Disinfection by Products

Drinking Water Research
Advancing the Science of Water
JanuaryMarch 2010 volume 20, number 1 traditional DBPs emerging DBPs health effects DBP regulations case studies historical perspective
Disinfection
By-Products
Drinking Water Research
Advancing the Science of Water
FEATURES
DEPARTMENTS
Historical Perspective on Foundations DBP Research

Chris Rayburn, Water Research Foundation director research
management
2
Acronyms and Abbreviations

70
A Summary of DBP Regulations in the United States

Steve Via, American Water Works Association, Government
Affairs, Washington, D.C.
7
Traditional DBPs
Organic Carboneceous DBPs: THMs and HAAs
Inorganic DBPs: Bromate, Chlorite, and Chlorate
12
Emerging DBPs
Nitrogenous DBPs
Iodinated DBPs
Others
43
Health Effects of DBPs
60
Foundation staff contributors to this issue are as follows:

Jonathan Cuppett, Alice Fulmer, Grace Jang, Ron Leblanc,
and Hsiao-wen Chen.
Because of the large number of studies the Foundation has
funded, it was impossible to highlight every single project
in this issue. A more complete list can be found on the
Foundation Website.
The Water Research Foundation is a member-supported, international, nonprofit organization that sponsors
research to enable water utilities, public health agencies, and other professionals to provide safe and affordable drinking water to consumers.
Editor: editor@WaterResearchFoundation.org
Contributing editor: Adam Lang
Art director: Cheri Dougherty
Drinking Water Research (ISSN 1055-9140) is published quarterly for $40 a year in North America ($50 elsewhere) by the
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No part of this publication may be copied, reproduced or otherwise utilized without permission.
JANUARY MARCH 2010 S DRINKING WATER RESEARCH
Foundation Contacts
73
Case Studies and Value of Research
In addition to highlighting research funded
by The Foundation over the years, six case
studies are presented that illustrate how the
research findings from different projects
have successfully been used by utilities to
optimize their treatment processes and
minimize DBP formation during treatment
and in the distribution system. These case
studies are as follows:
Foundation DBP ResearchChloramine
Perspective
Andrej Wilczak, San Francisco Public
Utilities Commission, California
5
How Foundation Research on Nitrosamines
has Benefited the Water Industry
Stuart W. Krasner, Metropolitan Water
District of Southern California
10
DBP Minimization Strategies
Michael Hotaling, Newport News, Virginia
40
Bromate Minimization Strategies
Richard Talley, City of Fort Worth, Texas
41
Localized Treatment for DBPs
Mao Fang and Laura Jacobson, Las Vegas
Valley Water District, Nevada
58
Application of Storage Facility Modeling to
Improve Mixing and Reduce Water Age
David J. Hartman and Jeff Swertfeger,
Greater Cincinnati Water Works, Ohio
68
VIEWPOINT
Practical Guidance, Real World Impact

Its a delicate balance. Drinking water disinfection is one of the great public health
achievements of the 20th century, eliminating the scourges of water related disease
including typhoid and cholera in the United States; but, at the same time, treatment
chemicals that safeguard public health can also produce potentially harmful
by-products.
The Water Research Foundation has been sponsoring research to help utilities measure
and control DBPs since the early 1980s, and we are leading the way in understanding new, emerging DBPs. In 1986, we
sponsored the research that discovered that THMs form during chlorination, providing some of the first practical guidance to
utility managers on DBP measurement and control.
During the early 1990s, we formed a council to advise the USEPA and other stakeholders about DBP rulemaking. We funded
over 21 projects through this council, including the study that found pregnancy loss was not correlated to DBP exposure.
Since the year 2000, we have funded numerous projects that examine nitrogenous DBPs (N-DBPs) and iodinated DBPs
(I-DBPs). Additionally, in partnership with the USEPA, we have conducted research on organic and inorganic nitrogen precursor
characteristics and water quality parameters that contribute to the formation of N-DBPs.
Clearly, interest in DBPs is growing. Thats why we devoted our first 2010 issue of Drinking Water Research to this topic. We
hope you find the research overviews instructive. Weve also included six case studies that demonstrate how your peers are
treating water while minimizing DBP formation.
Our goal is to help you, our valued subscribers, achieve that delicate balance: managing risks and protecting public health.
Sincerely,
David E. Rager
Chair, Board of Trustees
Robert C. Renner, P.E., D.E.E.

Executive Director
DRINKING WATER RESEARCH S JANUARY MARCH 2010
Historical Perspective
Historical Perspective on Foundations

DBP Research
Chris Rayburn, Water Research Foundation director research management
Introduction
The use of strong oxidants such as chlorine,

chloramines, and ozone to disinfect
drinking water has virtually eliminated
waterborne diseases such as typhoid,
cholera, and dysentery in developed
countries. In 1999, the Centers for Disease
Control and Prevention (CDC) identified
control of infectious diseases, through
practices such as drinking water treatment
and disinfection, as one of the ten great
public health achievements of the 20th
century. However, research in the early
1970s showed that chlorine interacts with
natural organic matter (NOM) present in
drinking water supplies to form disinfection
by-products (DBPs). Some of these
compounds have been linked to cancer
in laboratory animals and other adverse
health effects such as reproductive and
developmental anomalies.
The discovery of DBPs spawned a new era
in water treatment practice. Water suppliers
that relied on disinfection to protect the
public from waterborne disease were faced
with the new challenge of maintaining
this protection while also minimizing
public exposure to DBPs. In 1979, the U.S.
Environmental Protection Agency (USEPA)
established a maximum contaminant level
(MCL) for total trihalomethanes (TTHMs),
which are one class of halogenated organic
DBPs. USEPA regulations were later
broadened to include haloacetic acids
(HAAs), a second major class of organic
DBPs, as well as the inorganic compounds
bromate and chlorite. In recent years, other
DBP classes of potential health concern
2
have been identified, including nitrogenous

DBPs such as N-nitrosodimethylamine
(NDMA) and iodinated DBP species.
First Steps
Water Research Foundations involvement

in DBP research dates to the beginning of
the utility subscription program in 1983.
With the promulgation of the first MCL
for TTHMs in 1979, water utilities were
anxious to understand more about the
occurrence, measurement, and control of
these compounds in real-world treatment
scenarios. Some of the Foundations
earliest research projects, funded in
the early 1980s, focused on measuring
trihalomethane (THM) formation
potential, using ozone pre-oxidation
for THM control, and minimizing THM
formation in conventional surface water
treatment. In 1986, the Foundation funded
a nationwide survey of THM occurrence,
the first to be conducted since the 1979
MCL. Data on THM concentrations in
finished water were provided by 727 U.S.
water utilities. The project also estimated
national costs associated with controlling
THM formation and assessed the potential
effects of more stringent THM standards.
The results were published in the January
1988 Journal AWWA. Also in 1986, the
Foundation undertook its first international
collaboration, with the Netherlands-based
research organization Kiwa NV (now
KWR), to document research results and
operational experiences in the Netherlands
on the measurement and control of DBPs
THMs. Investigators in the Netherlands
were among the first to demonstrate that
THMs form during chlorination of drinking

water. This study provided some of the
first practical guidance for water utility
operators, engineers, and managers on the
measurement and control of DBPs.
M/DBP Research Council
In the early 1990s, USEPA was laying the

groundwork for a series of regulations
under the Safe Drinking Water Act (SDWA)
collectively known as the Microbial/
Disinfection By-Product (M/DBP) Rule
Cluster. USEPA and public stakeholders
recognized the need for additional
information to inform the rulemaking
process. In 1995, the M/DBP Research
Council was established to provide a vehicle
for the selection and funding of research
designed to support the development of
the M/DBP Rule Cluster. Council members
included representatives from USEPA, the
Foundation, and several other stakeholder
groups. The council provided a mechanism
for USEPA and the Foundation to fund
collaborative DBP-related research of
interest to both organizations.
The M/DBP Research Council met one
or more times each year from 19952001,
allocating a total of $9.5 million to 21
research projects. Among the many
important projects funded through the
council was Information Collection
Rule Data Analysis (2002, order#90947/
project#2799). USEPA promulgated the
Information Collection Rule (ICR) in
1996 to collect monitoring and treatment
information from utilities serving at least
100,000 people. A total of 296 U.S. utilities
collected and reported data from July
1997 through December 1998 under the
ICR. Information Collection Rule Data
Analysis examined various subsets of
ICR data to help utilities and members
of the scientific community make sense
of the massive amount of data collected
through the ICR. Another key M/DBP

Research Council project is Drinking
Water Disinfection By-Products and
Pregnancy Outcome (2005, order#91088F/
project#2579). This project investigated
whether exposure to THMs, HAAs, or other
DBPs may be associated with an increased
risk of pregnancy loss, preterm birth, and
reduced fetal growth. The study found no
strong association between these negative
pregnancy outcomes and exposure to
DBPs in drinking water. The results helped
reveal limitations in prior epidemiologic
research on this topic and were used by
USEPA to frame the Stage 2 Disinfectants/
Disinfection By-Products Rule (DBPR) that
was promulgated in 2006.
Focus on Regulated DBPs
While it has long been recognized that

reactions between chlorine and NOM
can form a very wide range of potential
DBPs, drinking water regulatory activity to
date has focused largely on establishing
standards for THMs and HAAs. For this
reason, most of the Foundations DBPrelated research through the early part of
this decade focused on helping utilities
better understand and cope with these
two classes of halogenated organic DBPs.
Additional Foundation research has sought
to improve understanding and control
of bromate and chlorite and regulated
inorganic DBPs associated with drinking
water disinfection using ozone and chlorine
dioxide, respectively.
The range of topics addressed by this
research includes the following:
Characterization and control of DBP
precursors in source water
Precursor removal during treatment
DBP formation mechanisms and kinetics
Treatment process controls, including
disinfectant staging, timing, and dose
Chlorine alternatives; e.g., chloramines,

ozone, ultraviolet (UV) light
Analytical methods
Monitoring and sensor technologies
Emerging DBPs
As knowledge of regulated DBPs has

become well-established, attention has
shifted in recent years to new classes
of DBPs with potential public health
implications. Nitrogenous DBPs (N-DBPs)
are compounds that contain a nitrogenbased functional group. N-DBPs, in
particular NDMA, have received increasing
attention due to the trend towards use
of chlorine alternatives, in particular
chloramines, to reduce THM and HAA
formation. Chloramination has been
shown under some conditions to form
more of certain N-DBPs than chlorine
disinfection. A second driving factor is
steadily increasing N-DBP precursor
concentrations in some source waters
owing to increased agricultural runoff and
wastewater discharges. Consideration of
indirect potable reuse in supply-limited
areas and the prospects for increasing
supply pressures due to climate change has
also spurred interest in N-DBPs. Finally,
studies have suggested that N-DBPs may
be far more toxic than the regulated classes
of organic DBPs. Compounding the issue
is that NDMA and some other N-DBP
compounds can potentially originate
from other sources, including industrial
contamination and treatment of water with
anion exchange resins. NDMA and several
other N-DBPs have been included on the
USEPAs Contaminant Candidate List 3
(CCL3). The Foundation has responded
with a series of research projects since 2000
that have provided utilities and regulators
with crucial information on N-DBP
occurrence, formation, fate, and control.
Iodinated DBPs (I-DBPs), halogenated

organic compounds in which one or
more iodine is incorporated within the
molecule, are a second class of emerging
DBPs of concern. I-DBPs may form through
disinfection of source water containing
relatively elevated levels of iodine. Like
N-DBPs, I-DBPs have been shown to be
potentially much more toxic than the
regulated organic DBPs. Beginning in 2004,
the Foundation funded two projects aimed at
improved assessment and understanding of
I-DBP toxicity and additional work to better
understand the formation, fate, and control
of non-regulated DBPs, including I-DBPs.
Future Directions
While the drinking water community has

gained a detailed and effective body of
knowledge about DBPs since the early
1970s, Foundation subscribers continue
to recognize knowledge gaps and research
needs for both regulated and emerging
DBPs. The Foundations project funding
recommendations for 2010, which are still
under development, include ideas related
to both regulated DBPs (precursor source
characterization, optimizing chlorine
dioxide for THM control) and unregulated
DBPs (sources of N-DBP precursors). The
research community and Foundation
subscribers have also continued in recent
years to propose DBP-related research in
submittals to the Foundations Unsolicited
and Tailored Collaboration research
programs. It is likely that DBP research in the
near future will continue the current trend of
increasing focus on emerging DBPs, with an
emphasis on understanding the true public
health risk posed by these compounds.
The focus will also be on optimization of
available tools and technologies rather than
development of entirely new technologies, to
control these compounds.
The Foundation has been involved in DBP

research for over 25 years. Foundation
research has contributed fundamentally
to the understanding of DBP occurrence,
formation mechanisms, and health risk.
Our research has helped water utilities
optimize treatment and control strategies
to minimize DBP formation and comply

with existing and emerging DBP regulations.
Foundation research has also been used
extensively in the DBP rulemaking process
to help ensure that the regulations are
based on sound science.
Case StudIES and Value of Research

Foundation DBP ResearchChloramine Perspective
Andrej Wilczak, San Francisco Public Utilities Commission, California
The Water Research Foundation has been instrumental in chloramine and DBP research. The report, Optimizing
Chloramine Treatment (1993, order#90620/project#610) and its second edition (2004, order#90993/project#2760),
provided valuable guidelines on chloramine conversion to minimize regulated chlorinated DBPs. The work on chloramine
chemistry conducted at the University of Iowa provided in the report, Chloramine Decomposition in Distribution
System and Model Waters (1998, order#90721/project#937) and in the report, The Role of the Pipe - Water
Interface in DBP Formation and Disinfectant Loss (2000, order#90812/project#293), were very valuable in
elucidating mechanisms responsible for monochloramine decomposition and formation of the DBPs in the bulk water
phase and at the water-pipe interface, especially in terms of chlorine to ammonia ratio, the importance of pH, chloramine
demand from natural organic matter (NOM), and reduced iron. The understanding of chloramination process, chloramine
stability, and the resulting DBPs has increased as a result of this work. The San Francisco Public Utilities Commission
(SFPUC) utilized this research in preparing for its 2004 conversion to chloramine. As a result of chloramine research
by the Foundation, SFPUC has been able to reduce the levels of regulated DBPs and comply with the new USEPA DBP
regulations. SFPUC has also utilized this research in addressing questions from the public regarding chloramine and DBPs
and referenced these reports in questions and answers regarding chloramines on the SFPUC Website.
Several reports provided valuable information regarding speciation of chlorinated and brominated DBPs and practical
factors minimizing their formation during treatment and fate in the distribution systems:

Factors Affecting Disinfection By-Product Formation During Chloramination

(1998, order#90728/project#803)
Disinfection By-Product Formation and Control During Chloramination

(2004, order #91040/project#2677)
Formation and Decay of Disinfection By-Products in the Distribution System

(2006, order#91115/project#2770)
Recent reports on emerging DBPs provided guidance on how to minimize regulated halogenated DBPs,
nitrosamines, and other potential DBPs:

Factors Affecting the Formation of NDMA in Water and Occurrence

(2005, order#91063/project#2678)
Strategies for Minimizing Nitrosamine Formation During Disinfection

(2008, order#91209/project#2979)
Formation of Hydrazine as a Chloramine By-Product

(2006, order#91122/project#2997)
Thanks to increased understanding of the factors contributing to their formation, we can better optimize water
treatment; e.g., in terms of the sequence of the disinfectants, the importance of providing efficient mixing, and
contact time. The work on nitrosamines allowed SFPUC to focus the monitoring program on N-nitrosodimethylamine
and confirm that treatment is optimized to minimize formation of this DBP. Several of these reports are referenced on
the SFPUC Website.
Finally, health effects research conducted by scientists funded by the Foundation provided valuable background
information on health effects issues of DBPs:

Health Effects of Disinfectants and Disinfection By-Products

(1991, order#90577/project#501)
Health Effects and Occurrence of Disinfection By-Products

(2001, order#90827/project#448)
Drinking Water Disinfection By-Products and Pregnancy Outcome

(2005, order#91088/project#2579)
These reports were helpful to better understand the relative significance of DBPs. SFPUC has utilized this research in
addressing questions from the public regarding DBPs and referenced these reports in questions and answers regarding
DBP health effects on the SFPUC Website.
Regulations Summary
A Summary of DBP Regulations

in the United States
Steve Via, American Water Works Association, Government Affairs, Washington, D.C.
DBP formation during chlorination of

drinking water came to the attention of
the scientific community and drinking
water industry with research published
in the early 1970s (Rook 1974 and
Bellar et al. 1974). Subsequent research
confirmed widespread occurrence of
chloroform, dichlorobromomethane,
chlorodibromomethane, and bromoform,
known collectively as total trihalomethanes
(TTHMs), in finished water across the
United States. Animal study data available
in this same time frame indicated that
chloroform was a carcinogen.
Wisconsin experienced an outbreak of

cryptosporidiosis, which was linked to
the drinking water supply.
The U.S. Environmental Protection Agency

(USEPA) proposed regulation of TTHMs in
February 1978 and promulgated an interim
maximum contaminant level (MCL) for
TTHMs on November 29, 1979. The MCL was
100 micrograms per liter (g/L) as an annual
average. The interim MCL only applied to
systems serving 10,000 or more people.
Work on a DBP rule occurred at USEPA

in the late 1980s and early 1990s with
two major milestones being the 1989
Strawman Rule and 1991 Status Report
on disinfectants/disinfection by-product
(D/DBP) Rule Development. This early
rule development stage remains visible
in the features of the final regulations
systems comply with today. The rule was
expanded to cover all system sizes and
types of systems, recognition of TTHMs
as a surrogate for unknown (and as yet
uncharacterized) DBPs, inclusion of
limits on disinfectants, and expansion of
the list of regulated DBPs. Compulsory
treatment changes with no proven health
benefits raised sufficient concerns that
the policy discussion included a phased
implementation.
On June 19, 1986, the 1986 Amendments

to the Safe Drinking Water Act (SDWA)
were signed into law and set the stage
for additional change in regulation of
DBPs. The 1986 Amendments explicitly
required USEPA require disinfection and,
in particular, it required USEPA regulate
Giardia lamblia. The task of increasing
disinfection became more complicated
in the 1980s as DBP research identified
additional by-products including haloacetic
acids (HAAs), chlorite and chlorate from
chlorine dioxide, and bromate from ozone.
This regulatory conundrum became more
challenging when in 1993, Milwaukee,
Ultimately the level of uncertainty in

the available science led to a negotiated
rulemaking process in 1992, where USEPA,
water utilities, consumer advocates, and
other interested parties negotiated a
path forward. Key elements of that path
included promulgation of five rules on a
set schedule (Stage 1 and 2 Disinfectants/
Disinfection By-Product Rule [DBPR],
Interim Enhanced Surface Water Treatment
Rule [IESWTR], Long-Term 2 Enhanced
Surface Water Treatment Rule [LT2ESWTR],
and the Information Collection Rule
[ICR]); regulatory language including
a treatment technique based on total
Regulations Summary
organic carbon (TOC) removal; maximum

residual disinfectant levels (MRDLs)
for chlorine, chloramines, and chlorine
dioxide; and MCLs of 0.080 and 0.060g/L
for TTHM and HAA5 respectively. The
Stage 2 DBPR MCL placeholders were
0.040 and 0.030g/L for TTHM and HAA5
respectively, but the Stage 2 DBPR MCLs
were contingent on data collected and
evaluated both through an active research
agenda, the Microbial/Disinfection ByProduct (M/DBP) Research Council, and
the ICR. Similarly, timing of the IESWTR
and LT2ESWTR were linked to the timing
of the DBP rules to assure a balance
between disinfection and DBP control.
The negotiated rulemaking was reflected
in July 29, 1994 proposals of both the
Stage 1 DBPR and IESWTR.
The 1996 Amendments to the SDWA
were signed August 6, 1996. The 1996
Amendments incorporated by reference
the schedule agreed upon in 1993 and
subsequently proposed by USEPA in July
1994. USEPA followed through on the
agreed upon schedule promulgating the
ICR in 1996, a Notice of Data Availability
following a short stakeholder process in
1997, and finalizing both the Stage 1 DBPR
and IESWTR on December 16, 1998. In
finalizing the Stage 1 DBPR, compliance
was extended to all community and
noncommunity water systems. Quarterly
monitoring became plant-based increasing
the number of samples taken by larger
systems and the new MCLs and maximum
contaminant level goals (MCLGs) proposed
in 1994 were finalized. The Stage 1 DBPR
also changed conventional treatment
making TOC reduction as well as solids
removal a central element of water
treatment plant design and operation. In
parallel, the IESWTR dramatically increased
the stringency of combined filter effluent
(CFE) requirements. Online monitoring was
required and CFE turbidity 0.3 NTU had

to be met by 95% of all measurements taken
at 15 minute intervals when a treatment
train is in operation. IESWTR also included
individual filter reporting triggers to assure
both that individual filters were managed to
prevent CFE exceedances and disinfection
profiling and benchmarking provisions to
assure that efforts to comply with TTHM
and HAA5 MCLs did not lead to reduced
treatment efficacy. In January 2002, USEPA
promulgated the Long-Term 1 ESWTR,
which extended these controls to systems
serving less than 10,000 persons. Complying
with these rules has been a challenge for
many drinking water utilities. Since 2005,
more than 1,500 systems have violated
these rules annually. This compares to the
60 systems that violated volatile organic
compound (VOC) or synthetic organic
chemical (SOC) standards or the 1,136
systems that violated the Lead and Copper
Rule in 2008. Violations aside, these three
rules have not driven large percentages of
systems to granular activated carbon (GAC),
membranes, or alternative disinfectants,
though there was a substantial increase
in the number of systems employing
chloramines for secondary residual.
The remaining regulatory stage following
from the 1993 negotiation provided an
opportunity for USEPA and stakeholders
to respond to data collected through the
ICR. All community water systems serving
100,000 people or more were required to
collect DBP occurrence data, information
about water quality and treatment, and
data from bench-scale treatment studies.
Surface water systems also collected
Cryptosporidium oocyst occurrence
data. As the ICR was ongoing while the
Stage 1 DBPR and IESWTR were being
finalized, development of the Stage 2
DBPR and LT2ESWTR began before
Stage1 DBPR and IESWTR were effective.
Regulations Summary
studies, affordable treatment without

The M/DBP Federal Advisory Committee
known downside DBP risks set the stage
Act (FACA) began meeting in September
for agreement on the principle features
1999. Development of the rule options
of LT2ESWTR. The M/DBP FACA reached
progressed as occurrence data began
agreement in July 2000.
to emerge from the 18-month ICR data
collection period and subsequent quality
Stage 2 DBPR and LT2ESWTR were not
assurance/quality control procedures. The
finalized as rapidly as anticipated by the M/
FACA determined that there was adequate
DBP FACA, but were proposed on August 18,
basis for the Stage 2 DBPR to be based on a
2003 and September 22, 2003 respectively
concern that DBPs may lead to cancer. The
and subsequently promulgated as final
FACA indicated it was not appropriate for
rules on January 4, 2006. At present, water
the standard to be based on reproductivesystems, depending on their size, are either
developmental health risk. Alternatives
in the midst of IDSEs and Cryptosporidium
to the initial 40/30 MCL placeholders
monitoring or determining what approach
were considered and ultimately the goals
they will take to comply based on those
of reducing very high levels system wide
studies. The M/DBP regulatory process
and of achieving more uniform reduction
will continue based on a second round of
in DBPs across the distribution system
Cryptosporidium monitoring, which occurs
became central to option selection. Hence,
in 2015 under the current LT2ESWTR and
the resulting Stage 2 DBPR provisions
it is worthwhile to recognize that several
water systems are currently responding to
DBPs (e.g., nitrosamines) are included in
include the following: conducting initial
the agencys latest Contaminant Candidate
distribution system evaluations (IDSEs) to
List published in the October 8, 2009
determine where high levels of TTHMs and
Federal Register.
HAA5 occur, complying with an MCL based
on a locational-running annual average,
Bibliography
and a population-based sampling scheme.
The Stage 2 DBPR is accompanied by the
Bellar, T.A., Lichtenberger, J.J., and
LT2ESWTR, which is a risk-based regulation, Kroner, R.C., 1974. The Occurrence of
where systems monitor their source water
Organohalides in Chlorinated Drinking
and when observed occurrence exceeds
Water, JAWWA, 66(12):703-706.
fixed thresholds the water treatment
plant must install additional treatment
Rook, J.J. 1974. Formation of Haloforms
(e.g., improved conventional removal;
During Chlorination of Natural Water,
add membranes; install ultraviolet
Water Treatment and Examination,
(UV); ozone; or chlorine dioxide). Just
23(2):234-243.
as chloramination in combination with
enhanced coagulation shaped the costRoutt, J.C., Mackey E., Noack R. 2008.
benefit analysis for the Stage 1 and Stage
Drinking Water Disinfection Practices
2 DBP rules, the widespread recognition
Part 2 Alternatives, Experiences & Future
of UV disinfection as a treatment for
Plans, JAWWA, 100(11):110-126.
reduction of Cryptosporidium significantly
altered earlier expectations for the cost of
Waller, K., S.H. Swan, G. DeLorenze, B.
Cryptosporidium removal. In combination
Hopkins. 1998. Trihalomethanes in
drinking water and spontaneous abortion,
with low realized Cryptosporidium
Epidemiology, 9(2):134140.
oocyst occurrence in the ICR and related

How Foundation Research on Nitrosamines has Benefited
the Water Industry
Stuart W. Krasner, Principal Environmental Specialist, Metropolitan Water District of Southern California
Nitrosamines are emerging contaminants in water where there is health and regulatory concern. Since the 1970s,
numerous researchers have reported on the presence of various nitrosamines in many foodstuffs (e.g., beer, meat, and
cheese products preserved with nitrite) and consumer products (e.g., tobacco smoke and latex products). Nitrosamines
can cause cancers in a wide variety of animal species and the USEPA classified a number of them as probable human
carcinogens. They have 10-6 risk levels at low nanogram-per-liter (ng/L) levels.
In the 1990s, Nnitrosodimethylamine (NDMA) was found in drinking water in Ontario, Canada and in California.
Initially, its presence was associated with industrial contamination. Soon after, it was found to be a by-product of
drinking water treatment, in particular at plants that used certain (polyamine) polymers and/or chloramines. In addition,
it was found in treated wastewater. As a result, Ontario set a maximum acceptable concentration for NDMA at 9ng/L
and California established notification levels for three nitrosamines (NDMA, Nnitrosodiethylamine [NDEA], and
N-nitrosodipropylamine [NDPA]) at 10ng/L each. Although there is currently no federal standard for nitrosamines in
drinking water, the USEPA included several nitrosamines in the Unregulated Contaminant Monitoring Rule 2 (UCMR2)
and on the Contaminant Candidate List 3 (CCL3). Preliminary results indicate that NDMA and other nitrosamines are in
a number of U.S. drinking waters. Thus, it is likely that this class of chemicals will be regulated in the future.
To provide valuable information to the water industry on this emerging class of chemicals, the Water Research
Foundation has been funding research on NDMA and other nitrosamines since 2000. The first completed project,
Factors Affecting the Formation of NDMA in Water and Occurrence (2006, order#91063/project#2678),
included a survey of drinking water, recycled water, and treated wastewater in the United States and Canada.
This groundbreaking project established that NDMA could be formed via a non-nitrosation mechanism during
chloramination and that certain amine-based polyelectrolytes and anion-exchange resins used in drinking water
treatment were important sources of NDMA precursors.
Subsequently, the Foundation has supported a wide range of projects to examine the sources of nitrosamine precursors
in water and the occurrence, formation, and control of nitrosamines, which is providing the water industry with critical
information. One report, Contribution of Wastewater to DBP Formation (2008, order#91206/project #2948),
showed that wastewater treatment plants could be an important source of nitrosamines and their precursors. With
both planned and unplanned reuse, this has become a substantial issue for drinking water treatment plants, especially
in arid parts of the United States, as well as in highly urbanized regions. This study included the development of a
reactivity-based formation potential (FP) test to determine the levels of nitrosamine precursors in treated wastewater
and in drinking water, photolysis studies to examine the degradation of nitrosamines in receiving waters, and the fate
and transport of nitrosamine precursors in effluent-impacted water supplies.
The Foundation funded research conducted in Germany and Switzerland, Strategies for Minimizing Nitrosamine
Formation During Disinfection (2006, order#91209/project#2979), to support international research on identifying
different ways of controlling nitrosamines. This report demonstrated that NDMA precursors could be naturally removed
through riverbank filtration or artificial groundwater recharge and that NDMA precursors could be destroyed or
transformed during pre-oxidation (with ozone or chlorine). Moreover, this innovative completed project examined a
wide range of amine-based chemicals to determine their likelihood as NDMA precursors. For example, ranitidine, a
pharmaceutical used as an antacid, had a much higher conversion efficiency to NDMA than dimethylamine (DMA).
10
Nitrosamines are just one of many emerging classes of nitrogenous disinfection by-products (N-DBPs) of concern.
In another report, Occurrence and Formation of Nitrogenous Disinfection By-Products (2009, order#91250/
project#3014), model compounds and natural organic matter (NOM) were examined as sources of precursors for
NDMA and other N-DBPs. Although carbon-rich NOM fractions can be an important source of precursors for regulated
DBPs (trihalomethanes [THMs] and haloacetic acids [HAAs]), this study demonstrated that it was certain nitrogen-rich
NOM isolates that were important sources of N-DBP precursors. Although algae and treated wastewater were both
found to be sources of precursors for many emerging N-DBPs, treated wastewater was the major source of NDMA
precursors. An important aspect in this project was to show how to best balance the control of regulated DBPs and that
of emerging N-DBPs.
Ongoing research funded by the Foundation continue to provide state-of-the-art information for the water industry.
Currently, researchers have focused on several nitrosamines in water. Project#4089, Method Development for
Disinfection By-Products Associated With Bladder Cancer, will examine if there are unidentified DBPs (e.g.,
nitrosamines from alkaloidal material) that may better explain the cancer risk associated with chlorinated drinking water
in epidemiology studies. Another project#4209, Development and Application of a Total Nitrosamine Assay for
Disinfected Waters, will develop a method to measure the total amount of nitrosamines in water instead of just one
associated with the few chemicals typically measured.
Because DBP FP tests do not provide a true indication of the likely amount of DBPs formed during actual drinking water
treatment, a new project#4180, Development of a Protocol to Predict the Formation of Nitrosamines While
Minimizing the Formation of Regulated DBPs, is developing a bench-scale test to simulate nitrosamine formation
in a distribution system (a simulated distribution system [SDS] test). Moreover, this project is examining the formation
and control of regulated and other emerging DBPs during these tests. As more utilities consider a switch to chloramines
or the use of water from impaired watersheds, this SDS test will provide utilities with a new tool to access how best to
meet existing DBP regulations and that of emerging DBPs that may be regulated in the future.
Metropolitan Water District of Southern California (Metropolitan) and other utilities have benefited immensely
from the Foundation-supported research on nitrosamines. This research has resulted in many utilities, including
Metropolitan, conducting internal studies to better understand the source of NDMA precursors in their waters and
the most cost-effective means of controlling NDMA formation. Although Metropolitan found that their watershed
is impacted to some extent by treated wastewater, the pre-oxidation (e.g., ozone) step was found to destroy NDMA
precursors. At Metropolitan plants, a major source of NDMA precursors was associated with the amine-based
polymer they use. So Metropolitan is examining means of achieving their treatment objectives with a lower polymer
dose and more coagulant. Information from Foundation studies is providing insights on how best to meet potential
future regulatory issues.
Although the UCMR2 will provide the USEPA and stakeholders with a tremendous amount of occurrence data on
NDMA and other nitrosamines, it is well-crafted studies conducted for the Foundation that will provide the water
industry with the type of scientific information upon which a regulation on nitrosamines can be constructed based
on sound science. Metropolitan looks forward to participating in and following up on new Foundation studies that
allow them to best manage their resources to produce water that minimizes the formation of nitrosamines and other
emerging DBPs of health concern.
11
Traditional Disinfection By-Products
Traditional DBPs
Traditional disinfection by-products (DBPs)
include chlorinated and brominated
trihalomethanes (THMs) and haloacetic
acids (HAAs), bromate, chlorite, and
chlorate. Although occurrence of hundreds
of DBPs in drinking water has been
reported in the scientific literature, only 11
are currently regulated: 4 THMs, 5 HAAs,
bromate, and chlorite. U.S. regulations have
established maximum contaminant levels
(MCLs) for these DBPs to limit consumer
exposure and protect public health. The
current MCLs for total THMs and HAA5
in drinking water are 80g/L and 60g/L,
respectively. The MCL for bromate is
10g/L and 1 mg/L for chlorite. No MCL
has been established for the four remaining
HAAs and chlorate.
THMs and HAAs
THMs (chloroform, bromodichloromethane,

dibromochloromethane [DBCM], and
bromoform) and HAA5 (monochloroacetic
acid, dichloroacetic acid, trichloroacetic
acid, monobromoacetic acid, and
dibromoacetic acid) are the most prevalent
DBPs in drinking water. They are produced
upon the reaction of halogenated oxidants
(chlorine, chloramine, and chlorine
dioxide) with natural organic matter (NOM).
Since their discovery in 1970s, a significant
amount of research has been dedicated
to a better understanding of their sources,
analysis methods, formation, control, and
health effects.
NOMthe Precursor
An essential step in understanding the
formation of DBPs is to characterize
the nature of NOM and its reactivity
with disinfectants. Previous research
suggests that the reactive parts of NOM
have apparent specific functional group
12
characteristics, such as THMs are produced

from resorcinol type sites on the molecules.
A thorough review of NOM characteristics
and reactivity can be found in the ongoing
project#4039, By-Products of Potential
Concern in Drinking Water Treatment.
An initial set of separations (prefiltration) is commonly performed prior to
characterization. Characterization of NOM
properties requires other types of nonspecific separations or fractionations.
As summarized in the comprehensive
report, Natural Organic Matter in
Drinking Water: Recommendations
to Water Utilities (2000, order#90802/
project#2543), NOM is a very complex
mixture of substances that cannot be
completely identified as individual
compounds. It is usually characterized
through aggregate measures such as
total organic carbon (TOC), molecular
weight ranges, and hydrophobicity or
hydrophilicity. The report serves as
a resource document for utilities in
developing NOM mitigation and
treatment techniques.
Characterization of Natural Organic
Matter in Drinking Water (2000,
order#90780/project#159) developed
methods to isolate, fractionate, and
characterize NOM. The primary isolation
methods were reverse osmosis (RO);
nanofiltration (NF); and adsorption onto
resins, iron-oxide-coated sand (IOCS), and
iron-oxide-coated-olivine (IOCO). The
study concluded that it was not feasible
to recover 100% of the NOM in any water
matrix. Evaporation was very efficient
for non-volatile NOM but did not isolate
it from the inorganics. RO and NF were
efficient but also did not isolate NOM from
inorganics. XAD-8 and XAD-4 resins
in series recovered 6080% of NOM and

produced NOM concentrates of high purity.
The disadvantage of this concentration
method was that it required extensive time
and preparation. IOCS was 6080%efficient
at NOM recovery. However, it also adsorbed
sulfate and caused sulfate to accumulate in
the NOM isolates. Thus, IOCS would not be
suitable for water containing high levels of
sulfate. In contrast to XAD resins and IOCS,
IOCO retained a significant amount of NOM
at pH 7. It would be a desirable method to
isolate NOM when minimal or no water
sample pretreatment is needed. The caveat
was that the capacity of IOCO was lower
than that of XAD resins or IOCS.
Once the primary NOM isolates are
collected, a secondary method of
fractionation based on hydrophobicity
and acidity is performed. As described in
the report, Natural Organic Matter in
Drinking Water: Recommendations to
Water Utilities, the hydrophobic (humic)
fraction is defined as the fraction of NOM
that is adsorbed on XAD-8 resin at pH
2. Both humic and non-humic substances
are responsible for DBP formation. The
hydrophobic fraction is further separated
into humic and fulvic acids. Humics
precipitate at low pH, while fulvics do not.
Humics are more aromatic in nature than
fulvics. Both have carboxylic acids that
are dissociated and therefore negatively
charged in most natural pH conditions.
The negative charge is a main reason why
positively charged metal coagulants are
effective at removing them. While humics
are considered to be the dominant factor
in DBP formation, the most important
non-humics are amino acids, proteins, and
carboxylic acids.
Characterization of Natural Organic
Matter in Drinking Water was the first
Foundation report in which NOM was
fractionated into hydrophobic, transphilic,

and hydrophilic fractions. Each fraction
was further divided into acid, neutral,
and base subfractions. Similarly in
another Foundation report, Polar NOM:
Characterization, DBPs, Treatment (2002,
order#90877/project#451), NOM was
fractionated into one nonpolar hydrophobic
fraction and four polar fractionstransphilic,
hydrophilic acids plus neutrals (A+N),
hydrophilic base, and colloids. The report
concluded that the hydrophilic A+N fraction
was the most reactive with chlorine and
chloramines and resulted in high THM
yields and very high HAA yields. The colloid
fraction was the least reactive. The report also
recommended that utilities consider NOM
removal as a primary step in DBP control.
Specific Ultraviolet Absorbance (SUVA)
can be used as a surrogate parameter for
NOM reactivity and is defined as the UV254
absorbance (in cm-1) multiplied by 100
divided by the dissolved organic carbon
(DOC) concentration (in mg/L). SUVA has
been shown to be well correlated with a
wide range of parameters of interest to
water treatment including humic content
of NOM. SUVA numbers under three
generally indicate non-humic DOC and
SUVA numbers of 45 indicate primarily
humics. Several Foundation projects were
funded to refine the method and determine
the significance of the SUVA number.
Relative Dominance of HAAs and
THMs in Treated Drinking Water (2002,
order#90844/project#339) reported that
waters with high SUVA had more aromatic
compounds, had more hydrophobic NOM,
and tended to have higher HAA/THM ratios.
SUVA correlated more with HAA formation
potential (HAAFP) than with THM
formation potential (THMFP), suggesting
HAA precursors are more aromatic in
nature, as aromatics have higher UV
absorbance than aliphatic compounds.
continued next page
13
A standard protocol for the measurement

While the developed method was used with
of SUVA was developed as part of the report, artificial solutions of humics as precursors
in Development of Haloform Potential
The Role of Filtration in DOC, UV-254,
Tests
for Water Treatment Plant Control,
and SUVA-254 Determinations (2005,
it was used to test real raw and treated
order#91060F/project#2722). The project
water in Development and Laboratory
investigated several types of filtration
Evaluation of the Haloform Potential
membranes, cleaning procedures, filterTests (1989, order#90547/project#204). The
to waste wash volume, and developed
study found the bromoform FP test to be
a reproducible proven method for the
unsuited for natural samples due to spectral
determination of SUVA. Many finding
interferences
at 223 nm. The method also
from this study have been included in the
suffered
from
large and unpredictable bias.
published USEPA method (Method 415.3:
Determination of Total Organic Carbon and The iodoform test showed better suitability
and correlation with THMFP. The one-hour
Specific Ultraviolet Absorbance at 254 nm
standard method did not perform well in
in Source and Drinking Water).
this study; however, it was recommended
that further validation of the one-hour
Analytical and Monitoring Methods for
alkaline iodoform method be conducted.
THMs and HAAs
The Foundation has funded several method
development and optimization studies.
These include methods for individual
compounds, classes of compounds, as well
as surrogate parameters and formation
potential (FP) protocols. FPs can be a useful
tool to predict the formation of DBPs under
specific treatment conditions.
After the discovery of THMs in disinfected
drinking water, the Foundation funded
research into simpler methods of
determining the THMFP. Development
of Haloform Potential Tests for
Water Treatment Plant Control (1987,
order#90520/project#73) developed a
spectrophotometric method based on
using iodine or bromine as a disinfectant,
which would form primarily iodoform or
bromoform. The methods are also rapid
and can be completed in as little as 1.5
hours for the rapid version at 100C or
two days for the standard test at 25C. The
detection limit was near 0.1 M. The study
confirmed that iodoform and bromoform
correlated more closely to THMFP than
TOC or UV absorbance (UVA).
14
In addition to FP tests, spectrophometric

methods for the analysis of individual or
classes of compounds were investigated in
several Foundation projects.
The most used method for the analysis
of THMs is USEPA method 551.1. The
method includes liquid-liquid extraction
followed by gas chromatography-/electron
capture detection (GC/ECD). A Simple
Spectrophotometric Method for the
Determination of THMs in Drinking
Water (1992, order#90608/project#428)
looked into the possibility of a simple
spectrophotometric method, as the
equipment would be less costly than a gas
chromatograph and probably require less
analyst training. The project was successful
in developing a method for THMs that was
rapid and relatively inexpensive. However,
the method suffered from a lack of precision
for chlorodibromomethane (CDBM) and
low recoveries for brominated THMs in
high-bromide waters.
A spectroscopic method was developed
in Development of Differential UV
Spectroscopy for DBP Monitoring (2002,

order#90888/project#2563). The study
further explored less expensive and complex
methods for the detection of various DBPs.
Differential absorbance spectroscopy (DAS)
was used for the analysis of individual
DBPs and total organic halogen (TOX).
The concentrations of stable DBP species
formed were correlated with DAS (at 272 nm
wavelength) at all pH conditions studied (6.0,
7.0, 8.0). Most of the DBPs were detectable
at single-digitg/L levels. The concentration
of TOX formed during chlorination or
chloramination was strongly and linearly
correlated with DAS but no correlation was
found with water dosed with chlorine dioxide.
The Foundation has also funded research
aimed at optimizing analytical methods for
HAAs. Development of an Experimental
Procedure for Haloacetic Acids Using
Ion Chromatography (2000, order/
project#163) investigated several extraction
techniques and an ion-chromatographic
method for parts-per-billion detection
of HAAs in drinking water. The project
determined that although the method
detection limits were adequate, the nine
HAAs interferences from sulfate could not
be completely suppressed.
Many researchers have sought alternative
methods for analyzing HAAs, because
the currently approved method is timeand chemical-intensive. Application
of ESI-FAIMS-MS to Drinking Water
Contaminant and DBP Analysis (2004,
order/project#2640) applied a unique
analytical instrument to the measurement
of HAAs and other organics in water. The
instrument is known as electrospray
ionizationhigh field asymmetric
waveform ion mobility spectrometrymass
spectrometry (ESIFAIMSMS). The
researchers were able to detect HAAs at the
0.1 to 0.6g/L level without derivatization.
Development of a Novel Method for the

Analysis of Haloacetic Acids in Drinking
Water (2004, order#91013F/project#2644)
used capillary electrophoresis for
the analysis of HAAs. The method
employed solid phase extraction for
sample preparation. Detection was in
the low ppb range for all HAAs except
chlorodibromoacetic acid, which co-eluted
with an unknown contaminant. The project
resulted in a robust method of analyzing
HAAs that does not require lengthy
derivatization, with sensitivity comparable
to the existing USEPA method.
Methods for Real-Time Measurement of
THMs and HAAs in Distribution Systems
(2004, order#91003F/project#2873) was
funded by the Foundation to develop faster
methods for the analysis of THMs and
HAAs. Faster methods are necessary for
the detection of short-time variations and
transient peaks in DBP formation.
Phase 1 of the project was a very extensive
literature review of existing analytical
methods. The methods were classified
according to cost, expertise required,
detection limit, recovery, relative standard
deviation (RSD), equipment required,
analysis time, and adaptability to online
monitoring. Criteria for the ideal method
were identified as low detection limit
(<5g/L), minimum of one sample per
hour throughput, portability, and ease of
use. The project concluded that none of the
existing known methods for THM and HAA
analysis could be considered close to the
ideal method defined in the project.
Phase 2 of the project (2007, order#91173/
project#2873) selected several technologies
for testing and comparison with approved
methods. THMs were analyzed via
three methods: capillary membrane
sampling gas chromatography (CMSGC),
15
online monitoring purge and trap gas

chromatography (OPTGC), and capillary
membrane sampling flow injection analysis
(CMSFIA). All three methods compared
favorably with approved methods and
generally had near 100% recovery and
generally under 15% RSD.
Two methods were developed and tested
for HAA analysis, CMSFIA and postcolumn ion chromatography (PCIC).
These methods also performed well though
recoveries were in the 80% range and RSD
was as high as 20%. The CMS-FIA method
was able to analyze as many as four samples
per hour, which meets the criteria for nearreal-time results.
All methods were subjected to detailed
comparison studies to USEPA methods
in the laboratory as well as diverse and
challenging real world situations. The
report provides detailed information on
construction, operation, and maintenance
of the most promising analyzers.
THM and HAA Formation
A complete understanding of the kinetics and

the mechanisms involved in the formation
of DBPs is difficult because of the complex
structure of NOM and various parameters
involved, such as disinfectant type and dose,
pH, contact time, and temperature.
Several attempts have been made to
investigate the mechanisms of DBP
formation. Some of these studies have
involved model compounds and others
have used mechanistic models to
predict the formation of these DBPs. The
objective of Modeling DBP Formation
Kinetics: Mechanistic and Spectroscopic
Approaches (2004, order#91000F/
project#2597) was to develop a mechanistic
model for THM and HAA formation The
model accounted for the effect of chlorine
16
dose, pH, temperature, and bromide

concentration on DBP formation kinetics
and speciation. The study found that
the model relating DBP formation to the
change in absorbance was successful and
suggested that measurement of absorbance
can greatly reduce the need to rely on
time-consuming and costly analyses for
individual DBPs. The experimental results,
especially for waters with very low bromide,
could be reproduced quite well by the
mechanistic model. In addition, the study
found that DBP formation at very short
reaction times is consistent in virtually all
ways with that at longer times, suggesting
that the highly reactive sites in NOM have
very similar structures to those that were
much less reactive.
The study of DBP formation in real water
was investigated in Relative Dominance
of HAAs and THMs in Treated Drinking
Water. The study examined the effect of
water quality, treatment, and distribution
system conditions of the formation of
THMs and HAAs. It determined that pH
was the dominant factor controlling the
relative distribution of THMs and HAAs in
finished drinking water. Low pH favors the
formation of HAAs while high pH favors
THM formation. More trihalogenated acetic
acid (TXAA) species are formed at lower pH,
while dihalogenated species formation was
independent of pH. The project also found
that waters with more hydrophobic NOM
and high SUVA favored the formation of
HAAs over THMs. The HAA9 to THM4 ratio
increased with decreasing temperature.
In the absence of residual chlorine, HAAs
were found to be biodegradable, while
THMs were not.
The project also researched full-scale
operation. THMs were dominant over
HAAs except in the case where chlorination
was performed right after coagulation at
pH 6.57 or where the NOM was mostly

hydrophobic. It also showed that removal
of TOC without removal of bromide shifted
the dominance of the halogenated DBPs to
brominated species.
In order to comply with various
regulations, many utilities started using
chloramine as a disinfectant and many
others opted for the use of ozone as a
primary disinfectant and chloramine as a
secondary disinfectant. The objective of
Factors Affecting Disinfection By-Product
Formation During Chloramination
(1998, order#90728/project#803) was to
investigate the chemical and operational
factors that influence DBP formation and
identify both known and unidentified DBPs
formed during chloramination. The study
showed that, in general, the formation
of DBPs decreased in increasing pH and
decreasing chlorine/nitrogen ratio (Cl2/N).
In addition to pH and Cl2/N, bromide
concentration was found to be an important
parameter in DBP formation. As bromide
levels increase, DBP formation increases
and the speciation within the individual
classes of DBPs shifts toward the brominesubstituted chemicals. The study also
showed that significant concentrations
of dihalogenated acetic acids (DXAA) are
formed during chloramination. Another
significant finding of the study was that
although chloramination generally does not
produce high concentrations of regulated
chemicals (THMs and HAAs), formation of
unregulated and uncharacterized halogensubstituted chemicals, as measured by the
TOX analysis, is significant under some
conditions. The study showed that THMs
and HAAs account for less than 35% of the
TOX formed during chloramination.
The chemistry of THMs has been wellstudied and their formation has been the
focus of numerous studies. However, less
is known about HAAs and their kinetics

of formation is not as well characterized.
Two Foundation reports, Disinfection ByProduct Formation and Control During
Chloramination (2004, order#91040F/
project#2677) and Exploring HAA
Formation Pathways During
Chloramination (2007, order#91192/
project#2993), investigated the effect of
water quality and treatment conditions
on the formation of HAAs, and more
particularly DXAA.
Disinfection By-Product Formation
and Control During Chloramination
determined that the most influential factors
in DXAA formation were pH and NOM
character. The formation of DXAA was very
rapid with up to 73% of the 72-hour total
formed in 30 minutes. Brominated species
formed even faster, being essentially
complete in 30 minutes. Higher pH tended
to decrease the amount of formation.
This project found that the hydrophilic
fraction of NOM was more reactive than
the hydrophobic fraction. A kinetic model
was developed and analyzed for parameter
sensitivity. The model showed excellent
correspondence with real performance and
that pH was the most sensitive parameter
and temperature the least.
The fast kinetics of formation of DXAA
reported in Disinfection By-Product
Formation and Control During
Chloramination were not confirmed in
Exploring HAA Formation Pathways
During Chloramination, which showed
that these fast kinetics were actually
an artifact associated with the use
of ammonium chloride (NH4Cl) as a
quenching agent (USEPA Method 552.3).
The study concluded that since NH4Cl does
not quench residual chloramine, there is a
possibility of overestimating HAA formation.
Limited experiments were performed to
17
identify the best quenching approach for

chloraminated DBP samples but no final
recommendation could be made.
The study found that the direct reaction of
monochloramine with dissolved organic
matter (DOM) is the major pathway for HAA
formation during chloramination and that
when preformed chloramine is used, 80%
of the DBPs are in the form of DXAAs. The
study determined that formation was much
slower than reported in previous studies,
but no kinetic equations were developed.
Wastewater was looked at as a possible
source of DBPs and precursors for systems
that use river water downstream from
a wastewater discharge. Contribution
of Wastewater to DBP Formation
(2008, order#91206/project#2948)
found that high levels of ammonia in
wastewater upon disinfection results in
chloramination and formation of HAAs
and N-nitrosodimethylamine (NDMA). The
river ecosystem promotes the degradation
of each DBP in different ways; HAAs are
biodegraded, NDMA is photolyzed, and
THMs are volatilized. Wastewater plants
that nitrify well have lower ammonia
levels and when disinfected, form higher
levels of THMs. As human sources do not
contribute significantly to humic material,
much of the halogenated DBP precursors
in the wastewater effluent originate from
disposal of drinking water with high NOM.
Nitrogenous DBPs were a different matter
and are discussed in the unregulated/
emerging DBP section of this issue.
A lot of research has been published on
DBP formation mechanism, reactivity, and
control at the treatment plant, but very
little was known about fate and transport
of precursors through the watershed to
the plant intake. Long-Term Variability
of BDOM and NOM as Precursors in
18
Watershed Sources (2007, order#91186/

project#2868) examined the fate and
transport of DBP precursors in watersheds.
It studied the generation of DOC at the water
source and its cycling in the ecosystem.
The project conducted a survey of over 500
utilities concerning their DBP and precursor
(TOC and DOC) data collection. Most of the
utilities had extensive data on precursors.
One of the most surprising results was that
THM and HAA precursor levels were very
uniform across the continent. Bench-scale
experiments were conducted with real leaf
litter biodegradation. The experiments
showed that significant DOC was leached
in 24 hours from pine, maple, and oak
material, while SUVA levels increased after
81 days of biodegradation in all species.
Two watersheds were analyzed over several
seasons. The data showed that precursor
level actually decreased with increasing
TOC. This, along with rain event data,
showed that the first flush was generally
high in TOC, but low in reactive precursors.
Younger TOC that has not undergone
biodegradation is not as reactive as aged
TOC and tends to form less DBPs.
A quantitative model was developed and
calibrated. It had parameters for many
different classes of NOM such as proteins,
sugars, lignins, etc. The model accounted
well for actual DBP formation. It predicted
that biodegradation would increase precursor
levels and that tannins and lignins would be
the most reactive for THM formation.
A large survey of utilities was compiled into
a database to look for temporal and spatial
variations. Generally, TOC levels increased
in more populated areas and decreased
in rural locations, however, there was no
strong, consistent correlation. Wetlands
were shown to be a major contributor to
TOC increase.
Occurrence
The occurrence of THMs and HAAs in

disinfected water has been the subject of
numerous studies. The most comprehensive
occurrence database of THMs and HAAs in
the United States was assembled as part of
the Information Collection Rule (ICR).
The ICR involved 296 large utilities and
over 500 treatment plants. The 18-month
study required sampling of raw water,
finished water, distribution systems, and
in some cases after each unit process. The
information was analyzed in Information
Collection Rule Data Analysis (2002,
order#90947/project#2799).
One expected conclusion was that
groundwater supplies were generally lower
in DBPs than surface water suppliesmost
likely due to lower amounts of NOM. The
data confirmed that NOM was generally
correlated to DBP production, though not
nearly as strongly as expected. Chloroform
was found to be the most dominant THM
and increasing bromine content produced
more brominated THMs, but at no time was
chloroform not dominant.
Concentrations of THMs exceeding 300g/L
were found in some water systems. The
discovery of these outliers had a direct effect
on regulations in that system-wide averages
would no longer be used. The regulation
changed to locational running annual
averages (LRAA), meaning that each sampling
location had to comply on its own. It was also
surprising that the Northeast utilities had
high THMs as the water is usually very cold
and the NOM level is not high.
The project also concluded that treatment
type did not make much difference and that
using chloramine as a secondary disinfectant
did not result in lower THMs. Some of the
highest levels were in a Mississippi

system using chloramine as a secondary
disinfectant. The positive information was
that THM levels had decreased 5060% over
the 24 years preceding 1998.
The project collected information on HAAs
as well. Most utilities measured HAA5
and HAA6, but only 143 plants measured
HAA9. The mean HAA5 concentration was
23g/L. The mean HAA6 concentration
was 26g/L. The data showed that 90%
of reporting utilities were below 50g/L,
but that there were outliers and extreme
systems. The dominant species of HAA
were dichloroacetic acid (DCAA) and
trichloroacetic acid (TCAA), the 90th
percentile for each being equal at 24g/L.
The treatment plant type did not show great
variation, though groundwater usually was
lower in HAAs than surface water. The type
of disinfectant did make a difference, with
chlorination followed by chloramination
producing the highest levels of HAAs. In
those systems DXAA averaged twice as high
as TXAA (17.6 vs. 9.6g/L) and also twice
as high as DXAA from chlorine-only
systems (17.6 vs. 8.7g/L).
TOC was strongly correlated to HAA
formation. Source water with various TOC
levels were tested: low TOC (<1 mg/L),
moderately low TOC (13 mg/L), moderate
TOC (35 mg/L), and high (>5 mg/L). The
concentrations of HAAs increased with
increasing TOC levels.
Bromide concentration was not correlated
to HAA formation in general, except
for TXAA that actually decreased with
increasing bromide. The parameter that
showed the greatest effect was pH, as TCAA
decreased as pH increased. Chloraminated
systems showed greater pH influence with
approximately 50% decrease in TCAA from
pH <7.3 to >8.3.
continued next page
19
The Foundation funded an industry-wide

survey to determine the prevalence of
THMs in drinking water titled, AWWARF
Trihalomethane Survey, and published
in Journal AWWA (McGuire, 1988). Results
showed that THM levels had declined by
40 to 50% from the earlier National Organics
Reconnaissance Survey and National
Organics Monitoring Survey conducted
by USEPA. The survey provided data to
estimate that with a 50g/L MCL, 26%
of utilities would be out of compliance.
More utilities have switched from free
chlorine to chloramine to minimize THM
formation. This practice often results in
nitrification events in the distribution
system. To prevent and control nitrification,
these utilities switch periodically to free
chlorine and back to chloramine after a
set amount of time. In order to determine
the effects of the changeover, Seasonal
Chlorination Practices and Impacts
to Chloraminating Utilities (2006,
order#91144/project#2833) looked at
the impact on DBPs and water quality in
general from switching back and forth
between free chlorine and chloramine.
The study found switching from chloramines
to free chlorine can result in significant
increase in THM concentrations in the
distribution system.
A study was funded by the Foundation to
look at the long-term effects of changes
in disinfectant. Long-Term Effects of
Disinfection Changes on Water Quality
(2007, order#91169/project#2940)
conducted extensive utility surveys and
a literature review. Utilities that switched
from chlorine to chloramine generally
saw reductions not only in THMs and
HAAs, but also in heterotrophic plate count
(HPC) in the distribution system. Utilities
that switched to ozone from chlorine also
found generally less THMs and HAAs;
20
however, the HPC generally increased

most likely due to more easily degradable
organic matter. Only two utilities switched
to chlorine dioxide, so representative data
is not available. The two utilities observed
a decrease in the formation of THMs and
HAAs. Five utilities changed over to UV
radiation for primary disinfection. The
effect on THM and HAA formation overall
was expected to be minimal, as UV does
not form DBPs.
Control and Minimization of THMs
and HAAs
There are several options for DBP control

including removing precursor material
or NOM before it interacts with the
disinfectant, using a disinfectant that
minimizes the formation of these DBPs,
changing the disinfectant point of addition,
or removing DBPs after they are formed.
As mentioned earlier in this article, the
main precursor of THMs and HAAs is NOM,
thus source water protection, NOM removal
treatment processes, and operational
changes offer the first opportunity to
control DBPs. Natural Organic Matter
in Drinking Water: Recommendations
to Water Utilities states that one way
to mitigate DBP formation in drinking
water is to reduce the entry of NOM
into water supplies. Summarized in this
report are natural and human factors that
influence NOM formation in source waters,
the possible effect of each factor, and
recommended mitigation measures such
as watershed management and in-reservoir
water quality management. If NOM
formation cannot be prevented, utilities
are advised to characterize it to choose the
most appropriate removal process.
Polar NOM: Characterization, DBPs,
Treatment evaluated the types of precursors
several treatment processes preferentially
removed. Coagulation mainly removed

high-molecular weight NOM, hydrophobic
DOC, and THM precursor DOC. Membrane
filtration was the best option for removing
hydrophilic DOC. With powdered activated
carbon (PAC) addition, ultrafiltration (UF)
removed transphilic DOC predominantly
and THM precursor DOC selectively.
Ozonation removed or transformed
hydrophobic NOM into transphilic and
hydrophilic NOM, which was preferentially
removed by biofiltration over hydrophobic
NOM. Biofiltration selectively removed
HAA precursors but not THM precursors.
Finally, anion exchange removed primarily
hydrophobic and transphilic NOM.
For Removal of DBP Precursors by

Enhanced Coagulation and Lime
Softening (1999, order#90783/project#814),
researchers conducted testing of enhanced
coagulation on 19 raw water supplies at
bench-scale and at pilot- or full-scale at
six sites. The results demonstrated that,
on both equivalent basis and weight basis,
ferric coagulants at high dosage were more
effective in removing TOC than aluminum
coagulants. However, at a dosage lower than
20 mg/L, aluminum coagulants sometimes
removed slightly more TOC than ferric
coagulants. With a given coagulant, removal
of TOC can be optimized by increasing the
coagulant dose and lowering the pH.
In-depth studies of NOM removal processes

are described below, along with other THM
and HAA control options the Foundations
research has looked into, including removal
of THMs and HAAs themselves and
strategic treatment operations.
Aiming at THM control, the authors of the

report, Humic Substance Removal and
Minimizing Trihalomethanes by Ferric
Chloride Coagulation (1989, order#90665/
project#531), performed coagulation jar tests
on DOM isolated from the Suwannee River
and Lake Allatoona using ferric chloride. The
supernatant in the jar tests was subsequently
filtered and chlorinated for THMFP testing.
The results showed that the removal efficiency
of non-purgeable organic carbon ranged
from 15 to 85% depending on composition
and characteristics of the organic matter. The
removal was, in general, effective within the
pH range of 46 and coagulant dosage range
of 10100 mg/L ferric chloride. This study also
concluded that THMFP for a particular water
depended on specific conditions of dosage
and pH. Therefore, achieving minimum
THMFP may require pH adjustment and
laboratory- or pilot-scale testing to determine
the optimal conditions.
Enhanced Coagulation and Enhanced

Softening for Precursor Removal
Stage 1 Disinfectants/Disinfection ByProducts Rule (DBPR) requires water
systems that use surface water or
groundwater under the direct influence of
surface water and use conventional filtration
treatment to remove set percentages of
TOC that may react with disinfectants to
form DBPs with enhanced coagulation or
enhanced softening. Based on the DBP data
collected under the ICR from 296 public
water systems (500 treatment plants) during
the period from July 1997 to December
1998, the Foundation report Information
Collection Rule Data Analysis concluded
that the ICR data supported the Stage 1
DBPRs 3 3 matrix of source water, TOC,
and alkalinity. On average, ICR plants TOC
removal was consistent with the removal
specified in the matrix.
A case study presented in the report, Case

Studies of Modified Treatment Practices
for Disinfection By-Product Control (2003,
order#90946F/project#369), demonstrated
that for the water tested, reducing coagulation
pH effectively improved removal of DOC,
21
total trihalomethanes (TTHMs), and UV254.

Enhanced lime softening was investigated for
precursor removal in the Removal of DBP
Precursors by Enhanced Coagulation and
Lime Softening. It reported that increasing
lime dosage only modestly increased TOC
removal. More importantly, enhanced lime
softening could not remove as much TOC
or UVA as enhanced coagulation at high
coagulant dosage because the amorphous
flocs formed during coagulation were more
adsorptive than the precipitates formed
during lime softening. For softening treatment
plants that also desire to remove THM and
HAA precursors, addition of supplemental
coagulant of 1015mg/L of alum or ferric
sulfate may increase TOC removal by an
average of 15%. Higher coagulant dosage
would not lead to further removal.
Information Collection Rule Data
Analysis pointed out that, with few
exceptions, the ICR softening plants
were able to consistently comply with
DBP regulations. The ICR data did not
demonstrate systematic trends to elucidate
the mechanisms for either TOC removal
or DBP formation in softening plants. No
correlations between TOC removal and
the removal of calcium or hardness were
identified and only a weak correlation
between TOC removal and magnesium
removal was observed. As a result, it would
be difficult for operators to optimize the
softening process for TOC removal.
GAC Adsorbers for Precursor Removal
In both the Stage 1 and Stage 2 DBPRs,
granular activated carbon (GAC) filtration,
with an empty-bed contact time (EBCT)
of 10 or 20 minutes, is identified as a best
available technology for TTHMs and HAA5
compliance. Several factors influence
the effectiveness of GAC in removing the
precursors of these DBPs. Removal of
DBP Precursors by GAC Adsorption (1998,
22
order#90744/project#816) addressed
(1) the breakthrough characteristics of
the naturally occurring DBP precursors,
(2) GAC contactor operation, and (3)
the type of pretreatment before the
adsorption process. The study found that
the breakthrough of DOC during GAC
adsorption was a conservative indicator for
the breakthrough of DBP precursors. The
higher the humic fraction, the more DBPs
were produced. The study also showed that
the humic fraction exhibits a higher affinity
for GAC rather than the nonhumic fraction.
Although the breakthrough of precursors
could be delayed with a longer EBCT, the
water throughput (or the number of bed
volumes treated) was not affected by EBCTs
between 10 and 20 minutes. Thus, a shorter
EBCT within this range might be more
desirable to reduce the capital cost of GAC
contactors. However, utilities should note
that a shorter EBCT would require more
frequent GAC replacement or regeneration.
When operating multiple GAC contactors
in parallel, blending the effluents from
the contactors could significantly prolong
the breakthrough and substantially lower
the operational costs, according to the
experiments and modeling results in this
study. This finding was corroborated
by the report, DBP Control in High
Bromide Water While Using Free Chlorine
During Distribution (2006, order#91119/
project#3075).
The experimental results presented in
Removal of DBP Precursors by GAC
Adsorption indicated that with additional
optimized coagulation pretreatment, the
GAC run time could increase by 129148%.
It should be noted, however, that the
coagulation dosage evaluated in this study
was significantly higher than the dosage
required for enhanced coagulation.
DBP Formation Control by Modified
Activated Carbons (2007, order#91181/

project#2998) also suggested that using
conventional treatment processes such as
coagulationflocculationsedimentation to
remove high molecular weight components
of DOM could significantly increase the
operational life of GAC contactors.
Additional factors were examined in DBP
Formation Control by Modified Activated
Carbons. This study systematically
evaluated these factors to tailor GAC
accordingly for enhanced DOM removal.
One of the essential factors was the pore
size of GAC. The authors discovered
that within the typical pH range of water
treatment (5.58.0), the great majority of
DOM could not access pores smaller than
1 nm. Thus, the volume of pores greater
than 1 nm would be a far more appropriate
GAC selection criterion than total pore
volume. Another factor deemed important
was the pH at the point of zero charge
(pHPZC) of the GAC. The study showed
that acidic pHPZC significantly decreased
the adsorption of DOM onto GAC. When
pHPZC > 7, the effect of pore size distribution
became more important than pHPZC. Based
on these findings, utilities should select
GAC with large surface area and basic pHPZC
containing a high volume of pores greater
than 1 nm for DOM removal.
The authors of DBP Formation Control by
Modified Activated Carbons explored the
possibility of enhancing the effectiveness of
GAC in removing DOM by steam-treating
GAC or impregnating iron onto GAC. After
being treated with high-temperature steam,
the pores in the GAC were enlarged and
exhibited higher DOM uptake. However, the
increase in DOM uptake was not always
proportional to the extent of steam-treatment.
The increased uptake was due to removal of
NOM components with higher specific UVA
and more hydrophobic character.
The iron-impregnated GAC did not

consistently improve DOM uptake.
Although the specific UVA and weightaverage molecular weight values of the
DOM in the two source water samples were
similar, for one source water the removal of
NOM was considerably improved by iron
impregnation, whereas the effect of iron
impregnation was minimal for the other
source water. Other DOM characteristics
might be responsible for the inconsistency.
For utilities interested in modifying GAC
to enhance DBP precursor removal, steam
treatment would be a more practically
feasible and more effective option than
iron impregnation.
Regeneration experiments were performed
using the steam-treated GAC. The
results showed that high-temperature
treatment under hydrogen or nitrogen gas
atmospheres effectively restored the GACs
DOM uptake capacity for at least two cycles
of regeneration. In contrast, regeneration
with hydrogen peroxide continuously
decreased DOM uptake capacity with each
regeneration cycle.
DBP Formation Control by Modified
Activated Carbons also provides
recommendations on testing the
effectiveness of various types of GAC.
Although batch isotherm experiments are
simple and thus can be used for screening
GAC, the authors recommend utilities
perform rapid small-scale column testing
(RSSCT) to obtain practical information for
full-scale application. Utilities are advised
to test the effluent of RSSCT for THMFP
and HAAFP because TOC or UVA data
alone cannot provide conclusive
information about the effectiveness
of GAC for THM and HAA control.
In addition to RSSCT, Evaluation of
Available Scale-Up Approaches for the
23
Design of GAC Contactors (project#4235)

will evaluate the appropriateness of other
GAC scale-up approaches to develop a
methodology that can be successfully
adopted by drinking water utilities to scale
up bench-scale results to simulate fieldscale GAC adsorbers. The goal is to save
time, effort, and cost over the use of pilotscale adsorbers. This project is expected to
be completed in 2013.
For utilities currently using GAC filter caps,
project#4101, Evaluation of Granular
Activated Carbon Filter Caps for Control
of Disinfection By-Product Precursors
and Trace Organic Contaminants, will
demonstrate the feasibility of retrofitting
filter caps for DBP control. This project
will also provide guidance for improving
efficiency and long-term performance
of GAC. This project is expected to be
completed in 2011.
Another new project#4294, Effectiveness
of Sub-Micrometer Sized Powdered
Activated Carbon for the Combined
Removal of Disinfection By-Product
Precursors and Trace Organic Pollutants,
will investigate the effects of the particle
size of PAC on DBP precursor and
micropollutant removal. This project
will identify physical and chemical submicrometer PAC characteristics that
produce effective DBP precursor and
micropollutant removal. This project is
expected to be completed in 2012.
GAC Biological Filters
for Precursor Removal
In the studies discussed above, GAC was
operated as an adsorber. The Foundation
has also sponsored research on removal
of THM and HAA precursors using GAC
in a biological mode. As early as 1994, the
24
Foundation published the report, Ozone

and Biological Treatment for DBP
Control and Biological Stability (1994,
order#90649/project#504). It concluded
that the combination of ozonation and
biological filtration reduced the formation
of chlorinated by-products to a greater
extent than conventional treatment without
ozone. The combination, on the other hand,
did not appear to remove chlorinated byproducts as effectively as physical-chemical
treatment such as sedimentation.
One concern utilities may have is bacterial
regrowth in distribution systems after
biological filtration. The authors of Ozone
and Biological Treatment for DBP
Control and Biological Stability did not
observe regrowth problems in distribution
systems even though ozone increased
the bioavailability of NOM, as long as the
water was filtered after ozonation or high
disinfectant residual was maintained in
distribution systems.
Recently the Foundation and its utility
subscribers have co-funded two GAC
biological filtration projects for removal of
DBP precursors and other contaminants.
GAC Biofilters in Retrofit Applications:
An Approach for Cost Effective Regulatory
Compliance (project#4155) aims to
demonstrate the efficacy of GAC biological
filters retrofitted in a conventional
treatment plant. The research phase of
this project is complete and the report is
under review. Enhancing Biofiltration to
Achieve Sustained Removal of Multiple
Inorganic and Organic Contaminants,
Including EDCs, MIB, and Geosmin
(project#4215) focuses on evaluating
methods for restoring and enhancing the
performance of existing ozonebiological
filtration systems. This project is expected
to be completed in 2010.
Membrane Filtration
for Precursor Removal
Membranes are utilized for DBP precursor
removal partly due to their size exclusion
property. The molecular weight cutoff
(MWCO, Dalton) of a membrane is
generally the starting criterion for
selection of membranes for NOM removal.
Evaluation of Ultrafiltration Membrane
Pretreatment and Nanofiltration of
Surface Waters (1994, order#90639/
project#601) tested three groups of
membranes for DBP precursor removal
with three surface source waters at pilot
scale. These membranes were one hollowfiber UF membrane (100,000 MWCO), two
hollow-fiber NF membranes (400600 and
600800 MWCO), and two spiral-wound
NF membranes (200300 MWCO). The
UF membrane removed less than 22% of
TOC and UV254 and less than 7% of THM
precursors based on 7-day simulated
distribution system (SDS) tests. In
comparison, the NF membranes removed
5583% of TOC, 7197% of UV254, and 3194
percent of 7-day SDS THM precursors. The
spiral-wound NF membranes removed
slightly more TOC, UV254, and 7-day SDS
THM precursors than the hollow-fiber NF
membrane with 400600 MWCO.
Additional membrane selection criteria
and membrane fouling by NOM were
examined in the report, NOM Rejection by,
and Fouling of, NF and UF Membranes
(2001, order#90837/project#390). The
report provides the following guidelines for
membrane selection and operation:
1. Choose between UF and NF membranes.
UF membranes are primarily for
microbial removal and achieve modest
NOM removal, whereas NF membranes
significantly remove NOM.
2. Select specific UF or NF membranes

based on the MWCO, which influences
NOM rejection and pure water
permeability.
3. Optimize operational conditions
according to the hydrodynamic
condition f/ka ratio of the permeation
flux to the overall mass of the transfer
coefficient. As f/k increases, productivity
increases, but fouling also becomes more
severe while rejection decreases.
4. Implement effective membrane cleaning
strategies to ensure that most of the
NOM-related fouling is reversible.
For step 3 above, the recommended optimal
operation conditions for maximum NOM
rejection and minimum flux decline are
as follows:
For NOM with low SUVA (<3.0 L/mgm), use NF membranes and operate
at relatively high f/k ratio, or use tight
MWCO UF membranes and operate at low
f/k ratio.
For NOM with intermediate SUVA (3.04.5
L/mg-m), use NF at relatively high f/k
ratio, or use tight MWCO UF membranes
and operate at intermediate f/k ratio.
For NOM with high SUVA (>4.5 L/mgm), use tight MWCO UF membranes and
operate at relatively high f/k ratio, or use
loose MWCO UF membranes and operate
at intermediate f/k ratio.
Combining Adsorbents with Membranes
for Water Treatment (2002, order#90894/
project#2557) looked into heated iron oxide
particles (HIOPs) and PAC as additives to
UF systems for NOM removal at bench scale
and at pilot scale. The researchers observed
that the sorption of NOM onto HIOPs was
virtually complete within 15 minutes and
25
that the sorption was greater at pH 6 than

at pH 8. HIOPs not only removed NOM but
also reduced fouling rate of the membranes.
As the dose of HIOPs increased, more
NOM was removed, and the fouling rate
was reduced further. In addition, there
was no evidence that the HIOP particles
contributed substantially to fouling of the
UF systems. In comparison, PAC removed
more NOM than HIOPs; however, PAC also
aggravated membrane fouling. The higher
the PAC dose, the worse the fouling became.
The results of the pilot-scale testing
suggested that the efficacy of HIOPs might
be critically affected by the engineering
associated with introducing the HIOPs
and mixing the suspension. The HIOPs
would need to form a reasonably uniform
coating on the large number of membrane
fibers. The HIOPs not coating membranes
would need to remain suspended in the
water. Furthermore, the HIOP coating
would need to be efficiently removed from
membrane fibers during backwashing. Thus,
utilities that are interested in implementing
this technology will need to design an
engineering system that meets these criteria.
Other Non-Conventional Treatments for
Precursor Removal
The MIEX Process consists of using
a proprietary magnetic ion exchange
resin to remove organic carbon in water
and recovering the resin in downstream
settlers. In the report, Advanced Water
Treatment of Estuarine Water Supplies
(2007, order#91183/project#3004), the
effectiveness of the MIEX resin to remove
NOM was assessed at bench scale for
a contact time of 10 minutes in three
configurations: MIEX alone, MIEX
combined with coagulation, and MIEX
combined with UF. The experimental
results determined that the resin could
26
not remove all components of NOM even

with increased dosage; nevertheless, the
exchangeable fraction of NOM was nearly
removed completely at resin doses lower
than 1 mL/L. The competition from sulfate
and other ions for the exchange sites on the
MIEX resin appeared to be negligible.
The combination of MIEX and coagulation
was proven to be synergetic. MIEX
pretreatment effectively removed a small
amount of humic substances and low
molecular weight NOM. Coagulation
subsequently removed much of the
remaining humic substances. Thus, the
MIEX process followed by coagulation
was suitable for NOM removal. When a
UF membrane was utilized to separate
the MIEX resin from the product water,
the membrane did not appear to remove
additional NOM.
The performance of this process was
evaluated under a range of conditions in
the report, Evaluation of MIEX Process
Impacts on Different Source Waters (2005,
order#91067F/project#2840). According
to bench-and pilot-scale testing at four
utilities, the DOC removal and UVA
reduction appeared to be site-specific,
ranging from 22 to 64% and from 56 to 78%,
respectively. As a result, the 3-day uniform
formation condition THMFP was reduced
by 3065% and the 3-day uniform formation
condition HAAFP was reduced by 4573%.
A full-scale study at a water treatment
plant (WTP) using a groundwater source
containing TOC greater than 10 mg/L
was documented in Evaluation of MIEX
Process Impacts on Different Source Waters.
The MIEX Process removed about 50% of
DOC. The average resin turnover time was
estimated to be greater than one year, and
resin fouling did not appear to be an issue.
Based on the bench-, pilot-, and full-scale

testing, the report concluded that key factors
affecting the performance of the MIEX
Process were resin concentration, contact
time, and resin regeneration percentage.
In contrast, the investigation in DBP
Control in High Bromide Water While
Using Free Chlorine During Distribution
detected no effect of resin concentration
(with 2030 mg/L) or contact time (within
7.525 minutes) on TOC removal in a raw
water with high bromide (180or430g/L)
and moderate TOC (3.9mg/L on average)
using the MIEX Process. Another
parameter that did not exhibit impact was
pH (within5.5to9).
A new project#4298, Impact of MIEX on
Reduction and Control of DBPs, Turbidity,
Residuals Generation, and Corrosion,
investigates the impact of the operating
conditions of MIEX, coagulant, and the
combination of MIEX and coagulant on
the extent of DBP precursor removal. It will
also characterize the precursors removed
and remaining in treated water. This project
is expected to be completed in 2011.
THM and HAA Removal
Aside from removal of DBP precursors,
the Foundation has also funded projects
investigating removal of THMs and HAAs.
HAA removal by GAC via adsorption
and biodegradation were examined in
Haloacetic Acid Removal Using Granular
Activated Carbon (2004, order#91041F/
project#2825). The results of the benchscale isotherm experiments using organicfree water revealed the following:
The GAC adsorption capacity was higher
for HAAs with a higher halogen number.
The GAC adsorption capacity was higher
for brominated HAAs and THMs than for
their chlorinated analogues.
The GAC adsorption capacity was

higher for THMs than for HAAs except
trichloroacetic acid (Cl3AA).
A field study was performed on a newly
replaced GAC filter in a WTP. The profile
of HAA concentrations in the GAC filter
effluent suggested initial removal via
adsorption, a breakthrough point, and
subsequent removal via biodegradation.
Occurrence of biodegradation was
demonstrated by drastic reduction of
HAA removal when the GAC filter columns
packed with acclaimed GAC from the field
study treatment plant were subjected
to cold shock treatment (4C) and heat
shock treatment (50C). Furthermore, as
50mg/L of chloramines were introduced
to the columns for one hour, no HAA
removal was observed. Several days after
the disinfectant shock, the HAA
concentrations in the effluent started to
decrease, indicating recovery of microbial
activity in the GAC filters.
The factor examined in Haloacetic Acid
Removal Using Granular Activated
Carbon that exerted little impact on
HAA removal was dissolved oxygen. In
GAC batch tests, all HAAs were almost
completely degraded in both aerobic
and anoxic conditions except Cl3AA, the
removal of which dropped to 45% after 170
hours under anoxic conditions. The GAC
column tests, however, indicated no effect
of an anoxic environment on HAA removal.
A biological treatment process was
developed in the report, Cometabolism of
Trihalomethanes in Nitrifying Biofilters
(2005, order#91100F/project#2824),
for removal of THMs in drinking WTPs.
Cometabolism can be defined as the
fortuitous biodegration of a target chemical
(THMs in this case) through reactions
catalyzed by one or more non-specific
27
microbial enzymes. This process utilizes

GAC to destroy chloramines with its
reactive surface and as filter media on
which nitrifying bacteria can grow. Thus,
this approach allows upstream disinfection
and is most applicable to utilities that
prechlorinate prior to ammonia addition
to form chloramines.
Results from testing of the THM cometabolism
process showed that after a period of higher
removal of monochloramine, a steadystate monochloramine concentration was
reached, suggesting that the GAC would not
need frequent replacing or regenerating.
Almost all monochloramine was found
converted to total reduced inorganic
nitrogen (TRIN, i.e., NH3 and NH4+), which
would serve as substrate for nitrifying
bacteria. The nitrifying biofilters were
able to degrade all four THMs (chloroform,
bromodichloromethane [BDCM], DBCM,
and bromoform); the higher the bromine
substitution, the higher the degradation.
Increased THM degradation corresponded
with increased TRIN degradation.
Cometabolism of 1015g/L of THMs
per mg/L of ammonia could be expected
when chloroform was a significant fraction
of the THMs. Utilities should note that
THMs formed during prechlorination
would not be completely removed using
this cometabolism process but the process
could potentially remove 1530g/L of
THMs. Thus, this process is more applicable
to utilities with THM levels close to the
drinking water MCL.
Localized Treatment for Disinfection
By-Products (2009, order#91254/
project#3103) is a unique report. The
process was not designed for centralized
treatment of source water but for localized
treatment of water in distribution systems
for THM and HAA removal. The main
objective of the study was to investigate
28
the effectiveness of simple treatment

processes in removing THM and HAAs
in the distribution system.
Air stripping removed 75 to 85% of THMs
but had no effect on HAA removal. Fresh
GAC was very effective at removing both
THMs and HAAs. However, HAA removal
decreased after 10,000 bed volumes but
increased upon establishment of biological
activity in the filters. (For more details, see
LVVWDs case study on page 58.)
Treatment and Disinfection Strategies
An alternative to removing THMs, HAAs,
and their precursors, process modification
is another means to achieve THM and
HAA minimization. A case study presented
in Case Studies of Modified Treatment
Practices for Disinfection By-Product
Control demonstrated that for the water
tested, eliminating prechlorination before
coagulation could decrease THM formation
by 2030g/L. This study also determined
that adding PAC during the rapid mix step of
coagulation did not improve NOM removal;
neither did applying ozone or ozone
hydrogen peroxide before or after coagulation.
As mentioned previously, DXAAs are
the most commonly formed HAAs
during chloramination. Disinfection
By-Product Formation and Control
During Chloramination recommends
that treatment changes be implemented
to minimize DXAA formation during
chloramination in the following order:
1. Raise the pH during chloramination to
above 7. Approximately 50% decrease
in DXAAs can be achieved by raising
the pH from 7 to 9.
2. Decrease free chlorination interval.
Simultaneous addition of chlorine
and ammonia is preferred.
3. Decrease NOM/DOC precursors.

Both hydrophobic and hydrophilic
NOM fractions should be removed,
but preference should be given to
the hydrophilic.
4. Decrease Cl2/N ratio.
5. Decrease chloramine residuals. The
amount of DXAA reduction was limited;
thus, this method should be used as a
last resort.
Advanced Water Treatment of Estuarine
Water Supplies experimented with
combining disinfectants and treatment
scenarios to minimize DBP formation. For
the water tested, the following combination
of disinfection yielded the lowest THM and
HAA concentrations:
1. Pre-oxidation with chlorine dioxide.
2. Intermediate oxidation with ozone.
3. Post-filter disinfection with UV.
4. Final disinfection with chloramines
without a contact period between
addition of free chlorine and ammonia.
Selection and Implementation
of Technologies
Numerous drinking water utilities have
modified their treatment practices to
comply with DBP regulations. Some of
the experiences were documented in
two reports: Case Studies of Modified
Disinfection Practices for Trihalomethane
Control (1990, order#90574/project#201)
and Case Studies of Modified Treatment
Practices for Disinfection By-Product
Control. Details of each case study can be
found in these reports. The main issues that
influenced a utilitys decision on selecting
and implementing a treatment practice
modification were regulatory compliance,
utility business, and customer acceptance.
The latter report recommended that for
selection of a DBP control technology, a
utility should consider compliance with

not only the DBPR but also other water
quality objectives such as the Enhanced
Surface Water Treatment Rule, the Total
Coliform Rule, and the Lead and Copper
Rule. Alternatively, better optimization of
existing treatment processes might be a
cost-effective solution.
After selecting a technology, the utility
should follow the steps below for successful
implementation:
The information used in the decisionmaking process would need to be
summarized and presented to the utilitys
governing body and consumers.
To persuade the governing body, the
utility would need to make a series of
presentations to provide background
information and the underlying logic for
implementing the selected technology.
The utility would need a public
information program to ensure consumer
acceptance.
After approval of treatment modification,
the utilitys operating staff would need
additional training.
The utility would need an implementation
plan developed and supported by a
multi-disciplinary, interdepartmental
implementation team.
The utility would need a contingency
plan to address how to handle expected
and unexpected problems during
implementation.
There might need to be shifts in the
overall operational strategy or operating
paradigms to make the modifications
successful.
If implementation problems or tradeoffs
arose, the utility would need to resolve
some of them immediately, whereas the
others might need a period of adjustment.
continued next page
29
It would probably take a period of time

for the operational staff to feel at ease
with the new or modified technology and
for the treatment plant to operate like an
integral unit, other than as a treatment
plant with a new process.
Inorganic DBPs
The best disinfection scenario varies widely

for each treatment plant depending on
the goals, source water characteristics,
budget, regulatory constraints, and many
other factors. Alternative disinfection
treatments will usually have both positive
and negative features associated with them.
The use of ozone and chlorine dioxide
has been increased due to the benefit of
forming limited THMs and HAAs. However,
these disinfection methods produce other
types of DBPs such as bromate, chlorite,
and chlorate. Since the early 1990s, the
Foundation has funded research to advance
the knowledge of inorganic DBPs.
Bromate (BrO3-)
Application of ozone in drinking WTPs
in the United States is growing because
of its excellent disinfection and oxidation
qualities. Ozone improves finished water
quality by reducing turbidity, it reduces the
formation of many halogenated disinfection
by-products, and it is capable of
inactivating microorganisms such as
protozoa, which are very resistant to
conventional disinfectants. However, in
the presence of bromide ion, ozone
produces bromate, which is a genotoxic
carcinogen. The current MCL for bromate
in the United States is 10g/L and the
maximum contaminant level goal (MCLG)
is zero. Since the late 1980s, the Foundation
has been a leader on funding research
related to bromate formation and control.
Before the report, Identification and
Occurrence of Ozonation By-Products
30
in Drinking Water (1993, order#90625/

project#510), only a few studies of ozonation
by-products had been conducted and
understanding of ozonation by-products
was limited. Project#510 was the first study
to measure bromate concentration in
drinking water and examine methods for its
control. To date, a number of Foundation
projects have been funded examining
bromide and bromate occurrence, bromate
formation, and control strategies.
Bromate Formation
Under normal water treatment conditions,
bromate can be formed during oxidation
of bromide by ozone and its formation
is affected by water quality and water
treatment variables. An understanding
relating these parameters to bromate
formation is crucial to controlling its
formation during ozonation. Identification
and Occurrence of Ozonation ByProducts in Drinking Water was the
first study funded examining bromate
formation. The study consisted of two
interconnected components: (1) a
laboratory phase, in which methods to
analyze targeted ozonation by-products
were developed or optimized, and (2)
a survey phase, in which ozonation byproducts were analyzed in water samples
taken from selected treatment plants
that utilized ozone. The laboratory phase
demonstrated that bromate formed at
significant levels with elevated bromide
levels and its formation was enhanced at
high pH values. In addition, the survey
provided the information that bromate
was by far the most prolific bromated
species resulting from ozonation and its
formation was a function of the initial
bromide concentration. This study also
indicated that an additional external factor
such as ozone transfer efficiency, contact
time, or the demand of the water were also
responsible for determining bromate FP.
As a follow up to project#510, the pathway

and mechanisms of bromate formation was
investigated by another report, Formation
and Control of Brominated Ozone ByProducts (1997, order#90714/project#830).
The research showed that the time frame
for ozone decomposition and bromate
formation ranged from minutes to tens of
minutes in true-batch ozone experiments
(instantaneous introduction of ozone dose).
A linear relationship was observed between
the moles of ozone decomposed and moles
of bromate formed, leading to definition of
a parameter defined as the bromate yield
(BY). BY is a direct index of the efficiency
of bromide conversion to bromate and
varies as a function of water quality and
treatment variables. Project#830 also
found that various water quality and water
treatment variables affect bromate levels.
These variables influenced the oxidation
reactions involved in bromate formation
primarily through affecting hydroxyl radical
(HO) concentration. The study also showed
that chemical factors, as encompassed by
both water quality and water treatment
variables, tend to be more influential on
bromate formation than ozone reactor
configuration, based on ozonation
conditions to meet CT (concentration of
disinfectant in mg/L multiplied by time in
minutes) requirements.
Before the Long-Term 2 Enhanced Surface
Water Treatment Rule (LT2ESWTR) was
finalized, the Foundation had funded
Bromate Formation and Control During
Ozonation of Low Bromide Waters (2001,
order#90866/project#493). This research
evaluated the formation and control of
bromate in low bromide waters under
ozone dosages capable of inactivating
Cryptosporidium. It demonstrated that
bromate formation in natural waters
must proceed through pathways in which
hydroxyl radical are utilized. Also, this
research showed that bromate formation

is not currently predictable a priori. Water
specific tests must be performed in order
to predict bromate formation. Experiments
were run under a wide variety of water
qualities and testing conditions that
may be used by utilities to assess bromate
formation and control. The project
also evaluated various bromate
control strategies.
Bromate Occurrence
A North American and European survey of
ozonation utilities is presented in Bromate
Formation and Control During Ozonation
of Low Bromide Waters to understand
bromate occurrence at full-scale WTPs
under current levels of ozone applications.
The average bromate concentration at 24
full-scale ozonation plants, based on 78
samples from three separate sampling
campaigns for the existing levels of
ozonation, was 3.9g/L. The average
percent conversion of bromide to bromate
was 6.7%. The 10th, 50th (median), and 90th
percentile bromate values were determined
to be 0.2, 1.2, and 13g/L, respectively. The
survey indicated that several utilities were
forming bromate at levels in excess of MCL
of 10g/L. Eleven percent of the samples
analyzed were out of compliance.
Another report, Information Collection
Rule Data Analysis, presented bromate
occurrence data from the ICR plants that
used chlorine dioxide or ozone. Bromate
was detected in 11% of the finished water
samples collected by ICR plants using
chlorine dioxide, with concentrations
ranging from below the minimum reporting
level of 0.2g/L up to 2.4g/L. This
suggests that bromate is not an important
by-product of chlorine dioxide disinfection.
Finished water bromate concentrations at
the 20 ICR plants using ozone ranged from
below 0.2g/L up to25.1g/L. Increases in
31
influent bromide concentration and ozone

dosage were each associated with increased
bromate formation.
Bromide Removal
Bromide is a precursor for the formation of
bromate and other brominated oxidation
DBPs. In source waters, bromide can come
from both natural (geochemical weathering,
seawater) and anthropogenic (industrial
and oil brine discharge, agriculture, road
salting, auto exhaust) sources. Bromide
itself in drinking water supplies has no
direct public health ramifications. However,
the oxidation of bromide by ozone forms
bromate, which is a genotoxic carcinogen.
An understanding of the sources and levels
of bromide in different source waters is a
key for an understanding of the bromate
formation potential in drinking water. In
1992, the Foundation funded a nationwide
survey documenting the occurrence of
bromide, Survey of Bromide in Drinking
Water and Impacts on DBP Formation
(1995, order#90662/project#825). This
research evaluated bromide levels at
100 water utilities from throughout the
United States, representing variations
in geographical distribution (USEPA
region), source type (surface water versus
groundwater), and utility size (>50,000
versus <50,000 population). Generally,
lakes exhibited lower bromide levels than
rivers and groundwater. Geographically,
the highest bromide levels generally
occurred in the Southwest United States
and the lowest levels were found in
the Northwest. Raw, untreated water
samples were acquired from each utility
and characterized. Average bromide
concentration in samples collected from
88 random utilities was 62g/L, whereas,
average bromide concentration in samples
collected from 12 targeted utilities (those
with known elevated bromide levels) was
210g/L. Bromate was detected in only 24
32
of the 100 utility samples after ozonation,

with an average level slightly above 10g/L
MCL. This study found that virtually any
level of bromide in source water can lead to
bromate formation.
One technique to reduce bromate in
finished water is to remove bromide.
Several Foundation projects have been
conducted to evaluate bromide removal
technologies. Strategies to Control
Bromate and Bromide (1999, order#90751/
project#156) assessed options for bromide
ion removal before ozonation. This research
had shown that bromide can potentially
be removed using ion exchange resins,
nanofiltration membranes, and activated
carbon (carbon specific), as well as during
optimized coagulation and softening.
The degree of bromide removal by these
processes varied from none to almost
complete removal.
Another approach, MIEX, has been tested
to evaluate the removal of inorganic
anions (bromide, arsenic, sulfide, and
percolate) in Evaluation of MIEX Process
Impacts on Different Source Waters.
Although the MIEX Process exhibited
capability to remove bromide, it was highly
variable. Another report, Advanced Water
Treatment of Estuarine Water Supplies,
also examined the effect of MIEX resin
as well as MIEX in combination with
coagulation and membrane. The research
found that MIEX is not very efficient at
removing bromide, and bromide removal
only occurs to any appreciable degree
when the resin dose overcomes the sulfate
demand. On the other hand, using MIEX
as a polishing step following coagulation
can improve bromide removal and DBP
formation. Under very high bromide
concentrations, MIEX needs to be
combined with membranes such as UF to
offer significant removal of both bromide
and organic precursors. Furthermore, the

first long-term pilot study with the MIEX
Process has been documented in the report,
DBP Control in High Bromide Water While
Using Free Chlorine During Distribution
to investigate and optimize bromide
removal. This was also the first study to test
ceramic membranes with in-line MIEX
resin addition for the removal of bromide
and DOC. This research provided operating
conditions and costs for four advanced
processes (the MIEX Process, fixed-bed
ion exchange, post-filter GAC adsorber, and
post-clearwell GAC adsorber) to achieve
sufficient precursor (bromide and organic
matter) removal to comply with the Stage 1
and 2 DBPR.
As shown above, bromide is not removed
by conventional water treatment. Ionexchange and high-pressure membrane
filtration remove bromide but they
produce a concentrated brine waste
stream. Another emerging technique
for removing bromide is electrolysis. An
Electrochemical Reactor to Minimize
Brominated DBPs in a Conventional
Treatment Plant (2008, order#91202/
project#3182) examined bromide removal
using an electrochemical reactor for
drinking water treatment applications.
Under optimal conditions of current,
electrolysis was capable of removing 50 to
60% of the total influent bromide. Unlike
other technologies examined above, no
waste was generated with electrolysis. The
Foundation recently funded the followup, Phase II: Demonstration of an
Electrochemical Reactor to Minimize
Brominates DBPs in a Conventional
Water Treatment Plant (project#4216),
to confirm the findings from project #3182,
fill in the data gaps, and collect long-term
data under conditions more representative
of full-scale applications. This research will
conduct a cost to benefit analysis to assess
the feasibility of electrolysis for bromide

removal in a full-scale application.
Bromate Control and Minimization
Strategies
Bromate is currently regulated by the USEPA
with an MCL of 10 mg/L, a level capable
of being exceeded by a significant number
of drinking water utilities. To achieve the
goal, bromate minimization strategies are
required to control its formation during
ozonation. A general option is to minimize
bromate formation during ozonation
through either chemical addition or
modified contactor design and operation.
Ammonia addition and pH depression
are two well researched and established
methods for minimizing bromate formation.
Ammonia addition can inhibit bromate
formation by preferentially forming
bromamines, ultimately leading to
minimized bromate formation. Decreasing
the water pH can preferentially shift the
chemical equilibrium to conditions less
favorable for bromate formation. Formation
and Control of Brominated Ozone ByProducts found that chemical factors are
more important than contactor design and
operation. The research was conducted using
true-batch reactors that simulate plug flow
reactors. Both pH depression and ammonia
addition were shown to be effective at
decreasing bromate formation. However,
of all the chemical addition approaches
to bromate minimization, acid addition is
the most effective and predictable within
its window of applicability (e.g., source
waters with medium to high pH). Another
report, Bromate Formation and Control
During Ozonation of Low Bromide Waters,
supports these findings. Ammonia addition
or pH depression may be used either
together or separately to reduce bromate
formation. If used together, synergistic
effects are likely to be observed. Bench-scale
33
reactors provided reasonable simulations of

pilot-/full-scale bromate formation results
adding strength to the idea that chemical
addition and not hydraulic conditions
control bromate formation.
Hydrogen peroxide (H2O2) in conjunction
with ozone is also one of the methods
for controlling bromate formation.
Demonstration-Scale Evaluation of Ozone
and PEROXONE (2000, order#90790/
project#525) evaluated the ozone/
PEROXONE (O3+ H2O2) process at a scale
large enough to provide design criteria
for retrofitting full-scale WTPs. This study
found that reducing the pH of ozonation
greatly reduced bromate formation while
concurrently increasing CT. The largest
reductions in bromate formation were seen
when pH was lowered from 8 down to 7.
Reducing the pH to 6.5 reduced bromate
further, though at a greatly increased
chemical cost. Little additional benefit was
realized by reducing the pH lower than
6.5. Staging ozone within a contactor only
minimally reduced the amount of bromate
formed, but its performance depended
on water quality conditions and generally
coincided with a reduction in CT.
A comprehensive review of bromate
minimization methods is provided in
Strategies to Control Bromate and
Bromide. The project evaluated chemical
factors (acid addition, ammonia [NH3]
addition, H2O2 addition, and hydroxyl
radical scavenger addition) and
hydrodynamic factors (tapered versus
single-stage ozonation) as bromate
minimization methods. The study found
that pH depressions were the most effective
approach in minimizing bromate for
conditions in which either the molecular
ozone or hydroxyl radical pathway were
dominant. NH3 addition was more effective
in interrupting the molecular ozone
34
pathway. H2O2 addition provided mixed

results, with pH conditions being very
influential. Hydroxyl radical scavenger
addition was effective, but would likely
be subject to institutional constraints.
Pilot- and demonstration-scale contactor
studies indicated that chemical factors
(e.g., ozone dose) were more influential
than hydrodynamic factors (e.g., CT) in
minimizing bromate formation.
Reducing disinfectant doses by
substituting other disinfectants is one
way to optimize the disinfectant strategy.
Use of Chlorine Dioxide and Ozone for
Control of Disinfection By-Products (2004
order#90981F/project#2742) evaluated the
benefits of using chlorine dioxide (ClO2)
in combination with ozone. Special fullscale testing was conducted to evaluate
bromate mitigation techniques such as
preoxidation with ClO2, pH adjustment, and
ammonia addition. The data from this study
showed that preoxidation with ClO2 and pH
adjustment to a value of 6.0 were effective
methods to reduce bromate formation in
a preozonation contactor, while ammonia
addition was less effective. In addition to
reducing the bromate formation by reducing
the ozone dose through substitution with
ClO2, an unexpected result was that ClO2
preoxidation also reduced the bromate
formation at a constant ozone dose. Special
testing showed that chlorite, which is formed
after ClO2 addition, plays an important role
in the bromate formation reduction. For
utilities that use ozone, preoxidation with
ClO2 may offer an alternative approach to
reduce bromate formation.
Bromate formation can be also controlled
by adding chlorine to the water to rapidly
oxidize the bromide to hypobromous acid
and then adding ammonia to convert the
hypobromous acid to monobromamine
prior to the ozone application. Recently, the
Foundation funded project#4159, Role of

Bromamine on Disinfection By-Product
Formation and Impact on Application
of Chloramination and Ozonation. This
ongoing project will evaluate optimized
bromamine formation to minimize bromate
formation during ozonation. The impact of
multiple water quality and process conditions
on bromamine formation and subsequent
bromate formation will be assessed.
Bromate Removal
Prevention of bromate formation is one
technique to comply with DBP regulations.
However, in some circumstances, the
utilities have to deal with bromate removal
after its formation. Several options to
remove bromate after its formation include
ferrous iron (Fe2+) reduction, GAC surface
reduction, UV irradiation, and high energy
electron beam irradiation. Fe2+ reduction,
GAC surface reduction, and decomposition
by UV light irradiation were assessed
for bromate removal after ozonation
in Strategies to Control Bromate and
Bromide. Bench-scale evaluations were
performed with varying spiked levels
of bromate and subsequent pilot tests
were performed for all bromate removal
techniques. While bench-scale results with
Fe2+ were encouraging, pilot tests showed
premature turbidity breakthrough, a result
rectified by simultaneous addition of both
Fe2+ and ferric iron (Fe3+) salts. While both
lab- and pilot-scale results for GAC were
encouraging, the pilot tests were not run
long enough to assess the effects of biofilm
development on GAC. Medium-pressure
UV light irradiation proved to be effective
in bromate decomposition at very high
irradiation doses.
The biological reduction of bromate
using biological active carbon (BAC)
was evaluated in the report, Removal of
Bromate and Perchlorate in Conventional
Ozone/GAC Systems (2001, order#90836/

project#2535). This research found that
biological bromate reduction can be
achieved in BAC filters. However the mass
of bromate removed in the filters can be
affected by concentrations of dissolved
oxygen (DO), nitrate, pH, type of influent
water, and influent bromate concentration.
Filter history can also greatly affect the
subsequent mass of bromate removed in
a BAC filter. Increasing the influent DO
and nitrate concentrations to the BAC
filters decreased bromate removal, but an
increased sulfate concentration did not
have much effect on bromate removal.
Depending on the empty bed contact
time, an increased influent bromate
concentration could cause an increase
in the mass concentration of bromate
removed. Additionally, bromate removal
increased as the influent pH to the BAC
filters decreased to near-neutral values.
Chlorite (ClO2-) and Chlorate (ClO3-)
Chlorine dioxide (ClO2) has been used for
drinking water treatment in the United
States since the 1960s. It was primary used
for preoxidation of NOM, removal of iron
and manganese, taste and odor control,
color removal, algal growth prevention,
and as an alternative to chlorinated
disinfection practices. Due to the discovery
of chlorinated DBPs in the 1970s, various
regulatory changes (e.g. Stage 2 DBPR,
LT2ESWTR), and the prevalence of
chlorine resistant organisms, ClO2 has seen
increased popularity. The current number
of WTPs using ClO2 for disinfection may
range from 5001,200. However, the actual
number of plants is difficult to estimate
because some plants may only use ClO2
seasonally or intermittently.
The use of ClO2 within the disinfectant
strategy has the potential to decrease the
concentration of regulated DBPs (e.g.,
35
THM, HAA) typically produced during

chlorination and chloramination. However,
the use of this disinfectant can lead to the
formation of other types of DBPs such as
chlorite and chlorate in finished water.
Chlorite is regulated by the USEPA with a
MCL of 1.0 mg/L and a MCLG of 0.8 mg/L.
Chlorate, while not currently regulated by
the USEPA, is an emerging health concern
and is listed on the Contaminant Candidate
List3 (CCL3). A textbook recently published
by the Foundation, State of the Science of
Chlorine Dioxide in Drinking Water (2009,
order#91248/ project#3150), provides
information on all aspects of using ClO2
for drinking water disinfection, including
legislative history, chemistry, generation
issues, application strategy, inactivation,
distribution system topics, monitoring,
health effects, and future research needs.
Chlorite and Chlorate Formation
One of disadvantages of the use of ClO2 is the
formation of chlorite and chlorate. Sources,
Occurrence, and Control of Chlorine
Dioxide By-Product Residuals in Drinking
Water (1994, order#90656/ project#611)
found that the ClO2 generator can account for
as much as 35% of the chlorate concentration
that appears in the distribution system.
Results from this research also found that
chlorite levels following ClO2 treatment
can be as much as 70% of the applied ClO2
dose and those utilities that apply doses
approaching 1mg/L may be required
to institute chlorite control. State of the
Science of Chlorine Dioxide in Drinking
Water summarized information on chlorite
and chlorate formation reactions. ClO2 can
participate in redox reactions and serve as
an electron acceptor to form chlorite or as
an electron donor to form chlorate. ClO2 can
react with amines, amino acids, phenols,
alkenes, polycyclic aromatic hydrocarbons
(PAHs), and inorganic compounds to form
chlorite and chlorate. More broadly, when
36
ClO2 reacts with NOM and other materials

it breaks down into chlorite, chloride, and
chlorate. The levels of each of these can vary
based on many different factors, but chlorite
levels can be as high as 70% of the ClO2 dose
while chlorate usually comprises less than
25% of the initial ClO2 dose. Chlorate can also
be present due to inefficient ClO2 generation
or when ClO2 treatment basins are exposed to
bright sunlight.
Chlorate is also known to be a factor in
hypochlorite decomposition. Minimizing
Chlorate Ion Formation in Drinking Water
When Hypochlorite Ion Is the Chlorinating
Agent (1995, order#90675/project#833)
studied decomposition of the hypochlorite
ion (OCl-) from sodium hypochlorite
(NaOCl) or calcium hypochlorite (CaOCl2)
and the formation of chlorate to understand
the fundamental chemistry of each
process. This project evaluated chlorate
presence and formation when using
hypochlorite within the treatment train. A
predictive model was developed from the
laboratory studies. The model is based
on the observed rate laws of hypochlorite
decomposition and chlorate formation as
a function of storage conditions. A survey
of utilities using sodium hypochlorite
or calcium hypochlorite was performed
for chlorate formation levels. Raw water,
finished water, and liquid bleach feedstock
samples were measured for chlorate levels.
Chlorite and Chlorate Occurrence
Information on chlorite and chlorite
occurrence in treated water is rather
limited. Of the 500 plants surveyed
between 1997 and 1998 for the ICR, only
28 plants used ClO2 for disinfection. The
survey results showed that median levels
of chlorite and chlorate were 0.29 and
0.12 mg/L respectively for these 28 plants
using ClO2 for disinfection. Before the ICR
survey, Sources, Occurrence, and Control
of Chlorine Dioxide By-Product Residuals

in Drinking Water found the medians
of chlorite in the distribution system at
locations where the ClO2 dosage to the raw
water was 1.0 mg/L or less ranged from
0.03to0.78 mg/L.
Chlorite and Chlorate Detection Methods
Several methods are available for the
analysis of chlorate and chlorite such
as flow injection analysis (FIA), ion
chromatography (IC) (USEPA 317.0),
spectrophotometric method (USEPA 327.0),
and amperometric titration (Standard
Method 4500). Sources, Occurrence, and
Control of Chlorine Dioxide By-Product
Residuals in Drinking Water compared the
effectiveness of FIA and IC for the detection
of low levels of chlorite and chlorate
in the treatment plant and distribution
system. Chloramine and other oxidants
were found to cause interferences during
FIA but not during IC analysis. These
results suggested that IC is more suitable
for analyses of both ions for low levels
expected in the distribution system and
minimum detection limits using IC can be
in the 12g/L range. Ion chromatography
(USEPA methods 300.0 or 300.1) is typically
the most common method used for chlorite
and chlorate detection. Ion chromatography
minimum detection limits can be in the
12g/L range.
Chlorite and Chlorate Control and
Minimization Strategies
Since removal of chlorite and especially
chlorate is difficult, it is usually more
effective to not form the DBPs than to try
to remove them. Minimizing Chlorate
Ion Formation in Drinking Water When
Hypochlorite Ion Is the Chlorinating Agent
provides practical recommendations to
mitigate hypochlorite ion decomposition
and chlorate ion formation. Three basic
strategies are available to utilities for

minimizing chlorate formation in liquid
bleach. The strategies are: (1) dilution of
the concentrated liquid bleach immediately
after delivery, (2) the use of lower storage
temperatures, and (3) the avoidance of
sunlight during storage. The bottom line
for utilities is that delivered liquid bleach
should meet a minimum set of specifications.
Bleach should be measured periodically
for chlorite and chlorate. The measured
concentrations can be used in conjunction
with the predictive model to minimize
chlorate ion levels in the finished water.
Lowering the required ClO2 dose by
introducing other disinfectants into the
treatment scheme and/or optimizing the
current disinfection strategy is one of the
strategies for controlling chlorite and
chlorate. Use of Chlorine Dioxide and
Ozone for Control of Disinfection ByProducts evaluated the potential benefits
of using ClO2 and ozone together in the
disinfectant strategy. The data from this
study showed that ozone oxidized the
formed chlorite to chlorate and then GAC
filters removed chlorite so that the plant
effluent chlorite concentration was below
the detection limit. This study supported
the idea of optimizing disinfectant dose
to minimize required doses and therefore
lower by-product formation.
One Foundation report evaluated real-world
case studies of treatment plants that had
to manipulate their disinfectant strategy
when using ClO2. Long-Term Effects of
Disinfection Changes on Water Quality
reported that chlorite formation from using
chlorine dioxide does occur and could be
controlled by altering the chlorine dioxide
dose through various disinfection strategies
and doses. Several interesting impacts were
also noted in this research. One interesting
finding was that addition of chlorine to water
37
that was pre-treated with chlorine dioxide can

form additional chlorine dioxide. This can be
beneficial as it adds additional disinfectant,
although alternatively negative effects
through additional chlorate formation can
also be observed. Another interesting finding
of this research is that applying chloramine
as a secondary disinfectant to water pretreated with ClO2 does not appear to produce
additional chlorine dioxide or chlorate.
Several technologies are available to

remove or minimize chlorite and chlorate
once they are formed. Reduced iron, sulfur
compounds, and activated carbon have
been investigated for potential chlorite
and chlorate reduction. State of the
Science of Chlorine Dioxide in Drinking
Water discusses ferrous iron, sulfur-based
reagents, and activated carbon for control
of chlorite and chlorate. The project shows
that while success can be achieved using
these technologies for chlorite removal,
most of these technologies are not as
effective for chlorate removal.
Another report, A Zero-Valent Iron (Fe)

Packed-Bed Treatment Process (2001,
order#90857/project#2555), investigated
the basic feasibility of zero-valent iron (Fe)
for removal of oxo-anions. Experiments
were designed to evaluate different sources
of Fe and to evaluate the performance
of Fe in batch and column tests (lab
and field) under different water quality
conditions. The key factors investigated
that influence the operation and feasibility
of the system were removal capability, byproduct formation, and sustainability of
the process. This project developed and
tested elemental iron in a packed-bed water
treatment process for electrochemically
reducing problematic inorganics in
groundwater. Results showed that Fe could
completely electrochemically reduce
chlorate to chloride; the kinetics of the
reactions varied as a function of ionic radii
and strength of the element-oxygen bond.
In addition, the use of iron for chlorite

removal has been evaluated in several
Foundation projects. Chlorite Ion
Removal by Ferrous Iron Addition (1993,
order#90627/project#633) studied the
potential to use Fe2+ for the chemical
reduction of chlorite in drinking water. The
experimental results indicated that Fe2+
can be used effectively for the control of
residual chlorite in drinking water facilities
that use ClO2. Due to the rapid reaction
kinetics observed during this study, the
Fe2+ may be added at several points within
the treatment train and still promote
efficient chlorite removal. While this study
emphasized Fe2+ addition during rapid
mixing, it is conceivable that Fe2+ could be
added as late as in the filter-applied water.
Impact of Disinfectants on Transmission,

Treatment, and Distribution System
Performance: Phases I and II (2005,
order#91082 and order#91140/
project#2843) looked at the consequences
of replacing Cl2 with ClO2 for biofouling
suppression in an aqueduct and in open air
treatment basins with the goal of reducing
THM and HAA concentrations without
sacrificing biofouling performance. Results
of this research showed that chlorite
and chlorate concentrations should be
monitored if a change to ClO2 is made. This
project found that at a pH of 7 or below, Fe2+
can be effectively used to remove up to 90%
of chlorite; at a higher pH, dissolved oxygen
inhibits chlorite removal by Fe2+ through
competitive reactions.
Chlorite and Chlorate Removal
38
Water utilities contemplating such treatment

should conduct pilot-scale testing to insure
effective capture of the resulting iron(III)
hydroxide (Fe(OH)3)solids within the filters.
Research has also been conducted on

evaluating activated carbon for removal of
chlorite and chlorate. Another objective
of Sources, Occurrence, and Control of
Chlorine Dioxide By-Product Residuals
in Drinking Water was to evaluate PAC as
a potential chlorite control technique. This
study found that chlorite can be controlled
by PAC, but the required dosages may be
higher than is practical if PAC is used only
for that purpose. This study also found that
chlorite can be removed by GAC, but that
breakthrough may occur early.
Summary
In the last four decades and since the

discovery of THMs, much knowledge has
been gained on most aspects of the science
of regulated DBPs. Based on this knowledge,
drinking water utilities now have the ability
to provide their customers with water that
meets existing regulations.
However, more work needs to be done.
As water demand increases because of
population growth, water purveyors are
resorting to alternative source waters such
as recycled water or sea water that exhibit
different water matrix characteristics and

requires different operating conditions. For
example, higher levels of bromide and iodide
and low TOC in seawater may favor the
formation of brominated DBPs and possibly
iodinated DBPs. Recent reports have linked
a shift in speciation and concentration
of certain regulated DBPs (THMs and
HAAs) to climate change and its effects on
drinking water sources (i.e., increased algal
growth). The objective of a recently awarded
project#4302, Climate Change Impacts
on Lake Erie Disinfection Byproduct
Formation, is to gain a better understanding
of the relationships between Lake Erie algal
population, DOM, and DBP formation. This
work will document how water quality
changes potentially linked to climate change
can impact treated drinking water quality and
help better prepare water agencies to adapt to
climate change so that they may continue to
provide high quality water.
Reference
McGuire, M.J. and R.G. Meadow. (1988).

AWWARF Trihalomethane Survey. JAWWA.
80 (1). Pp 61-68.
39

DBP Minimization Strategies
Michael Hotaling, Newport News, Virginia
Newport News Waterworks (Waterworks) treatment choices over the last thirty years have been driven primarily by
compliance with the family of DBP regulations. The following graphic displays the annual average total trihalomethane
The Compliance Graph: December, 1981June, 2009

0.160
Raw Water Chlorination
0.140
0.120
Intermediate Chlorination
Chloramination
Ozone
TTHM, mg/L
0.100
0.080
0.060
0.040
0.020
0.000
D-81
D-83
J-86
J-88
Moving Avg.
J-90
J-92
J-94
J-96
F-98
M-00
Quarterly Compliance Samples
1979 TTHM Limit
D/DBP Stage 1
M-02
M-04
M-06
D-07
2001 Limit -20%
(TTHM) concentration and subsequent treatment choices made to reduce those levels.
After the initial maximum contaminant level (MCL) of 100g/L for TTHM became effective in the early 1980s, raw
water chlorination was no longer a viable strategy. Several Water Research Foundation projects had shown that it was
possible to reduce TTHM concentration by removing precursors prior to the application of chlorine, so the application
point for chlorine addition was relocated from the raw water to the filter influent (post coagulation and settling).
The intermediate chlorination strategy was successful in keeping Waterworks narrowly in compliance with the TTHM
MCL, but the promulgation of the Stage 1 Disinfectants/Disinfection By-Products Rule (DBPR) in 1998 necessitated
further changes. Again, Foundation research was key in leading Waterworks to the use of chloramination, wherein
ammonia is added to the process to react with free chlorine to form monochloramine. Foundation research, together
with pilot testing, gave Waterworks confidence the chloramination would insure compliance with Stage 1 by providing:

Knowledge of the formation rates of TTHMs and 5 haloacetic acids (HAAs) while in contact with free chlorine.
Estimates of the chloramine decay rate in the distribution system.
Formulation of a successful nitrification control strategy.
At the time, the Agreement-in-Principle set a placeholder MCL of 40 and 30g/L on an annual average for TTHM and
HAA5, respectively. While chloramination was adequate to meet the 80/60 limit of Stage 1, it would be unable to meet
a potential 40/30 limit for Stage 2.
40
Research had shown that ozone had the potential to effectively kill Giardia and viruses more effectively than chlorine,
without producing regulated chlorinated DBPs. Ozone would allow Waterworks to meet the future 40/30 standard
and as it turned out, the final Stage 2 as promulgated in 2006. Foundation work was also instrumental in convincing
Waterworks that it would have no trouble meeting a bromate standard of 10g/L, also regulated by Stage 1, while
using ozone. The research showed that while employing intermediate ozonation at a pH of approximately 6.2, bromate
formation is virtually nonexistent, regardless of bromide levels.
Waterworks has spent millions of dollars to comply with the DBP rules over the last thirty years. Waterworks
investment in Foundation funding has been repaid handsomely by allowing the implementation of successful
technologies and avoiding any negative simultaneous compliance issues at the same time.

Bromate Minimization Strategies
Richard Talley, City of Fort Worth, Texas
The City of Fort Worth Eagle Mountain Water Treatment Plant (WTP) was constructed and placed into operation in
1992. The plant process consists of raw water ozonation, conventional rapid mix, flocculation and sedimentation,
and biological filters using deep bed anthracite media. Chlorine and ammonia are added to the filtered water for
chloramines residual disinfection. Ferric sulfate and cationic polymer are used as the coagulant and coagulant aid.
Lime is added upstream of the rapid mix basins for pH control.
The original Eagle Mountain WTP was designed for a treatment capacity of 30 million gallons per day (mgd). The plant
was expanded in 2000 and again in 2007 to increase plant capacity to 70 mgd and 105 mgd respectively.
Raw water is supplied from Eagle Mountain Lake. This lake has a relatively stable water quality including the
following characteristics:
pH
Alkalinity
Hardness
Turbidity
Total Organic Carbon
Bromide
7.7 to 8.5
100 to 130 mg/L
120 to 160 mg/L
2 to 10 NTU
4 to 6 mg/L
0.100 to 0.220 mg/L
41
The ozonation process was successfully implemented to provide primary disinfection for Giardia and viruses and to
control tastes and odors. Raw water ozonation has also shown to provide microflocculation benefits, including lower
ferric sulfate and lime use and improved filtered water quality. Approximately 2.5 mg/L ozone is typically required to
meet disinfection requirements. Ozone residuals are maintained to achieve a City disinfection inactivation ratio goal of
1.5. The raw water bromide levels, coupled with relatively high pH, are in a range that could lead to excessive bromate
formation following ozonation.
The City did not monitor bromate at the Eagle Mountain WTP until the Stage 1 Disinfectants/Disinfection By-Products
Rule (DBPR) was finalized in 1999. At that time, the City began monitoring the treated water for bromate and found
that levels near or slightly exceeding the 10g/L were being produced.
Findings from the report, Strategies to Control Bromate and Bromide (1999, order#90751/project#156) proved to
be very useful in selecting the best strategy to minimize bromate formation. That study showed that ammonia addition
prior to ozonation could reduce the formation of bromate by the formation of bromamines. Bromamines would be less
reactive to the ozone and not form as much bromate.
As a result of examining the Foundation study, the City began feeding ammonia gas into the raw water, upstream of
the ozone contact basins. It was determined that an ammonia dose of approximately 0.1 to 0.12 mg/L limits bromate
formation in the treated water to levels typically below the detection limit of 5g/L when the ozone dose is maintained
at approximately 2.5 mg/L and the raw water pH is approximately 8.0.
Using a low dose of ammonia in the raw water has enabled the Eagle Mountain WTP to control bromate
formation and meet the regulatory limit of 10g/L. However, the bromide levels have been consistently above
0.200 mg/L for the past two years requiring the plant staff to closely monitor the ozonation process to keep
bromate levels below the regulatory limit.
42
Emerging Disinfection By-Products
Emerging DBPs
In the last decade, a large number of U.S.
drinking water utilities already have or are
considering switching from chlorine to
alternative disinfectants (ozone, chlorine
dioxide, and chloramine) to comply with
stricter regulations for trihalomethanes
(THMs) and haloacetic acids (HAAs). These
alternative disinfectants may minimize the
formation of the regulated DBPs (THMs
and HAA5), but there is increased evidence
that they may favor the formation of other
DBP species of toxicological concern.
In recent years, nitrogenous and iodinated
DBPs (N-DBPs and I-DBPs, respectively)
have gained increased attention because
of their potential health effects. Results
from numerous studies, using cytotoxicity
and genotoxicity assays, show that several
N-DBPs (haloacetonitriles, haloacetamides,
and halonitromethanes) are 12 orders
of magnitude more toxic than the
regulated THMs and HAAs. Although
results of these assays for nitrosamines
are not yet available, previous studies
have indicated that they are extremely
carcinogenic. The USEPA estimates that a
drinking water concentration of 0.7 ng/L
for N-nitrosodimethylamine (NDMA) is
associated with 10-6 lifetime cancer risk
levels. No U.S. federal regulatory limit
has been established for NDMA and only
California and Massachusetts have set a
10 ng/L notification level. Iodinated DBPs
such as iodoacids have been reported in
some chloraminated drinking water and
are believed to be highly cytotoxic (e.g.,
iodoacetic acid is more than 250 times more
cytotoxic than chloroacetic acid, which is
one of the regulated HAAs).
A comprehensive review on the formation,
occurrence, and health effects of both
regulated and unregulated DBPs will be
covered in the ongoing project#4039,

By-Products of Potential Concern in
Drinking Water Treatment. In addition
to DBPs formed during oxidation, the
report covers by-products that can be
formed during many processes, involving
mechanisms such as hydrolysis, ultraviolet
(UV) photolysis, and biological reactions in
source waters, reservoirs, and distribution
systems.
The following section covers ongoing and
published Water Research Foundation
projects focusing on unregulated/
emerging DBPs.
Nitrogenous DBPs
Due to population growth and climate

change, increased contributions from
wastewater discharges and algal activity
in drinking water supplies have led to
elevated levels of dissolved organic nitrogen
(DON), which could serve as precursor
material for N-DBPs. By-Products of
Potential Concern in Drinking Water
Treatment will provide an extensive
review of formation pathways, precursor
characteristics, and occurrence of the
most important groups of N-DBPs,
including nitriles (e.g., cyanogen halides,
haloacetonitriles, dimethylcyanamide),
haloacetamides, halonitroalkanes
(e.g., halonitromethanes), hydrazine,
nitrosamines, and nitrosoureas.
Methods, Formation, Monitoring, and
Occurrence
The first step towards a better understanding
of the occurrence, formation, and treatability
of these emerging DBPs is the development
of reliable analytical methods. These
analytical methods can include analysis
43
of individual species (e.g., NDMA) or bulk

parameters (e.g., DON as a precursor). In
addition, formation potential tests can be
very useful tools to predict the formation of
specific classes of DBPs.
44
conditions. The colloidal NOM isolate

and other nitrogen enriched isolates had
the highest NDMA yield compared to
hydrophobic acid isolates. The project
showed that NOM isolates with higher
nitrogen content had lower THM and higher
HAN formation.
In the past, relatively minor attention

has been focused on DON, despite
observations implicating it as a precursor
to several DBPs including haloacetonitriles
(HANs), nitromethanes, and nitrosamines.
Organic Nitrogen in Drinking Water
and Reclaimed Wastewater (2006,
order#91116/project#2900) performed
a comprehensive assessment of DON
occurrence in raw and finished drinking
waters and reclaimed wastewaters and
provided information on its chemical
characteristics and reactivity with metal
hydroxides and oxidants/disinfectants.
Prior to this project, methods for DON
determination suffered from high reporting
levels that were not suitable for drinking
water applications and/or were inaccurate
in the presence of elevated inorganic
nitrogen species such as nitrate or
ammonia. The project developed a dialysisbased pretreatment method and validated
a high temperature oxidation method
suitable for measuring DON in drinking
waters. The method was used to conduct
a DON occurrence survey for 28 treatment
plants. The mean DON concentrations were
0.19mg/N/L for raw waters and 0.15mg/
N/L for finished waters.
Methods for the analyses of NDMA and

other N-nitrosamines already exist (e.g.,
USEPA method 521) and are routinely
used. However, no method is available
for the analysis of secondary and tertiary
amines. As a class, secondary and tertiary
amines are subject to transformation to
their nitrosated analogues. A wide array
of nitrosamines has been discovered in
disinfected waters, raising concerns among
utilities and regulators because of their
cancer potency. The goal of a recently
awarded project#4209, Development
and Application of a Total Nitrosamine
Assay for Disinfected Waters, is to
develop a bulk analytical technique
capable of quantifying the total nitrosamine
concentration in water. The method will be
based on an existing test that quantifies the
total concentration of several categories of
nitrosated species, including nitrosamine
in blood. The developed method will be
applied to a range of disinfected waters
and used to compare concentrations of
total nitrosamines vs. NDMA and other low
molecular weight nitrosamines covered by
USEPA Method 521.
In addition, the project conducted limited

experimentation on DBP formation from
natural organic matter (NOM) isolates with
a range of dissolved organic carbon (DOC)/
DON ratios. The study found that NDMA
did not form during chlorination but did
form during chloramination of nitrogen
containing NOM isolates. This observation
confirmed that NOM can serve as precursor
material for NDMA under drinking water
Formation potential tests have been used

extensively to predict the formation of
specific classes of DBPs (e.g., TTHMs) during
water treatment and distribution processes.
Generally, the existing tests do not take into
consideration the formation of other DBPs.
Ongoing project#4180, Development of
a Protocol to Predict the Formation of
Nitrosamines While Minimizing the
Formation of Regulated DBPs, will develop
a bench-scale protocol that simulates the

formation of regulated DBPs and
nitrosamines. The test will develop a uniform
formation condition (UFC) bench-scale
protocol using a uniform set of typical
chloramination conditions to examine
nitrosamine and regulated DBP formation.
The test will provide a tool for comparing DBP
formation between many utilities. The
developed test will be used to assess tradeoffs
in the formation of regulated DBPs (THMs
and HAA5) and nitrosamines with that of
other toxicologically significant emerging
DBPs. The project will also evaluate the
impact of important water quality parameters
(i.e., bromide, nitrite) on the formation of
nitrosamines and other DBPs.
The effect of bromide and nitrite on the
formation of NDMA was investigated in
a previous Foundation report. Factors
Affecting the Formation of NDMA in Water
and Occurrence (2006, order#91063/
project#2678) showed that nitrite can be
involved in NDMA formation and that
the formation mechanism is significantly
influenced by the addition of bromide.
The primary focus of the study was to
investigate the formation of NDMA during
chloramination. The study demonstrated
the effect of chloramination on aminebased coagulant polymers, including
polydiallyldimethylammonium chloride
(polyDADMAC) and anion exchange
resins and proposed an NDMA formation
mechanism. It concluded that NDMA most
likely originated from quaternary amine
used to prepare these resins. The role of
anion exchange resins in the formation
of NDMA and other nitrosamines will be
further investigated in a new project#4295,
Anion Exchange Resins as a Source
of Nitrosamines and Nitrosamine
Precursors. The project will evaluate
the extent to which nitrosamines and
nitrosamine precursors leach from an array
of anion exchange resins currently used

in water treatment practices, determine
factors contributing to their leaching, and
identify treatment schemes and conditions
to avoid in order to prevent such leaching.
An extensive review of the formation
pathways and precursor characteristics
of important groups of N-DBPs will be
available in By-Products of Potential
This review builds upon results from
numerous studies, including Factors
Affecting the Formation of NDMA in
Water and Occurrence and Occurrence
and Formation of Nitrogenous
Disinfection By-Products (2009,
order#91250/project#3014). Similar to
Organic Nitrogen in Drinking Water
and Reclaimed Wastewater, another
report, Occurrence and Formation of
Nitrogenous Disinfection By-Products,
showed that the most important sources
of precursors for certain N-DBPs are the
colloidal, hydrophilic base, and hydrophilic
acid-neutral fractions of dissolved organic
matter (DOM) isolated from algal or
wastewater impacted source waters and
that the mechanisms of formation and the
impact of treatment/disinfection processes
on N-DBPs were different from those of
chlorinated DBPs.
Occurrence and Formation of Nitrogenous
Disinfection By-Products used model
compounds as precursors to investigate
N-DBP formation and focused on amine
precursors, as they are more reactive
with oxidants than amides. Quaternary
amines are important functional groups in
anthropogenic chemicals used in consumer
products and water treatment. Because
quaternary amines and tertiary amines
can degrade to secondary amines, these
compounds also serve as nitrosamine
precursors. Application of formation
45
potential tests to a series of model

compounds indicated, with few exceptions,
that precursors most similar in structure
to the targeted by-products yielded the
highest concentrations of by-products.
The quaternary amine benzalkonium
chloride was a significant NDMA precursor,
but dimethylbenzylamine was the most
significant precursor for NDMA.
Of the nitrogenous DBPs and more
specifically nitrosamines, NDMA has
received the most attention. As part of the
report, Factors Affecting the Formation
of NDMA in Water and Occurrence, a
limited occurrence survey was conducted
at drinking water, wastewater, and
recycled water treatment plants in North
America for a preliminary indication of
the potential extent of NDMA occurrence.
The 21 drinking water utilities surveyed
represented various vulnerability factors,
such as influence of wastewater or
agricultural runoff, pH level (expected
to affect possible formation/degradation
mechanisms), and treatment (e.g., use
of ion exchange resins). NDMA was
detected in treated drinking water from
the 21 drinking water utilities surveyed,
but the median NDMA concentrations
in the treatment plant effluents were less
than 1 ng/L for both chlorinated and
chloraminated systems. On the other hand,
higher NDMA levels (up to 30 ng/L) were
found in groundwater treated with anionexchange resin and in chloraminated water
impacted by agricultural runoff. Wastewater
and recycled water NDMA concentrations
were found to be much higherup to 960
ng/L in one of the wastewater treatment
plants effluents. Distribution system
samples generally had higher levels of
NDMA than plant effluent samples. The use
of chloramine in the distribution system
correlated with slightly higher NDMA levels
than the use of free chlorine. The levels
46
of NDMA generally appeared to increase

with detention time. The study concluded
that NDMA formation does not appear
to be a potential problem for drinking
water agencies using surface water as long
as NDMA is not regulated below 9 ng/L,
except for special circumstances when
organic nitrogen precursors are in high
concentrations (e.g., certain ion exchange
resins or source waters).
Elevated NDMA levels in wastewater
concur with the findings of another
recently completed report, Contribution
of Wastewater to DBP Formation (2008,
order#91206/project#2948), in which up
to 3165 ng/L of NDMA was detected at one
of the wastewater treatment plants after
chlorination. While the concentration was
an extreme outlier, elevated levels of NDMA
(209 and 1470 ng/L) were also found in
treated wastewater where the chlorine-to
nitrogen ratio was less than 10. Elevated
levels of N-Nitrosomorpholine (NMOR)
were consistently detected in the influent
of one participating wastewater treatment
plant. However, NMOR is believed to be a
wastewater contaminant, not a DBP. The
study also found that wastewater treatment
plants without advanced treatment (i.e.,
reverse osmosis, powdered activated carbon,
or soil aquifer treatment) are likely to produce
nitrosamine precursors that can later react to
form nitrosamines at downstream drinking
water treatment plants. Wastewater treatment
plants that did not practice nitrification or
utilize advanced treatment technologies
yielded the highest NDMA formation on
formation potential tests.
A limited occurrence study of NDMA
in distribution systems was completed
in the report, Formation and Decay
of Disinfection By-Products in the
Distribution System (2006, Order #91115/
project#2770). Results showed an
association between NDMA levels and

temperature. NDMA concentrations were
greater in warm water than in colder water
in the systems studied, although this trend
was not evident at each sampling location.
Significant concentrations of NDMA were
found in some locations of the distribution
system. However, no particular trend could
be identified with increasing water age in
the distribution system.
Hydrazine is another N-DBP that has been
associated with potential health effects. It
has been designated by the USEPA as a
probable human carcinogen with a 10-6
cancer risk level of 10 ng/L in drinking
water. Since the 1950s, hydrazine has
been widely used in a variety of industrial
applications. While hydrazine is formed
by the reaction between monochloramine
and ammonia, there was no mention in
the drinking water or wastewater literature
of concerns about hydrazine formation
as a by-product of chloramination until
the Foundation funded Formation of
Hydrazine as a Chloramine By-Product
(2006, order#91122/project#2997). This
research found that hydrazine formation
was not significant (<5 ng/L) under
conditions typical of most water treatment
applications (pH <9.0, NH3-N <0.5 mg/L
as N). However, this study identified
conditions under which hydrazine
formation may be significant, including
pH >9.0 in combination with the presence
of free ammonia and chloramine, which
may result from chloramine decay in the
distribution system or poor control of
chemical dosing. Hydrazine may form
in the distribution system even if it is
not detectable in water leaving the plant.
This project also introduced a modified
analytical method for hydrazine with
a detection limit <5 ng/L. As a followup project, Quantifying Hydrazine in
Chloraminated Water and Wastewater
(project#4141), is now underway. This

research will confirm the model predictions
of hydrazine formation in natural water
matrices and determine if the predicted
levels of hydrazine are present in
chloraminated water and wastewater
systems that operate under conditions that
may promote hydrazine formation. This
project will provide a better understanding
of the significance of hydrazine formation
in chloraminated water and wastewater.
Nitriles constitute another important
class of N-DBPs. Compounds in this class
include cyanogen halides (CNX), HANs,
and dimethylcyanamide. By-Products
of Potential Concern in Drinking Water
Treatment will review the mechanisms
of formation of these compounds via the
decarboxylation pathway (from free amino
acids) and the aldehyde pathway (from
aldehydes). Specific nitriles resulting from
amino acids depend on the structure of the
amino acid side chain. Cyanogen chloride
results from chlorination of free glycine,
while acetonitrile forms from alanine. The
aldehyde pathway involves the reaction of
monochloramine with aldehydes to form the
corresponding nitrile (e.g., acetonitrile in
reaction with acetaldehyde) and ultimately
to HAN formation upon chlorination.
The report shows that nitriles can also form
from precursors other than free amino
acids. Chlorination and chloramination
of NOM isolates from natural waters and
wastewaters found that dichloroacetonitrile
(DCAN) was the most prevalent HAN
formed. Alkaline hydrolysis of HANs can
form haloacetamides and ultimately HAAs.
For example, hydrolysis of DCAN leads to
dichloroacetic acid. During chloramination,
DCAN formation was not correlated to
the nitrogen content of the fractions,
suggesting that nitrogen incorporation from
chloramine could be important.
continued next page
47
Four HANs, (trichloroacetonitrile

[TCAN], DCAN, bromoacetonitrile
[BAN], dibromoacetonitrile [DBAN], and
cyanogen chloride [CNCl]) were among
the unregulated DBPs surveyed in the
Information Collection Rule (ICR). In
Information Collection Rule Data Analysis
(2003, order#90947/project#2799), the
survey data showed that CNCl and HANs
formation were higher in chloraminated
surface water than in groundwater
systems. The ICR evaluated the speciation
of HANs and the effect of bromide on
their formation and showed that, when
compared to THMs and HAAs, the amount
of bromine incorporation in HANs was
much higher than both classes. In a
comparison of formation and speciation
of HANs versus THMs, the percentage
increase in HANs resulting from increased
bromide concentrations was greater than
that for THMs. Bromine-substituted HANs
constituted more than 30% of the total
HANs produced. As expected because
trihaloacetonitriles are known to be unstable,
all TCAN levels were below the minimum
reporting levels (MRLs).
Halonitromethanes are yet another type
of N-DBP and similar to the HAAs, there
are nine halonitromethanes (HNMs).
Trichloronitromethane (also known as
chloropicrin or TCNM) was one of the
unregulated DBPs surveyed in the ICR.
By-Products of Potential Concern in
Drinking Water Treatment discusses
the formation of chloropicrin with chlorine,
chloramine, chlorine dioxide, and ozone
in the presence of nitrite. Chlorination
of phenols in the presence of nitrite can
form nitrophenols, which are chloropicrin
precursors. Research has shown that
pre-ozonation can increase the formation
of chloropicrin or other HNMs upon
post-chlorination.
48
Similar results were obtained in the ongoing

project#4063, Exploring Formation and
Control of Emerging DBPs in Treatment
Facilities: Halonitromethanes and Iodotrihalomethanes, which investigated
the formation and speciation of HNMs
during drinking water treatment. The
study investigated the effect of several
disinfection processes and combinations
on the formation of HNMs. Results showed
that HNM formation was greatest from
ozonation-chlorination, confirming
previous results found in Occurrence and
Formation of Nitrogenous Disinfection
By-Products. Comparatively, other
disinfection strategies formed HNMs in
the order of ozonation-chlorination >>
chlorination ozonation-chloramination >>
chloramination. This is in agreement with
the previous observations that ozonation
significantly enhanced TCNM formation.
Chloramination after ozonation or
chloramination alone significantly reduced
HNM formation.
Project#4063 also examined the formation
and speciation of HNMs in wastewater
treatment plant effluents. Similar results
to those for drinking water treatment were
obtained. HNM formation was greatly
reduced by applying monochloramine,
especially after ozonation. However, when
formation potential tests were used to
compare HNM yields from treated drinking
water and treated wastewater, the results
showed that HNM yields were higher
in the wastewater effluents than in the
treated drinking water. This indicated that
HNM precursors in the treated wastewater
are significantly more reactive than the
hydrophilic NOM in treated drinking water.
The project also found that the presence
of bromide and nitrite in water increased
HNM formation. Monochloramination
alone did not form any measurable
HNMs. No significant amounts of HNMs,

even in the presence of bromide, were
formed. However, the presence of nitrite
significantly increased HNM concentrations
during chlorination.
Although not a DBP per se, organic
chloramines have been known to form
during chloramination of drinking water.
They present a problem for water utilities
because they can reduce the likelihood that
the desired inorganic chloramine will form.
Furthermore, organic chloramines interfere
with N,N-diethyl-p-phenylenediamine
(DPD) analysis of combined chlorine
residuals. This interference causes a
false indication of disinfectant residuals
because organic chloramines are much
weaker disinfectants than free chlorine
or inorganic chloramines. Therefore,
understanding organic chloramine
formation is important to achieve adequate
disinfection of pathogens and prevention
of microbial regrowth in water distribution
systems. Ongoing project#4065, Organic
Chloramine Formation in Water
Distribution Systems and Influence on
Disinfection Efficacy and Nitrification,
quantified organic chloramine yields
upon exposure of biofilms to free chlorine
or monochloramine and evaluated the
biocidal efficacy of organic chloramines.
The research team found that biofilm
and biomass can be organic nitrogen
sources and that their chlorination
and chloramination can form organic
chloramine. Also, the team found that
formed organic chloramines do not
inactivate microorganisms.
Control and Minimization
Several Foundation reports provide
recommendations for minimizing
nitrosamine formation. However, because
the formation pathways for nitrogenous
DBPs differ, minimization strategies for
nitrosamines do not always correlate with

those for other nitrogenous DBPs, such
as HNMs, CNXs, HANs, or TCNM. In fact,
strategies to control one class of DBPs often
result in increased formation of another
class, so unintended consequences must be
considered when making treatment changes.
DBP control strategies include ways
to treat or minimize DBP precursors
prior to disinfection as well as strategies
to minimize DBP formation during
disinfection. The first opportunity to
minimize nitrogenous DBP formation
is through source water selection. Since
treated wastewater is a source of DON
and thus a possible source of precursors
for nitrosamines, HNMs, and HANs,
wastewater-impacted surface waters are
more prone to formation of nitrogenous
DBPs. This has been demonstrated by
multiple reports:
Factors Affecting the Formation of
NDMA in Water and Occurrence
Contribution of Wastewater
to DBP Formation
Strategies for Minimizing Nitrosamine
Formation During Disinfection (2008,
order#91209/project#2979)
Occurrence and Formation of
Nitrogenous Disinfection By-Products
Water utilities that have no alternative to
using wastewater-impacted surface water
should consider treatment processes to
remove nitrogenous DBP precursors as
discussed below.
Another way utilities can minimize
nitrosamine precursors is to minimize
the use of amine-based polyelectrolytes,
as these have been found to promote
significant nitrosamine formation upon
chlorination and chloramination. Factors
Affecting the Formation of NDMA in Water
49
and Occurrence first identified NDMA

formation potential from chlorination of
dimethylamine polymers and recommends
that dosage rates of such polyelectrolytes be
minimized to be consistent with turbidity and
other water quality objectives. Occurrence
and Formation of Nitrogenous Disinfection
By-Products advises utilities to especially
minimize the use of coagulation polymers
featuring tertiary amines. Since these polymers
are thought to be removed by filtration, an
alternative or additional precaution is to
hold off adding chlorine or chloramine until
the filter effluent. Strategies for Minimizing
Nitrosamine Formation During Disinfection
proposes the use of membrane technologies
for separation to reduce the need for polymers
and thus help eliminate this nitrosamine
precursor source. Also, as stated in the
previous section, certain anion exchange
resins used to remove inorganic contaminants
and NOM have been found to serve as
precursors for nitrosamines. Anion Exchange
Resins as a Source of Nitrosamines and
Nitrosamine Precursors, will investigate this
further and identify treatment schemes and
conditions to be avoided in order to prevent
nitrosamine precursors from leaching.
In addition to minimizing N-DBP
precursors, removal of precursors is an
option for controlling N-DBPs. Strategies
for Minimizing Nitrosamine Formation
During Disinfection recommends that
utilities consider treating water sources with
slow sand filtration, artificial groundwater
recharge, or riverbank filtration, all of
which have been found to reduce levels
of nitrosamine precursors. Besides the
removal of nitrosamine precursors, these
treatment steps have the added benefit of
reducing concentrations of nitrosamines
already present in surface waters. Biological
filtration is also capable of removing
significant levels of HNM precursors and
aldehyde precursors for CNXs, according to
50

Disinfection By-Products. While neither
study showed coagulation or lime softening
to be efficient at removing nitrosamine
precursors, Occurrence and Formation
of Nitrogenous Disinfection By-Products
found these treatment options capable of
removing approximately 30% of precursors
for CNXs and HANs. This study also
found lime softening capable of removing
approximately 30% of HNM precursors.
However, conventional treatment processes
do not remove HNM precursors from
water, according to a nearly complete
project, Exploring Formation and
Facilities: Halonitromethanes and Iodotrihalomethanes.
Another option for minimizing N-DBP
formation is pre-oxidation of precursors.
In Strategies for Minimizing Nitrosamine
Formation During Disinfection,
laboratory-scale experiments as well as
full-scale tests at several water utilities
proved that oxidation is an efficient tool
for removal of nitrosamine precursors.
Reduction in NDMA formation rates
of greater than 90% were observed
after pre-ozonation as well as after
pre-chlorination. Likewise, Occurrence
and Formation of Nitrogenous
Disinfection By-Products found
application of chlorine or ozone upstream
of chloramine will hinder nitrosamine
formation. It also found free chlorine
will rapidly destroy CNXs. However, in
this same study, pre-oxidation with chlorine
promoted the formation of regulated DBPs
and HANs. While pre-oxidation with ozone
promoted the formation of HNMs and
CNXs, HNMs and CNXs can be removed
by biological filtration.
In addition, pre-ozonation can increase
bromate formation, and, as stated in
the previous section, HNM formation

is likely to be most problematic at
plants using ozonation followed by
chlorination. Exploring Formation and
Facilities: Halonitromethanes and
Iodo-trihalomethanes recommends
chloramination and ozonation followed
by chloramination as an effective way to
minimize HNM formation. Pre-oxidation
steps have to be carefully optimized with
respect to location, dose of oxidant, contact
time, and pH in order to optimize oxidation
efficiency and minimize both regulated and
emerging DBP formation. Development
of a Protocol to Predict the Formation
of Nitrosamines While Minimizing the
Formation of Regulated DBPs is focusing
on optimizing disinfection strategies to
balance the formation of regulated DBPs,
nitrosamines, and other emerging DBPs of
health concern.
In general, the different characteristics of
THM and N-DBP precursor material suggest
that treatment process units designed for
THM precursor removal may not be as
successful at N-DBP precursor removal.
Fortunately, conventional treatment
designed to remove organic acids removes
comparable percentages of organic colloids,
thus contributing to the reduction of a
major pool of N-DBP precursors.
Optimizing operational parameters in the
disinfection process is another possibility
for minimizing nitrogenous DBP levels.
Using lower chlorine/chloramine doses
leads to a reduction of all DBP levels,
although this may not always be practical.
Strategies for Minimizing Nitrosamine
Formation During Disinfection found
that lowering pH is also an option,
as nitrosamine formation during
chloramination is more efficient at pH
values of 8 and above compared to a pH of
around 7. Development of a Protocol to

Predict the Formation of Nitrosamines
while Minimizing the Formation of
Regulated DBPs found HNM formation
to increase with pH too so lowering pH
should help reduce HNMs. However, when
changing operational parameters, the
microbiological safety of the disinfected
water, as well as possible corrosion
problems, must always be taken into
account. In most cases, the use of chlorine
(or hypochlorite) as the disinfectant instead
of chloramine will also lead to significantly
lower nitrosamine formation, but this
comes with an associated increase in
formation potential for regulated DBPs.
A more promising strategy is to
chloraminate by adding chlorine far
enough ahead of ammonia to allow
sufficient free-chlorine contact time to
oxidize nitrosamine precursors prior
to ammonia addition. In lab-scale
experiments conducted in Strategies
for Minimizing Nitrosamine Formation
During Disinfection, this strategy was
also found to minimize the production of
dichloramine, which reacts with nitrogencontaining precursors to form NDMA
much faster than monochloramine does.
Nitrosamine formation potential tests
conducted as part of Contribution of
Wastewater to DBP Formation showed
that a short free-chlorine contact time
(e.g., 25 minutes) before chloramination
minimized THM formation but resulted
in NDMA formation greater than 10 ng/L,
whereas a longer free-chlorine contact
time (e.g., 2060 minutes) resulted in
minimal NDMA formation, but produced
THM levels close to or greater than the
maximum contaminant level. Thus, as
with the pre-oxidation strategy identified
above, additional research is necessary
to investigate and optimize this strategy
in order to minimize and balance the
51
formation of all DBPs. The aforementioned

project, Development of a Protocol to
While Minimizing the Formation of
Regulated DBPs, will help in this regard.
Occurrence and Formation of
Nitrogenous Disinfection By-Products also
recommends future research to evaluate
nitrosamine concentrations in distribution
systems since, as mentioned in the previous
section, formation studies indicate that
distribution system concentrations could
be more significant due to slow formation
kinetics. To combat this potential problem,
this research suggests that nitrosamine
formation could be minimized over
extended contact times within distribution
systems by minimizing dichloramine
formation. Dichloramine formation can be
minimized by adding chlorine upstream of
ammonia, elevating pH, and minimizing
the free chlorine to ammonia molar ratio.
Unfortunately, minimization of the free
chlorine to ammonia molar ratio may
promote nitrifying biofilms, which is
another area in need of research. When
utilities apply free chlorine to nitrifying
sections of distribution systems to hinder
the growth of nitrifying biofilms, care
should be taken to ensure a significant
free chlorine residual to avoid enhanced
nitrosamine and cyanamide formation
during chloramination near the breakpoint.
However, the potential for significant
nitrosamine and nitramine formation via
the reaction of free chlorine with nitrite
in these regions should be evaluated.
Project#4242, Fate of Non-Regulated
DBPs in Distribution Systems, will
investigate the formation, biodegradation,
and abiotic degradation of multiple classes
of non-regulated DBPs, including NDMA.
Post-treatment removal of nitrogenous
DBPs formed during disinfection is not
readily feasible in the United States since
52
chlorination or chloramination is typically

the final treatment step before distribution.
Furthermore, the options for nitrogenous
DBP removal are limited, given the findings
presented above. For nitrosamines that
enter a drinking water treatment plant,
UV has been shown in several studies
to degrade NDMA. One such study was
published as Innovative UV Technologies
to Oxidize Organic and Organoleptic
Chemicals (2004, order#91033F/
project#2599). However, the UV doses,
and thus energy, required for substantial
NDMA degradation are significantly
higher than those required for equivalent
Cryptosporidium inactivation. Moreover,
Disinfection By-Products observed
some of the highest NDMA formation at
wastewater-impacted treatment plants
employing chloramine combined with
UV. To further investigate the impact of UV
and disinfectant combinations on a suite
of regulated and non-regulated DBPs as
well as nitrite/nitrate, there is an ongoing
project#4019, Impact of UV Location and
Sequence on By-Product Formation.
Iodinated DBPs
Iodinated DBPs (I-DBPs) are a

relatively new area of concern, thus our
understanding of their formation and
control is very limited. Although iodinated
THMs (I-THMs) have been the subject of
several studies, mainly because of their
association with medicinal tastes and odors,
iodinated acids (IAs) are getting increased
attention because of their cytoxicity and
genotoxocity. By-Products of Potential
Concern in Drinking Water Treatment
will provide detailed information on their
formation and occurrence in drinking water.
I-DBPs can form under both chlorination
and chloramination conditions. However,
data shows that their formation is favored
under chloramination conditions.
Methods, Monitoring, Formation,

and Occurrence
While the mechanisms of formation for
I-DBPs are known, our understanding of
their formation in real water treatment
scenarios has been somewhat limited
because, until recently, methods were
not sensitive enough to detect the low
levels of I-DBPs formed in real waters. As
stated above, I-DBPs can form from both
chlorination and chloramination of iodinecontaining water. However, the formation
of I-DBPs appears to be favored during
chloramination, especially when chlorine or
ozone is used as a pre-oxidant. The reaction
pathway that leads to these DBPs is favored
when either preformed chloramine is used
or ammonia is added before chlorine. In
full-scale drinking water plant operations,
the presence of multiple reaction
precursors may prevent the complete
oxidation of iodide to iodate, allowing for
some formation of iodine-containing DBPs.
Project results obtained to date show

that chlorinating prior to ammonia
addition may not always result in lower
I-THM concentrations than preformed
chloramine, which simulate the addition
of chlorine and ammonia at the same
location in practice. On the contrary, prechlorination increased I-THM formation
under some circumstances. For preformed
chloramination, the results demonstrated
that I-THM formation depends on the
ratio of iodide to DOC (I-/DOC) and
characteristics of NOM. I-THM species
formed when the I-/DOC ratio was high
and more I-THM formation was observed
in waters with low Specific Ultraviolet
Absorbance (SUVA) rather than high SUVA.
Therefore, higher I-/DOC ratios will be
necessary in high-SUVA waters for I-THM
formation to occur. For pre-chlorination
followed by ammonia addition, Cl2/DOC
ratio was found to be one of the critical
parameters to control both the extent of
THM and I-THM formation and the ratio
of THMs to I-THMs in a water sample.
Results also show that I-THM formation
is not prevented by practicing 20 minute
pre-oxidation with permanganate, chlorine
dioxide, or hydrogen peroxide. As with
pre-chlorination, I-THM formation
increased under some circumstances due to
reactions of the pre-oxidants with NOM or
chloramine. Research on I-THM formation
and speciation is still ongoing.
One of the objectives of the project,

Exploring Formation and Control
of Emerging DBPs in Treatment
Facilities: Halonitromethanes and
Iodo-trihalomethanes, is to gain a better
understanding of I-THM formation. In order
to accomplish this objective, the project
systematically investigated the formation
of I-THMs during disinfection of drinking
waters and wastewater treatment effluents.
The roles of several important factors
Although methods for I-THMs already
were examined, including alternative preexist, only semi-quantitative methods with
oxidation strategies, optimization of time
limited application for fate and occurrence
interval between ammonia and chlorine
have
been available for IAs. Project#3175,
addition, bromide, and pH. In addition,
Iodinated Acids and Iodide Drinking
DBP formation potential tests were
Water Supplies: Method Development
conducted with raw and treated drinking
for Nanogram-per-Liter Levels of
water samples and various fractions of
Detection Relevant for Application
NOM. I-THM formation under uniform
in Occurrence Surveys, developed a
formation conditions was then investigated
quantitative method for the extraction
to evaluate the effects of the factors
and analysis of 4 target IA species (as
mentioned above.
53
low as 20ng/L). The method combines

liquid-liquid extraction with solid-phase
extraction to clean up the sample and
methylation of the isolated acids. A limited
occurrence survey showed that IAs were
found at each of the chloramination plants
studied. The survey included high bromide
waters from a diverse group of geographical
locations in the United States (coastal and
inland communities impacted by various
sources of salinity). Concentrations for
individual species ranged from 5.7 ng/L for
diiodo acetic acid in one of the treatment
plant effluents studied to 376 n/L for
mono-iodoacid I in one of the distribution
systems. IA concentrations were impacted
by pre-oxidation; less was formed during
post-chloramination after ozonation or
long free chlorine contact times. Typically,
bromine incorporation into IAs was similar
to that of the HAAs, in particular to that of
the dihaloacetic acids. IAs were found to be
stable in the distribution systems studied.
In general, the concentrations did not
increase except at one of the plants.
Iodinated DBPs Control and Minimization
As with formation, knowledge regarding
control and minimization of I-DBPs is
still somewhat limited. Although the
aforementioned project, Exploring
Formation and Control of Emerging
DBPs in Treatment Facilities:
Halonitromethanes and Iodotrihalomethanes, is not quite complete,
some important conclusions can already
be drawn from the study. Because prechlorination increased I-THM formation
under some circumstances (as stated
above), pre-chlorination strategy requires
a balanced and water specific approach to
control both I-THMs and other DBPs. For
pre-chlorination followed by ammonia
addition, the ratio of chlorine to DOC was
found to be one of the critical parameters to
54
control both the extent of THM and I-THM

formation and the ratio of THMs to I-THMs
in a water sample. The optimum Cl2/DOC
ratio to control both the concentrations
of THMs and I-THMs will need to be
determined for specific source waters.
This research project is still ongoing.
When complete, the results should further
identify strategies to control the formation
of I-THMs. The final report is expected to
be published in 2010.
Other Non-Regulated DBPs
In addition to N-DBPs and I-DBPs, many

other non-regulated DBPs have been
identified, and still others remain unknown.
Total organic halogen (TOX) can be used as
a non-specific surrogate measurement of
the total halogenated DBPs formed upon
the reaction of halogenated disinfectants
with NOM. THMs and HAAs constitute
only a portion of the TOX. The Foundations
Information Collection Rule Data Analysis
looked at TOX concentrations in influent
water as well as finished water. The data
showed that only 5.6% of the surface water
plants reporting had measurable (>50g/L)
TOX in the source water. Of the reporting
groundwater plants, 3.4% had measurable
TOX in the influent. It also reported that the
25th, 50th, and 90th percentiles in all finished
waters were <50, 102, and 242g/L TOX
respectively. Of the different disinfection
scenarios, the combination of chlorine
and chloramine produced the highest 50th
percentiles and chloramine alone had the
highest 90th percentile. That level may be due
to systems that have high NOM levels and
adopted chloramine to comply with the THM
and maximum contaminant level (MCL).
The analysis attempted to correlate TOX
with TTHM and HAA5 with limited success.
Previous articles showed high correlation
only when source water supplies and
treatment methods were similar. Neither

TOC, UV254, and pH correlate well with TOX.
It also showed that, on average, 2040% of
TOX was accounted for by THMs and HAA5.
While USEPA was the driving force and
implementer of the ICR, Information
Collection Rule Data Analysis added value
in that much understanding was gained
in regard to issues such as TOX and DBP
correlation that could never be validated
without a very large sample size.
One significant contribution of the
report, Comparative Genotoxicity
Assessment of DBPs in Drinking Water
(2003, order#90939/project#554), was the
development of a new method that could
differentiate between the chlorine and
bromine components of TOX. The method
was used to characterize DBPs produced
from selected waters and Suwannee River
fulvic acid samples in terms of known
compounds, TOX, total organic chloride
(TOCl), and total organic bromine (TOBr).
In addition, the percentage of TOX
attributable to known compounds was
evaluated for chlorination, chloramination,
bromination, and chlorine dioxide
treatment. The study found that in all cases,
the majority of the TOX was attributable to
unknown compounds. Chlorination yielded
the highest TOX but also the greatest
fraction of identifiable compounds.
One question left to be answered was
the prominence of unidentified TOX.
Characterization of Total Organic
Halogen Produced During Disinfection
Processes (2007, order#91176/
project#2755) was a study of the nature
and content of NOM and TOX produced by
disinfection. The researchers refined the
TOX method such that they were able to
achieve complete recovery of TOCl, TOBr,
and total organic iodine (TOI) in model
compounds. As mentioned previously in

the N-DBP section, bromine incorporation
was shown to be more prevalent in
HANs than in THMs and HAAs. The TOX
produced by chloramine disinfection
was significantly less than that produced
by chlorine as expected since chlorine
is a stronger oxidant. Ozone prior to
chlorination produced less unknown TOX
(UTOX), but ozone prior to chloramination
actually increased the amount of UTOX.
The project also showed that chlorination
of high molecular weight and hydrophobic
NOM produced more THMs, HAAs, and
UTOX than the transphilic, hydrophilic,
and low molecular weight NOM. Higher
pH favored the formation of THMs and
HAAs over UTOX. Bromine and iodine were
more reactive with the hydrophilic and low
molecular weight NOM.
In addition to N-DBPs and I-DBPs, ByProducts of Potential Concern in
Drinking Water Treatment presents
information on several other classes of
non-regulated DBPs, such as haloketones,
haloadehydes, and halogenated furanones.
It is well known that ozonation of NOM
can produce non-halogenated DBPs
such as aldehydes, carboxylic acids, and
ketoacids. Identification and Occurrence
of Ozonation By-Products in Drinking
Water (1993, order#90625/project#510)
investigated the formation of several
by-products of ozonation in lab scale
experiments and confirmed their presence
in water samples from selected treatment
plants. Study results showed that the
most significant aldehydes formed were
formaldehyde, acetaldehyde, glyoxal, and
methyl glyoxal. The formation of these
compounds is also presented in ByProducts of Potential Concern in Drinking
Water Treatment. Results indicate that
some of these simple, partial oxidation
products can also be formed during
55
chlorine dioxide (ClO2) oxidation. Because

these oxidation by-products are highly
biodegradable, utilities that use ClO2 should
consider the subsequent use of biological
filtration as practiced at many ozone plants.
phenazine and chlorophenazine, along with

N-nitrosodiphenylamine in chloraminated
water. Further investigation of precursors,
formation, and occurrence of phenazines
is underway.
In addition to DBPs that have actually been

detected in water, the use of structuretoxicity relationship predictive models
has identified potential DBPs with a high
probability of being potent carcinogens or
developmental toxicants. Building upon the
report, Use of Toxicological and Chemical
Models to Prioritize DBP Research (2006,
order#91135/project#2867), project#4089,
Method Development for Disinfection
By-Products Associated With Bladder
Cancer, is developing sensitive and
reliable analytical tools to verify the
formation and occurrence of these
predicted DBPs (haloquinones, organic
chloroamines, halonitriles, nitrosamines,
and cyclopentenoic acids) upon
chlorination and chloramination of water.
In addition to the chemical methods,

the research team has evaluated the
cytotoxicities and genotoxicities of organic
N-chloramines to prioritize further
studies. Fifteen organic chloramines have
been tested for their genotoxicity in the
micronucleus assay (some as mixtures with
their dichloramines). Four of these have
been shown to be genotoxic. Chemical
methods for target N-chloramines,
halopropionitriles, and halobutyronitriles
are being developed for use in future
occurrence studies. This project is expected
to be completed late 2010.
The research team has developed a highly

sensitive and selective liquid chromatography/
tandem mass spectrometry method
(LC/MS) for analysis of haloquinones
at low ng/L levels. DCBQ (2,6-dichloro1,4-benzoquinone) has been consistently
found in chlorinated and chloraminated
drinking water. Subsequent investigation
of DCBQ in drinking water distribution
systems has found higher levels at the
water treatment plants than in the
distribution systems, which is attributed
to the instability of DCBQ in water.
DCBQ concentrations may also undergo
seasonal variation. The occurrence of
haloquinones in water supply systems
from various raw waters is being studied
along with the occurrence of nitrosamines
and related compounds in chlorinated
and chloraminated water. In addition,
the project has identified two new DBPs,
56
Control and Minimization

There are many additional classes of
DBPs that are not currently regulated in
the United States and optimizing treatment
strategies to minimize and balance the
formation of all DBPs is an area in need
of further research. The aforementioned
project, Development of a Protocol to
While Minimizing the Formation of
Regulated DBPs, will help solve this need
by developing a bench-scale protocol for
predicting the formation of nitrosamines,
regulated DBPs, and other emerging
DBPs of health concern. Contribution
of Wastewater to DBP Formation found
that treated wastewater can be a source of
haloacetaldehyde precursors. Therefore, just
as is the case for minimizing nitrosamine
formation, the first opportunity for drinking
water utilities to minimize haloacetaldehyde
formation is through source-water selection.
Non-halogenated DBPs formed during
ozonation and chlorine dioxide oxidation,
such as aldehydes, carboxylic acids, and

ketoacids, are highly biodegradable and can
thus be mitigated by subsequent biological
filtration, according to research summarized
in a project soon to be published by the
Foundation, By-Products of Potential
Many utilities are considering UV
disinfection to obtain Cryptosporidium
inactivation credit for the Long-Term
2 Enhanced Surface Water Treatment
Rule (LT2ESWTR), while simultaneously
complying with the Stage2 Disinfectants/
Disinfection By-Product Rule (DBPR)
and minimizing the formation of nonregulated DBPs. Past research has
shown that UV does not contribute to
significant formation of DBPs. Whether
the location and sequence of UV when
used in combination with chlorine and/

or chloramine impacts DBP formation is
the subject of the project, Impact of UV
Location and Sequence on By-Product
Formation. This project is investigating
several classes of by-products, including
oxidation by-products, halogenated DBPs,
and nitrogenous DBPs. Another area in
need of research for other non-regulated
DBPs is their fate in the distribution system.
Another project discussed previously,
Fate of Non-Regulated DBPs in
Distribution Systems, will investigate
the formation, biodegradation, and abiotic
degradation of multiple classes of nonregulated DBPs. However, the full DBP
list has not yet been determined.
57

Localized Treatment for DBPs
Mao Fang and Laura Jacobson, Las Vegas Valley Water District, Nevada
The Las Vegas Valley Water District (LVVWD) provides water to about 1.2 million people. Water age can be 12 to 15
days at the extremities of the distribution system because of the size of the area served. Due to the long detention time
in the distribution system, total trihalomethanes (TTHMs) at several locations can approach and exceed the Stage2
Disinfectants/Disinfection By-Products Rule (DBPR) TTHM limit of 80g/L. It would be extremely expensive and of
little value to treat for DBPs at a centralized location because of the size of the central treatment plants. The project
objective was to provide information on how well simple treatment processes might perform in the distribution system
for removing TTHM and 5 haloacetic acids (HAAs).
The LVVWD uses a water distribution system modeling approach to track and address water quality issues. To
address TTHM issues in its distribution system, the LVVWD has employed operating strategies to reduce water age
in its distribution system. A real-time based water age simulation program was developed to assist with day-to-day
operational planning activities. Using the program to evaluate water age results, the LVVWD successfully reduced water
age in problem areas through refinement of its daily operating strategies. Although the TTHM levels are well controlled
as a result, TTHM reduction through operating strategies may be vulnerable to changes in local water demand,
limitations in distribution network configuration, and potential variations in water temperature and organic matters.
The LVVWD further enhanced this approach by evaluating the concept of using decentralized or localized DBP
treatment as an alternative to typical centralized treatment methods such as chloramination. This concept has the
following unique characteristics and requirements:

The treatment targets local areas where the distribution system may have a greater potential to form high DBPs.
The treatment facilities are installed within the water distribution network.
The treated water needs to meet local hydraulic conditions and operating criteria for water distribution.
Adequate chlorine residual must be maintained or restored after treatment.
Treated water may be mixed with the non-treated water after DBP treatment.
From 2004 to 2007, the LVVWD actively participated in a Water Research Foundation tailored collaboration project,
entitled Localized Treatment for Disinfection By-Products (2009, order#91254/project#3103). A pilot-scale study
of three different localized treatment technologies (air stripping, granular activated carbon, and biological activated
carbon) for reduction of DBPs was conducted. The project demonstrated that localized treatment of DBPs is a viable
approach to meeting the Stage 2 DBPR.
As a result of this project, the LVVWD focused on air stripping as the most cost effective technology for the LVVWD to
use in its water distribution system where HAA5 treatment was not required. The pilot testing results for air stripping
technology indicated that:
58
Air stripping was effective for TTHM removal (75 to 85%) at air-to-water ratios of 40 to 45:1.
Air stripping did not remove a significant amount of chlorine (less than 10%).
Water temperature differences of 6C did not significantly affect TTHM removal.
After air stripping treatment to reduce TTHM, TTHM will continue to form at about the same rate as before
treatment.
As expected, air stripping was not effective for HAA5 removal.
This study enabled the development of a conceptual design for a full-scale air stripping plant at a remote reservoir.
The conceptual design identified the following issues:

Both water pumps and air blowers would be necessary.
Noise reduction measures would be required for the commercially available water pumps and air blowers to
minimize impacts to adjacent residents.
The height of the air strippers would need to be restricted to avoid visual impacts to adjacent residents.
Available low-profile air strippers would meet height restrictions, but would also be limited in flow capacity for
treatment.
A large space would be required to accommodate multiple low-profile air stripping units.
To identify other improvement options and further reduce implementation costs, the LVVWD researched fine-bubble
aeration technology as an alternative to air stripping using a model based on Henrys Law. The model results were also
well represented by the extended curve of air to water ratios versus TTHM removal derived by the Foundation project.
The benefits of using fine bubble aeration included no pumping requirements, energy efficient blowers, and reduced
space for equipment.
The design of a full-scale fine-bubble aeration treatment installation was recently completed and is currently under
construction at the Alta Reservoir site. The LVVWD performed worst-case air emission calculations of volatile organic
compounds to demonstrate air quality compliance. The treatment plant aims at 40% of TTHM removal during high
water age winter months when approximately 5 million gallons per day (mgd) of water is treated. It is also estimated
that over 20% of TTHM removal is achieved during low water age summer months when approximately 10 mgd of
water is treated. The total construction cost for this project is approximately $1.8 million. Construction is scheduled
to be completed in March 2010.
After the fine-bubble aeration system is installed and operational, field testing will be carried out to investigate TTHM
removal efficiency and reformation potential, to monitor water quality parameters such as temperature and chlorine,
and to study effects of varying air-to-water (A/W) ratios and other design considerations. Effects of reservoir aeration
on water mixing and the potential impact to pumping operations will also be evaluated. The field data will be used to
calibrate the aeration model and the distribution system TTHM model. The LVVWD long-term TTHM control plan will
be updated on an ongoing basis to ensure compliance with the Stage 2 DBPR.
59
Health Effects of Disinfection By-Products
Health Effects of DBPs

The use of chlorination in drinking water
has led to a substantial reduction in deaths
and illnesses from waterborne pathogens
and its benefits for public health protection
are well established. However, research
in the early 1970s showed that chlorine
reacts with natural organic matter (NOM)
to form DBPs raising concerns of potential
health risk. Following the discovery of
trihalomethanes (THMs), a considerable
research effort has been dedicated to
their formation, control, and whether
they pose a public health risk, mainly in
the form of cancer or adverse reproductive
outcomes. Several epidemiological studies
reported a modest increase in the risk of
bladder cancer associated with exposure
to chlorination by-products. Studies of
colon and rectal cancer are less consistent.
In order to minimize exposure and reduce
the risk of potential health effects, U.S.
regulations have concentrated on THMs
and haloacetic acids (HAAs) as the most
prevalent and as surrogates for other
DBPs. Today, major advances in analytical
methods have allowed the identification of
more than 300 DBPs and there is now strong
evidence that some of these emerging
DBPs may be associated with adverse
health effects.
While the Water Research Foundation
does not initiate or take the lead on
original health effects research (e.g.,
epidemiological or dose-response studies),
the Foundation does partner selectively
on such studies and also funds research
to synthesize, analyze, and critically
review the results of health effects
research. Several Foundation projects have
contributed to epidemiologic studies on
cancer and reproductive risks associated
60
with DBPs and to studies that improve

understanding of DBP toxicology.
Following the discovery of THMs, the
Foundation undertook several research
efforts aimed at assessing the health
significance of disinfectants and DBPs.
The objective of the Foundations first
international collaboration, Chlorination
By-Products: Production and Control
(1986, order#90512/project#224), was
to review results of investigations on the
formation and toxicological effects of THMs.
The study evaluated information reported
in the literature on the toxicological effects
of the use of chlorine, chlorine dioxide,
and chloramine. At the time, no data
reported in the literature indicated that
chlorine, chlorine dioxide, and chloramine
or their by-products exert acute or chronic
health effects. The review did not identify
any carcinogenicity or mutagenicity
from the disinfectants themselves and,
other than chloroform, no carcinogenic
effect was established for the reaction
by-products. However, it was found that
the use of chlorine, chlorine dioxide, and
chloramine lead to the formation of
mutagenic compounds. Chlorine appeared
to produce higher levels of mutagenicity
than comparable doses of chlorine dioxide
or chloramine. Generally, epidemiological
investigations did not reveal any causative
relationship between products formed by
chlorination and health effects. However,
some investigations suggested a relationship
between reaction products and tumors of the
bladder, large intestine, and colon. The study
recognized the limitations of the available
data and recommended that more research
be done to assess the formation, occurrence,
and health significance of low and high
molecular by-products.
Another report, Health Effects of

Disinfectants and Disinfection ByProducts (1991, Order #90577/project#501),
was initiated to review toxicological effects
identified with drinking water disinfectants
and their by-products by taking into
consideration anticipated regulations
that might restrict the use of alternative
disinfectants. Similar to Chlorination
By-Products: Production and Control,
the study determined that there is likely
no significant risk from chlorine at the
levels commonly used in disinfection.
No recommendation was provided for
chloramine as results from the National
Toxicology Program carcinogenesis bioassay
were not available at the time. Chlorine
dioxide was determined to be a risk above
0.2 mg/L. In terms of by-products, the
largest database existed for chlorination byproducts. In this group, compounds present
in the highest concentrations had received
considerable attention and could be ranked
(in descending order of importance)
as: chlorinated acetic acids, THMs, and
haloacetonitriles. When comparing
chlorine and chloramine, assuming that
chloramine by-products were similar to
that of chlorine, the study suggested
that the use of chloramine could reduce
potential cancer risks in a given water
supply by as much as 80%.
The report concluded that because of
the great variability in the available
toxicological data for most commonly
considered alternative disinfectants and
uncertainty in the data, additional research
was needed to truly quantify the risks.
Building on the studies described above,
Health Effects and the Occurrence
of Disinfection By-Products (2001,
order#90827/project#448) reviewed and
evaluated data that has been collected
on the relationship between exposure
to DBPs and the potential occurrence of

human disease. The study provided an indepth analysis of existing epidemiological
and toxicological data to determine
qualitatively and quantitatively the health
risk associated with DBPs. The study found
a large difference in the two data sets,
with the epidemiological data pointing
to a high level risk of bladder cancer
from chlorinated drinking water and a
lesser threat of colon cancer; however the
toxicology data pointed to risks of liver,
kidney, and colon cancer, but at much lower
risk levels. The study concluded that the
difference was that toxicology studies were
focused on individual compounds, whereas
epidemiology looks at the whole picture
and that there could possibly be risks
associated with yet unknown compounds
in chlorinated drinking water. The report
provides some guidance to utilities
regarding treatment options that might be
used to minimize problems related to DBPs.
Key factors for a successful epidemiology
study include a good experimental design
and good exposure data. Selection of
the appropriate location is also critical,
especially for reproductive effects. While
the temporal scale for chronic exposure
may be relevant for cancer risks, acute
exposure windows and the potential effect
of peak exposure levels would be more
appropriate for effects on reproduction.
Significant spatial and temporal variations
in DBP concentrations have been reported
in drinking water distribution systems. In
order to improve exposure assessment and
provide a good estimate of human exposure,
the report, Exposure Assessment Methods
for THM and HAA in Water Distribution
Systems (2001, order#90842/project#341),
used models that predict THM and HAA
concentration in distribution systems
to develop a link between these models
and ongoing reproductive and cancer
61
epidemiological research efforts. The

study used a demand/hydraulic modeling
simulation to predict individual exposure
and attempted to correlate THM levels
found water in distribution systems to
THM concentration in blood. This was
one of the first studies to test blood
levels of THMs. The study confirmed that
significant spatial and diurnal variations
of DBP concentrations can exist in a water
distribution system. However, true human
exposure is difficult to assess due to
individual water use activity, so that there
was great variation in the amount of THM
reaching the blood.
The first step for a high-powered
epidemiological study is to identify
appropriate study areas where occurrence
and health data was likely to be available.
Identifying Geographic Regions for
Potential Future Epidemiology Research
on Disinfection Byproducts (2001,
order#90810/project#384) was intended
to provide guidance and information to
help epidemiologists identify specific
locations that might serve as suitable sites
for investigations of the potential risks
posed by DBPs. To this end, the study
assembled a considerable amount of data on
adverse health effect outcomes (cancer and
reproductive effects), types and quantities
of health endpoint data and locations, and
relevant water quality characteristics. Data
from a wide variety of sources were compiled
and reviewed to examine these issues. The
most limited data was found to be in the
DBP-related occurrence area. The study
identified locations in which DBP exposure
scenarios of interest were likely to occur
and also where high quality health data
were likely to be available for a sufficient
population base to support relatively high
confidence, high power epidemiological
studies. In addition, the study provided a
description of several important issues in the
62
interpretation of DBP-related data that could

help in the development of better exposure
assessment studies.
Two well-documented epidemiology
studies carried out in 1987 and 1993 in
Iowa and Ontario, Canada have reported an
increased risk of bladder cancer associated
with chlorinated drinking water and THMs.
The objective of Improved Exposure
Assessment on Existing Cancer Studies
(2005, order#91062/project#2582) was to
reevaluate these epidemiological studies
using information that was not available at
the time these studies were conducted. DBP
exposure databases, initially used in these
studies, were submitted to DBP prediction
models to predict individual DBPs from
existing information on precursors, water
quality, and disinfection conditions.
Missing data on certain DBPs, including
bromodichloromethane (BDCM) and total
and specific HAAs were estimated from
other DBPs (e.g., THMs). The re-estimation
of DBPs of the Ontario data set resulted in
a more robust database, which was used
to calculate an average exposure over 50
years for three types of cancer including
bladder, colon, and rectal cancers. The
largest bladder cancer risk was found
linked with exposure to brominated byproducts: BDCM and bromochloroacetic
acid. For colon cancer, excess risk was only
observed in males and was linked with
total trihalomethane (TTHM) and HAA5
exposure. No excess risk was found for
rectal cancer.
Re-estimation of the Iowa DBP database
confirmed previously reported increased
risk for bladder and rectal cancer. While
no significant increase for colon cancer
was originally reported, the recalculated
exposure data showed a 64% excess risk
of colon cancer for males exposed to
high TTHM levels (>96g/L) compared
to males exposed to 0.5g/L. Excess risk

for bladder and rectal cancer for the top
exposure category (TTHM > 96g/L) were
equal to 80% and 166%, respectively. Excess
risks calculated for the three cancer types
in males were comparable or higher for
subjects exposed to levels of HAA6 greater
than 52.6g/L compared to very low
HAA6 levels. This improved DBP exposure
assessment supported some of the original
findings and further elucidated and
revealed other epidemiological trends.
Several studies have demonstrated that
exposure to DBPs can occur via several
routes: inhalation, dermal absorption, and
ingestion and that showering can result in
substantial transdermal exposure to DBPs.
The objective of Evaluating Alternative
Data Gathering Methods for the 1999
Disinfection By-Product Field Study (2005,
order/project#2831) was to evaluate the
correlation of actual post-shower-event
blood concentrations and the predicted
dose using a computer-based statistical
exposure model. The study focused on
THMs as they were the most common DBP
and were subject to maximum contaminant
level (MCL) regulations. Home visits
allowed for the evaluation of shower
performance and measurements of preand post-shower blood concentrations
of each of the four THMs. The study
showed that the most important factor
regarding exposure is the mass of chemical
entering the environment. This finding
was confirmed by both the theoretical and
empirical models. In spite of many obvious
variables and unknowns such as airflows,
time actually in the shower, mass transfer
coefficients, etc., the model showed strong
predictive capability.
Although cancer endpoints were the
focus of early epidemiological studies
and regulations, more recent studies have
raised concerns regarding the potential

effects of exposure to DBPs in drinking
water and reproductive and developmental
outcomes. The National Birth Defects
Prevention Study (NBDPS) was designed
to identify infants with major birth defects
and evaluate genetic and environmental
factors associated with the occurrence of
birth defects for the purpose of exposure
assessment in an epidemiological study of
birth defects. As part of this effort, Linking
Water Utility Data and Residences in
the National Birth Defects Prevention
Study (2004, order/project#2832) sought
to evaluate the feasibility of using public
record data to link DBP data from water
treatment facilities to the residential
addresses of participants in the NBDPS.
The study assessed the feasibility of several
methods designed to address exposure
assessment issues in the epidemiology
study of DBPs. These issues included
the significant spatial variability of DBP
concentrations that can occur within a
distribution system and the difficulty
encountered by many epidemiology
studies in matching participant address
history to specific water utilities during
critical periods of exposure. As a result,
methods to address each of these issues
were developed. The study recommended
that validation of each of these methods
was necessary prior to their application in
a national epidemiological study of DBPs
(specifically THMs) and birth defects.
Several epidemiology studies suggested
the possibility of adverse effects caused by
DBPs including early term miscarriages
and neural tube defects. Two reviews of 16
and 14 epidemiological studies discussed in
the Stage 2 Disinfectants/Disinfection ByProduct Rule (DBPR) showed inconsistent
results for fetal growth (often defined as
small for gestational age), fetal viability
(spontaneous abortion, stillbirth), and
63
fetal malformations. The objective of a

jointly funded project by the Foundation
and USEPA, Drinking Water Disinfection
By-Products and Pregnancy Outcome
(2005, order#91088F/project#2579), was
to address the hypothesis that exposure
to DBPs causes pregnancy loss. Key
methodology improvements over previous
studies were made in regard to the
assessment of DBP exposure, the range of
DBP exposure evaluated, and the quality
of assessment of pregnancy outcome.
Three study sites were selected to reflect
a wide range of DBP concentrations and
speciation typical of those found across
the United States. The study took into
account exposure by ingestion, plus bathing
and showering, and involved weekly or
biweekly examination of THM, HAA9, and
total organic halogen (TOX). The study
did not find the same associations relating
THM concentration combined with water
consumption to the risk of pregnancy
loss, as reported in previous research.
However, there were sporadic indications
of increased risk of pregnancy loss and fetal
growth restriction associated with higher
exposure to selected DBPs that may warrant
further consideration.
The levels of specific DBPs in a water
sample does not always reflect the true
levels to which an individual is exposed.
As mentioned earlier, exposure to DBPs
can occur via several routes: inhalation,
dermal absorption, and ingestion. The use
of biological measurements can provide
a better estimate of human exposure. The
use of blood as a biological marker to
estimate exposure has been investigated
in Body Levels of Haloacetic Acids from
Chlorinated Drinking Water (2005, order/
project#489). The greatest challenge to the
investigation of DBPs in the human body
has been the lack of appropriate analytical
64
methods. Methods used to analyze DBPs

in water cannot easily be applied in human
plasma, especially in the case of HAAs, as
they are polar along with much of human
serum. A gas chromatography/mass
spectrometry (GC/MS) method for detecting
HAAs in blood at picogram levels was
developed to use in this study. Treatment
of study volunteers with chlorinated water
containing various levels of DBPs showed
that increase in dose and treatment time
correlated with an increase of HAA levels
in the body. One important finding from
this study was that HAAs can be absorbed
from drinking water and enter the blood
circulation. However, the fate of these
compounds in the body was not investigated.
The use of biomarkers of exposure is
further illustrated in Identification and
Quantitation of DNA Adducts Derived
from DBPs (2003, order#90968F/
project#491). The main objectives of this
project were to characterize and quantify
DNA adducts derived from DBPs and
to study the effects of exposure to DBPs
on endogenous DNA adducts. DBPs
investigated were BDCM and chlorinated
hydroxyfuranones. The study demonstrated
that several carcinogenic DBPs do not form
direct DNA adducts and do not enhance
endogenous adducts. This indicates
that they are different from well known
genotoxic carcinogens.
Another research report was Effect of
Dichloroacetic Acid and Trichloroacetic
Acid on Cell Proliferation in B6C3F1 Mice
(1995, order#90700/project#738), which
looked specifically at dichloroacetic acid
(DCAA) and trichloroacetic acid (TCAA).
Mice were fed water with DCAA and TCAA
at 0.86 g/L and 0.32 g/L respectively. After
362 days it was concluded that those
levels were insufficient to promote liver
tumors. Furthermore, those levels were to

be considered thresholds for carcinogenic
activity in those mice.
The principal component of Comparative
Genotoxicity Assessment of DBPs in
Drinking Water (2003, order#90939/
project#554) was the development of
novel cytotoxicity and genotoxicity assays
that allowed analytical biology to be
integrated with analytical chemistry. The
project developed a rapid cytotoxicity assay
employing mammalian cells and optimized
the single-cell electrophoresis (SCGE) assay
to determine the genotoxicity activity of
specific DBPs. The study represents the
largest comparative cytotoxicity analysis
ever conducted of drinking water DBPs in
mammalian cells. It was shown that there
is a statistically significant correlation
between cytotoxicity and genotoxic potency
in mammalian cells.
Continuing on the track of yet
uncharacterized and unknown DBPs
being more toxic than known, Mammalian
Cell Cytotoxicity and Genotoxicity
of Disinfection By-Products (2009,
order#91249/project#3089) investigated
the mammalian cell chronic cytotoxicity
of priority DBPs and emerging DBPs.
The project compiled a database of
the cytotoxicity of 66 DBPs and related
chemicals. The rank of cytotoxicity
was diiodoacetamide highest and
bromodichloromethane lowest. By class, it
was haloacetaldehydes > haloacetamides>
halonitromethanes > haloacetonitriles>
2C haloacids > haloacetic acids >
halomethanes from highest to lowest.
Cell genotoxicity was also studied, which
found that iodoacetic acid was the most
genotoxic and chlorodibromoacetic acid was
the least. Another significant finding was that
nitrogen containing DBPs were more toxic

than DBPs that did not contain nitrogen.
Human Toxicogenomic Analysis of the
Monohaloacetic Acids (project#4132)
is evaluating the toxicity mechanisms of
iodoacetic acid (IAA), bromoacetic acid
(BAA), and chloroacetic acid (CAA). The
general hypothesis of this project is to
determine if IAA, BAA, and CAA of the
HAAs differentially modulate the expression
of human DNA damage/repair genes and
human toxic response genes. Some of the
objectives include determining the DNA
damage/repair kinetics of the mono HAAs
to Chinese hamster ovary (CHO) and
human embryonic cells. Concentrations
of each HAA that generate similar DNA
damage to the CHO and human cells were
chosen. Preliminary results seem to show
that CHO cells subjected to IAA, BAA,
and CAA expressed different DNA repair
kinetics. The DNA repair rate rank order
was IAA>CAA>BAA. This shows that BAA
exhibits the lowest rate of DNA repair and
may suggest different distributions of DNA
lesions by these HAAs. Future research
will evaluate the effect these HAAs have on
human embryonic cells. A comparison of
the genotoxic sensitivity of the human and
CHO cells will then be performed.
The application of ozone to bromidebearing source water results in the
formation of bromate. Bromate has been
shown to produce cancer of the kidney
in rats, mice, and hamsters, although
the potency across species varies widely
(rat>mouse>hamster). It also produces
thyroid tumors and mesotheliomas in
rats. Bromate is one of the 11 regulated
DBPs (four THMs, five HAAs, chlorite,
and bromate) The current MCL in the
United States is 10g/L and the MCL goal
(MCLG) is zero, because of the possibility
65
that bromate may function as a genotoxic

carcinogen. Recently, the Office of
Environmental Health Hazard Assessment
(OEHHA) has finalized a public health goal
(PHG) for bromate of 0.1g/L.
However, cancer risk assessments for
bromate have been based upon responses
in male rats. Research suggests that there
is a substantive contribution of a nongenotoxic mechanism to the carcinogenic
responses of the male rat kidney much
below the doses that induce mutation
and that utilizing the male rat data for
estimating cancer risks in humans is
inappropriate. Project#4042, Low Dose
Risks from Bromate: The Relationship
Between Drinking Water Concentrations
and the Actual Dose to Susceptible
Organs in Rats and Humans, will quantify
the pre-systemic and systemic metabolism
of bromate at low environmentally relevant
doses and will check the resulting detailed
quantitative pharmacokinetics model of
bromated metabolism in rats.
Preliminary findings show that bromate
could be measured in both blood and urine
even in the absence of exposure indicating
that it may be generated endogenously.
However, this endogenous formation
seems to be exacerbated by inflammation
resulting from catheters needed to facilitate
blood sampling. Approximately 20% of an
administered dose reaches the systemic
circulation suggesting that there is a
substantial first pass effect on bromate
absorption. Non-genotoxic mechanisms
are active in the kidney of male rats at lower
doses than those that produce measurable
genotoxic responses and proliferative
responses are also observed in other target
organs at minimally carcinogenic doses,
but no data exists related to genotoxicity in
these tissues.
66
As a significant amount of research has

been focused on finding associations
between cancer or reproductive effects on
already identified compounds (e.g., THMs
and HAAs), a novel approach is to use
structure-activity relationship to predict the
formation of possible DBPs with potential
carcinogenic or reproductive activity.
Use of Toxicological and Chemical
Models to Prioritize DBP Research
(2006, order#91135/project#2867) used
reasonably well known substructures of
NOM to predict DBPs likely to be formed
through various reaction pathways upon
chlorination. These probable DBPs were
then evaluated using quantitative structuretoxicity relationships (QSTR) to identify
DBPs most likely to possess carcinogenic
activities, or reproductive properties.
Probabilities of Ames mutagenic activity,
carcinogenic activities, and developmental
toxicities were made with the TOPKAT
model, using general data or data from
the carcinogen potency database (CPDB).
Several of the postulated DBPs were found
to have predicted chronic lowest observed
adverse effect level (LOAEL) in the low
g/kg day-1 range. QSTR analysis of DBPs
identified in the literature failed to identify
candidates potent enough to be credible
as potential causes of the epidemiological
association between chlorinated drinking
water and carcinogenic toxicities. On
the other hand, the study pointed to
several classes of putative DBPs requiring
more research, including haloquinones,
which appeared as the most capable
of inducing bladder cancer. Within
this group, 2,6-dichloro-3-methyl-1,4benzoquinone showed the greatest
toxicological potential to be a bladder
carcinogen. Consistent predictions of
carcinogenic and developmental toxicities
were found for specific members of this
group, halonitriles and haloamides. The
research suggests that N-nitrosamines and

nitrosamides be further investigated due
to their very high carcinogenic potency.
Based on these findings, the Foundation
has funded a follow-up project #4089,
Method Development for Disinfection
By-Products Associated With Bladder
Cancer, with the objective to develop
sensitive and reliable analytical tools to
confirm the formation and occurrence of
the target DBPs.
Summary
Epidemiological studies with meaningful

exposure assessment are needed to resolve
the question of health effects, however the
chemical(s) or mixture to which we must
measure exposure have not been identified.
In addition, DBP formation is influenced
by water parameters and while several
hundred DBPs have been identified, many
more remain unknown. As different classes
of DBPs may be formed from different
organic precursors, additional information
is needed to aid in future exposure
assessment studies.
Subscribers may
download free copies
of most Foundation
reports from the
Web site at www.
WaterResearch
Foundation.org. They
may also request free
printed reports by
contacting Foundation
Customer Service by
telephone at
+1 888.844.5082 or
by e-mail to rfreports@
WaterResearch
Foundation.org.
67

Application of Storage Facility Modeling to Improve
Mixing and Reduce Water Age
David J. Hartman and Jeff Swertfeger, Greater Cincinnati Water Works, Ohio
Sometimes the solution to DBP problems lies not only in adjusting treatment and water chemistry, but also
reducing water age in the distribution system. Water Quality Modeling of Distribution System Storage
Facilities (2000, order#90774/project#260) describes the influence of water storage facilities on water age. This
report describes how it is not just a simple calculation of average residence time in a facility that is important,
but that the mixing characteristics inside the facility can also greatly influence the age of water leaving the tank.
Improper mixing can cause high water age, which can lead to low chlorine and high DBPs in the tank effluent.
This project is important not only because it describes these problems, but because it also contains two software
tools (HydroTank and CompTank) to assist utility staff in assessing mixing in their storage facilities and in designing
solutions to mixing problems.
The Greater Cincinnati Water Works (GCWW) has continuous chlorine monitors at the effluent of most of their
tanks. These monitors are connected to a supervisory control and data acquisition (SCADA) system, which tracks
the data and GCWW sets goals and action levels based on these monitors. This monitoring and evaluation
system is part of an overall strategy to control water age, thus maintaining the state-mandated chlorine level and
minimizing DBPs.
In evaluating this data, GCWW noticed steep drops in chlorine levels at one particular tank that occurred when the
level in that tank dropped to a certain elevation. This drop in chlorine was much greater than would be expected
based on calculated water age using simple residence time calculations. This led GCWW to believe that stratification
may be occurring in the tank, a zone of stagnant water was forming under normal operation, and the water from
this zone would leave the tank only when the tank level dropped below a certain elevation. To confirm this, GCWW
turned to the HydroTank model included in Major Ion Toxicity in Membrane Concentrates (2000, order#90824/
project#290) and developed a simple computational fluid dynamics (CFD) model.
The tank itself is a 2-million gallon tank with a 100-foot diameter and a maximum water depth and overflow 35
feet from the bottom. The main leading to the tank has a diameter of 2 feet, but the common inlet/outlet riser
of the tank had a diameter of 5 feet. Upon running the model, GCWW was able to see that the velocity of water
going into the tank was inadequate in a typical fill and drain cycle to break the stratification largely because of
the large diameter of the inlet. The model demonstrated that the influent water was contained in an area directly
above the inlet and very little if any mixing occurred with the rest of the water in the tank. In a drawdown cycle,
this is the first water to leave the tank, i.e., the last water in is the first water out. In extended drawdowns, the
older water from the upper zones would also leave the tank resulting in low chlorines measured in the tank
effluent. For a 5-foot diameter inlet, the model demonstrated a fill time of over 20 hours would be required to
completely mix the tank. However, the tank is typically operated with a fill time of around 8 hours. This 20 hour
fill time would also exceed the capacity of the tank during a normal tank cycle. This led GCWW to realize that
operationally there was little it could do to mix the tank to address water quality issues and still meet operational
pressure and flow requirements.
As a result of the modeling, GCWW realized that a modification to the tanks inlet diameter was needed to allow
mixing. GCWW used the model to experiment with several different configurations to balance the need for mixing,
but still maintained pressure and flow requirements over the entire range of operation. GCWW also needed to
be sure that restricting the influent diameter would not create significant enough headloss that would affect
pumping costs.
68
The HydroTank model showed that modifying the riser with a restrictor plate to a 2-foot diameter (the same
diameter as the pipe leading to the tank) would provide a good mixing pattern and that complete mixing should
be achieved in 8.2 hours, which is a typical fill cycle for this tank. This is in comparison to over 20 hours required
for the 5-foot inlet. In addition, an evaluation of the historical pressure loss over a variety of operating conditions
indicated that a reduction in inlet diameter to 2 feet would not have much difference on headloss largely because
the pipe leading to the tank already had a 2-foot diameter.
The reduction of the inlet diameter was then included in a planned tank renovation project. This project also
included the installation of sampling taps at the 25, 50, and 75% elevations as well as the continuous monitor
on the common inlet/outlet. Figure 1 is a photo of the modification that was made to the tank inlet reducing the
opening from 5 feet to 2 feet in diameter.
In the three years subsequent to the inlet riser modification, the steep drops in chlorine levels that were once
commonplace do not occur anymore. The chlorine levels observed in the tank effluent are remarkably stable over
the operational cycle. In addition, water quality measurements taken at the newly installed sample taps show
there is very little variation in the water quality and temperature, thereby, indicating a well-mixed tank.
Additional software called CompTank was also included in Water Quality Modeling of Distribution System
Storage Facilities. GCWW compared the chlorine levels observed with those predicted from an ideally mixed
tank. The observed levels that GCWW sees is very close to those predicted by CompTank indicating that the
mixing achieved after the inlet modification is very close to the mixing predicted in an ideal tank.
In conclusion, tank mixing and turnover can be a significant area for improvement and should be considered by
any utility who wishes to reduce water age, improve disinfection residual, and reduce DBPs. Utilizing tools like
those developed for and included with Water Quality Modeling of Distribution System Storage Facilities
are extremely powerful, easy to use, and can be used by utility designers and engineers to evaluate the design of
existing and planned storage facilities to optimize mixing and reduce water age.
Figure 1: Photo of restrictor plate modification installed on riser pipe opening into bottom of tank bowl.
69
Acronyms
Acronyms and Abbreviations

g/L
M
micrograms per liter

micrometer
A
A+N
A/W
AWWA
AwwaRF
acids plus neutrals

air-to-water ratio
American Water Works
Association
Awwa Research Foundation
B
BAA
BAC
BAN
BCAA
BDCM
Bro3-
BY
bromoacetic acid
biological active carbon
bromoacetonitrile
bromochloroacetic acid
bromodichloromethane
bromate
bromate yield
C
CAA
CaOCl2
CCL3
CDBAA
CDBM
CDC
CFD
CFE
CHO
Cl2/DOC
Cl2/N
70
chloroacetic acid
calcium hypochlorite
Contaminant Candidate List 3
chlorodibromoacetic acid
chlorodibromomethane
Centers for Disease Control and
Prevention
computational fluid dynamics
combined filter effluent
Chinese hamster ovary
chlorine/dissolved organic
carbon ratio
chlorine/nitrogen ratio
Cl3AA
ClO2
ClO2-
ClO3-
CMSFIA
CMSGC
CNCl
CNX
CPDB
CT
trichloroacetic acid
chlorine dioxide
chlorite
chlorate
capillary membrane sampling
flow injection analysis
capillary membrane sampling gas
chromatography
cyanogen chloride
cyanogen halides
carcinogen potency database
concentration of disinfectant
in mg/L multiplied by time in
minute
D
DAS
DBAN
DBCM
DBP
DBPR
DCAA
DCAN
DCBQ
D/DBP
DMA
DO
DOC
DOM
DON
DPD
DXAA
Differential absorbance
spectroscopy
dibromoacetonitrile
dibromochloromethane
disinfection by-product
Disinfectants/Disinfection ByProducts Rule
dichloroacetic acid
dichloroacetonitrile
2,6-dichloro-1,4-benzoquinone
disinfectants/disinfection byproduct
dimethylamine
dissolved oxygen
dissolved organic carbon
dissolved organic matter
dissolved organic nitrogen
N,N-diethyl-p-phenylenediamine
dihalogenated acetic acids
Acronyms
E
EBCT
empty-bed contact time
ESIFAIMSMS electrospray ionizationhigh
field asymmetric waveform ion
mobility spectrometrymass
spectrometry
ESWTR
Enhanced Surface Water
Treatment Rule
F
FACA
Fe(OH)3
Fe
Fe2+
Fe3+
FIA
Foundation
FP
Federal Advisory Committee Act

ferric iron hydroxide
zero-valent iron
ferrous iron
ferric iron
flow injection analysis
Water Research Foundation
formation potential
GC/MS
GCWW
grams per liter

granular activated carbon
gas chromatography-/electron
capture detection
gas chromatography/mass
spectrometry
Greater Cincinnati Water Works
H
H2O2
HAA
HAAFP
HAN
HIOP
HNM
hydroxyl radical
heterotrophic plate count
I
IAA
IA
IC
ICR
I-DBPs
I-/DOC
IDSE
IESWTR
IOCO
IOCS
I-THMs
iodoacetic acid
iodinated acid
ion chromatography
Information Collection Rule
iodinated disinfection byproducts
iodide to DOC ratio
initial distribution system
evaluation
Interim Enhanced Surface Water
Treatment Rule
iron-oxide-coated-olivine
iron-oxide-coated sand
iodinated trihalomethanes
G
g/L
GAC
GC/ECD
HO
HPC
hydrogen peroxide
haloacetic acid
haloacetic acid formation
potential
haloacetonitriles
heated iron oxide particle
halonitromethane
JAWWA
Journal AWWA
L
LC/MS
LOAEL
LRAA
LT2ESWTR
LVVWD
liquid chromatography/tandem
mass spectrometry method
lowest observed adverse effect
level
locational running annual
averages
Long-Term 2 Enhanced Surface
Water Treatment Rule
Las Vegas Valley Water District
71
Acronyms
M
MCL
MCLG
M/DBP
Metropolitan
mg/L
mgd
MRDL
MRL
MWCO
O
maximum contaminant level
maximum contaminant level goal
microbial/disinfection byproduct
Metropolitan Water District of
Southern California
milligrams per liter
million gallons per day
maximum residual disinfectant
level
minimum reporting level
molecular weight cutoff
N
N2H4
NaOCl
NBDPS
N-DBPs
NDEA
NDMA
NDPA
NF
ng/L
NH3
NH3-N
NH4+
NH4Cl
nm
NMOR
NOM
NTU
hydrazine
sodium hypochlorite
National Birth Defects Prevention
Study
nitrogenous disinfection byproducts
Nnitrosodiethylamine
N-nitrosodimethylamine
N-nitrosodipropylamine
nanofiltration
nanograms per liter
ammonia
nitrogen ammonia
ammonium
ammonium chloride
nanometer
N-Nitrosomorpholine
natural organic matter
nephelometric turbidity unit
O3+ H2O2
OCl-
OEHHA
OPTGC
P
PAC
PAH
PCIC
PHG
pHPZC
polyDADMAC
powdered activated carbon

polycyclic aromatic hydrocarbon
post-column ion chromatography
public health goal
point of zero charge
polydiallyldimethylammonium
chloride
Q
QSTR
quantitative structure-toxicity
relationships
R
RO
RSD
RSSCT
reverse osmosis
relative standard deviation
rapid small-scale column testing
S
SCADA
SCGE
SDS
SDWA
SFPUC
SOC
SUVA
72
ozone/PEROXONE
hypochlorite ion
Office of Environmental Health
Hazard Assessment
online monitoring purge and trap
gas chromatography
supervisory control and data

acquisition
single-cell electrophoresis
simulated distribution system
Safe Drinking Water Act
San Francisco Public Utilities
Commission
synthetic organic chemical
Specific Ultraviolet Absorbance
Acronyms
T
TCAA
TCAN
TCNM
THM
THMFP
TOBr
TOC
TOCl
TOI
TOX
TRIN
TTHM
TXAA
U
trichloroacetic acid
trichloroacetonitrile
trichloronitromethane (also
known as chloropicrin)
trihalomethane
trihalomethane formation
potential
total organic bromine
total organic carbon
total organic chloride
total organic iodine
total organic halogen
total reduced inorganic nitrogen
total trihalomethane
trihalogenated acetic acid
UCMR2
UF
UFC
USEPA
UTOX
UV
UVA
Unregulated Contaminant
Monitoring Rule 2
ultrafiltration
uniform formation condition
U.S. Environmental Protection
Agency
unknown total organic halogen
ultraviolet
ultraviolet absorbance
V
VOC
volatile organic compound
W
Waterworks
WTP
Newport News Waterworks

water treatment plant
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73
Ground-Breaking Research
Disinfection By-Products have plagued the drinking water industry since the 1970s. Your subscription
to the Water Research Foundation allows us to deliver credible research that helps water utilities
monitor and control DBPs. Some of this research is shown below:

Abiotic Degredation of DBPs in Distribution Systems

Mammalian Cell Cytotoxicity and Genotoxicity of Disinfection By-Products
Occurrrence and Formation of Nitrogenous Disinfection By-Products
Localized Treatment for Disinfection By-Products
Disinfection By-Products Formation and Control During Chloramination
Exploring HAA Formation Pathways During Chloramination
Contribution of Wastewater to DBP Formation
Characterization of Total Organic Halogen Produced During Disinfection Processes
Methods for Real-Time Measurment of THMs and HAAs in Distribution Systems
Use of Toxicological and Chemical Models to Prioritize DBP Research

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Drinking Water Research

Advancing the Science of Water

Drinking Water Research

Advancing the Science of Water

Historical Perspective on Foundations DBP Research

Acronyms and Abbreviations

A Summary of DBP Regulations in the United States

Foundation staff contributors to this issue are as follows:

JANUARY MARCH 2010 S DRINKING WATER RESEARCH

Practical Guidance, Real World Impact

Robert C. Renner, P.E., D.E.E.

DRINKING WATER RESEARCH S JANUARY MARCH 2010

Historical Perspective on Foundations

The use of strong oxidants such as chlorine,

JANUARY MARCH 2010 S DRINKING WATER RESEARCH

have been identified, including nitrogenous

Water Research Foundations involvement

THMs form during chlorination of drinking

In the early 1990s, USEPA was laying the

through the ICR. Another key M/DBP

While it has long been recognized that

Chlorine alternatives; e.g., chloramines,

As knowledge of regulated DBPs has

JANUARY MARCH 2010 S DRINKING WATER RESEARCH

Iodinated DBPs (I-DBPs), halogenated

While the drinking water community has

The Foundation has been involved in DBP

to minimize DBP formation and comply

Case StudIES and Value of Research

Factors Affecting Disinfection By-Product Formation During Chloramination

Disinfection By-Product Formation and Control During Chloramination

Formation and Decay of Disinfection By-Products in the Distribution System

DRINKING WATER RESEARCH S JANUARY MARCH 2010

Case StudIES and Value of Research

Factors Affecting the Formation of NDMA in Water and Occurrence

Strategies for Minimizing Nitrosamine Formation During Disinfection

Formation of Hydrazine as a Chloramine By-Product

Health Effects of Disinfectants and Disinfection By-Products

Health Effects and Occurrence of Disinfection By-Products

Drinking Water Disinfection By-Products and Pregnancy Outcome

JANUARY MARCH 2010 S DRINKING WATER RESEARCH

A Summary of DBP Regulations

DBP formation during chlorination of

Wisconsin experienced an outbreak of

The U.S. Environmental Protection Agency

Work on a DBP rule occurred at USEPA

On June 19, 1986, the 1986 Amendments

Ultimately the level of uncertainty in

DRINKING WATER RESEARCH S JANUARY MARCH 2010

organic carbon (TOC) removal; maximum

JANUARY MARCH 2010 S DRINKING WATER RESEARCH

required and CFE turbidity 0.3 NTU had

studies, affordable treatment without

DRINKING WATER RESEARCH S JANUARY MARCH 2010

Case StudIES and Value of Research

JANUARY MARCH 2010 S DRINKING WATER RESEARCH

Case StudIES and Value of Research

DRINKING WATER RESEARCH S JANUARY MARCH 2010

Traditional Disinfection By-Products

THMs (chloroform, bromodichloromethane,

JANUARY MARCH 2010 S DRINKING WATER RESEARCH

characteristics, such as THMs are produced

Traditional Disinfection By-Products

in series recovered 6080% of NOM and