tox avg time toxl tox2 tox avg tox2 tox avg
time toxl
0 15 15 15 0 15 15 15 15 15
0 15
20 60 62 61 20 60 62 61 62 61
20 60
25 56 61 58.5 60 59
25 58
.40 67 68 67.5 40 59 60 59.5 58.5
40 56 61
STACKED CURVES
CURVE 10 (CL02 AS BASELINE)
CL02 CL02 +CL2
CL02 +NH2CL
time toxl tox2 tox avg time toxl tox2 tox avg time toxl tox2 tox avg
0 15 15 15 0 15 15 15 0 15 15 15
20 12 15 13.5 20 12 15 13.5 20 12 15 13.5
25 20 23 21.5 25 12 12 12
40 11 13 12 40 27 31 29 40 17 18 17.5
*
STACKED CURVES
CURVE 11 (NH2CL AS BASELINE)
NH2CL NH2CL +CL2 NH2CL +CL02
time toxl tox2 tox avg time toxl tox2 tox avg time toxl tox2 tox avg
0 15 15 15 0 15 15 15 0 15 15 15
20 18 19 18.5 20 18 19 18.5 20 18 19 18.5
25 24 27 25.5 25 23 24 23.5
40 22 24 23 40 27 30 28.5 40 26 29 27.5
CURVE # 25: CHLORINE CURVE # 26: CHLORINE CURVE # 27: CHLORINE DIOXIDE
DATE: 05-01-85 DATE: 05-10-85 DATE: 05-16-85
pH=8 . 5 temp=70 dose= pH=6.5 temp=72 dose= pH=8.5 temp=71 dose=
residual= .79 free, .83 total residual= .45 free, .55 total residual=l.35 free, 1.4 total
0 15 16 15.5 0.2 0 10 11 10. 0 0 14 19
1 52 50 51 1.7 1 74 74 74 0.3 1 35 23
2.5 65 66 65.5 2.4 2.5 85 86 85. 1.2 2.5 22 24
5 73 68 70.5 2.9 5 102 99 100 2.3 5 24 20
30 100 102 101 11 30 148 160 154 6.9 30 23 22
60 105 126 115.5 10.5 60 166 167 166 11.1 60 22 23
CURVE # 28: CHLORINE DIOXIDE CURVE # 29: CHLORAMINE CURVE # 30: CHLORAMINE
DATE: 05-28-85 DATE: 06-04-85 DATE: 06-04-85
pH=6.5 temp=72 dose= pH=8.5 temp=72 dose= pH=6.5 temp=72 dose=
residual= 0.66 residual= 0.7 residual= 0.71 total
0 17 14 15.5 0.8 0 17 17 17 0 0 17 17
1 27 26 26.5 1 1 24 22 23 0 1 29 27
2.5 26 25 25.5 0.8 2.5 24 24 24 0 2.5 28 28
5 28 28 28 2.3 5 25 27 26 0 5 31 30
30 30 28 29 0.7 30 24 26 25 0 30 30 34
60 30 27 28.5 1.5 60 29 29 29 0 60 37 34
CURVE #31: STACKED CURVE, CHLORINE RASE
DATE: 06-11-85
pH= 73 dose=
Water:
residual=
T (min) TOX 1 TOX 2 TOX AVG
0 15 20 17.5
20 138 141 139.5
40 165 163 164
1440 295 289 292
CHLORINE + CHLORINE DIOXIDE

40 151 156 153.5
1440 225 218 221.5
CHLORINE + CHLORAMINE
40 160 157 158.5
1440 166 166 166
. 174
APPENDIX C
OPERATIONAL DATA
PILOT PLANT RUNS #51 TO 56
175
TABLE C-l. SECTION VI, RUN # 51; OPERATIONAL DATA, PP1=CHLORINE, PP2OZONE/CHLORINE
DATE TIME PPl PP2 SAMPLE CHLORINE PPl CHLORINE PP2 OZONE C102 pH pH TEMPERATURE TURBIDITY
(mg/L) (mg/L) (mg/L) (mg/L) (C) (NTU)
OXIDANT OXIDANT LOCATION FREE MONO DI FREE MONO DI in:out/dir PPl PP2 PPl PP2 PPl PP2 PPl PP2
6/12 4pm C12 C12 + 03 CONTACT 2.39 0.10 0.18 1.34 0.04 0.08 7.43 7.36 22.5 22.5 0.82 0.77
6/12 4pm C12 C12 + 03 SAND 2.55 0.07 0.09 1.40 0.15 0.11 22.5 22.5 0.30 0.27
6/13 llpm C12 C12 + 03 CONTACT 2.20 0.14 0.11 1.54 0.09 0.11 /o .88 7.49 7.46 1.30 1.30
6/13 3pm C12 C12 + 03 CONTACT 2.35 0.18 0.08 1.42 0.08 0.09 1.30 1.40
6/14 9am C12 C12 + 03 CONTACT 2.12 0.10 0.13 1.34 0.12 0.10 /o .61 1.00 0.93
6/14 1pm C12 C12 + 03 CONTACT 1.81 0.15 0.09 1.07 0.10 0.06 7.50 7.50 1.30 1.30
6/15 1pm C12 C12 + 03 CONTACT 1.86 0.12 0.08 1.23 0.10 0.06 7.47 7.44 1.60 1.30
6/15 1pm C12 C12 + 03 SAND 1.55 0.17 0.10 0.13 0.20 0.08 7.49 7.52 0.16 0.16
6/16 6am C12 C12 + 03 CONTACT 0.71 0.15 0.07 1.21 0.19 0.08 0.36/ 7.44 7.51 1.40 1.10
6/18 Sam C12 C12 + 03 CONTACT 1.78 0.07 0.10 NO C12 FEED 0.50/0 .16 1.10 0.89
6/18 8pm C12 C12 + 03 SAND 2.11 0.18 0.10 NO C12 FEED 0.22 0.42
AVERAGE VALUES 1.95 0.13 0.10 1.19 0.12 0.09 0.43/0 .55 7.47 7.46 22.5 22.5 1.24 1.12
TABLE C-2. SECTION VI, RUN f 52; OPERATIONAL DATA, PP1=CHLORAMINE, PP2=OZONE/CHLORAMINE
DATE TIME PPl PP2 SAMPLE CHLORINE PPl CHLORINE PP2 OZONE C102 pH PH TEMPERATURE TURBIDITY
OXIDANT OXIDANT LOCATION FREE MONO DI FREE MONO DI in:out/dir PPl PP2 PPl PP2 PPl PP2 PPl PP2
6/20 2pm NH2C1 NH2C1 + OCONTACT <0.01 1.94 0.65 <0.01 1.68 0.47 7.59
6/20 4pm NH2C1 NH2C1 + OCONTACT <0.01 3.08 0.37 <0.01 2.88 0.47
6/20 5pm NH2C1 NH2C1 -H OCONTACT <0.01 3.06 0.18 <0.01 2.97 0.25
6/20 6pm NH2C1 NH2C1 -H OCONTACT <0.01 3.03 0.25 <0.01 3.07 0.38 7.60 7.54 22.5 22.5 2.00 1.20
6/21 8am NH2C1 NH2C1 -t- OCONTACT <0.01 2.82 0.10 <0.01 2.54 0.14 0.36/ 1.00 1.30
6/21 3pm NH2C1 NH2C1 -H OCONTACT <0.01 2.73 AMP <0.01 2.45 AMP 0.42/0 .20
6/22 1pm NH2C1 NH2C1 -1- OCONTACT 0.06 2.61 0.11 0.16 1.99 0.10 7.49 7.40
6/22 3pm NH2C1 NH2C1 -1- OCONTACT <0.01 2.42 0.01 <0.01 2.08 0.07
6/23 1pm NH2C1 NH2C1 -1- OCONTACT 0.92 1.76 <0.01 0.18 2.05 0.08 7.46 7.48 0.78 1.30
6/23 1pm NH2C1 NH2C1 -1- OCONTACT <0.01 2.28 AMP <0.01 2.05 AMP
6/23 1pm NH2C1 NH2C1 -1- OSAND <0.01 2.34 0.12 1.88 0.09 0.12 0.63/0 .65 7.48 7.48 0.25 0.12
6/23 8pm NH2C1 NH2C1 -h OCONTACT <0.01 1.97 AMP <0.01 1.78 AMP 7.53 7.43 1.40 2.10
6/24 9am NH2C1 NH2C1 -H OCONTACT <0.01 2.21 AMP <0.01 1.99 AMP 1.10 1.10
6/24 9am NH2C1 NH2C1 'h OCONTACT <0.01 2.36 0.08 <0.01 2.18 0.06 0.61/0 .71
6/25 Sam NH2C1 NH2C1 -h OCONTACT <0.01 2.05 AMP <0.01 1.67 AMP 7.51 7.47 0.98 1.50
6/25 9am NH2C1 NH2C1 JK OSAND <0.01 2.07 AMP <0.01 1.68 AMP 0.54 0.21
6/25 11am NH2C1 NH2C1 -V OCONTACT 0.85/0 .77
AVERAGE VALUES 0.06 2.42 0.21 0.13 2.07 0.21 0.57/0 .58 7.52 7.47 22.5 22.5 1.21 1.41
TABLE C-3. SECTION VI,RON ft 53; OPERATIONAL DATA, PPl=CHLORINE DIOXIDE, PP2=OZONE/CHLORINE DIOXIDE
DATE TIME PP1 PP2 SAMPLE CHLORINE PP1 CHLORINE PP2 OZONE C102 PH pH TEMPERATURE TURBIDITY
(mg/L) (mg/L) <mg/L) (mg/L) (C) (NTU)
OXIDANT OXIDANT LOCATION FREE MONO DI FREE MONO DI in:out/dir PP1 PP2 PP1 PP2 PPl PP2 PP1 PP2
6/27 11am C102 03 + C102CONTACT 1.11 0.24
6/27 Iptn C102 03 + C102CONTACT 0.51 0.14 0.85 0.79
6/27 2pm C1O2 03 + C1O2CONTACT 0.00/0.00 0.54 0.38
6/27 4pm C102 03 + C1O2CONTACT 0.00/0.00 0.49 0.54
oo 6/28 4pm TURNED OFF SYSTEM CONTACT
6/31 lam RESTART SYSTEM CONTACT 0.08 0.03
6/31 lam C102 03 + C102CONTACT 0.24 0.37
7/1 9am C102 03 + C102CONTACT 0.87/0.85 0.26 0.00 1.10 0.83
7/1 12N C102 03 + C102CONTACT 0.20 0.10
7/1 3pm C102 03 + C102CONTACT 0.18
7/1 8pm C102 03 + C102CONTACT 0.37 0.00 7.38 7.35 1.00 0.88
7/2 11am C102 03 + C102CONTACT 0.00/0.00 0.76 0.84
7/2 2pm C102 03 + C102CONTACT 0.52 0.08
7/3 10am C1O2 03 + C102CONTACT 0.78/0.82 0.41 0.09 7.42 7.40 1.10 1.40
7/4 7am C102 03 + C102CONTACT 0.44 0.07
AVERAGE VALUES 0.33/0.33 0.44 0.22 7.40 7.38 1.01 0.98
TABLE C-4. SECTION VI,RUN # 54; OPERATIONAL DATA, PP1=CHLORAMINE, PP2=CHLORINE DIOXIDE
DATE TIME PPl PP2 SAMPLE CHLORINE PPl CHLORINE PP2 OZONE C102 PH PH TEMPERATURE TURBIDITY
OXIDANT OXIDANT LOCATION FREE MONO DI FREE MONO DI in:out/dir PPl . PP2 PPl PP2 PPl PP2 PPl PP2
7/7 4pm NH2C1 C102 JAR <0.01 2.54 0.09 1 .10
7/9 9am NH2C1 C102 SAND <0.01 2.60 0.14 0 .40 7 .58 7 .50 25.0 25.0 0.20 0.33
7/9 4pm NH2C1 C102 JAR 0.15 1.65 0.08 0 .41
7/10 9am NH2C1 C102 JAR 3.10 0.62 0.07 0 .18
7/10 10am NH2C1 C102 JAR <0.01 1.76 0.07 0 .75
7/10 2pm NH2C1 C102 JAR <0.01 1.75 0.07 0 .46
7/11 2am NH2C1 C102 JAR 0.32 1.63 0.18 0 .41 7 .39 7 .39 1.10 1.10
7/11 11am NH2C1 C102 JAR 2.18 <0.01 0.08 0 .45
7/11 11am NH2C1 C102 JAR <0.01 2.10 AMP
7/11 3pm NH2C1 C102 JAR <0.01 2.64 0.03 0 .70 7 .35 7 .37 1.10 1.10
7/11 3pm NH2C1 C102 SAND <0.01 2.38 0.03 0 .32 0.22 0.57
7/12 lam NH2C1 C102 JAR 0.18 2.35 AMP 7 .46 7 .45 1.30 1.30
7/12 10am NH2C1 C102 JAR <(0.01 0.01 0.01) 0 .28
7/12 12N NH2C1 C102 JAR <0.01 3.10 AMP
7/13 llam NH2C1 C102 JAR 0.14 3.92 AMP 0 .41 7 .35 7 .38 2.20 2.60
7/13 llam NH2C1 C102 SAND 0.08 3.88 AMP 0 .27 7 .41 7 .45 0.21 0.12
AVERAGE VALUE 0.36 2.13 0.08 0 .45 7 .42 7 .42 25.0 25.0 1.43 1.53
TABLE C-5. SBCTION VI, Run # 55; OPERATIONAL DATA, PP1=CHLORINE DIOXIDE, PP2=OZONE/CHLORINE DIOXIDE
CO DATE TIME PP1 PP2 SAMPLE CHLORINE PPl CHLORINE PP2 OZONE C102 PH PH TEMPERATURE TURBIDITY
O (mg/L) (mg/L) (mg/L) (mg/L) (0 (NTU)
OXIDANT OXIDANT LOCAr FREE MONO DI FREE MONO DI in:out/dir PPl PP2 PPl PP2 PPl PP2 PPl PP2
7/22 7pm C102 03 + C10JAR /0.60 0.51 0.59 7.59 7.58 0.82 0.79
7/22 2pm C102 03 + C10SAND 7.55 7.55 0.22 0.18
7/23 10am C102 03 + C1OJAR 0.34 0.41
7/24 2pm C102 03 + C10JAR /0.33 0.45 0.67
7/25 1pm C102 03 + C1OJAR /0.27 0.40 0.33 21.1
7/26 4pm C102 03 + C1OJAR /0.60 0.64 0.62
7/27 Sam C102 03 + C10JAR /0.56 0.72 0.67 7.33 7.27 1.10 0.82
AVERAGE VALUES /0.47 0.51 0.55 7.49 7.47 21.1 0.96 0.80
TABLE C-6. SECTION VT, RUN # 56; OPERATIONAL DATA, PPlODjORINE/CHLORAMINE, PP2OZONE/CHLORINE/CH
LORAMINE
DATE TIME PPl PP2 SAMPLE CHLORINE PPl CHLORINE PP2 OZONE C102 oH pH TEMPERATURE TURBIDITY
(mg/L) (mg/L) (mg/L) (mg/L) (C)
OXIDANT OXIDANT LOCATION (NTU)
FREE MONO DI FREE MONO DI in:out/dir PPl PP2 PPl PP2 PPl PP2
12/20 9AM NH2CL 03 -H NH2CJAR 4.3L <0.01 3.08 0.15 PPl PP2
0. 30 1.98 0. 08
12/20 9AM NH2CL 03 -h NH2CJAR 2.0L 1.98 0.11 0.08 0. 53 0.03 0. 07
00 12/20 9AM NH2CL 03 -^ NH2CCONTACT
/3.31 7. 15 7.13 1.6 1.9 1.8
12/20 1PM NH2CL 03 -h NH2CJAR 4.3L 1.54 0.34 0.07 0. 47 0.07 0. 07
12/20 1PM NH2CL 03 -1- NH2CJAR 2.0L 0.05 2.66 0.18 0. 22 1.07 0. 03
12/20 1PM NH2CL 03 -h NH2CCONTACT
7. 46
12/21 11AMNH2CL 03 -I- NH2CJAR 4.3L 3.29 0.20 0.16 7.24 5.9 1.6
2. 16 0.27 0. 13 7. 14 7.20 1.1 2.1
12/21 11AMNH2CL 03 -h NH2CJAR 2.0L <0.01 3.65 0.08 <0 .01 2.72 0 .07
12/21 11AMNH2CL 03 -(• NH2CCONTACT 7. 21 7.13 1.6 1.0
/4.8
12/24 9AM NH2CL 03 -iI- NH2CJAR 4.3L 3.31 0.13 0.17 2. 67 0.16 0. 10
12/24 9AM NH2CL 03 -H NH2CJAR 2.0L <0.01 3.46 0.19 7. 18 7.04 1.3 10.0
0. 35 2.44 0. 41 7. 08 1.1 9.7
12/24 9AM NH2CL 03 Hh NH2CCONTACT /2.67
1P-5C-90517-4/87-TC ISBN 0-89867-391-7

AWWA Chloro Organic Changes Due To WT Pract

Uploaded by

Document Information

Original Title

Copyright

Available Formats

Share this document

Share or Embed Document

Sharing Options

Did you find this document useful?

Is this content inappropriate?

Copyright:

Available Formats

AWWA Chloro Organic Changes Due To WT Pract

Uploaded by

Copyright:

Available Formats

AWWA RESEARCH

RESULTING FROM MODIFICATION OF

WATER TREATMENT PRACTICES

Prepared for AWWARF by:

Stephen A. Hubbs and G.C. Holdren

Published by American Water Works Association

This study was funded by the American Water Works Association

Literature Cited 147

Table III-l Comparison of observed and expected THM concentrations 19

Table IV-1. Six Cities Survey: Water Treatment Techniques. 26

Table IV-3. Analysis of TOX, TTHM, TOC and Temperature 39

Table V-l. TOX Temperature Dependence Reaction Model: 51

Table VI-1. Determination of retention times for the contact chambers 73

Table VI-2. Schedule of pilot plant runs 13 to 50. 75

Table VI-4. Pilot plant turbidity levels. 88

Table VI-5. Pilot plant pH levels. 89

Table VI-6. Pilot plant bacteriological results, SPC. 91

Table VI-7. Pilot plant bacteriological results, total coliforms. 92

Table VI-9. Chlorine dioxide dosages and residuals. 95

Table VI-10. Pilot plant TOC concentrations. 97

Table VI-16. Analysis of variance for changes in TTHM levels 109

Table VI-17. Analysis of variance for changes in TOX levels 110

Table VI-18. Analysis of variance for changes in TOC levels 111

Table Vl-21. Run 51 organics data: PPl=chlorine, PP2=ozone/chlorine. 131

Table VI-22. Run 52 organics data: PP1 = chlorine dioxide, 133

Table VI-23. Run 53 organics data: PP1 = chlorine dioxide, 134

Table VI-24. Run 55 organics data: PP1 = chlorine dioxide, 135

Table VI-25. Run 54 organics data: PPl = chloramine, 137

Table VI-26. Run 56 organics data. 138

Table A-l. City A: Finished Water Temperature and pH 153

Table A-2. City A: Organics Data, Six Cities Survey 154

Table A-3. City B: Raw Water Quality 156

Table A-5. City B: OrganicsData, Six Cities Survey 157

Table A-6. City C: Raw Water Quality 159

Table A-8. City C: Organics Data 160

Table A-9 City D: Raw Water Quality 162

Table A-ll. City D: Organics Data: Six Cities Survey 163

Table A-12. City E: Raw Water Quality 164

Table A-13. City E: Organics Data: Six Cities Survey 165

Table A-14. City F: Finished Water Temperature and pH Data 167

Table A-15. City E: Organics Data: Six Cities Survey 168

Table B-l. Reaction Curve Data: Curve #1 through #30 171

Table C-l. Run #51,. Operational Data 175

Table C-3. Run #53, Operational Data 177

Table C-4. Run #54, Operational Data 178

Table C-5. Run #55, Operational Data 179

Table C-6. Run #56, Operational Data 180

Figure III-l, Value of TTHM standards (October, 1984 through 18

Figure III-2. Apparatus for Chlorine Dioxide Generation 21

Figure IV-1. Six Cities Survey, Raw Water TOX Values 28

Figure IV-2. Six Cities Survey, Raw Water TTHM Values 29

Figure IV-3. Six Cities Survey, Raw Water TOC Values 31

Figure IV-4. Six Cities Survey, Finished Water TOX Values 32

Figure IV-5. Six Cities Survey, Finished Water TTHM Values 33

Figure IV-6. Six Cities Survey, Finished Water TOC Values 35

Figure IV-7. Six Cities Survey, TOX vs TTHM, City D 40

Figure IV-8. Six Cities Survey, TOX vs Temperature, City D 41

Figure IV-9. Six Cities Survey, TTHM vs Temperature, City D 42

Figure V-l. TOX Reaction Curve #2: Free Chlorine 46

Figure V-9. TOX Reaction Curve #15, #21,#27: C102, pH 8.5 56

Figure V-12. TOX Reaction Curves, Pre-Ozone, Free Chlorine, 63

Figure V-13. THM Reaction Curve, Pre-Ozone, Free Chlorine, 64

Figure VI-1. Layout of pilot plant system. 67