Water Treatment: Disinfection Processes

Current Technology Vs. Alternatives

 Table of Contents
Abstract................................................................................................................................2
Introduction..........................................................................................................................3
Regulations..........................................................................................................................3
Water Treatment...................................................................................................................4
Methods of Disinfection......................................................................................................4
Chlorination.........................................................................................................................5
Chlorine...............................................................................................................................5
Disinfection By-Products.....................................................................................................6
Alternative Disinfection Methods........................................................................................6
Ozone...................................................................................................................................7
Chlorine Dioxide.................................................................................................................7
Chloramines.........................................................................................................................8
Disinfection By-Product / Trihalomethane Control Methods..............................................8
Other Research.....................................................................................................................9
Discussion............................................................................................................................9
Appendix – Figures and Tables..........................................................................................11

Abstract
Regulation of the drinking water industry has led to large quantities of research dealing
with the water treatment processes, especially disinfection. Chlorination research has
shown by-products (THM’s) are potentially carcinogenic. This has spurred research into
alternatives such as ozone, chlorine dioxide, and chloramines. Other additional
treatments like enhanced coagulation are being tested. Research goes on to find out how
efficient all of these processes will be in achieving standards, disinfecting , controlling
by-products, and removing particles. No conclusive answers have been found to date,
only speculation with a small amount of data to back up the theories. All of these things
must take into account the realistic ability of the treatment plants to function with the new
procedures and techniques that the research discovers.

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Introduction
Water is the most important thing for human survival and is the basis of all life.
Though 70% of the earth is covered in water, very little of that is actually usable as
drinking water. With this in mind, water must be treated in one way or another to make it
safe for human consumption. There are many parts to the treatment process, from the
raw water to the finished water that is delivered to the distribution system. The goal of
drinking water treatment is to minimize levels of potentially harmful organisms and
Disinfection By-Products (DBPs) while maintaining adequate disinfection protection in
the distribution system to protect against recontamination. 8 Figure I illustrates the
relationship between chlorine dose and Trihalomethane (THM) formation, through
contact time and residual. There is ongoing research regarding the side effects of
disinfection chemicals and processes used to meet the United States Environmental
Protection Agency (US EPA) standards 9. There are possible alternatives to chlorine to
disinfect water of microorganisms. The research into these alternatives continues to try
to learn as much as possible so that educated decisions can be made to determine if they
are equal, better or worse than chlorine.

Regulations
Health and aesthetic qualities of the water are the driving forces behind water
treatment and water quality regulations 13. Water quality is regulated by the US EPA as
well as health departments. The regulation of water treatment started in the 1970’s when
the US EPA instituted regulations on things like water quality parameters and
Disinfection By-Products levels. The EPA does studies and determines different
Maximum Contamination Levels (MCL) for different chemicals which are then used to
set limits. There are different regulations for ground water sources vs. surface water
sources. Ground water sources are thought to be much more pure and need less treatment
to meet regulations and standards than surface water sources.
There are two major Federal Regulations for water quality: the Safe Water
Drinking Act (SWDA) of 1979, 1986 and the Surface Water Treatment Rule (SWTR) of
1989 1. The Safe Drinking Water Act (Public Law 93-523) set standards for treatment
techniques that the water utilities use. It also requires every water quality regulation to
contain a statement as to which techniques to use to achieve compliance 2. This was
amended in 1986 to add two regulations dealing with disinfection 3. The EPA regulates
the THM levels allowed in finished potable water. The MCL was set at 100 g/l or 100
ppm of Total THMs, which includes all the different forms combined.
The SWTR requires all systems relying on surface water sources or ground water
sources directly influenced by surface water to provide filtration and disinfection capable
of 99.9% removal and/or inactivation of Giardia cysts and 99.99% removal and/or
inactivation of enteric viruses. This reduces the worst case scenario of risk to 1 / 10,000
for Giardiasis. A timeline was set up for compliance with these regulations. Many
systems may not be able to reach these goals with the current treatment processes and
would require capital improvements to successfully meet the new standards. Many of the
200+ New York State systems will have such problems 1,15.
The Disinfection/Disinfection By-Products Rule (D/DBP Rule) was added in
1994. This new regulation was supposed to lower the THM MCL to 80 g/l or 80 ppm
starting in 1996 but has been delayed a couple of years 7. There are 2 parts to the D/DBP

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Rule, Stage I deals with Total Organic Carbon (TOC) removal rates and Stage II proposes
even lower MCLs for Disinfection By-Products 10. These new lower MCL requirements
affect how the water treatment industry will conduct water treatment. White et al 11
carried out jar tests on 31 different water sources and his results suggest that even with
enhanced coagulation, compliance will be difficult for many water companies with the
promulgation of the D/DBP rule without alternative criteria.
Metcalf & Eddy, Inc did a pilot study to determine if these regulations were
realistic without having to change the existing facility. They make comparisons between
the existing system in place at the Rockville Water Treatment Plant (RWTP) and the pilot
study done on the same water source, which lasted one season. The pilot study results
showed that the existing facility could use enhanced processes to meet and comply with
standards and regulations. 10
These are research projects ongoing to assess the realistic solutions to help meet
compliance regulations. With the results from these experiments, hopefully educated
decisions will be made to balance out the risks of water treatment and the levels of
chlorine (and/or other disinfectants) needed to provide satisfactory disinfection.

Water Treatment
Watershed issues are important when considering the sources used for drinking
water. (Figure II) Point and Non-Point pollution threaten to contaminate the raw water
supplies around the world. The Clean Water Act was passed to institute regulations that
require states to monitor for contaminants to control pollution and protect water quality 14.
Using the watershed as an indicator is challenging because it is hard to isolate or quantify
pollution sources and even harder to regulate them once they are found. Contamination
of surface water by microorganisms as well as high starting turbidity measurements
require water utilities to treat the water in order to meet federal standards. 9
All the parts of water treatment work together to remove particles present in raw
water. A brief description of the overview of conventional treatment includes
coagulation, flocculation, sedimentation, filtration, and disinfection. Coagulation is the
method of adding and mixing chemical coagulants into the raw water. A coagulant is a
chemical which will bind to particles, including abiotic substances and living organisms.
Flocculation is the slow mixing of these chemicals with the water to create “floc” (the
natural matter in the water combined with the coagulant). Sedimentation is the settling
out of the floc, which weighs more than the water, to the bottom of the basin. Filtration is
the removal of the remaining suspended matter into the filters as the water passes through
the filter media 9. The process of disinfection is very complicated because it can be more
than one step. Generally, disinfection involves adding a gas, chlorine for example, to the
water. This gas will act as an oxidant and react with the pathogens and particles in the
water. All of these processes combined make up water treatment though not every water
treatment facility uses all of them to meet the requirements.

Methods of Disinfection
Disinfection of water refers to the inactivation or destruction of undesirable
pathogenic organisms living in the water 3. It is not the sterilization of water. The risks
from microbial agents have to be compared to those from disinfection to find a balance
that is safe and efficient with the least amount of side effects 8. Disinfection of water

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started back in 500 BC with the boiling of water. Later chlorination started in Europe
(1880’s) and finally in the U.S. (1909). Three general types of disinfection treatment are
heat, radiation, and chemical. The heat method is to boil the water. This procedure is
still used in cases of emergency. The use of UV light to disinfect the water is radiation
treatment. This process disinfects when the UV light is passed through the water at close
proximity to the water. Only a small area of water can be treated by this method,
therefore is only used for small quantities of water. 9 Last, the chemical treatment is the
most common form used to disinfect the water. Chemicals will disrupt the life processes
of an organism and it usually dies before it can adjust. There are many different
chemicals that can be used depending on the situation and the targeted results. Many of
the chemicals have multiple purposes. Any of these different methods can be used to
disinfect water depending on how different treatment plants are equipped.

Chlorination
Chlorination is the most widely accepted and adopted method of disinfection. It
has been looked upon as the solution of problems and the creator of others. Prior to
chlorination, waterborne disease was a regular occurrence. Throughout the 1800’s and
1900’s there was a high rate of incidence of illness due to diseases like typhoid, dysentery
and cholera. The rate of illness and death due to these diseases dropped off with the
institution of chlorination. 3
Factors influencing disinfection by chlorination are: concentration of the chlorine,
contact time, temperature of the water, pH of the water, and how many foreign substances
there are in the water. Chlorine gas can be added at different points in the water
treatment process, and each step has different effects. Adding the chlorine at the
beginning of the process, prechlorinating, to the raw water would give the most contact
time which would guarantee disinfection but it also insures that the concentration of
THMs will be highest and sometimes above the regulated MCL. Another choice is to
postchlorinate, which means adding the chlorine after the water has been coagulated,
settled, and filtered. The chlorine feed point would be right before the entrance to the
clearwell but before the distribution system, to ensure that the required residual is in the
distribution system. 9 This might not be enough contact time to sufficiently disinfect the
water. Many plants chlorinate just before filtering the water. A counterbalance between
disinfection contact time and THM formation has to be found. All of these things
combine make up the science of disinfecting potable water.

Chlorine
Chemical symbol Cl which exists as a gas in molecules as Cl 2. At room
temperature, chlorine is a greenish yellow poisonous gas. When it is bubbled into water
it reacts quickly and completely to produce hypochlorous acid. The hypochlorous acid
then dissociates into a hypochlorite ion and a hydride ion (Figure III). An equilibrium is
reached in aqueous solutions 5,13.
Cl2 + H2O  HOCl + H+ + Cl-
HOCl  H+ + ClO-
Chlorine is very effective, efficient, convenient, and economical. These
characteristics, along with the versatility to treat taste and odor, algae, and disinfect
mains, have made it the primary choice for disinfection of drinking water. 3

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 There are two kinds of reactions in which chlorine reacts with natural organic
matter, oxidation and substitution. Oxidation reactions remove organic matter from the
water and are favored when there is a high chlorine dose. Chlorine will oxidize carbon
and nitrogen to cleave molecules. Substitution reactions are where one ion replaces an
element or elements in a molecule, in this case to produce THM’s by adding chlorine to
the organic matter (Figure IV). Substitutions dominate when the chlorine doses are
lower. Carbon and nitrogen are sites for chlorine substitution. One example is resorcinol
(Figure V), which after a series of quick reactions results in a few products, one of which
is chloroform.5

Disinfection By-Products
Water is almost never pure H2O. In rivers and reservoirs there is organic matter
naturally floating in the water. This natural organic matter (NOM) complicates simple
reactions, allowing side reactions to take place. These side reactions form by-products
other than the desired products of the primary reaction. The chlorine reacts on a
secondary level with natural organic matter. A scientist in the Netherlands discovered
Trihalomethanes (THMs) in 1974 7. THMs are a by-product of chlorine disinfection.
Four of the common THMs are Chloroform, Bromodichloromethane,
Dibromochloromethane, and Bromoform. 12 The mechanism is not exactly known for the
formation of THMs but the general equation is as follows:
Free Chlorine + Precursors  THM’s + Other Halogenated
(Humic Substances & Non-Halogenated
& Bromide) By-products
These precursors come from sources like plants, algae and human activity. Some
plants examples are fulvic and humic acid, degradation products like resorcinol, and plant
pigments like chlorophyll. Algae in the water add biomass as well as amino acids like
uracil to the water. And the human influence on the water comes from industry which
releases organics, one example being Phenols. All of these precursors are then available
for the substitution reactions seen in figures IV and V commonly found with the addition
of chlorine. 5
If the THM precursors could be removed, it would allow chlorination to remain as
the primary form of disinfection. Some chemicals have been found to assist in removal
of precursors, one of which is Potassium Permanganate. The other option is the remove
the THMs after they are formed. 2
These halogenated compounds have been shown to be carcinogenic in animal
experiments. The chloroform compound has the best known toxicology. In the medical
field it was used because of its effects on the nervous system. For many years it was an
anesthetic. Then it was discovered to have adverse long-term effects. Glaze et al 8
compiled research that indicates the induction of liver, kidney and thyroid tumors in mice
and rats (Figure VI). The amounts of chloroform that water treatment and disinfection
with chlorine produce is no where near the amounts used in the experiments.12

Alternative Disinfection Methods

Some additional techniques are being researched which can be used in addition to
current disinfection methods to reduce the formation of by-products. Some of the other

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chemicals used for disinfection treatment of potable water sources are: Ozone, Chlorine
Dioxide, and Chloramines.

Ozone
Ozonation provides efficient disinfection initially, with few DBPs, and can even
treat taste and odor problems 8. Ozone is a gas which is not stable enough to be stored, it
has to be manufactured as needed on-site. It is a powerful oxidizing agent, but is unstable
in water and in distribution systems. This instability causes a lack of a “long lasting
residual”, which makes it difficult to determine if it has effectively destroyed the
pathogens. A second disinfectant is needed in the distribution system due to this lack of
residual with ozone alone 7. This increases chemical costs. An advantage to using ozone
is that it can improve coagulation. This allows for longer time periods between filter
washes 9. The research done by Song et al illustrates the side effects of ozone 4. For
water sources containing Br-, Bromate (BrO3-) (Figure VII) and Total Organic Bromine
(TOBr) can be formed during Ozonation as seen below. The MCL of Bromate is 10g/l
or 10 ppm 4. TOBr is not yet very regulated and little is known about their potential
health risks. In aqueous solutions, bromine that is present will react with ozone to form
bromate, hypobromate or hypobromous acid.
Br- + O3 OBr - + O2
OBr - + 3O3 BrO3-
OBr - + H+  HOBr
HOBr/ OBr - + NOM  TOBr
Upon addition to water, ozone reacts with hydroxide ions to form hydroxyl radicals and
organic radicals. All these radicals increase the decomposition of ozone. Some ions act
as scavengers and steal radicals, therefore slowing oxidation power of the ozone 13. Some
research has been done to evaluate the practicality of installing ozone systems 4. Adding
ozone to a water treatment system is very expensive and requires major capital
investments 2. It would be very hard for an existing water treatment plant to add Ozone
to its current treatment processes. Though when planning new plants, it is a viable option
to consider as part of the treatment process in some cases.

Chlorine Dioxide
Chlorine Dioxide gas has a greenish yellow appearance 13. Chlorine Dioxide is
another chemical which must be prepared on-site. Under alkaline conditions, the
following reaction takes place between chlorine dioxide and water:
2 ClO2 + 2 OH-  H2O + ClO3- + ClO2-
This reaction is usually catalyzed by carbonate, but if that is not present then the reaction
follows the rules of first and second order kinetics 13. Chlorine Dioxide is a good
disinfectant, but it produces Chlorite (ClO2-) and Chlorate (ClO3-) as by-products. These
each have their own side effects on water quality. There are concerns that the chlorite
and chlorate have their own potential to be toxic. Chlorine Dioxide can also add a
specific taste which is not desirable 9. Chlorine Dioxide is capable of oxidizing Iron and
Manganese. Presence of ClO2 reduces the formation of THM’s by chlorine 2. Chlorine
Dioxide converts to Chlorite in the human gastric system 13. So it is a trade off between
THM’s or Chlorite and Chlorate 8. The reactivity of Chlorine Dioxide is very selective
and it is slow to react with organic compounds found in water 13,5. It has a very short half-

7
life, and as a result has very low residuals in the distribution system 13. So a secondary
disinfectant is required for the residual in the distribution system. This raises the
chemical costs for the utility.

Chloramines
Chloramines are weak oxidants but produce improvements in taste and odor of
water which contains aromatic molecules such as phenol 3. Chloramines result from the
reaction between Hypochlorous acid and ammonia as follows:
NH4+ + HOCl  NH4Cl + H2O + H+
NH2Cl + HOCl  NHCl2 + H2O
NHCl2 + HOCl  NCl3 + H2O
Since ammonia exists in nature, some chlorine will automatically be consumed in
forming chloramines. There is a phenomenon known as the “breakpoint” (Figure VIII)
which is the amount that is required to destroy the chloramines and achieve a stable
residual of Chlorine 13. The residual is very important in maintaining disinfection in the
distribution system.

Disinfection By-Product / Trihalomethane Control Methods

Researchers are working to find new methods which could control the by-
products caused by current methods, or better alternatives to the complex situation of
chlorination and the by-products formed during the chemical reactions. Some reactions
are good and others produce unwanted compounds. Two suggestions for controlling or
removing the THM precursors are addition of Potassium Permanganate and enhanced
coagulation.
Potassium Permanganate can be used as a THM control. Potassium
Permanganate (KMnO4) is a very strong oxidant. It is especially effective with taste and
odor problems. When added to water it turns purple, and the color changes to clear as the
oxidation reaction goes to completion. There are side effects to the color characteristics.
If the concentration is not carefully monitored so that the reaction goes to completion,
then there could be residual color in the finished water. Sometimes the KMnO 4 will react
with substances differently than chlorine and control conditions that chlorine is unable to.
By using KMnO4 at the beginning of the water treatment process, you can delay the
addition of chlorine till later and therefore reduce the time in which THMs can form. The
KMnO4 is known to oxidize iron and manganese, and is used to control THM
precursors.7,9
Enhanced Coagulation is a hot topic of research. Researchers hope to find a
solution to DBP formation during disinfection processes. “Enhanced Coagulation” refers
to a modification in the conventional coagulation process to gain better rates of removal
of Natural Organic Matter (NOM) 11. The enhanced coagulation process changes
parameters of water treatment such as pH and coagulant dose. Because most of the water
treatment plants that exist today are working with old technology, it is hard to expect
them to be able to comply with the regulations without some extra help in the treatment
process. Enhanced coagulation is being tested to see how effective it is at removing
particles and THM precursors. Tests are done on the raw water as well as the filtered
water to measure the turbidity, TOC levels, UV254 absorbance, and THM formation
potential. Testing the characteristics of these two types of water can predict the TOC

8
removal rate. This can forecast whether or not the changes in water treatment will help to
be in compliance with the newer, stricter regulations. 17 Many of the results depend on
the raw water. Samples with higher starting TOC levels tend to have better removal
rates11. To ensure that the extra work being performed to remove TOC does not add more
particles to the water and deteriorate the turbidity, close monitoring of the turbidity must
continue.
There is still a lot of research to be done to determine the possible side effects of
these processes. It is possible that these alternatives may be no better than the processes
in use currently.

Other Research
Experiments, including the combinations of alternative methods are being done in
different parts of the country at different facilities to find the best finished water results.
One example is the work done by Nicholas Pizzi and Margaret Rodgers at a plant in
Cleveland 18. Studies were done on Lake Erie raw water (Table 1) to see if combining
enhanced coagulation, ozonation, and Granular Activated Carbon on a bench scale and
pilot scale could improve the TOC removal rates. Pizzi et al concluded that ozonation
does not improve TOC removal rates, while enhanced coagulation does better than the
conventional treatment. Tables 2 & 3 show the data which was compiled from the
experiments done at the Crown Water Treatment Plant.
A conclusion made was that ozone may be a good disinfectant but it has no
significant benefits on THM Formation Potential or THM removal. On top of that, there
are other side effects from using ozone in water disinfection. An example of these
alternative by-products is the research done by Song et al dealing with the formation of
bromates. 4 With Bromate formation mechanisms in mind, Bromate has a few different
pathways in which it can be formed. (Figure VII) These pathways all have intermediate
forms which can react to form TOBr if they do not follow all the way to the Bromate
compound. Tests with ozone were done to postulate formation control methods for the
bromide by products as a result of the ozonation. Formations are very dependent on the
water quality and composition of the source water. The catch is that when Bromate
(BrO3-) is controlled with pH and O3 doses, then the TOBr compounds are effected.
Sometimes adding NH3 can help if changing the O3 dose does not. But again it is all
dependent on the water quality of the source water. It is all interlinked and finding a way
to control these compounds is a challenge which will be research projects for the future.

Discussion
Regulations are promulgated with the intention of protecting the consumer. Over
time, as more knowledge is gained from research there will be more changes to the
regulations. With these revisions, alterations in the water treatment process will
constantly be needed to keep up with the standards. Many of the alternative disinfectants
have one or more serious limitation that prevents their acceptance and adaptability to be
used alone to disinfect water. All disinfectants differ in the ability to carry out the
oxidation and substitution reactions. Though ozone, chlorine dioxide, and chloramines
may not react to form THMs they have their own by-products and it is uncertain if they
are more or less harmful than those formed during chlorination. The side effects of
chlorine seem to outweigh the alternatives either due to cost or lack of enough

9
information about the possibilities being more detrimental than those of chlorine.
Enhanced coagulation can raise the chemical cost for a treatment plant, but at the same
time if they do not use enhanced coagulation, then they will be faced with having to make
capital improvement investments to bring the technology up to date. The Mianus Filter
Plant of the Connecticut American Water Company is a treatment plant which is faced
with the dilemma of choosing a disinfection method which will disinfect efficiently while
not costing a fortune. The contact time is not sufficient unless they pre-chlorinate, which
then causes the THM levels in the distribution system to be high. Alternatives are being
considered and a decision will be made in the best interest of the water quality as well as
the company.
Pilot studies allow small scale experiments to test out different scenarios in the
attempt to find the best treatment methods for various kinds of source waters. There is no
black and white answer for all water treatment companies in the case of disinfection. The
gray area of possibilities is a range which allows companies to customize a plan to fit
special circumstances so that they comply with regulations.

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Appendix – Figures and Tables

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References:
1. PONTIUS, F.W. Microbial/Disinfection By-Products Rule on Expedited Schedule.
Journal AWWA, 89:5:17 (May 1997)
2. SYMONS, J.M. et al. Treatment Techniques for Controlling Trihalomethanes in
Drinking Water, AWWA 1982.
3. CONNELL, G.F. Water Disinfection Series, The Chlorination / Chloramination
Handbook. AWWA Denver Co. (1996).
4. SONG, R. et al. Bromate Minimization During Ozonation. Journal AWWA, 89:6:69,
(June 1997).
5. JOHNSON, J.D. et al. THM and TOX Formation, Routes, Rates and Precursors. AWWA
Seminar Proceedings on Strategies for the Control of THM’s, (1983).
6. MOSER, R.H. & LEE, R.G. Field Experiences with Controlling TTHM’s. AWWA
Seminar Proceedings on Strategies for the Control of THM’s, 1983.
7. MEDD, D.L. Potassium Permanganate in the Removal of Trihalomethane Precursors,
April 1994.
8. GLAZE, W.H. et al. Determining Health Risks Associated with Disinfectants and
Disinfection By-Products: Research Needs. Journal AWWA, 85:3:53 (March 1993).
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an Existing Conventional Treatment Plant and a Pilot-Scaled Advanced Treatment
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11. WHITE, M.C., et al. Evaluating Criteria for Enhanced Coagulation Compliance.
Journal AWWA, 89:5:64 (May 1997).
12. BULL, R.J. & KOPFLER, F.C. Health Effects of Disinfectants and Disinfection By-
Products. AWWA and AWWARF, Denver, Co (1991).
13. HAAS, C.N. Disinfection. Water Quality and Treatment (F.W. Pontius, Editor).
McGraw Hill, New York (4th Edition, 1990)
14. FREEDMAN, P.L. et al. A Watershed Event in Water Quality Protection. Water
Environment & Technology. 6:9:76 (September 1994)
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Systems and Budgets. CLEARWATERS, 21:4:19 (1992).
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17. VRIJENHOEK, E.M et al. Removing Particles and THM Precursors by Enhanced
Coagulation. Journal AWWA 90:4:139 (April 1998)
18. PIZZI, N.G. & RODGERS, M.L. Preliminary Testing for Control of DBPs in Cleveland.
Journal AWWA 89:8:79 (August 1997)

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