EXECUTIVE SUMMARY OF
COAGULANT AIDS
IN THE
TREATMENT OF DRINKING WATER
	T>AT?T T	
Submitted to the Environmental Protection Agency

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EXECUTIVE SUMMARY OF
COAGULANT AIDS
IN THE
TREATMENT OF DRINKING WATER
PART I
May 22, 1981
Final Report
Submitted to:
Environmental Protection Agency
Office of Drinking Water
Criteria and Standards Division
Washington, D.C. 20460
EPA Contract No. 68-01-4839, DOW #20
JRB Project No. 2-813-00-200-20
Mr. Arthur Perler, Project Officer
Dr. Krishan Khanna, Project Officer
Submitted by:
Chang-Jen Sun
Andy Chen
Jolanda Janczewski
Roberta Comer
JRB Associates, Inc.
8400 Westpark Drive
McLean, Virginia 22102

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NOTICE
This report has been reviewed by the Office of Drinking
Water, EPA, and approved for publication. Approval does
not signify that the contents necessarily reflect the
views and policies of the Environmental Protection Agency,
nor does mention of trade names or commercial products
constitute endorsement or recommendation for use.

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ACKNOWLEDGEMENTS
This final report "Executive Summary of Coagulant Aids in the Treatment
of Drinking Water, Part I" has been prepared by a JRB Associates team
consisting of Andy Chen, Chang-Jen Sun, Roberta Comer and Jolanda Janczewski.
Information for catalogs, usage procedures, and treatment facilities was
provided by manufacturers and/or distributors of coagulant aids, as well
as by water treatment plants.
The authors wish to thank Dr. Patricia Hilgard of the EPA Office of Toxic
Substances for stimulating discussion.
The support and encouragement of the Project Officers, Mr. Arthur Perler and
Dr. Krishan Khanna of the EPA Office of Drinking Water, are deeply appreciated.

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TABLE OF CONTENTS
Page
Summary	i
1.	Introduction	1
2.	Mechanism of Coagulation	4
2.1	Basic Mechanism o Coagulation	4
2.2	Synthetic Polymers as Coagulant Aids	7
2.3	Natural Products as Coagulant Aids	9
3.	Classification of Coagulant Aids	11
3.1	Manufacturers' Classification	11
3.2	Based on Monomeric Component	16
3.2.1	Polyacrylamide	16
3.2.2	Quaternary Ammonium Polyelectrolyte	17
3.2.3	Polyamine	18
3.2.4	Starch	20
3.2.5	Cellulose and Gum	22
3.2.6	Sodium Alginate	25
4.	Procedures for Using Coagulant Aids	64
4.1	Overall Treatment Facility	64
4.2	Feeding of Coagulant Aids	65
4.3	Dosage Level and Jar Test	71
5.	Contaminants in Coagulant Aids	78
5.1	Residual Monomers	78
5.1.1	Acrylamide	79
5.1.2	Epichlorohydrin	82
5.1.3	Dimethylamine	84
5.1.4	Methylamine	84
5.1.5	Ethylenimine	85
5.2	Other Contaminants	^
5.2.1	Polyacrylamide	87
5.2.2	Copolymer of Monomethylamine and Epichlorohydrin	89

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Page
6.	Stability of Coagulant Aids in Aqueous Environment	95
6.1	Thermal Degradation	95
6.2	Chemical Degradation	101
6.3	Biological Degradation	103
6.4	Photodegradation	103
6.5	Mechanochemical Degradation	104
7.	Estimates of Polyelectrolyte Concentrations in Drinking Water	106
8.	Production and Market	112
9.	Conclusions and Recommendations	119
Bibliography	121
Appendix I: Recommended Dosage Levels of Available Coagulant Aids	127
Appendix II: Protocol Tests for Polyacrylamide and Acrylamide	145
Appendix III: Recommendations Regarding Application for Approval	150
of New Products Intended for Use as Coagulant Aids
for the Treatment of Drinking Water

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TABLES
Page
3-1 Synthetic Coagulant Aids, based on Polymer Structure	12
3-2 Natural Coagulant Aids, based on Polymer Structure	13
3-3 List of Coagulant Aids and Physical Properties	26
3-4 Coagulant Aids Based on Monomeric Component	51
5-1 Chemical Structure and Physical Properties of Selected
Monomers	79
5-2 Residual of Acrylamide in Polyacrylamide	81
5-3 Summary of Acute Toxicity Data on Epichlorohydrin	83
5-4	Summary of Acute Toxicity Data on Ethylenimine
6-1	Volatile Products of Thermal Degradation of Some
Addition Polymers	98
6-2	Temperature Ranges for Thermal Degradation of Polymers	99
7-1	Estimation of Annual Intake of Polyelectrolyte in
Drinking Water	107
7-2	Estimation of Annual Intake of Monomer in Drinking Water	]_q9
8-1	U.S. Production and Sales of Organic Flocculants	115

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FIGURES
Page
2-1 The Structure of the Stern-Gouy Double Layer and
the Corresponding Potentials	6
2-2 Schematic Representation of the Destabilization of
Colloids by Polymers	8
4-1 Flowchart Illustrating the Treatment of a Public
Water Supply	66
4-2 Typical Schematic of a Dry Polymer Feed System	68
4-3 Typical Automatic Dry Polymer Feed System	69
4-4 Positive Displacement Pumps	70
4-5 Schematic Diagram of Horizontal Clarifying Equipment	72
4-6 Schematic Diagram of Solid-contact Clarifier	72
4-7 Schematic Diagram of Solids-contact Solids-recirculation
Clarifier	73
4-8 Jar Test Units with Mechanical and Magnetic Stirrers	76
8-1 Estimates of Direct Additive Chemicals for Drinking
Water Treatment, 1978	114
II-l Calibration Curve of the Hach Method	145
II-2 Calibration Curve of the Kleet Method	145

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SUMMARY
Synthetic and natural coagulant aids are used in the treatment of drinking
water to improve the removal of suspended solid particles. The use of coagu-
lant aids, especially the synthetic polyelectrolytes, has increased, and this
trend is expected to continue. There are numerous reasons for the use of
coagulant aids:
	Sludges formed with polyelectrolyte coagulant aids are denser than
those formed with aluminum or iron salts alone (alternative with
traditional inorganic coagulants).
	Coagulant aids are effective at very low dosage levels.
	The coagulation mechanism of polyelectrolytes is not temperature-
dependent; cold weather does not slow down the rate of floe formation
when coagulant aids are used.
	Coagulant aids are generally non-corrosive and are, therefore, easy
to handle.
Two theories are used to describe the effect of coagulants on colloidal
particles: chemical theory and physical theory. The chemical theory assumes
that colloids have definite chemical features and that coagulation is the
result of precipitation of insoluble complexes formed by chemical interaction
between the colloid and coagulant. The physical theory assumes that the
reduction of effective electric charge on the particle allows colloidal
particles to approach each other and coagulate.
More-than 400 commercial coagulant aids are marketed for drinking water
treatment. This large number of products can be classified into six groups
based on each group's major chemical components; i.e., polyacrylamide,
quaternary ammonium salts, polyamine, starch, cellulose and gum, and sodium
alginate. Currently, between four to five million pounds of coagulant aids
are used for drinking water treatment. Polyacrylamide, which has about 62%
of the market share, is the most frequently used coagulant aid. The major
manufacturers in the coagulant aid industry are American Cyanamid, Dow,
Nalco, Mogul, Calgon, Drew, Hercules, and Betz Laboratories.
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Commercial coagulant aids are available in dry powder or liquid forms.
Dry powder coagulant aids can normally be stored in unopened containers for
12 months while most liquid coagulant aids can only be stored in unopened
containers for 6 months. After these periods, the coagulant aids will deteri-
orate and will be less effective. Coagulant aids may also present contamination
problems in drinking water. Care must be taken to ensure that such usage does
not adversely affect human health. Natural coagulant aids such as starch are
considered to be practically nontoxic and have been used extensively in food
and pharmaceutics. Synthetic coagulant aids, on the other hand, are usually
nontoxic polymers made from organic monomers, some of which are suspected
carcinogens. Five monomers have been proposed by JRB for future study based
on the preliminary toxicity data. These five monomers are acrylamide, epichloro-
hydrin, methylamine, dimethylamine, and ethylenimine.
Coagulant aids are degraded in the aqueous environment by: (1) thermal
degradation, (2) chemical reaction, (3) biological reaction, (4) photolysis,
and (5) mechanochemical decomposition.
Although the added coagulant aids are expected to precipitate out in the
floe, the amounts remaining in the water may be significant. We estimate that
about 7-70 mg per person of unprecipitated coagulant aids are ingested each year
The annual intake of the unreacted monomeric contaminants of the coagulant aids
is estimated to be 30-300 jig per person.
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1. INTRODUCTION
The high quality of drinking water in the United States is recognized
throughout the world and is reflected by the freedom with which water is
consumed. Nevertheless, mounting concern over the spread of pollution, and
the availability of increasingly sensitive methods of detecting contaminants
of concern, have led to new legislation which seeks to ensure that drinking
water poses no hazard to public health.
Recently, coagulant aids have found increasing use in the drinking water
industry for the treatment of raw water to improve the effectiveness of floccu-
lation, thereby causing a more efficient removal of turbidity, bacteria,
viruses, asbestos, etc. Coagulant aids can also be used to strengthen a floe
to prevent floe breakthroughs during filtration. Questions concerning potential
adverse health effects from the use of coagulant aids were first addressed
officially in 1958 when the Public Health Service began "approving" coagulant
aids on an advisory basis in response to requests from the States and the
American Water Works Association. These "approvals" were made by a committee
of experts on the basis of the toxicological properties of the coagulant aids
in question. This advisory service later expanded and became a part of the
EPA's Office of Drinking Water.
The Office of Drinking Water, Criteria and Standard Division, is
responsible for establishing standards, developing regulations, policies,
and guidelines for drinking water quality; developing treatment regulations
or assignable maximum contaminant levels; developing site selection, surveil-
lance, and operation and maintenance guidelines; providing technical advice
and guidance to other Federal agencies in the development of standards and
regulations; identifying research needs for the development of criteria and
standards; initiating and monitoring contracts required in support of
regulations development; evaluating the need for and implementing appropriate
demonstration projects; and assisting in emergency situations by providing
scientific advice.
On July 20, 1979, the Food and Drug Administration (FDA) and the
Environmental Protection Agency (EPA) executed a memorandum of under-
standing (MOU) with regard to the control of direct and indirect additives
in drinking water. In this MOU, EPA and FDA agreed:
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(1)	That contamination of drinking water from the use and applica-
tion of direct and indirect additives and other substances poses a potential
public health problem;
(2)	That the scope of the additives problem in terms of the health
significance of these contaminants in drinking water is not fully known;
(3)	That the possibility of overlapping jurisdiction between EPA and
FDA with respect to control of drinking water additives has been the subject
of Congressional as well as public concern;
(4)	That the authority to control the use and application of direct
and indirect additives to and substances in drinking water should be
vested in a single regulatory agency to avoid duplicative and inconsistent
regulation;
(5)	That EPA has been mandated by Congress under the Safe Drinking
Water Act (SDWA), as amended, to assure that the public is provided with
safe drinking water;
(6)	That EPA has been mandated by Congress under the Toxic Substances
Control Act (TSCA) to protect against unreasonable risks to health and the
environment from toxic substances by requiring, inter alia, testing and
necessary restrictions on the use, manufacture, processing, distribution,
and disposal of chemical substances and mixtures;
(7)	That EPA has been mandated by Congress under the Federal Insect-
icide, Fungicide, and Rodenticide Act (FIFRA), as amended, to assure, inter
alia, that when used properly, pesticides will perform their intended
function without causing unreasonable adverse effects on the environment; and,
(8)	That FDA has been mandated by Congress under the Federal Food,
Drug, and Cosmetic Act (FFDCA), as amended, to protect the public from,
inter alia, the adulteration of food by food additives and poisonous and
deleterious substances.
Furthermore, it was the intent of the parties that:
(1)	EPA will have responsibility for direct and indirect additives
to and other substances in drinking water under the SDWA, TSCA, and FIFRA;
and,
(2)	FDA will have responsibility for water and substances in drinking
water used in food or for food processing, as well as responsibility for
bottled drinking water under the FFDCA.
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This study is conducted by JRB for the Criteria and Standards Divi-
sion of the EPA Office of Drinking Water in response to the concern over
possible contamination of drinking water through the use of coagulant aids.
These materials have been accepted in the past with the understanding that
they would produce no adverse health effects among the consuming populations;
however, increasing awareness of the presence of trace contaminants in drinking
water and the fact that these contaminants could pose health problems provided
the impetus for reevaluation by EPA of the suitability of these materials for
the water treatment purpose.
The main objectives of this project are
	to review, summarize and update the manufacture and usage of
coagulant aids for drinking water treatment,
	to identify and prioritize the potential contaminants in the
drinking water associated with the application of coagulant
aids.
To present a complete picture of coagulant aid use and the possible
resulting contamination, this report includes
	descriptions of the chemical and physical mechanisms of
coagulation and the role of coagulants and coagulant aids;
	classification and catalogs of coagulant aids according to
chemical structures;
	a description of current water treatment procedures;
	a thorough discussion of possible contaminants added to
drinking water through use of coagulant aids;
	a consideration of possible degradation and reaction products
of coagulant aids and of coagulant aid impurities;
	estimates of the amounts of coagulant aids remaining in
effluent drinking water; and
	estimates of annual production and use of coagulant aids.
Material in this report was obtained from the following sources:
(1)	literature describing coagulant aid and polyelectrolyte chemistry;
(2)	EPA documents; (3) information from product manufacturers and dis-
tributors; and (A) contributions from experts in the field of coagulant
aid chemistry.
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2. MECHANISM OF COAGULATION
2.1 BASIC MECHANISM OF COAGULATION
The addition of a coagulating chemical, e.g., aluminum sulfate (alum),
ferric sulfate, etc., to remove turbidity or color in water has long been
recognized as an important process in surface-water treatment.^ Substances
that cause turbidity or color in water are, for the most part, small colloidal
particles that are usually negatively charged. These charged colloidal
particles will repel each other; therefore, the colloidal suspension will be
quite stable. Unless the local negative charges are neutralized by adding a
positively charged coagulant, these suspended colloidal particles will not
agglomerate to form larger aggregates which can be readily removed by
sedimentation.
Two theories predominate in the description of the effect of coagulants
on colloidal particles: the chemical theory and the physical theory. The
chemical theory assumes that colloids are particles with definite chemical
features and that coagulation is the result of the precipitation of insoluble
complexes formed by chemical interaction.
The physical theory assumes that the reduction of the particles' surface
charge allows them to approach each other and coagulate. This theory emphasizes
the importance of the electrical double layers surrounding the colloidal
particles in the water and the effects of counter-ion adsorption.
Since a colloidal system cannot have a net electrical charge, the charge
on the particle at the particle/water interface must be balanced by an equal
number of oppositely charged ions in solution. An electrical potential exists
at the particle/water interface; counter ions are attracted to the interface
in proportion to the magnitude of the particle charge. Gouy and Chapman
introduced the concept of the diffuse double-layer to describe how the potential
(2)
falls off with distance from the particle surface. Stern suggested a
double-layer model in which the region near the surface was divided into two
parts. The first part consists of a layer of counter ions adsorbed at the
(2)
surface of a particle to form a compact so-called Stern layer.	This inner
layer is a consequence of the existence of strong electrostatic force as well
k

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as van der Waals forces. The second stratum of the counter ions extends into
the bulk of the solution and constitutes the Gouy diffusion layer. A proposed
double-layer model for colloidal particles and the corresponding potentials
are shown in Figure 2-1. The charge (iJO on these particles cannot be directly
measured. However, the related potential at the shear plane, which is
generally referred to as the zeta (5) potential, can be measured by several
techniques based on electrokinetic phenomena such as electrophoresis,
electroosmosis, streaming potential, and sedimentation potential.
The zeta potential is a function of the concentration of counter ions in
solution. As the level of concentration of counter ions is increased, the
diffuse layer contracts until the point where van der Waals attractive forces
are stronger than the repulsive forces indicated by zeta potential. This is
called the critical coagulation concentration.(CCC), at which coagulation
results. In general, polyvalent counter ions are more effective than mono-
valent counter ions. This is due to the fact that polyvalent counter ions
have higher charge densities and, consequently, greater ability to be accom-
modated more closely to the charged particle surface. The observed results
follow the Schulze-Hardy rule, which states that a bivalent ion is 60-70 times
more effective than a monovalent ion, and a trivalent ion 700-1000 times more
(3)
effective than a monovalent ion. A detailed descriotion of the double-layer
(4)
theory was presented by van Olphen.
Although the mechanism of the actions of coagulants on suspended particles
can be described by theories discussed above, no simple mathematical model
fully predicts the actual kinetics of the coagulation processes. The diffi-
culty is that too many variables, such as particle concentration, size, and
the relative tendency of the particles to cohere, are involved in the real
processes. A general review of the kinetics and sedimentation of flocculent
suspensions is given by Fitch.^
2.2 SYNTHETIC POLYMERS AS COAGULANT AIDS
Most coagulant aids are organic polymeric compounds that are used along
with inorganic coagulants. These organic polymers are generally called poly-
electrolytes. Polyelectrolytes possess ionizable sites or hydrophilic func-
tional groups along the polymer chain.^ Polymers exhibiting negative charges
at all ionizable sites upon dissociation are referred to as anionic polyelec-
trolytes; and those that exhibit only positive charges are called cationic
5

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polyelectrolytes. Polyelectrolytes that contain both positively and negatively
charged sites upon dissociation are called polyampholytes, whereas those that
are nonionic, possessing only hydrophilic groups, are referred to as nonionic
polyelectrolytes.
Polyelectrolytes are effective at extremely low concentrations generally
(7 g\
in the mg11 level. ' Simple charge neutralization theory does not fully
describe the function of polyelectrolytes in destabilization of colloids.
For example, some nonionic or anionic polyelectrolytes are used to destabilize
negatively charged colloids.	La Mer and Healy^^ and Black, et al^^
have developed a chemical bridging theory. The authors propose that poly-
electrolyte molecules attach themselves to the surface of colloidal particles
at one or more adsorption sites; the remainder of the molecule extends into
the solution. This process called flocculation is illustrated in Figure 2-2.
The extended segment may adopt several configurations: it may interact with
vacant adsorption sites on another colloid and form a chemical bridge between
the particles (Reaction 2); it may fail to find a suitable adsorption site on
another colloidal particle and eventually adsorb at other sites on the original
surface to form a restabilized colloid (Reaction 3); or, in the case of over-
dosage, the excess amounts of polyelectrolyte will saturate the adsorption
sites of the particle surface, and no polymer bridge can be formed (Reaction 4).
Adsorption of the polyelectrolyte on a colloidal particle may occur by a
number of different physical and chemical interactions, depending on the
characteristics of both the polyelectrolyte and the colloidal surface. When
polyelectrolyte and colloidal particles are of opposite charge, coulombic
attraction is likely to be the basis for the interaction. It is also possible
that adsorption may be caused by other chemical forces which can also lead to
(12)
destabilization of colloids.	Such possible chemical interactions include
ion exchange, hydrogen bonding, the formation of coordinative bonds and
linkages, van der Waals forces between the coagulant and the colloid, and
repulsion of the coagulant by the aqueous phase with subsequent adsorption of
the coagulant on the colloidal surface.
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Reaction 1
Initial Adsorption at the optimum Polymer Dosage
polymer
PARTICLE
destabilized particle
Reaction 2
Fldc Formation
flocculation
DESTABILIZED PARTICLES
FLOC PARTICLE
%
DESTABILIZED PARTICLE
Reaction 3
Secondary Adsorption of Polymer
No contact with vacant
sites on another particle
RESTABILIZED PARTICLE
Reaction 4
Initial Adsorption Excess
Polymer Dosage
+ o
excess polymers
stable particle %
(no vacant sites)
Fig. 2-2. Schematic Representation of the Destabi1ization of Colloids
by Polymers^'5)
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2.3 NATURAL PRODUCTS AS COAGULANT AIDS
Natural substances, such as starch, gelatin, and vegetable gums, have found
limited application as coagulant aids in the treatment of water. The traditional
starch products and natural gums were largely replaced by synthetic polyelec-
trolytes in the water treatment industries partially because some of these
natural products were found to cause a higher biological oxygen demand (BOD)
(13)
and would possibly cause problems in some industrial applications.
Most of the natural products used as coagulant aids are nonionic. However,
some of these natural products can be modified by chemical reagents, such as
sodium hydroxide, to become anionic or cationic macromolecules. Such modified
natural products are usually referred to as semisynthetics. Whether anionic,
cationic, or nonionic, the basic mechanism of coagulation of natural products is
postulated to be similar to that of the synthetic polyelectrolyte counterparts.
In brief, both the natural products and polyelectrolytes are macromolecules
having extended long chains with active sites which destabilize colloid particles
during coagulation via a proposed adsorption/bridging mechanism.
REFERENCES
1. Committee Report , "State of Art of Coagulation," J. AWWA, 63:99 (Feb. 1971).
2 Adamson, A.W., "Physical Chemistry of Surfaces," John Wiley and Sons,
Easton Pennsylvania (1971).
3.	Black, A.P., "Basic Mechanism of Coagulation," J. AWWA, 52:498 (April 1960).
4.	van Olphen, H., "An Introduction to Clay Colloid Chemistry," Interscience
Publishers, New York (1963).
5.	Fitch, B., "Sedimentation of Flocculent Suspensions: State of the Art,"
J. AIChE, 25(6):913 (1979).
6.	Fuoss, R.M., and Cathers, G.I., "Polyelectrolytes. I. Picrates of
4-Vinyl-Pyridine-Styrene Copolymers," J. Polymer Sci., 2:12 (1947).
7.	Cohen, J.M., Rourke, G.A., and Woodward, R.L., "Natural and Synthetic
Polyelectrolytes as Coagulant Aids," J. AWWA, 50:463 (April 1958).
9

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8.	Black, A.P., et al., "Effectiveness of Polyelectrolyte Coagulant Aids in
Turbidity Removal," J. AWWA, 51:247 (Feb. 1959).
9.	Brikner, F.A., and Edzwald, J.K., "Nonionic Polymer Flocculation of Dilute
Clay Suspensions," J. AWWA, 61:645 (Dec. 1969).
10.	La Mer, V.K., and Healy, T.W., "Adsorption-Flocculation Reactions of
Macro-Molecules at the Solid-Liquid Interface," Rev. Pure and Appl. Chem. ,
13:112 (1963).
11.	Black, A.P., Birkner, F.B., and Morgan, J.J., "Destabilization of Dilute
Clay Suspensions with Labeled Polymers," J. AWWA, 57:1547 (1965).
12.	O'Melia, C.R., "A Review of the Coagulation Process," Public Works,
100, 87 (May 1969).
13.	Meltzer, Y.L., "Water-Soluble Polymers. Recent Developments," Noyes Data
Corporation, New Jersey (1979).
10

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3. CLASSIFICATION OF COAGULANT AIDS
There are more than 400 coagulant aids which are currently manufactured
and/or available for distribution for use in the treatment of potable water
within the United States.^ These coagulant aids can be divided into two major
groups, natural and synthetic products. The synthetic products can further be
subdivided, according to polymer structure, into homopolymers and copolymers;
the natural products can be grouped into simple and modified products, then
further subdivided into nonionic, anionic, cationic, or amphoteric. The
synthetic products are shown in Table 3-1 and the natural products in Table 3-2.
In the following sections, the coagulant aids are classified by manufacturers
(Section 3.1) and by monomeric component (Section 3.2).
3.1 MANUFACTURERS CLASSIFICATION
Coagulant aids are manufactured and/or distributed by at least 50 companies
in the United States. The major manufacturers in the coagulant aid industry are
American Cyanamid, Dow, Nalco, Mogul, Calgon, Drew, Hercules, and Betz Laboratories.
These products are listed by trade name in Table 3-3 according to the alphabetical
order of the manufacturers and/or distributors, based on information from the
EPA "Report on Coagulant Aids for Water Treatment," April 1979. The following
physical properties of these coagulant aids are also presented in Table 3-3:
	Ionic nature - nonionic, anionic, cationic, or amphoteric
	Solution percentage - product concentration, as delivered, for liquid
polyelectrolytes
	Viscosity - product viscosity, as delivered, indicated in cps (centipoises)
(NV means nonviscous)
	Density - product density, as delivered, presented in g/mJl
	pH - pH value, as delivered, for liquid polyelectrolytes.
11

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.le
let
>ag
ba
Homopolvmer
Synthetic
Copolymer
ier " ct
Polyacrylamide
Dime thyldiallylammonium chloride
Poly (N,N-dimethyl-3,5-methylene piperidinium chloride)
Polymethylolmelamine
Polyethyleneimine
Acrylamide-Acrylic acid resin
Sodium Acrylate (acrylamide copolymer)
Acrylamide & acryloxyethylmethyldiethyl ammonium
methyl sulfate
Acrylamide & 8-methacryloxyloxyethyltrimethyl
Ammonium methyl sulfate
Dimethylamine & epichlorohydrin quaternized
Dimethylamino ethacrylate quaternary salt of
Dimethyl sulfate and acrylamide
Quaternized copolymer of monomethylamine and epichlorohydrin
Monomethylamine & epichlorohydrin
Linear polymer of dimethylamine and epichlorohydrin
Hydrolyzed Polyacrylamide

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"tfLF	: Narnrai i-naijuxanc hios. oaseu on ruivmei onutLuic
Simple
Potato Starch
Corn Starch
Staramic Starch
Sorbitol
Starch
Guar Gum
Sodium Alginate
321
Natural
Mod if ied
Potato Starch modified w/8-diethylaminoethylchloride
hydrochloride
Carboxymethylcellulose
Guar Gum treated w/diethylaminoethylchloride
hydrochloride

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EPA has no objection to the use of the following coagulant aids in the
treatment of drinking water. However, they are no longer available for purchase
within the United States:
Manufacturer and/or	Trade Name
Distributor
American Cynamid Company
Berdan Avenue
Wayne, NJ 07470
Berdell Industries
8-16 43rd Avenue
Long Island, NY 11101
Betz Laboratories, Inc.
Somerton Road
Trevose, PA 19047
Bond Chemicals Inc.
1500 Brookpark Road
Cleveland, OH 44109
Magnifloc 570-C
Magnifloc 1848-A
Magnifloc 1985-N
Berdell N-489 Flocculant
Berdell N-821 Flocculant
Berdell N-902 Flocculant
Betz Polymer 1140P
Betz Polymer 1150P
Betz Polymer 1240P
Betz Polymer 1250P
Betz Polymer 2840P
Betz Polymer 2850P
Betz Polymer 334OP
Betz Polymer 3350P
Polyfloc 4D
BondFloc Nl-101
(now carried by Metalene Chem.
Co.)
Celenese Polymer
P.O. Box 99038
Jeffersontown, KY
40299
Hallmark 81
Hallmark 82
Commercial Chemical
103 Pleasant Avenue
Upper Saddle River, NJ 07458
Dearborn Chemical (U.S.)	DearFloc 4943
300 Genesee Street
Lake Zurich, IL 60047
SpeediFloc //I
SpeediFloc if2
Dow Chemical USA
Barstow Building
2020 Dow Center
Midland, MI 48640
Cnlqon Corp.
Box 1346
Pittsburgh, PA 15230
Dowell M-143
PEI-600
PEI-1090
XFS-4145L
XFS-4192L
Coaeulant Aid #2
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Drew Chemical Corp.
701 Jefferson Road
Parsippany, NJ 07054
DrewFloc 21
DrewFloc 922
DuBois Research Laboratory
3630 E. Kemper Road
Sharonville, OH 45241
Fabcon International
1275 Columbus Avenue
San Francisco, CA 94133
Garratt Callahan
111 Rollins Road
Millbrae, CA 94031
GWP-16A-LT
FabFloc
Formula 74B
Formula 76
Formula 76A
Formula 78B
Formula 73
Formula 74E
M-701
M-702
M-705
Hercules Inc.
910 Market St.
Wilmington, DE
19899
Tretolite Division, Petrolite Corp,
369 Marshall Avenue
St. Louis, M0 63119
HercoFloc 805PWG
HercoFloc 821PWG
TolFloc 324
TolFloc 334
TolFloc 350
TolFloc 351
TolFloc 355
TolFloc 356
TolFloc 357
W.R. Grace & Company
Research Division
7379 Route 32
Columbia, MD 21044
FO-107
FO-115
GR-962
GR-963
Copolymer GR-989
Copolymer GR-996
Copolymer GR-997
Homopolymer GR-999
15

-------
3.2 BASED ON MONOMERIC COMPONENT
Since coagulant aids are high molecular weight organic polymers,
they can be classified according to the monomeric component. These coagulant
aids are grouped into six major classes based on the information on an EPA
(21
list of product and formulation for water additives. Polyacrylamide,
quarternary ammonium polyelectrolyte, and polyamine are the three synthetic
products. The three natural categories are starch, cellulose and gum, and
sodium alginate. Each category may be further divided into subclasses
(i.e., polyacrylamide and hydrolyzed polycrylamide are subclasses of the
acrylamide class). Coagulant aids, indicated by trade name, are listed
according to their class and subclass in Table 3-4.
A general description of these six classes is given in the follow-
ing sections.
3.2.1 Polyacrylamide
Acrylamide has long been known to produce water-soluble homopolymers
and copolymers of controllable molecular weight through vinyl polymeriza-
(3)
tion. The steps in the manufacture of acrylamide are given below:
2 + ^3. HCN Cu2Cl,	H,0
Hydrocyanic^ 2 2	2	0
155C 3Cld
2	HCHCH
1000C
Acetylene	Acrylonitrile Acrylamide
Purified acrylamide is a white crystalline solid having a molecular
weight of 71.08. It is soluble in water, alcohol, and acetone; but
insoluble in benzene and heptane. The solid is stable at room temperature
but may polymerize violently on melting. The melting point is 84.5C.
Reactions of acrylamide occur generally through the amide group and the
activated double bond. For example, acid or base-catalyzed hydrolysis of
acrylamide yields acrylic acid:
16

-------
CH2 = CH-CONH2 + H20 5or 0H > CH2 = CHCOOH + NH3
Various chemical properties of acrylamide are discussed in great
(A)
detail by American Cyanamid Company.
Acrylamide may be polymerized by a variety of techniques including
solution polymerization and emulsion polymerization. For the purpose of
drinking water treatment, some of the monomers with which acrylamide
has been copolymerized are: acrylonitrile (CH2=CHCN), acrylic acid
(ch2=chcooh).
Polyacrylamide is readily soluble in water. Most commercially
available polyacrylamides are in granular form or are dissolved in a
solvent rendering a solution suitable for application.
3.2.2 Quaternary Ammonium Polyelectrolyte
The reaction products of tertiary amines with alkyl halides are
referred to as quaternary ammonium compounds. ^ These compounds have
four carbon atoms linked directly to the nitrogen atom through covalent
bonds. The anion in the original alkylating agent is attached to the
nitrogen through an electrovalent bond. The chemical structure of a
quaternary ammonium compound is given below:
The R groups may be any hydrocarbon chain; X represents a halogen ion.
17

-------
There are a great variety of quaternary ammonium compounds and
their physical state ranges from highly crystalline solids to viscous
liquids. Copolymers of dimethylamine and epichlorohydrin, and cationic
homopolymers of dimethyl diallyl ammonium chloride are the most commonly
used quaternary ammonium coagulant aids.
The molecular structure of a copolymer of dimethylamine and epichlorohydrin
is
CH2 - CH - CH2-
CH,
. CH.
CH2 - CH - CH2-
OH
The cationic homopolymer of dimethyl diallyl ammonium chloride has the
following structure:

CH-CH
CH
I	I
N
,/\
CH.
CH
-*n
3.2.3 Polyamine
Amines can be polymerized to form water-soluble polyelectrolytes.
Polyamines such as polyethylenimine, copolymers of monomethylamine and
epichlorohydrin, polyalkylene polyamine, and polymethylolmelamine, have
been approved by EPA for use in the treatment of drinking water. The
polymerization of amines usually involves an initiation step and is
followed by a ring-opening reaction. The polymerization of ethylenimine
is illustrated below as an example.^
18

-------
ii ti	H H
+	--A
Step 1 HT\ / + H 	>	H \ J S
(Initiation) N	/ \
H	H H
ethylenimine
Step 2
(ring-opening)
H ? \ J1
c - c	c - c
H \ / H + H\/H
N*	N
H H	H
*
-V A
H N+ H
H NCH2-CH2-NH2
H, *
c - c
H \ /H
~ N+s
CH2CH2NH2
'V/*
H VH
I
H
H H
C - C
t	 >
H\ 'H
N>
vf (CHCHNH)H
H
H
C - C.
H
/h
,N
(CH2CH2NH)n_1H
C - C
H
N
i
H
H 
*C - C
rf N / ^
N
+ H
(CH2CH2NH)nH
19

-------
3.2.4 Starch
Starch is a carbohydrate composed of carbon, hydrogen, and oxygen in
the ratio 6:10:5. Starch is a polymer made up of many D-glucose units: ^
Starch can be modified by reactions of the hydroxy1 groups or by breaking
the polymeric chain at the bonds between the glucose units (depolymerization).
There are two structural forms of starch  amylase, a linear polymer,
(8)
and amylopectin, a highly branched, tree-like polymer.	Amylose has a
molecular weight range of roughly 40,000 to 340,000 (which corresponds to
250 to 2,000 glucose monomeric units), depending on the starch source and
method of isolation and measurement. It tends to form insoluble complexes
with iodine and many polar agents such as n-butanol, fatty acids, and
nitroparaffins.
On the other hand, amylopectin is a very large molecule with molecular
weight as high as 80 million, but with no general agreement about the size
of the molecule. Amylopectin is also composed of glucose chains but with
many branch points which usually occur as oxygen links between carbons
one and six:
20

-------
OH H	OH H
0
The relative proportions of amylose and amylopectin in the starch granule
(3)
vary with the starch source.
Starch
Granule size (vm)
Granule shape
% Amylose
Corn
4-26
round, polygonal
28
Waxy Corn
5-25
round, polygonal
0-6
Potato
15-100
oval
23
Tapioca
5-36
truncated, round, oval
18
Sago
15-65
oval, truncated
27
Wheat
2-38
oval, round
25
Rice
3-9
polygonal
17
The dispersibility and colloidal properties of starches can be
modified by a relatively simple chemical treatment. Cross-linking reactions
initiated by bifunctional reagents (e.g., epichlorohydrin, linear dicarboxylic
acid anhydrides, organic dihalides, divinylsulfone, formaldehyde, phosphorus
oxychloride, soluble metaphosphates, etc.) form reinforcing links between
molecules in the starch granules. Although the degree of cross-linking
is very small (one cross-link per 200 to 1000 glucose units), the treatment
21

-------
increases the resistance of starch pastes to the thinning effects of pro-
(3)
longed agitation, heating or prolonged exposure to acids or alkalies.
Other characteristics of starch can be modified by treatment with acids
or oxidizing agents. Controlled acid hydrolysis yields modified starches
in a wide range of viscosities all below that of the original starch.
They are prepared by heating a starch slurry with a small amount (0.2 to
2 percent) of strong acid until the desired fluidity is obtained.
Starch can be oxidized by agents such as sodium hypochlorite. Just
as with acid conversion, the oxidation takes place in an aqueous slurry
of the starch until the desired degree of conversion is reached. In addition
to cutting the chain length, hypochlorite treatment also oxidizes the
hydroxyl groups to carbonyl and carboxyl groups. The presence of these
*
bulky groups on the linear fraction of the statch disrupts the linearity
of the molecular chains somewhat so they cannot readily associate. Con-
sequently, retrogradation is hindered and these products yield more stable
dispersions and show less tendency to gel. The carboxyl groups also have
a solubilizing effect. Even though these converted starches are termed
"chlorinated starch", there are no chlorine groups bound to the polymer.
The contaminants present in starch, as in all natural coagulant aids
discussed in this section, are traces of chemicals used to modify the
substances. These contaminants are usually simple inorganic acids or
bases such as hydrochloric or sulfuric acid or sodium hydroxide or
bifunctional reagents listed above. Since these modifying agents are
introduced in such small quantities in relation to the natural coagulant
aid present, the cross-linking is carried to virtual completion. Because
of this, very little of the modifying agent is left unreacted in the
modified natural substance.
3.2.5 Cellulose and Gum
The sturcture of cellulose is very similar to that of starch: as shown
in the diagram below, cellulose is composed of D-glucose monomeric units.
The relative spatial arrangement of the oxygen atom connecting carbon atom
number one to the next glucose unit is the major sturctural difference
between starch and cellulose.
22

-------
In starch, this oxygen atom lies on the same side of the carbon ring as the
C-2 hydroxyl group. These atoms are in a "cis" arrangement, which is known
as an "alpha-linkage". Cellulose has a beta-linkage in which the connective
oxygen atom is trans, or on opposite sides, from the C-2 hydroxyl group.
This minor spatial difference is the main factor in the property differences
between starch and cellulose.
Cellulose tends to be more rigid than starch because of intermolecular
hydrogen bonding; its chains are bound closer together and are more extended
or more linear than starch chains. As a result, cellulose is insoluble
in water and generally less chemically reactive than starch.
A commonly used form of cellulose is a modified product, carboxymethyl-
cellulose. The basic manufacturing process consists of impregnating cellulose
with sodium hydroxide and causing the alkali cellulose thus formed to react
with monochloroacetic acid or sodium monochloroacetate to produce sodium
carboxymethylcellulose, the form in which the chemical is almost always
sold. The reaction to form carboxymethylcellulose is an etherification in
which the carboxymethyl group (-CH_COOH) is attached to the cellulose through
(3)
an ether linkage, R-O-CI^COOH. The reaction steps are as follows:
ROH + NaOH		 RONa + H20
RONa + ClCH2COONa	~ ROCH2COONa + NaCl
23

-------
Since there are several thousand hydroxyl groups in a typical cellulose
molecule, the extent of carboxymethylation may be controlled in order to
obtain desirable characteristics in the molecule. The chemical is stable
throughout a pH range of 2-10, and can easily be purified. As with other
polyelectrolytes, carboxymethylcellulose functions as a coagulant aid
by the process described in section 2.3. The hydroxyl and carboxyl groups
on the molecule offer potential sites for attachment of suspended material.
The chemical also produces a much lower biological oxygen demand (BOD)
than starch, so it is greatly favored. Unfortunately, carboxymethylcellulose
tends to absorb and hold moisture. For example, one common type of
carboxymethylcellulose at 77F and 50 percent relative humidity has an
(3)
equilibrium concentration of about 18 percent water.	For this reason,
its use as a coagulant aid is limited: the synthetic coagulant aids form
a much "drier" floe and a smaller volume of sediment.
Guar gum, another polysaccharide used as a natural coagulant aid, has
a molecular weight of approximately 220,000. Guar gum is isolated from
the endosperm of the guar seed, Cyamopsis tetragonalaba (L.), Taub. Leguminosae
which is cultivated in India as livestock feed. The water soluble fraction
of guar gum, which makes up 85 percent of the natural product, is composed
of D-galactose and D-mannose in a 1:2-ratio as shown below:
CHjOH
H OH
fH2	H h
I 	I i
H
0
H H
ch2oh

-------
The compound forms floe through its hydroxyl binding sites as do
(9)
the other natural polyelectrolytes discussed.
3.2.6 Sodium Alginate
This natural polyelectrolyte is extracted from giant brown seaweed
in which it makes up a large portion of cell walls. The chemical encom-
passes a family of polymers which contain varying proportions of D-man-
nuronic acid and L-guluronic acid. The free acid is quite hydrophilic;
(9)
it can absorb 200-300 times its weight of water and salts. It forms
a very bulky floe, and is not a good coagulant aid for use in sedimenta-
tion basins with limited volume. Synthetic polyelectrolytes which form
a more compact floe are usually preferred.
25

-------
TABLE 3-3
List of Coagulant Aids and Physical Properties



Water Solution Properties
Manufacturer
Trade Name
Ionic
Nature
Solution
Vlscoalty
cpa
Density
g/ml
pH
Allied Colloids, Inc.
U.I Itwlglit Place
Fairfield, NJ 07006
Percol LT-20
Percol LT-22
Percol LT-22S
N
C
C
1
1
1
500
830
1292
.641
.641
.641
6.0
5.0
5.0

Percol LT-24
C
1
123
.641
5.0

Percol LT-25
A
1
-
.641
6.0

Percol LT-26
A
1
-
.641
6.0

Percol LT-27
A
1
-
.641
6.0

Percol LT-28
C
1
1292
.641
5.0
AlKstiiic Chemical Co.
Ilox 3(14(1
Bid I.I, (III 44117
ALLSTATE NO. 2
ALLSTATE NO. 6





American Cyanainld Co.
Ucrdun Avenue
Wayne, N.I 07470
MAGNIFI.OC 513C
MAGNIFLOC S1SC
MACN1FL0C S17C
C
C
orlg.
NV

1.7-2.1

MAGNIFLOC 521C
C
orlg.
250

6. 5

MAGNIFLOC 571C
C





MACNIFLOC 572C
C

100-125

5.7

MAGNIFLOC 573C
C
orlg.
175-350

5.0-7.0

MAGNIFLOC 575C
C





MAGNIFLOC 577C
C





-------
TABLE 3-3
List or" Coagulant Aids and Physical Properties




Water Solution Properties



Ionic
Solution
Viscosity
Density

Manufacturer
Trade Name
Nature
Z
cps
g/ml
pH
American Cyanunld Co. (cont.)
MACNIFLOC
579C
C





MACN1FLOC
581C
C





MACNIFLOC
58 3C
C





MACN1FLOC
584C
C





MACNIFLOC
585C
C





MACNIFLOC
58 6C
C





MACNIFLOC
587C
C
orig.
100-200

5.0-7.0

MACNIFLOC
588C
C





MACNIFLOC
589C
C
orig.
200-500

5.0-7.0

MACNIFLOC
590C
C





MACNIFLOC
591C
C





MACNIFLOC
592C
C





MACNIFLOC
593C
C





MACNI F1.0C
594C
C





MACNIFLOC
59 5C
C





MACNIFLOC
596C
C





HACNIFLOC
598C
C





MACNIFLOC
84 3 A
A





MACNIFLOC
844A
A





MACNIFLOC
<
in
00
A





-------
TABI.E 3-3
List of Coagulant Aids and Physical Properties
Manufacturer
Trade Name
Ionic
Mature
Hater Solution Properties
Solution
X
Viscosity
cps
Density
g/ml
PH
American Cyanurold Co. (cont.)
MACNIFLOC
84 6A
A





HACNIFLOC
847A
A





MACNTFLOC
848a
A





MAGNI FI.OC
860A
A





MACNTFLOC
97 IN
N





MACNIPLOC
972N
N





MACNIFLOC
98 5N
N





MACNI FM)C
990N
N





MACNIFI-OC
1849A
A
orlg.
300-600



MACNIFLOC
1946A (with Actl-
A





vator 478 In ratio of 10:1.






MACNI Fl-OC
1986N
N
orig.
300-600



CYPLOC (R)
4500






CYF1.0C (R)
550






CYFLOC (R)
6000






SUPERFLOC
C577






SUPKRFI.OC
C587






-------
TABLE 3-3
List of Coagulant Aids and Physical Properties



Hater Solution Properties
Manufacturer
Trade Name
Ionic
Nature
Solution
Z
Viscosity
cpa
Density
g/ol
pH
AO HA IIIIN Cliemlcul
23881 Vlu Kubrlcante, STK 517
Mission Vltjo, CA 92691
Hydrofloc 40
llydrofloc 45
llydrofloc 62
Hydrofloc 65
Hydrofloc 225

1

.7
8.0
A<|uu liberatories and
Churn leal Co., Tnc.
I'.O. Box 5725
l-oni*vlcw, TX 7 5604
A1.CO-FLOC (1
AI.CO-FLOC 58





Aqua/Process, Inc.
CA-75
CA-82
CA-84
CA-86
CA-95
CA-96
CA-97
CA-98
CA-99
D-67






-------
TABLE 3-3
List of Coagulant Aids and Physical Properties



Water Solution Properties


Ionic
Solution
Viscosity
Density

Manufacturer
Trade Name
Nature
Z
cps
g/ml
pH
Atlas Clii-inlcal Division
ATLASEP-PWfi-11





IC1 America, Inc.
Wilmington, DE 19899
ATLASEP-PUC-44
ATLASEP-PUC-77
ATLASEP-PWG-255
AT1.ASEP-PWG-1010
SORBO





AVEliE America, Inc.
Plocgel
A




10?5 W. St. Ccorge Avenue
l.lnjen, N.I 07016
Flocgel A
A




(Formerly KSII Chemical a Corp.)
Flocgel SN
HlsproFloc 20
C




Hay Clieinlrul und Supply Co.
Bayfloc 901





P.O. bo* 1581






Corpus Clirlsti, TX 78403






Uetz laboratories, Tnc.
Betz Polymer HOOP
A


1.057

Somurton Koud
Trevose, I'A 19047
Betz Polymer 1110P
Betz Polymer 1120P
Betz Polymer 1130P
Betz Polymer 1160P
A
A
C


1.057
1.057
1.057
.446


Betz Polymer 1190

or lg.

1.112
7.1

-------
TABLE 3-3
List of Coagulant Aids and Physical Properties
Manufacturer
Trade Name
Ionic
Nature
Water Solution Properties
Solution
Z
Viscosity
cps
Density
g/ml
pH
BuLz Laboratories, Inc. (cont.)
Betz Polymer 1200P






Becz Polymer 1205P
A


1.057


Betz Polymer 1210P
A


1.057


Beti Polymer 1220P
A


1.057


Betz Polymer 1230P



1.057


Betz Polymer 1260P
C


.446


Betz Polymer 1290

orlg.

1.112
7,1

Betz Polymer 2B00P
A


1.057


Betz Polymer 2810P
A


1.057


Betz Polymer 2820P
A


1.057


Betz Polymer 2830P



1.057


Betz Polymer 2860P
C


.446


Betz Polymer 2B90

orlg.

1.112
7.1

Betz Polymer 3300P
A


1.057


Betz Polymer 3310P
A


1.057


Betz Polymer 3320P
A


1.057


Betz Polymer 3310P



1.057


Betz Polymer 3360P
C.


.446


Betz Polymer 3390

orlg.

1.112
7.1

-------
TABLE 3-3
List of Coagulant Aids and Physical Properties



Water Solution Properties
Manufacturer
Trade Name
Ionic
Nature
Solution
X
Viscosity
cps
Density
g/ml
P"
Bets: Laboratories, Inc. (cont.)
Betz Polymer 1115LP
A
5
750-900
1.008
5.0

Betz Polymer 121SLP
A
5
750-900
1.008
5.0

Betz Polymer 2815LP
A
5
750-900
1.008
5.0

Betz Polymer 3315LP
A
5
750-900
1.008
5.0

Betz DK-720
C
or lg.
6,600
1.148
5.1

Betz DK-724
C
orlg.
628
1.046
8.0

Betz Entec 600
N
orig.

1.005
5. J

Betz Entec 610

orlg.

1.112
7.1

Betz 620
A


1.057


Betz Entec 622
A


1.057


Poly-Floc 3
N
orlg.

1.005
5.3
Urennan Chemical Co.
7(l'i North First Street
SI. Louis, MO 61102
BRENCO 870
BRENCO 880





The llurton lie* Company
Nn I ley, N.I 07 UO
Burtonlte #78




6.0
Cal^on Corporation
I'.O. Box 1346
rittshurg, I'A 15210
Coagulant Aid 018
Coagulant Aid 0233
Coagulant Aid #250
N
.1
10
.72
7.0

-------
TABLE 3-3
List of Coagulant Aids and Physical Properties




Hater Solution
Properties



Ionic
Solution
Viscosity
Density

Manufacturer
Trade Name
Nature
Z
cps
g/ml
pH
Calgon Corporation (cont.)
Coagulant Aid >24]
A
1.0

.56
7.0

Coagulant Aid #253
A
l

.56
7.0

Coagulant Aid 0961






Cat-Floe
C
orlg.
2,000

3.5

Cat-Floe A
C
orlg.
15

3.5

Cat-Floe B






Cat-Floe C
c
orlg.
1,000-3,000

3.5

Cat-Floe R
c
orlg.
10

3.5

Cat-Floe S
c
orlg.
100

3.5

Cat-Floe T
c
orlg.
35

3.5

Cat-Floe T-l
c
orlg.
10

3.5

Cat-Floe T-2






Cat-Floe 21
II
ii
35-115

n

CatrFloc 121
II
ii


ii

Polymer M-502
II
ii
4,000

ii

Polymer M-503






Polymer M-50f






1.-650E
N
orlg.
10,000-20,(00

4.5-6.5

1.-675
A
or lg.
1,000-2,500


C-K Minerals
Zeta I.yte (TM) 1C
C
orlg.
100-200
1.03-1.05
5.0-7.0
Combust Ion KngIneer1ng, Inc.
Zeta I.yte (TM) 2C
c
orlg.
50-125
1.01-1.04
5.0-7.0
901 Kuat Hill Avtmuu




King ol' Prusslu, PA 19406
Zeta Lyte (TM) 3C
C
orlg.
NV
1.0-1.1
1.6-2.2
(Formerly Nnrvon Mining)







-------
TABLE 3-3
List of Coagulant Aids and Physical Properties



Water Solution Properties
Manufacturer
Trade Name
Ionic
Nature
Solution
Z
Viscosity
cps
Density
g/ml
pit
OR Minerals (cone.)
Zeta Lyte (TM) 4C
C
orlg.
175-350
1.14-1.18
5.0-6.0

Zeta Lyte (TM) 5C
C
orlg.
175-350
1.14-1.18
5.0-6.0

Zeta Lyte (TM) 1A
A
orlg.
1,000-2,500
1.0


Zetu Lyte (TM) 2A
A
.5
650
.705
7.0

Zeta Lyte 2N (NonIonic
Polyelectrolyte)
N





Zeta Lyte 7C (Cat Ionic
Polyelectrolyte)
C
orlg.
300
1.08
4.40

Zeta Lyte 23C






Zeta Lyte 43C






Zeta Lyte SIC (Cat IonJc
Polyelectrolyte)
C





Zeta Floe (R) HA

orlg.

2.5
5.2-5.5

Zeta Floe (R) UA Special

orlg.

2.5
5.2-5.5

Zeta Floe (R) UA 500

orig.

2.5
5.2-5.5

Zeta Floe (R) UA 1000

orlg.

.865
5.2-5.5

Zeta Floe (R) UA 3000

orlg.

.865
5.2-5.5

Zetu Floe WCF-312

2
68-72
2.5
4.7

-------
TABLE 3-3
Liat of CoagulanC Aids and Physical Properties



UaCer Solution Properties
Manufacturer
Trade Name
Ionic
Nature
Solution
I
Viscosity
cps
Density
g/ml
pll
Celanese Polymer Specialties Co.
P.O. Box 99038
.Iijffersontown, KY 40299
(Kormerly Stein, Hall & Co.)
Jaguar UPB
Jaguar UST
Jaguar HRL-22A
N
N
C
1
1
1
2,500
3.500
1,200
.721
.721
.721
5.9-6.3
5.9-6.3
5.5-6.0

Polyhal1 H-295-P.W.
A
.1
12.500
.721
7.0-8.5

Polyhall 347
C
orig.
550-750
1.14-1.18
5.5-7.5

Polyhall 351
C
orig.
4.000-6,000
1.14-1.18
4.5-5.5

Polyhall 355
C
orig.
30-60
1.03-1.05
5.0-7.0

Polyhall 357
C
orig.
100-200
1.03-1.05
5.0-7.0

Polyhall 361
C
orig.
700-2,000
1.03-1.05
5.0-7.0
Craig Adlieslves Co.
80 Wheeler Point Road
Newark, N.I 07105
Craig-FKCA-100

5

240
5.0-6.5
Cu11tgan , USA
One Culll^an Parkway
Northbrook, fl. 60062 -
F-86
C




Dearborn Chemical (U.S.)
100 Cene.sce Street
lake /.urleh, 11. 60047
Aquafloc 401
Aquafloc 408 (liquid)
Aqua floe 409
A
A
orig.
1
1,500
2,350
1.01
1.0
3.0-4.0
4.0-5.0

Aquafloc 411
A
2
480
1.0
4.0-5.0

-------
TABLE 3-3
List of Coagulant Aids and Physical Properties



Water Solution Properties


Ionic
Solution
Viscosity
Density

Manufacturer
Trade Name
Nature
Z
cps
g/ml
pH
Dow Chemical, USA
Purlfloc A22
A
1
4,800
1
10.0-11.0

Purlfloe A23P
A
0.1
950
1
9.8

Purlfloc A23P-S
A
0.1
950
I
9.8

Purlfloc C31
C
orlg.
12,000
1.2
8.0-10.0

Purlfloc N17-S
N
1
490
1
6.0-7.0

Purlfloc N20-S
N





Separan AP30
A
1
3,000-4,000
1
10. 1

Scparan AP30-S
A
1
3,000-4,000
1
1(1.3

Separan AP273
A
0.5
2,000
0.76
10.1

Separan NP10P
A
1
175-300
1
7.0

Separan NP10P-S
A
1
175-300
1
7.0

XD 7817.00 (exp. Polymer)





Drrw Churn lea I Corp.
AMERFI.0C 10
C
orlg.
NV

1.5-2.2
7(11 Jefferson Itond





I'arslppuny, NJ 07054
AMERFI.0C 265
A
1
100-250

5.4

AMERP1.0C 275
A
1
1,100-2,000

7.0

AMERFI.0C 307
N
1
70-140

5.0

AMERF1.0C 445
C
orlg.
175-200

4.7-5.1

AMERFI.0C 485
C
orlg.
200-400



AHERF1.0C 490
C
orlg.
3.50CI-6.000



-------
TABLE 3-3
List of Coagulant Aids and Physical Properties



Water Solution Properties


Ionic
Solution
Viscosity
Density

Manufacturer
Trade Name
Nature
Z
cps
g/ml
pH
lircw Chemical Corp. (cont.)
AMERFLOC 2265
A
0.5
40-90



Dreufloc 1
N
orlg.
100-150
1.47
11.5-12.5

Drewfloc 3

2
35-50
1
6-7.5

Rrewfloc 4
A
1
20

7.0-7.5
IfciHols ('hemleals
FLOCCULITE 550
A
1

1.1-1.2
10.0
lllv. uf W.R. Grace & Co.
1630 r*. Ki^nper Koad
F1.0CCUI.ITE 551
A
orlg.

8.35
9.5
Sli.i ronv 111 e, Oil 45241
SPLIT
N
orlg.

8.64
8.5
K.ilx-on International
Zuclar 110 PU





1 2 7 5 Cnltiiuliua Avenue
S;in Kranclbco, CA
Fabcon
Zuclar 220 PW
Zuclar 990 PW





llt:nry W. I'lilk & Co.
No. 102 Kleer-Floc
A
1
2,500
.577
10.3
Sllvertun Avenue
Cincinnati, OH 45236
No. KM Kleer-Floc
N


.533


No. 109 Kleer-Ploc
A
1
100
.513
7.0

No. 116 Kleer-Floc
C
orlg.

10 lb/gal.
8.0-10.0

No. 119 Kleer-Floc
A
1
500-3,500
.752
10.1

No. 120 Kleer-Floc
N
1
-
.497
8.2

No. 458 Kleer-Floc
C
orlg.
200-400
1.10-1.20


-------
TABLE 3-3
List of Coagulant Aids and Physical Properties



Water Solution Properties


Ionic
SolutIon
Viscosity
Density

Manufacturer
Trade Name
Nature
Z
cps
g/ml
pH
Henry U. Fink & Co. (cont.)
No. 460 Kleer-Floc
C
orlg.
175-200
1.03-1.05
4.7-5.1

No. 461 Kleer-Floc
C
orlg.
-
3,500-6,000
1.10-1.20

No. 462 Kleer-Floc
C
orlg.
NV
1.05
1.5-2.2

No. 4B1 Kleer-Floc
C
orlg.
2,000
1.025
3.5

No. 4B2 Kleer-Floc
C
orig.
35

3.5

No. 483 Kleer-Floc
C
orlg.
10

3.5

No. 1702 Kleer-Floc
A


.688
7.0

No. 117 Coagulant Aid


280-2,000
1 .451-1 .456


No. 118 Coagulant Aid





Cjailun Chemical Co.
Camlose W
A




4 Midland Avenue






Klmwoori, NJ 07407
<>amlen Wlsprofloc 20






Ganafloc Nl-702






Cumfloc PWS





Inlian
Coagulant Aid 72A
A
orlg.
65
1.32
11. 5
1 i1 llol1 Ins Koad



Mi 1 Hiriii.-, cn 94'.)31
Coagulant Aid 78B
C
orlg.
4,000-16,000

1.0

Kormuln 70A 760-N
A
1

.529
7.5

Formula 763N
A
1

.513
8.2

Formula 7 64N
A
1

.511
7.0

Formula 765N
A
1

.513
7.5

-------
TABLE 3-3
List of Coagulant Aids and Physical Properties



Water Solution Properties
Manufacturer
Trade Name
Ionic
Nature
Solution
X
Viscosity
cps
Density
g/ml
pH
Gnrratt-Callahan (cont.)
Formula 766N
A
.3

.561
7.5

Formula 746-A
A
1

.625
If). 3

Formula 748-A
A
.5

.753
10.1

Formtila 740-AP
A
.5

.737
10.1

Formula 720-CL
C
20


H.9

Formula 721-CI.
C.
orlg.

8.34 lb/gal.
10.11

Formula 741-A
A
.5

.737
10.1

Formula 742-A
A
.5

.737
10.1

Formula 743-A
A
.5

.801
10.1
Ili-iikel Chctnfrjil
4620 W. 77tli Street
Mlmied|>o) Is, MN 55435
(I'orinerly General Mills Chemical)
SUPERCOl. Guar Gum
CUAKTEC F
CUAKTEC S.I
N
1
3,200
1
6.0-7.0
Got-ium ('tii'm 1 cj 1 Compuny
27 Traverse Ave., P.O. Box 133
Port Chester, NY 10573
Ctrril0F1.0C 283 PWG
GOTIIOFLOC 383 PWC
C
C
1
1
10
11)

6.0-8.0
6.0-8.O
Hercules, Inc.
'JKI Market Street
Wl liulngton, DK 19899
Carkoxymethylcellulose
Hereofloc 812 PWG
Hereof Ion 815 PUG
A
C
C
2
1
1
780
950
.75
.7
.7
7.5
6.0
6.0

Hereofloc 818 PUG
A
1
1,300
.7
8.5

-------
TABLE 3-3
List of Coagulant Aids and Physical Properties



Water Solution Properties


Ionic
Solution
Viscosity
Density

Manufacturer
Trade Name
Nature
Z
cps
8/ml
pH
Hercules, Inc. (cone.)
llercofloc 863
C
1
AO-60

6.0-8.0

Hereofloc 1018 PUG
A
1
6-0
.7
8.5

Hercofloc 1021 PUG
A
1
1,250
.7
8. 5

llercofloc 1031 PUG
A
1
1,050
.7
8. 5

Hercules SP944 (with 2,000
A
1
1,300

7.5

mg/1 line slurry - 10%






CaO)





Krunk llerz 1 Corp.
Perfectamyl Ail 14/2





ISO Kast 58l1i Street






New York. NY 10022






Illinois Water Treatment Co.
Illco 1 FA 313

orlg.
15.000
1.08
6.6-7.5
840 Cuilnr Street






Hock lord. II. 61102






Kelco Company
Kelgln U

0.5
240
1
7.8
H22 5 Auro l)r 1 ve
San llleKo. CA 92123
Kelcosol

0.5
350
1
7.8
KIIKITA Mater Industries ltd.
KURIKI.0CK PA-322





i:/u C. ltoli & Co.
(America) Inc.
KIIRIFLOCK PA-331





270 Park Avenue






New York, NY 10017







-------
TABLE 3-3
1.1st of Coagulant Aids and Physical Properties




Water Solution
Propertles

Manufacturer
Trade Name
Ionic
Nature
Solution
X
Viscosity
cps
Density
g/ml
pll
Mi'Lalent! Chcmicdl Co.
U oil ford , nil 44014
Hetalene Coagulant P-6
C
orig.
50-70
1.45
7.H
I'lit: Mogul Corporation
Cii.irgln Pallu, Oil 44022
MOCUL-CO-940
MOGUL-CO-941
MOGUL-CO-982






MOGUL-CO-983
A
orlg.
3,000-4.000
1
6.0-7.0

MOGUL-CO-984

orig.

1.003
9.8

MOCtIL-CO-985






MOGUL-PC-1901A
A





M0CUL-PC-1905A
A





MOGU1.-PC-1911C
C





MOCUI.-PC-1913C
C





MOCUI.-PC-1914C
c





MOCI1I.-PC-1921N
N





MOGUL-PC-1943N
N





M0CUL-PC-1950






MOCUI.-6913A
A





MOCUL-6903C
C





MOCU1.-6921C
C





MOGUL-6923N
N





-------
TABLE 3-3
Llat of Coagulant Aids and Physical Properties
Manufacturer
Trade Name
Ionic
Nature
Water Solution Propertlea
Solution
Z
Viscosity
cps
Density
g/ml
pH
Tin; Mogul Corporation (cont.)
MOCUL-7903C
C





MOGUL-7913A
A





MOCUL-7923N
N





MOGUL-9001A
A
1
3.400

7.0

MOCIJ1.-9003C
C
orlg.
250

6.5

MOGIII.-9013A
A
orlg.
4,000

7.0

M0GUL-9021C
C
orlg.


1.7-2.0

MOGII1.-9023N
N





M0GUL-9032C
C
orlg.
4,000-6,000



MOCIJL-9035A
A





MOGUI.-9036N
N





MOGUL-9043N
N





M0CUL-9044A
A





MOCUL-9045C
C





MOCUI.-9046C
C





MOGU1.-9050C
C





MOGUL-907OC
C





M0CUI.-PC-194 5C
C





MOGUL-PC-1946C
C





-------
TABI.e 3-3
List of Coagulant Aids and Physical Properties



Uater Solution Properties
Manufacturer
Trade Name
Ionic
Nature
Solution
X
Viscosity
cps
Density
g/ml
pH
Nulco Chemical Co.
2901 Rutterfleld Road
Oakbrook, IK 60S21
Nalcolyte X10A
Nalcolyte 671
Nalcolyte 7870
N
N
5
1
560
450
.400
1
6.0-7.0
7.0-8.0

Nalcolyte 8100
C
orlg.
700
9.67 lb/gal.
3.0-1.5

Nalcolyte 8101
C
orlg.
100
9.17 lb/gal.
3.0

Nalcolyte 8102
C
orlg.
250
9.09 lb/gal.
4.5

Nalcolyte 8103
C
orlg.
900
9.09 lb/gal.
4.5

Nalcolyte 8104
C
orlg.
165
8.7 lb/gal.
4.0

Nalcolyte 8105
C
orlg.
150
9.57 lb/gal.
7.6

Nalcolyte 8106
C
orlg.
35
9.04 lb/gal.
7.3

Nalcolyte 8113






Nalcolyte 8114
C
orig.
90
9.6 lb/gal.
8.5

Nalcolyte 8142
C
orlg.
75
9.09 lb/gal.
4.5

Nalcolyte 8143
C
orlg.
900
9.09 lb/gal.
4.5

Nalcolyte 8170

.5

.721
8.0

Nalcolyte 8171






Nalcolyte 81 72






Nalcolyte 8173
A
.5
1800
.705
7.0

Nalcolyte 8174






-------
TABLE 3-3
List of Coagulant Aids and Physical Properties




Hater Solution Properties
Manufacturer
Trade Name
Ionic
Nature
Solution
Z
Viscosity
Cp8
Density
g/ml
P
Nulco Chemical Co. (cont.)
Nalcolyte
Na]colyte
8175
8180






Nalcolyte
8181
N
1
150



Nalcolyte
8182
A
1
300
B.A Lb/gal.


Nalcolyte
8184
A
1
2500
8.6 lb/gal.


Nalcolyte
8770






Nalcolyte
8771






Nalcolyte
8775






Nalcolyte
8780






Nalcolyte
8781






Nalcolyte
8783






Nalcolyte
8784






Nalcolyte
8790






Nalcolyte
8791






Nalcolyte
8792






Nalcolyte
8793






Nalcolyte
8794






Nalcolyte
8795






Nalcolyte
8796






-------
TABLE 3-3
1.1st of Coagulant Aids and Physical Properties



Water Solution Properties
Manufacturer
Trade Name
Ionic
Mature
Solution
Z
Viscosity
cps
Density
8/ml
pH
N:ilco Chemical Co. (cont.)
NALC0 600-SS1
NAI.C0 600-SS 1-0
NALCO 7852
NALC0 7865
NAI.C0 8850
NAI.C0 8852
C
orlg.
700-4,000
1.14
12.4
Njii fonuL Starch & Chemical Corp.
Floc-Aid 1038
N
0.5
20-30
1
<6.0-7.0
1700 W. Front Street
I'lalnfleld, NJ 07063
Floc-Ald 1063
C
0.5
45
1
<6.0-7.0
O'Brien Industries, Inc.
O'B Floe

2
10
9-10

9*i Dorsa Avenue






1. Iv ln};ton, NJ 07039






01 In Watei Services
01.IN A500





01 111 Corporation
31 *>5 Fiberglass Road
OI.TN 4502





Kjnsus City, KS 66115
OLIN 4515
Ol.l N 4517
0L1N 5108
OLIN 5109
OLIN 5110






-------
TABLE 3-3
List of Coagulant Aids and Physical Properties



Water Solution Properties
Manufacturer
Trade Name
Ionic
Nature
Solution
X
Viscosity
cps
Density
g/ml
PH
Oxford Chemical Dlv.
Consolidated Foods Corp.
P.O. Box 80202
Atlanta, CA 30341
OXFORD-HYDRO-FLOC





Puurl River Chemical Co.
P.O. Bux 1202
SUdell, \A 70459
PERCHEM 550





P() Systems, Inc.
P.O. Box 842
Vdlley Korge, PA
Actasol





Nnr lonnl Chemical
SKI.TC Chemical Industries
340 Sclig Drive
Atlanta, CA 30336
Superfloc 16228





W.A. ScholLcn's Chumtsche
K.ihr 1 ukcii H.V.
l-'oxhol , Posthus 1
Wlsprofloc P
C




A. K. iitaley Mfg. Co.
P.O. Box 151
Decatur, II. 62525
IIAMACO 196

1
<50
1
6.0-7.0
TUIeljnJs Chemicals
P.O. Box 487
Uestlake, I.A 70669
TTDE-TR0
TTDE-TR0 B
TIDE-TR0 B-l






-------
TAB1.E 3-3
1.1st of Coagulant Aids and Physical Properties
Manufacturer
Trade Name
Ionic
Nature
Hater Solution Properties
Solution
Z
Viscosity
cps
Density
g/ml
pH
Tretolltu Division
I'utrollte Corporation
*169 Marshall Avenue
St. Iiouls, MO 63119
lainus Vurley & Sons Inc.
120D Swltzcr Avenue
St. I.onls, MO 63147
Wall lily Chemical Company
P.O. Hox '.OR
Slotix Kails, SI) 57101
T0LFI.0C 333
VARCO-FLOC
Wall floe
615
Wallfloc
617
Wallfloc
621
Wallfloc
623
Uallfloc
672
Wallfloc
673
Wall floe
675
Uallfloc
677
Wall floe
679
Wa11floc
681
Wallfloc
685
Wallfloc
686
Uallfloc
687
orlg.
orlg.
2,00(1
1.02
1.005
3.4
U. 0

-------
TABLE 3-3
1.1st of Coagulant Aids and Physical Properties
Manufacturer
Trade Name
Ionic
Nature
Water Solution Properties
Solution
X
Viscosity
cps
Density
g/ml
PH
Walling Chemical Company (cont.)
X 1 nun 11 e Inc.
BIO Sharon Drive
West lake. Oil 44145
Uallfloc 688
Uallfloc 689
Uallfloc 690
Uallfloc 691
Uallfloc 944
Wall floe 945
Uallfloc 946
Uallfloc 947
Uallfloc 1085
Uallfloc 1090
Uallfloc 2849
Uallfloc 2986
Zimmlte ZC-301
Zimmlte ZT-600
Zimmlte ZT-601
Zimmlte ZT-601
ZM-100
ZM-130
ZM-137






-------
TABLE 3-3
List of Coagulant Aids and Physical Properties



Water Solution Properties
Manufacturer
Trade Name
Ionic
Nature
Solution
Z
Viscosity
cpa
Density
g/ml
PH
ZltumLCe Inc. (cont.)
ZT-616
ZT-621
ZT-622
ZT-623
ZT- 624
ZT-625
ZT-626
ZT-627
ZT-628
ZT-636
ZT-637
ZT-643
ZT-6 44
ZT-649
ZT-650
ZT-651
ZT-656
ZT-657
ZT-660
A





-------
TABLE 3-I
List of Coagulant Aids and Physical Properties



-Hater Solution Properties
Manufacturer
Trade Name
Ionic
Nature
Solution
Z
Viscosity
cps
Density
g/ml
PH
Z iminlce Inc. (cunt.)
ZT-661
ZT-669
ZT-680
ZT-684
ZT-686


-



-------
TABLE 3-4
Coagulant Aids Based on Monomeric Component
OVULATION
TRADE NAME
PHYSICAL APPEARANCE
S
SUBCLASS




\i flamide
U79-06-1
1.1 Sodium Acrylate
(acrylamide copoly-
mer)
ATLASEP PWG 11
ATLASEP PWG 44


ATLASEP PWG 77



ATLASEP PWG
L010



BETZ
ENTEC 620
P


BETZ
ENTEC 622
P


BETZ
POLYMER
hoop
P


BETZ
POLYMER
1110P
P


BETZ
POLYMER
1120P
P


BETZ
POLYMER
1130P
P


BETZ
POLYMER
1160P
P


BETZ
POLYMER
1200P
P


BETZ
POLYMER
1205P
?


BETZ
POLYMER
121 OP
P


BETZ
POLYMER
1220P
P


BETZ
POLYMER
123 OP
P


BETZ
POLYMER
1260P
P


BETZ
POLYMER
1290
L


BETZ
POLYMER
28 OOP
P


BETZ
POLYMER
2810P
P


BETZ
POLYMER
2820P
P


BETZ
POLYMER
2830P
P


BETZ
POLYMER
2860P
P


BETZ
POLYMER
2890
L


BETZ
POLYMER
3300P
P

51





-------
TABLE 3-A
Coagulant Aids Based on Monomeric Component
OVULATION
TRADE NAME
PHYSICAL APPEARANCE
S
SUBCLASS




BETZ POLYMER 331 OP
P


BETZ POLYMER 3320P
P


BETZ POLYMER 333OP
P


BETZ POLYMER 3360P
P


BETZ POLYMER 3390
L


NALCOLYTE 8173
P


NALCOLYTE 8174
P


NALCOLYTE 8172
L


NALCOLYTE 8175
P


NALCOLYTE 8170
P

1.2 Polyacrylamide
ALLSTATE NO. 6
P


FLOCULITE 550



FLOCULITE 551
P


ZUCLAR 110 PW
P


GOTHOFLOC 283 PWG
L


GOTHOFLOC 383 PWG
L


NO. 735 KLEER-FLOC



AQUAFLOC 409
P


AQUAFLOC 411
P


AQUAFLOC 408
L


PERCOL LT 25



POLYHALL M-295-PW
P


AMERFLOC 2265
L


BETZ POLYMER 1115LP
L


BETZ POLYMER 1215LP
L


CALGON COAGULAI1T AID v'233
L

52



-------
TABLE 3-4
Coagulant Aids Based on Monomeric Component
?l1ULATION
TRADE NAME
PHYSICAL APPEARANCE
>S
SUBCLASS




BETZ POLYMER 2815LP
L


BETZ POLYMER 3315LP
L


AMERFLOC 307
P


AMERFLOC 265
P


AMERFLOC 275
P


ZT-661
P


ZT-637



ZT-644
P


ZT-651
P


ZT-603
P


ZT-301



ZETA LYTE (TM) 1A
L


ZETA LYTE (TM) 2A
P


M0GUL-9025N
P


MOGUL-7913A



MOGUL-6913A



MOGUL-9013A
L


MOGUL-C0-983



MOGUL-9001A
P


MOGUL-CO-984



MOGUL-PC-1901A
P


MOGUL-9036N



MOGUL-PC-1905A



MOGUL-9035A


53



-------
TABLE 3-A
Coagulant Aids Based on Mbnomeric Component
C^mATION
TRADE NAME
PHYSICAL APPEARANCE
s
SUBCLASS
NALCOLYTE 8171
P




NALCOLYTE 8182
P


NALCOLYTE 8184
P


CYFLOC 4500
P


CYFLOC 5500



MAGNIFLOC 860-A
P


MAGNIFLOC 1849-A
L


MAGNIFLOC 1986-N
L


MAGNIFLOC 971-N
P


MAGNIFLOC 972-N
P


MAGNIFLOC 985-N
P


MAGNIFLOC 990-N
P


MAGNIFLOC 845-A
P


MAGNIFLOC 846-A
P


MAGNIFLOC 847-A
P


MAGNIFLOC 1946-A



PERCOL LT 20
P


PERCOL LT 22
P


PERCOL LT 22-S
P


PERCOL LT 25
P


PERCOL LT 26
P


PERCOL LT 27
P


PERCOL LT 28
P


ILLCO IFA 313
L


NALCOLYTE 671
P


54


-------
TABLE 3-4
Coagulant Aids Based on Monomeric Component
C"*IULATION
TRADE NAME
PHYSICAL APPEARANCE
b
SUBCLASS



-.3 Cationic copoly-



mer of acryla-



mide and acryl



oxyethylmethyl-



diethyl ammoni-



ummethyl sulfate
PERCOL LT 24
P


MOGUL-9046C
P


MOGUL-9045C
P

..4 Hydrolyzed poly-



acrylamide
NO 102 KLEER-FLOC
P


NO 109 KLEER-FLOC
P


NO 119 KLEER-FLOC
P


PURIFLOC N20-S
P


PURIFLOC N17-S
P


PURIFLOC A23P-S
P


SEPARAN AP30-S
P


SEPARAN AP273P-S
P


SEPARAN NP10P-S
P


ZT-657
P


MAGNIFLOC 843-A
P


MAGNIFLOC 844-A
P


MAGNIFLOC 848-A
P


CALGON #243



CALGON #253
L

1.5 Cationic copoly-



mer of acryla-



mide and 0-



methacryloxylox-



yethyltrimethyl



ammoniummethyl



sulfate




HERCOFLOC 815 PWG


55
HERCOFLOC 812 PWG


-------
TABLE 3-4
Coagulant Aids Based on Mbnomerlc Component
CUMULATION
TRADE NAME
PHYSICAL APPEARANCE
S
SUBCLASS
OLIN 4515


P


OLIN 4500
P


BRENCO #870


1.6 Acrylamide



acrylic acid



resin
OLIN 4517
P


OLIN 4502
P


BRENCO #880



GR-997
P


GR-996
P


GR-989
P


ZT-601



ZM-137

. Quaternary Amnion-
2.1 Copolymer of


um Polyelectro-
d imethylamine


yte
and epichloro-



hydrin, quater-



nlzed
BX-50



NALCOLYTE 8101



NALCOLYTE 8105



NALCOLYTE 8106



6WP-827



6WA-828



ALCO-FLOC if 8



AMERFLOC 445
L


AMERFLOC 490
L

56



-------
TABLE 3-4
Coagulant Aids Based on Monomeric Component
'(""IULATION
TRADE NAME
PHYSICAL APPEARANCE
IS
SUBCLASS
AMERFLOC 485
L


AMERFLOC 485
L


MAGNIFLOC 573C
L


MAGNIFLOC 575C
L


MAGNIFLOC 577C
L


MAGNIFLOC 579C
L


MAGNIFLOC 572C
L


MAGNIFLOC 581C
L


F-86
L


OLIN 5108



MOGUL 1914C



MOGUL 9032C
L


ZT-626



ZT-627



ZT-628



ZM-130



ZT-621



ZT-622



ZT-623



ZT-624



ZT-625



ZETA LYTE 4C
L


ZETA LYTE 5C
L

2.2 Cationic homo-
polymer of di-
methyl diallyl
ammonium chlor-
ide
NALCOLYTE 8100


57
NALCOLYTE 8142


-------
TABLE 3-4
Coagulant Aids Based on Monomerlc Component
CUMULATION
TRADE NAME
PHYSICAL APPEARANCE
S
SUBCLASS
NALCOLYTE 8132



CAT-FLOC
L


CAT-FLOC T
L


CAT-FLOC A
L


CAT-FLOC T-l
L


CAT-FLOC T-2
L


CAT-FLOC C
L


CAT-FLOC S
L


CAT-FLOC R
L


CAT-FLOC 21
t


CAT-FLOC 121
L


MAGNIFLOC 585C



MAGNIFLOC 586C



MAGNIFLOC 587C
L


MAGNIFLOC 58SC



MAGNIFLOC 589C



MAGNIFLOC 590C



MAGNIFLOC 591C



MAGNIFLOC 583C



MAGNIFLOC 584C



MAGNIFLOC 593C



MAGNIFLOC 592C



OLIN 5110



ZETA LYTE 2C
L


ZETA LYTE 1C
L


POLYMER M-502
L


POLYMER M-503
L


POLYMER M-506
L

58



-------
TABLE 3-4
Coagulant Aids Based on Monomeric Component
ODMULATION
TRADE NAME
PHYSICAL APPEARANCE
s
SUBCLASS



2.3 Poly (N,N-di-



methyl-3,5-



methylene piper>



idinium chlor-



ide




TOLFLOC 333
L

2.4 Copolymer of



dimethylamino



ethacrylate



quaternary salt



of dimethyl



sulfate and



acrylamide
ATLASEP-PWG 255



GR-962
P


GR-963
P


FO-107
P


F0-115
P

2.5 Quaternized



copolymer of



monomethy1amine



and epicloro-



hydrin
MAGNIFLOC 571C

. Polyamine
3.1 Poly alkylene


!i #29320-38-5
polyamine-



hydrochloride
VARC0-FL0C
L


NO. 116 KLEER-FLOC



PURIFLOC C 31



BAY FLOC 901


3.2 Polymethylome-



lamine
ZT-616


59
!


-------
TABLE 3-4
Coagulant Aids Based on Monomeric Component
MULATION
TRADE NAME
PHYSICAL APPEARANCE
S
SUBCLASS




MAGNIFLOC 513C



MAGNIFLOC 515C
L


MAGNIFLOC 517C



ZETA LYTE 3C
L


MOGUL 9021C
L


AMERFLOC 10
L

3.3 Copolymer of
monomethylamin e
and epichloro-
hydrln
MAGNIFLOC 521C
CYFLOC 6000
OLIN 5109
MOGUL 9003C
MOGUL 7903C
MOGUL 6903C
MOGUL PC-1911C
L
L

3.4 Polyethylenei-
mine
NALCOLYTE 8113
NALCOLYTE 8114


3 .5 Linear polymer
of dimethylam-
ine and epichlo-
rohydrin
BETZ POLYMER 1190
BETZ ENTEC 610
L
L

60
1


-------
TABLE 3-4
Coagulant Aids Based on Monomeric Component
ORMULATION
TRADE NAME
PHYSICAL APPEARANCE

SUBCLASS


Starch
4.1 Potato Starch
HAMACO 196
P
5 #9005-25-8

PERFECTAMYL A5114/2






0'B FLOC



GAMLOSE W



GAMAFLOC PWS .



FLOCGEL SN
P


FLOCGEL
G


FLOCGEL A
P


NALCOLYTE.110A



DREWFLOC #3
P


DREWFLOC //4
P

4.2 Potato Starch



modified with



8-diethylamino-



ethylchloride



hydrochloride
WISPROFLOC P



ZT-686



FLOC-AH) 1038



FLOC-AID 1063


i.3 Corn Starch
METALENE COAGULANT P-6
L

i.4 Staramic Starch



321
COAGULANT AID #961


4.5 Sorbitol
SORBO


1.6 Starch
ALLSTATE NO. 2


61



-------
TABLE 3-4
Coagulant Aids Based on Monomeric Component
EMULATION
TRADE NAME
PHYSICAL APPEARANCE
S
SUBCLASS


Cellulose and. Gum
5 .1 Guar Gum NH


// 9004-34-6
(80% Galacto-
GUARTEC F

#9000-30-0
mannen)




GUARTEC SJ



JAGUAR WPB



JAGUAR WST
P


SUPERCOL GUAR GUM
P


BURTONTTE #78
P

5.2 Carboxymethyl
CARBOXYMETHYLCELLULOSE
P

Cellulose



5.3 Guar Gum treat-



ed w/B-diethyl-



aminoethyl chlcr



ride hydrochlor
NO. 730 KLEER-FLOC
P

ide




JAGUAR MRL-22-A
P
sodium Alginate
5.1 Sodium Alginate
CRAIG FKCA-100
P
#9005-38-3





KELGIN W
P


KELC0S0L
P

62
I


-------
REFERENCES
1.	EPA "Report on Coagulant Aids for Water Treatment," Office of
Water and Waste Management, (April 1979).
2.	EPA "Compilation of Product and Formulation Listings for Water
Additives," (June 1978).
3.	Davidson, R. L. and Marshall Sittig, ed., "Water-Soluble Resins,"
Reinhold Publishing Corporation, New York, (1962)
A. American Cyanamid Company "Chemistry of Acrylamide," New York
(1969).
5.	Kirk-Othmer, "Encyclopedia of Chemical Technology," 2nd edition,
Interscience Publishers, New York Vol. 16 (1969).
6.	Panzer, H. P., and Dixon, K. W. "Polyquaternary Flocculants,"
U. S. Patent. Re. 28,807 May (1976).
7.	Dermer, 0. C., and Ham, G.E., "Ethylenimine and Other Aziridlnes,"
Academic Press, New York (1969).
8.	Kirk-Othmer, "Encyclopedia of Chemical Technology," 2nd edition,
Interscience Publishers, New York, Vol. 18, (1969).
9.	Windholz, M. et al, ed., "The Merck Index," 9th edition, Merck
and Company, Inc., Rahway, N. J., (1976).
63

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4. PROCEDURES FOR USING COAGULANT AIDS
4.1 OVERALL TREATMENT FACILITY
Raw water for public water treatment facilities comes from ground water such
as wells and infiltration galleries, and from surface water such as streams,
reservoirs, and lakes. In 1962, Durfor and Becker reported the sources of the
water supplies of the 100 largest cities in the United States. Among these cities,
20% use ground water exclusively for public supplies, and 14% use a combination of
ground and surface waters. The remaining 66% use surface water solely; of these
66 cities, two-thirds depend solely on reservoir water and one-third on natural
streams.^ Recent information shows that ground water is the source of drinking
(2)
water for about half of the U.S. population.
The necessary steps in the water treatment process are determined in part
by the particular properties of the raw water source, such as color, turbidity,
hardness, anion and cation content, bio-contamination, temperature, and by the
presence of specific contaminants. Municipal water treatment plants ideally can
produce potable water even from raw-water supplies that are of very low quality.
The principal steps in a complete water treatment process (not all of which are
used in each city) are:
	Raw water intake - pump station or gravity head
	Disinfection - chlorine addition (breakpoint or low level) or other
disinfectants (CIO2, O3, Ag)
	Sedimentation - sedimentation basin
	Chemical treatment - alum, iron salt, lime, or carbon addition
	Rapid mixing - hydrolic agitation
	Flocculation - flocculation basin
	Primary settling - sedimentation basin
	Secondary settling - sedimentation basin
	Intermediate chlorination
	Filtration - filter beds
	Post-chemical treatment - lime/florine addition
	Treated water storage - reservoir
	Post chlorination - chlorine addition for residual maintenance
	Storage tank - distribution system.
64

-------
Diagrams in Figure 4-1 illustrate these principal steps. Raw water is
pumped to the plant or supplied by gravity head. Chlorine or other disinfec-
tants may be added to eliminate the growth of plants and microscopic organisms
that could impart undesirable tastes and odors to the water, and/or to eliminate
odor causing chemicals. Disinfected water then flows into a sedimentation basin
so that the coarse particles of suspended matter may settle out. After sedi-
mentation, chemicals, most commonly alum, lime, and carbon, are added and allowed
to mix rapidly. After the chemicals are thoroughly dispersed in the water, the
water is continuously and gently mixed to develop large floes. In this process,
the objective is to obtain contact between the floes to promote agglomeration,
but to maintain the mixing at a level that will not shear the floes. The carbon
adsorbs odor-causing chemicals and settles with the floe. Polyelectrolytes used
as coagulant aids can be added to water during the mixing process in the
clarifier for floe gathering or agglomeration. The flocculated water flows
from the flocculation basin into a settling basin. Here the floes have an oppor-
tunity to entrap and settle most of the undesirable constituents that were not
removed in the sedimentation basin. The clarified water is then discharged to
the filters for final purification. The residual particulate is separated from
the liquid as it passes through filters. In the post-chemical treatment step,
the water is lime-softened and/or fluorinated.
The purified water is stored in a reservoir before it enters the many
smaller distribution water tanks. Prior to distribution, the water is normally
given a final treatment with chlorine in the post-chlorination step. Sufficient
chlorine is added to provide a free chlorine "residual,"which will suppress
bacterial growth from the time the water leaves the treatment plant until it flov/s
from the tap. The principal disinfectant used in U.S. water treatment is chlorine.
Ozone and chlorine dioxide are also used for disinfection in some water
(3)
treatment.
4.2 FEEDING OF COAGULANT AIDS
Polyelectrolytes are available commercially in dry powder or liquid forms.
Dry polyelectrolytes must be added as an aqueous solution at recommended concen-
trations to achieve their maximum effectiveness. The stock solution should be
prepared in mixing tanks equipped with a stirring mechanism. Vigorous mixing
65

-------
PAGE NOT
AVAILABLE
DIGITALLY

-------
could cause polymer shearing and possibly reduce polyelectrolyte effectiveness.
Usually mixing rates of 450 rpm or below are recommended by the manufacturers,
depending on the structure of the polyelectrolytes. The mixed polyelectrolyte
solution is transported to a holding tank where metering pumps or rotodip feeders
are used to deliver the prepared solution to the point of application. Poly-
electrolyte solutions should be kept in holding tanks no more than one to three
days to prevent product deterioration. A schematic of such a system is shown
(4)
in Figure 4-2. This solution system is controlled automatically by level
probes that maintain the polyelectrolyte solution at a constant level in the
holding tank, as shown in Figure 4-3.
Dilution of manufacturers' liquid polyelectrolyte solutions is similar to
the preparation*of the dry ones. Methods differ only in the equipment used to
blend the polymer concentrate with water. The liquid polyelectrolyte is stirred
in the drum first to ensure product uniformity. The normal procedure is to fill
the mixing tank half full with clean water, turn on the mixer, add the appropriate
volume of the uniformly mixed polyelectrolyte to the stirring water vortex, fill
the remaining mixing tank with water, and then mix for 10 to 20 minutes to ensure
complete dissolution. Some polymers are fed neat as supplied. The polyelectrolyte
solution is now fully activated. It can be delivered to the holding tank and is
ready for use.
The polyelectrolyte solution is generally added to the clarifier or ahead of
the floe basins at the desired rate by metering pumps or orifices. The maximum
dosage levels of available coagulant aids were approved for use by the Office of
Drinking Water, EPA, in April 1980. These products are listed in decreasing order
according to their recommended levels, in Appendix I. Usually positive-displace-
ment, plunger, or diaphragm types of metering pumps can give very accurate control
of coagulant aid dosage. Examples of these pumps are shown in Figure 4-4. The
choice of metering pump depends on the viscosity, corrosivity, solubility, suction
and discharge heads, and internal pressure-relief requirements of both the polymer
and the mechanical configuration of the plant and the feed system.^
There are three types of clarifiers: (1) horizontal, (2) solids-contact,
and (3) solid-contact/solid-recirculation. In the horizontal type clarifier,
inorganic coagulants are introduced into a rapid-mix chamber where the charges
of the solid suspensions are neutralized and pinpoint floes are formed. From the
67

-------
APPLICATION
Figure 4-2
Typical Schematic of a Dry Polymer Feed System
68

-------
Figure 4-3
Typical Automatic Dry Polymer Feed System

-------
Figure 4-4
Positive Displacement Pumps
70

-------
rapid-mix chamber, the treated water flows into a flocculation chamber where the
polyelectrolytes are usually added to agglomerate small floes to a larger one.
After leaving the flocculation chamber, the water flows into a settling basin,
and the large floes settle to the'bottom. Sludge accumulations are removed by
sludge scrapers. From the settling basin, the clarified water flows onto the
filters. A schematic diagram of the horizontal clarifying equipment is shown
in Figure 4-5.
In a solid-contact type clarifier, influent raw water and inorganic
chemicals are mixed in a central reaction zone by mechanical or hydraulic
agitation so that a large volume of previously formed floe is retained in the
system. The floe volume may be as much as 100 times that in a horizontal
"flow-through" system. The rate of agglomeration from particle contacts is
greatly increased.The polyelectrolytes are added to the slow-mix region
of the clarifier as shown in Figure 4-6. The water flows up through the sludge
blanket where fine particles are removed by adsorption onto the floe particles
forming the sludge bed. The clarified water then flows onto the filters. The
solid-contact type clarifier provides an improved clarifier performance and
reduces the size of the clarifying equipment as well as the cost of the process.^
In solid-contact/solidrecirculation units, the high floe concentration is
maintained in both rapid- and slow-mix zones by recirculation. The inorganic
coagulants are added to the rapid-mix chamber in the presence of previously
formed floe. The addition of polyelectrolytes to the sludge in the slow-mix
chamber enhances the floe formation process. The passage of water through an
expanded sludge blanket helps clarify the turbid water by removing floes
through adsorption and settling. Figure 4-7 shows a solid-contact/solid-recir-
culation clarifier schematically.
4.3 DOSAGE LEVEL AND JAR TEST
Because of the many and complex variations in natural water quality,
handbook designs of coagulation units do not always perform as intended.
Laboratory experimentation must be conducted to determine the best combination
of chemicals to treat water before full-scale operations are started. Many
techniques have been developed to predict the performance of coagulation processes.
A list of numerous tests used in design and control of the coagulation process
(g)
for removing turbidity was given by Tekippe and Ham.
71

-------
CHEMICAL
_EEEni_
"w
MOTOR
WATER
POLYELECTROLYTE FEEDS
43
rapidV
MIX .SLOW MIX
SETTLING BASIN
SLUDGE.SCRAPER
1_
LARIFIED
WATER
BAFFLE
 SLUDGE DRAW-OFF
Figure 4-5: Schematic Diagram of Horizontal Clarifying Equipment
Figure 4-6
Schematic Diagram of Solid-contact Clarifier
72

-------
MOTOR
Figure 4-7
Schematic Diagram of Solids-contact Solids-recirculation Clarifier
73

-------
1)	The conventional jar test
2)	A modified jar test
3)	The speed of floe formation
4)	Visual floe size comparisons
5)	Floe density
6)	Settled floe volume
7)	Floe volume concentration
8)	Residual coagulant concentration
9)	Silting index
10)	Filterability number
11)	Membrane refiltration
12)	Inverted gauze filtration
13)	Cation exchange capacity
14)	Surface area concentration
15)	Conductivity
16)	Zeta potential
17)	Streaming current detection
18)	Colloid titration
19)	Pilot column filtration
20)	Filtration parameters
21)	Cotton-plug filtration
22)	Electronic particle counting.
Among these various techniques, the jar test is the most convenient proce-
dure commonly used to determine the correct chemical program and the dosage
range. In this test, the degree of solids removal is indicated by measuring
the turbidity. Natural turbidity in surface water is essentially a suspension
of colloidal clay particles which are dispersed in water by erosion action of
runoff water on soils. The most direct method of measuring the residual suspended
solids is to weigh the residual solids, but this method is too time-consuming
to be practical. Therefore, turbidity is usually measured by a light scattering
method. When the character of the solids does not vary widely, the concentration
of suspended particles generally correlates with measured turbidity.
74

-------
The jar test is conducted in a series of containers, usually six, in which
fresh samples of raw water are placed. Coagulants and other chemicals are added
to the water in the containers in varying combinations and dosages at different
times. After completing a mixing cycle with either a mechanical or magnetic
stirrer, which simulates plant mixing conditions, the suspended particles
coagulate and are allowed to settle during a specified time. The clarity of
the supernatant in each jar is then measured to determine the optimum chemical
dosages. Pictures of jar test units are shown in Figure 4-8. Directions for
(9-12)
performing the jar test properly have been published by various authors.
An example of a jar test conducted with polyelectrolytes as coagulant aids has
(13)
been given by Johnson.	It should be noted that simple jar tests cannot duplicate
the exact conditions in the solids-contact clarifier and may indicate a somewhat
higher dosage level than needed in an actual process. Yet the jar test technique
was found to be of the most practical value for evaluating the settleability of a
coagulated suspension.
REFERENCES
1.	Durfor, C.N., and Becker, E., "Public Water Supplies of the 100 Largest
Cities in the United States, 1962," U.S. Government Printing Office,
Washington (1964).
2.	EPA, "Everybody's Problem: Hazardous Waste," Office of Water & Waste
Management SW-826 (1980).
3.	EPA-600/2-78-/47, "An Assessment of Ozone and Chlorine Dioxide
Technologies for Treatment of Municipal Water Supplies" (Aug. 1978).
4.	EPA-625/l-75-003a, "Process Design Manual for Suspended Solids Removal"
(Jan. 1975).
5.	Russo, F., and Carr, R.L., "Polyelectrolyte Coagulant Aids and Flocculants:
Dry and Liquid, Handling and Application," Water and Sewage Works,
Vol. 117, R-72 C1970).
6.	Hudson, H.E., Jr., and Wolfner, J.P., "Design of Mixing and Flocculating
Basins," J. AWWA, 57:1257 (Oct. 1967).
7.	Aitken, I.M.E., "Reflections on Sedimentation Theory and Practice, Part I,"
Eff. and Water Treatment Jour. (Br.), 74, 226 (April 1967).
8.	Tekippe, R.J., and Ham, R.K., "Coagulation Testing: A Comparison of
Techniques, Part I," J. AWWA, 62:594 (Sept. 1970).
9.	Cohen, J.M., "Improved Jar Test Procedure," J. AWWA, 49: 1425 (1957).
75

-------
FIGURE 4-8
JAR TEST UNITS WITH MECHANICAL (TOP)
AND MAGNETIC (BOTTOM) STIRRERS
SOURCE: EPA "PROCESS DESIGN MANUAL FOR
SUSPENDED SOLIDS REMOVAL" (1975).
76

-------
10.	Black, A.P., Buswell, A.M., Eidsness, F.A., and Black, A.L., "Review of the
Jar Test," J. AWWA, 49:1414 (1957).
11.	Black, A.P., and Harris, R.J., "New Dimensions for the Old Jar Test,"
Water & Wastes Engineering, 6:49 (Dec. 1969).
12.	Camp, T.R., and Conklin, G.F., "Towards a Rational Jar Test for
Coagulation," J. AWWA, 62:325 (1970).
13.	Johnson, C.E., "Polyelectrolytes as Coagulants and Coagulation Aids,"
Industrial and Engineering Chemistry, 48:1080 (June 1956).
77

-------
5. CONTAMINANTS IN COAGULANT AIDS
Polymeric materials are intended to be chemically and biologically inert.
They therefore have a broad spectrum of applications and have been used
extensively in the clarification of drinking water and as medical devices, packaging
materials, and pharmaceutical products.
However, synthetic polymers may contain a variety of other substances,
such as stabilizers, low-molecular-weight oligomers, olasticizers, and catalysts,
which are incorporated into the polymer during the Dolvmerization process or are
contained as impurities in the final product. Polymers may also contain residual
monomers and inhibitors as well as many other substances which were present in the
monomer. These substances may pose potential hazards to human health when poly-
electrolytes are used in the treatment of drinking water.
The contaminants may react with other treatment chemicals, such as chlorine,
during the water treatment process, and may produce additional kinds of contaminants.
This aspect will be examined closely in a separate report.
5.1 RESIDUAL MONOMERS
Polyelectrolvtes used in drinking water treatment may be contaminated with
toxic residual monomers. If these residual monomers are water soluble, and not
otherwise removed by treatment, they can be released into drinking water.
In Table 3-4, the commercial coagulant aids which are currentlv approved by
EPA for use in clarifying potable water are classified according to their
monoraeric component. Note that a new additives program will develop guidelines
and may re-examine the old approved list. Natural coagulant aids such as starch,
guar gum, and many others are considered to be practically nontoxic and are
used extensively in food and pharmaceuticsSynthetic polvelectrolytes, on the
other hand, are usually made frora organic monomers, some of which are suspected
carcinogens. For example, monomers such as epichlorohydrin and etbvlenimine are
ranked as "very toxic" and "extremely toxic" substances, according to Gosselin
(2)
et al. Excess exposure to these kinds of substances could cause tearing,
burning of the eves, sore throat, vomiting, coughinp, and slowly healing dermatitis.^
To ensure the safety of the drinking water, it is essential to determine the
amount of residual monomers in the polvelectrolytes, so that maximum allowable
concentrations of coagulant aids can be set. Of the monomers listed in
Table 3-4, five are considered to be highly toxic and were selected for
detailed study in this report. These five monomers are acrylamide,
78

-------
epichlorohydrin, methylamine, dimethylamine, and ethylenimine. The structures
and some relevant properties of these compounds are listed in Table 5-1.
Table 5-1. Chemical Structure and Physical Properties of Selected Monomers
Monomer
Acrylamide CH2CHCONH2 71.08
Ep i chlorohydrin (^H^OJHCl^ C
Methylamine CH3NH2
Dimethylamine (CI^^NH
Ethylenimine H2^NH^Hi
Molecular
Weight
Melting
Point
(C)
Vapor
Pressure
(mm.Hg)
Boiling
Point
(C)
Solubility
(/*)
Density
(g/m)
71.08
85.0
2 mm
(87C)
	
2,050
1.122
92.53
-57.2
12 mm
(20C)
116.1
60
(20C)
1.181
31.06
-92.5
2,356
(20C)
6.5
11,539
(12,5C)
0.769
45.08
-96.0
1,570
(10C)
7.4
Very
soluble
0.680
43.07
-71.0
160
(20C)
56.7
Infinitely
soluble
0.832
5.1.1 Acrylamide
Polyacrylamide is by far the most frequently used polyelectrolvte in the
water treatment process. The monomer, acrylamide, is classified as a toxic
substance. ^ There have been more than 40 cases of intoxication from acrylamide
renorted in humans. (5,6,7) Most resuited from occupational exposure. Toxic
symptoms are rhinorrhea, coughing, dizziness, and irrational behavior. Mental
changes consisting of poor orientation and memory, confusion, severe hallucinations
preceding unsteadiness in walking, sleepiness, and slurred speech were also
observed. Five cases resulted from a family ingesting and using well water
(8)
contaminated by seepage from a waste system grouting operation in Japan.1
They began to show symptoms about 4 weeks after the grouting was comnleted. A
concentration of 400 ppm acrylamide in the well water was found 33 days after
the grouting.
Studies of occupational incidents have shown that the main routes of
exposure to acrylamide are through dermal contact and ingestion. The symptoms
of the dermal exposure are skin peeling, eye irritation, and signs of neurotoxi-
(9-13)
city.	Various animal tests indicate that acrylamide possesses a high
79

-------
degree of cumulative toxicity.	dose 0f intraperitoneal
injection is reported to be 120 mg/kg in rats which died within 1 or 2 days.
Repeated oral administration of acrylamide to albino rats is reported to
cause death after 3 and 15 days at the dose levels of 100 and 50 mg/kg/day,
respectively.
Although studies have shown that acrylamide is acutely toxic to humans and
animals, no case reports or epidemiological studies concerning the carcino-
genicity, mutagenicity, teratogenicity or other chronic effects of acrylamide
have been found in the literature. Yet. because the structure of acrylamide
resembles that of other biologically active compounds, including the
known carcinogen vinylchloride, acrvlamide is suspected of being a potential
carcinogen.	There is definitely a need to establish the level of
acrylamide in drinking water that would cause no adverse health effects.
The amount of residual acrvlamide in polyelectrolytes can be measured
by techniques such as bromination, chlorobromination,	thiol
(20)	(21 22)	(23)
addition,	raorpholine addition, ' polarograohy,	ultraviolet
(2A)	(25)	(26)
spectrophotometry,	gas chromatography,	and pulse polarography.
Twenty-four commercial polacrylamides and their residual acrylamides were
analyzed by bromination, polarography, and ultraviolet spectrophotometry:
(23)
the results are shown in Table 5-2.	Residual acrylamide levels were
found to be between 0.004 and 0.88 percent.
Federal agencies control the amount of the residual monomer contained in a
polymer that may come in contact with foods or potable water. FDA limits the
maximum residual acrylamide in polyacrylamide to 0.05% (21 CFR 173.315) for boiler
water additive, and EPA's Office of Drinking Water has permitted that
concentration for coagulant aids used in clarifying potable water. EPA
has permitted concentrations of 1 mg/1 for the maximum allowable dosage level
of polyacrylamide used in clarifying potable water. As a result, the residual
monomer of acrylamide, which is less than 0.05 percent of the Dolyacrylamides,
must be measured at an extremely low level (less than 0.5 ppb) in an aqueous
(27)
environment. A method has been developed by Croll and Simkins	using electron
capture gas chromatography to detect the concentration of acrylamide to a level
(28)
of 0.1 ppb. Later, this technique was improved by Hashimoto	so that the minimum
detectable amount of acrylamide was reduced to 0.032 ppb. With such a sensitive
detecting technique, it is possible to determine the concentration of trace
80

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amounts of acrylamide remaining in the effluent after treatment with poly-
acrylamide. The maximum allowable concentration of acrylamide in potable
(4)
water has been recommended by McCollister et al. to be 0.01 ppm.	In
conjunction with setting a maximum allowable concentration, it will be necessary
to establish a protocol test based on the available analytical techniques to
detect the acrylamide in potable water effluent.
Table 5-2. Residual of Acrylamide in Polyacrylamide
Sample
Residual Acrylamide (%)
Measuring Method
1
0.72
-
0.88
Bromination and polarographic
2
0.11
-
0.18
It tl l
3
0.11
-
0.18
II If tl
4
0.12
-
0.19
It tt II
5
0.80
-
0.88
If If tf
6
0.152


Polarographic
7
0.232


If
8
0.099


ff
9
0.013
-
0.017
If
10
0.004
-
0.011
If
11
0.005
-
0.029
tt
12
0.008
-
0.020
tt
13
0.008
-
0.021
If
14
0.011


If
15
0.012


ft
16
0.304


tf
17
0.150


II
18
0.051
-
0.050
Ultraviolet and polarographic
19
0.043
-
0.041
It ft II
20
0.025
-
0.026
tt II II
21
0.020


tl II II
22
0.011
-
0.012
tf tt It
23
0.008


II tt II
24
0.006

0.007
II II II
81

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5.1.2 Epichlorohy drill
Quaternary ammonium and polyamine polyelectrolytes make up the
second and the third largest groups of coagulant aids, as listed in
Table 3-4. Of the 88 coagulant aids in these two categories, 47 are
(29)
possible carcinogens.	Among those possible carcinogens, 43 are
copolymers that have epichlorohydrin as a comonomer. These polymers
are classified as (1) copolymers of monomethylamine and epichlorohydrin,
(2)	quaternized copolymers of monomethylamine and epichlorohydrin,
(3)	quaternized copolymers of dimethylamine and epichlorohydrin, and
(4)	linear polymers of dimethylamine and epichlorohydrin. A typical structure
of these polymers is given in Section 3.2.2.
Epichlorohydrin is synthesized commercially from allyl chloride, allyl
alcohol, dichlorohydrin-glycerine, or propylene.	It is employed
(1) as a raw material for the manufacture of glycerol and glycidol deriva-
tives, (2) in the manufacture of epoxy resins, (3) as a stabilizer in
chlorine-containing materials, and (4) as an intermediate in the preparation
of condensates with polyfunctional substances. The total U.S. orodur.t-Ion
(31)
of epichlorohydrin was about 550 million pounds in 1975.	Epichlorohydrin
is intensely irritating and moderately toxic through oral ingestion, skin
contact, and inhalation of the vapors. The risks to the health of those
occupationally exposed to epichlorohydrin are reported by NIOSH to include
carcinogenesis, mutagenesis, sterility, and damage to kidneys, liver,
(32)
respiratory tract, and to the skin.	Except in the case of skin con-
tact, all evidence for the existence of the risks depends primarily on data
from experiments with animals.
Goldfish were exposed to epichlorohydrin and the LC (24 hr.) was
(33)
determined to be 23 ppm.	Animal tests with mammals are summarized
(34)
in Table 6-3.	Epichlorohydrin can be detected in concentrations as
(35)
low as 50 ppb with a gas chromatograph.	The odor of epichlorohydrin
is generally perceived as slightly irritating and chloroform-like. The
average odor threshold concentration is approximately 10 ppm. Although
marked nose and eye irritation of humans only occurs at levels above 100 ppm,
N10SH recommends that worker exposure to epichlorohydrin be limited to
0.5 ppm to minimize the probability of chronic effects. The value 0.5 ppm
was selected on the basis of professional judgement rather than on quantitative
analyses of the effect of epichlorohydrin on human health.
82

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TABLE 5-3
(34)
Summary of Acute Toxicity Data on Epichlorohydrin
Route
Species
Oral
Rat
Oral
Guinea :
Oral
Mouse
Inhalation
Mouse
Inhalation
Mouse
Inhalation
Rat
Inhalation
Rat
Inhalation
Guinea 1
Inhalation
Rabbit
Dose

Result
0.09 g/kg

^50
0.178 g/kg

LDS0
0.238 g/kg

LD
2,370 ppm

0/30*
8,300 ppm

20/20 *
250 ppm (8
hrs.)
LC50
500 ppm (4
hrs.)
LSo
561 ppm (4
hrs.)
LSo
445 ppm (4
hrs.)
LC50
*No. of deaths/total no. of testing animals
83

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5.1.3 Dimethyl ain't ne
Dimethylamine reacts with difunctional epichlorohydrin to form a
copolymer. This condensation polymerization reaction Is conducted In a
high pressure reactor because dimethylamine Is a gas at room temperature.
Of the 43 eplchlorohydrin-containlng coagulant aids, 34 have dimethylamine
(29)
as a co-monomer.
The toxicity of dimethylamine was studied through animal tests. In
(34)
one case, a rabbit died after orally consuming four grams of dimethylamine.
The critical range for a creek chub fish was determined to be 30-50 ppm
(32)
over 24 hours.	There is little published information on the toxicity
( 36^
of dimethylamine and its chronic effects on man.
The odor of dimethylamine is fishy. Sensory perception studies have
(33)
indicated that the mean threshold for odor recognition is 23.2 ppm.
5.1.4 Methylamine
Methylamine is manufactured by reaction of methanol and ammonia over
a catalyst at high temperature. It is widely used in chemical Industries
as an intermediate for vulcanization accelerators, a polymerization inhibitor,
and a solvent. It is also used by the pharmaceutical industry.
Aqueous solutions of 25 to 40 percent methylamine are available commercially.
Methylamine reacts with epichlorohydrin in aqueous solution to form a copolymer.
There are nine coagulant aids that are copolymers of methylamine and epichlorohydrin
(29)
in the list of EPA-recommended coagulant aids for potable water treatment.
They are suspected of being possible carcinogens.
Literature of Chemical Manufacturers, Inc., (formerly the Manufacturing
Chemists Association) states that methylamine is irritating to the lungs,
upper respiratory tract, and eyes, and that it is characterized by a fish-like
(34)
odor at concentrations of less than 100 ppm.	Little information on
toxicity in man has been published although there is some information based
on the studies of animals. The acute oral LD of rats to a 10% methylamine
(34)
solution was found to be 0.1-0.2 g/kg.	The critical range for a
( 37)
creek chub fish in Detroit River water is reported as 10-30 ppm over 24 hours.
84

-------
(36}
The average odor threshold of methylamine is 3.35 ppm.	The
mavlimmn permissible concentration of methylamine in the U.S.S.R. for drinking
(33)
water is set at 1.0 ppm.
5.1.5 Ethylenimine
Among those coagulant aids which were suspected of being possible carcin-
ogens in the EPA listing for water additives in 1978, polyethylenimine is the
(29)
only homopolymer.	The monomer, ethylenimine, is manufactured from
ethylene dichlorlde and ammonia by use of an acid acceptor; it is a strongly
caustic material which polymerizes easily and behaves much like a secondary
amine. Because of its reactivity, it has many uses  in fuel oil refining,
ion exchange, pharmaceuticals, protective coatings, polymer stabilizers,
surfactants, and in the paper industry.
Ethylenimine is classified acutely as a highly toxic substance when
administered orally or absorbed percutaneously and also as a toxic substance when
(38)
inhaled.	The acute effects of ethylenimine on experimental animals are
(36)
summarized in Table 5-4.
The acute toxic effects of ethylenimine on humans were also studied. Inhala-
tion of ethylenimine can cause inflammation of the respiratory tract and eyes,
(39)
nausea and vomiting, and albuminuria.	Ethylenimine can be absorbed
through the skin and cause blistering.	it has been reported that
(41)
two humans died from poisoning by ethylenimine.
The carcinogenicity of ethylenimine has been determined by OSHA. Ethylenimine
is listed as one of OSHA's 14 carcinogens.
Various analytical techniques are used to measure ethylenimine concentrations.
These methods include titration^42), colorimetry , and gas-liquid partition
(44)
chromatography.	The lowest detectable concentration of ethylenimine is
0.2 ppm with the colorimetric method and 0.1 ppm with gas-liquid partition
chromatography.
85

-------
TABLE 5-4
Summary of Acute Toxicity Data on Ethylenimine
Route
Species
Dose
Result
Oral
Cat
3
1.0 mm /kg
^50
Oral
Rat
6-15 mm^/kg
LD50
Oral
Rabbit
5 mm^/kg
LD50
Inhalation
Cat
250 ppm (30 mins.)
LC50
Inhalation
Rabbit
50 ppm (30 mins)
LC50
Inhalation
Rat
250 ppm (30 mins)
LC50
Inhalation
Mouse
1,000 ppm (30 mins)
LC50
Inhalation
Guinea Pig
1,500 ppm (30 mins)

86

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5.2 OTHER CONTAMINANTS
Because different polymerization processes are used to produce poly-
electrolytes, the types of contaminants which are incorporated in the
polyelectrolytes are varied. Thus it is important to study these poly-
merization processes in order to identify the possible contaminants in
the polymers. Polymerization may occur with the monomer distributed in
(45)
the (1) vapor phase, (2) solid phase, or (3) liquid phase.	In most
polymerization processes, the monomer is in the liquid phase, and polymer-
ization occurs in bulk, in solution, in suspension, or in emulsion. In
bulk polymerization, the polymer may be soluble in the monomer, swollen
by the monomer, or insoluble in the monomer. In solution polymerization,
the monomer is soluble, but the polymer may or may not be soluble in solvent.
Both suspension and emulsion polymerization occur in two-phase systems (with
monomer and non-solvent as two separate phases): in suspension polymerization,
the initiators dissolve in the monomer phase; in emulsion polymerization, the
initiators dissolve in the non-solvent phase.
The possible contaminants of several polyelectrolytes are discussed in
the following sections.
5.2.1 Polyacrylamide
Acrylamide undergoes vinyl polymerization to yield many homopolymers and
copolymers of controlled molecular weight and performance characteristics.
There are different manufacturing processes used to meet special needs; the most
commonly used are solution polymerization and emulsion polymerization. Both
solution and emulsion polymerization involve free radical mechanisms. Inhibitors
in the acrylamide must be completely removed before free radical polymerization
can occur. Inhibitors such as oxygen and cupric ion can easily be deactivated.
Oxygen is deactivated by deaeration and cupric ion removed by ion exchange or
through chelation with sodium salts of ethylene diamine tetracetic acid (EDTA)
or nitrilotriacetic acid (HTA).
Acrylamide is readily polymerized in aqueous solution at elevated temperatures
in the presence of free radical initiators. Among the initiators commonly used
are t-butyl hydroperoxide, hydrogen peroxide, alkali metal and ammonium persulfates,
chlorates, perborates, percarbonates, photochemical systems, and radiation.
Polyacrylamide polymers with molecular weights of 5,000,000 or greater are used as
87

-------
coagulant aids for potable water treatment. High-molecular-weight polymers
are polymerized in the presence of redox catalyst systems. A typical redox
system is ammonium persulfate and potassium meta-bisulfite. Special redox
agents, such as bromate-sulfite, or persulfate tertiary amine, have been used
to produce very-high-molecular-weight polymers. The molecular weight of
polyacrylamide polymers can be controlled by chain-transfer agents such as the
water-soluble lower alcohols (methanol, ethanol, and 2-propanol) and the thiols
(mercaptosuccinic acid, 2-mercaptoethanol, and mercaptoacetic acid).
In industrial practice, acrylamide is dissolved in water at concentrations
of 10 to 30% at 30 to 60C using catalyst concentrations of 0.01 to 1.0% of the
monomer concentration. The pH is usually adjusted between 3 and 7. The viscosity
increases rapidly during polymerization. Reaction is usually completed in three
to six hours, and conversions of more than 98% can be obtained. The final product
is a tough, rubbery gel which may be put into solution by mixing with water or
converted to a dry powder by conventional techniques such as drum drying, spray
drying, or precipitation in lower alcohols. The amounts of unreacted monomer
can be reduced by the additional treatment of the polymer solution with ammonia or
sulfite.
In emulsion polymerization an emulsion of liquid acrylamide is often, but
not always, dispersed in an aromatic hydrocarbon in which acrylamide and poly-
acrylamide are insoluble; surfactants such as sorbitan monostearate are used as
emulsifiers. Redox initiators are added to start the polymerization reaction.
An example of a typical emulsion polymerization is given belw.
A mixture of 50 g acrylamide, 0.5 potassium persulfate, and 5 g cellulose
acetobutyrate with free hydroxyl groups is added to 200 mi. toluene which acts as
the non-solvent phase while the solution is stirred rapidly and heated in a water
bath at 90C. The aqueous droplets are dispersed throughout the toluene. The
temperature is maintained at 90C by using an ice bath. The final product of
polyacrylamide settles in the form of white beads.
Acrylamide can also be polymerized when irradiated with y (gamma) rays both
in the solid state and in solution. Because of the strongly exothermic nature
of the reaction, bulk polymerization of acrylamide should be carried out with
very small quantities. The reaction rate of photopolymerization of acrylamide
in aqueous solution can be increased by adding various dyes and reducing agents
as sensitizers or catalysts.
88

-------
The contaminants of polyacrylamide vary with the polymerization process.
In solution polymerization, the unreacted monomer, redox initiator, and catalyst
may be the ma^or contaminants. The contaminants of polyacrylamide produced
through emulsion polymerization may contain other additional substances such as
surfactants, emulsion stabilization additives, and solvents. In certain
cases, plasticizers are added to improve the flexibility of polyacrylamide if
it is hard and brittle. Such plasticizers include polypropylene glycol,
tridecyl alcohol-ethylene oxide adduct (e.g. C^^yOH +
(OCH2 CI^jjOH) ,and sorbitan monooleate-ethylene oxide adduct. Some poly-
electrolytes are available in liquid form. Usually these polyelectrolytes are
(29)
dissolved in aqueous solution with various additives.	For example, methyl
para-hydroxybenzoate is used as an antimicrobial agent in MOGUL 7913A, MOGUL
6913A, MOGUL 9013A, MOGUL C0983, and MOGUL C0984. Some polyelectrolytes such
as AMERFLOC 2265, MOGUL PC1905A, and MOGUL 9035A contain many additives. The
formulations of these polyelectrolytes are water, polyacrylamide, t-butyl
hydroperoxide, mineral spirits, sorbitan monooleate, ferric sulfate, sodium
meta-bisulfate, sodium dioctyl sulfosuccinate, octylphenol-ethylene oxide
(29)
adduct, acrylic acid, and ammonium hydroxide.
Manufacturers recommend that the storage time for these polyelectrolytes be
no more than six months. After six months their coagulation capacity is reduced.
Because the quantitative formulations of most coagulant aids are not available and
are often kept secret by manufacturers, the identity and therefore the behavior
of contaminants before and during the water treatment process is unknown. The
effects of the contaminants can be further investigated when manufacturers make
available detailed formulae of coagulant aids.
5.2.2 Copolymer of Monomethylamine and Epichlorohydrin
The reaction between monomethylamine and epichlorohydrin produces a
copolymer that is able to flocculate suspended solids in aqueous media.
This copolymer is stable indefinitely in an aqueous medium at storage
temperatures up to 150F. Because the amine units and the hydroxypropylene
units of the copolymer are strongly hydrophilic, the polymer is water-soluble.
The molecular weight of the polymer must be 1,000,000 or more for it to
be an effective coagulant aid.
89

-------
An example of solution polymerization is given below:
In a reaction flask provided with stirrer, thermometer, and reflux
condenser, 100 g methylamine is dissolved in 400 g water. To this solution,
260 g epichlorohydrin is then added over a 60-minute period. The reaction
temperature is kept between 25 and 40C during the first half of the
reaction and 50 to 80C during the second half.
The temperature is adjusted to 85C,. and 160 g of 36% aqueous sodium hydroxide
solution is added to the reaction mixture. The reaction mixture is heated
to 95C and epichlorohydrin is added In 1 nil portions. After 132 minutes,
the reaction mixture becomes very viscous. The viscosity of the reaction
*
mixture is measured by the glass tube method. As a reaction terminator,
274g cold water which contains 0.8 tai methylamine is added, and the reaction
mixture is heated to 94C. The viscosity changes are given in the following
table:
Time	Epichlorohydrin	Temperature	Viscosity*
(minutes)**	Added (mjL)	(C)	(seconds)
110
1
95
4
115
1
95
5
123
1
95
10
157

94
48
220

94
90
250

94
120
310

94
136
345

94
125
605

94
60
**From start of reaction
*A vertical glass tube with a 6 mm inner diameter is filled with a sample
of the reaction mixture. The time required for the solution to fall 13"
when the bottom of the tube is opened is recorded as a measurement of the
viscosity.
90

-------
Note that after 310 minutes the viscosity of the reaction mixture begins
to decrease. This decrease is caused by scission of bonds within the polymer
molecule. The reaction mixture with pH 8.7 is cooled, acidified to pH 6.3,
and diluted with water. The product contains 19.3% polymer and has a
viscosity of 900 cps at 20C. The solution is stable at 70F and pH 8.7
or 135F and pH 4.5.
91

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Toxicology of Commercial Products Actue Poisoning," edition
The Williams & Wilkins Co., Baltimore (1976).
3.	Weightman, J., Hoyle, J.P. "Accidental Exposure to Ethylenimine and
N-ethylethylenimine Vapors," J.A.M.A., 189:543 (1964).
'4. McCollister, D.D., Oyen, F., and Rowe, V.K., "Toxicology of Acrylamide,"
Toxicol. Appl. Pharmacol., 6:172 (1964).
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6.	Davenport, J.G., Farrell, D.F., and Sumi, S.M., "Giant Axonal
Neuropathy Caused by Industrial Chemicals: Neurofilamentous Axonal
Masses in Man," Neur. (Mpls.), 26, 919 (1976).
7.	Kesson, C.M., Baird, A.W., and Lawson, D.H., Postgrad. Med. J.,
53:16 (1977)
8.	Igisu, H., Goto, I., Kawamura, 7., Kato, M., Izumi, K., and
Kuroiwa, Y., "Acrylamide Encephaloneuropathy Due to Well Water
Pollution," J. Neurol. Neurosurg. Psychiatry, 38:581 (1975).
9.	Auld, R.B., and Bedwell, S.F., "Peripheral Neuropathy with Sympathetic
Overactivity from Industrial Contact with Acrylamide," Can. Med.
Assoc. J. 96:652 (1967).
10.	Cavigneaux, A., Cabasson, G.B., "Acrylamide Poisoning," Archs. Mai.
Prof. Med. Trav., 33:115 (1972).
11.	Garland, T.O., and Patterson, M.W.H., "Six Cases of Acrylamide Poisoning,"
Brit. Med. J., 4:134 (1967).
12.	Takahashi, M., Ohara, T., and Hashimoto, K. , "Electrophysiological
Study of Nerve Injuries in Workers Handling Acrylamide," Int.
Arch. Arbeitsmed^ 28:1 (1971).
13.	Fujita, A., Shibata, J., Kato, H., Amami, Y. , Itomi, K., Suzuki, E.,
Nakazawa, T., and Takahashi, T. "Clinical Observations on Acrylamide
Poisoning," Nippon Ijo Shimpo 1869:27 (1960).
14.	Davis, L.N., Durkin, P.R., Howard, P.H., and Saxena, J., "Investigation
of Selected Potential Environmental Contaminants: Acrylamides,"
EPA 560/2-76-008, (July 1976).
15. Hashimoto,K., and Ando, K., "Studies on the Percutaneous Absorption
of Acrylamide," presented at the XVIII International Congress on
Occupational Health (abst), Brighton, England, Sept. 14-19, p. 453 (1975).
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16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
Hamblin, D.O., "The Toxicity of Acrylamide - A Preliminary Report,"
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a Neurotoxic Agent," Biochem. Pharmacol. 19:2591 (1970).
Narita, H., Uchino, N., and Machida, S., J. Soc. Text. Cellul. Ind.
Japan, 19:225 (1963).
Belcher, R., and Fleet, B., "Submicro Methods for the Analysis of
Organic Compound No. 19 Determination of Olefinic Unsaturation"
J. Chem. Soc., 1740 (1965).
Beesing, D.W., Tyler, W.P., Kurtz, D.M., and Harrison, S.A.,
"Determination of Acrylonitrile and a,B-unsaturated carbonyl Compound
Using Dodecanethiol," Analyt. Chem., 21:1073 (1949).
Critchfield, F.E., Funk, G.L., and Johnson, J.B., "Determination of
a,B-unsaturated Compound by Reacting with Morpholine," Analyt. Chem.,
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Belcher,R., and Fleet, B., "Direct Determination of 02 in Organic
Compound, A Study of Various Modification," Talanta 12:43 (1965).
MacWilliams, D.C., Kaufman, D.C., and Waling, B.F., "Polarographic and
Spectrophotometric Determination of Acrylamide in Acrylamide Polymers
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Vajda, F., Acta Chim. Hung., 53:241 (1967).
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Croll, B.T., and Simkins, G.M., "Determination of Acrylamide in Water
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Hashimoto, A., "Improved Method for the determination of Acrylamide
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32.	NIOSH "Occupation Exposure to Epichlorohydrin," No. 76-206 (1976).
33.	Verschueren, K., "Handbook of Environmental Data on Organic Chemicals"
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35.	White, L.D., Taylor, D.G., Maver, P.A., and Kupel, R.E., "A Convenient
Optimized Method for the Analysis of Solvent Vapors in the Industrial
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36.	Sax, N.I., "Dangerous Properties of Industrial Materials," Van Nostrand
Reinhold Company, New York (1975).
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Chemical Waste Problem by Fish Toxicity Test," Sewage Ind. Wastes,
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3&. Hodge, H.C., and Sterner, J.H., Am. Ind. Hyg. Assoc. Quart, 10:93 (1949).
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40.	Mills, E.J., and Bogert, M.T., "The Synthesis of Some New Pyrimidines
and Uric Acid from Cystamine," J. Am. Chem. Soc. 62:1173 (1940).
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Academic Press, New York (1969).
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VIII Dissociation Constant" J. Am. Chem. Soc. 78:2159 (1956).
43.	Bykhovskaya, M.S., and Makedonskaya, R.V., "Determination of Ethylenimine
in the Presence of Monoethanolamine and Polyethylenimine in the Air
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Noyes Data Corporation, Park Ridge, New Jersey, 43, (1977).
94

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6. STABILITY OF COAGULANT AIDS IN AQUEOUS ENVIRONMENT
The chemical structure of the polymer may be degraded through chemical
reactions or when external stresses are applied. The average molecular
weight of the polymer is usually decreased during degradation, but degrada-
tion may also include reactions that produce a negligible change or even
an increase in molecular size.
Many water-soluble polymers used as coagulant aids in water treatment
have been tailor-made for specific end uses. The efficiency of a polyelectrolyte
can be dramatically reduced if its structure is changed by degradation
before or during the flocculation process: the degradation products may
have different physical or chemical properties from the original poly-
electrolytes. A toxic or even a carcinogenic agent may be generated
through degradation of the polymer. However, it is possible that the
degradation products will be less toxic than the original substances. It
is important to identify possible degradation products and the ways in which
they are formed. However, little information is available in the literature
regarding the degradation of a polymer in an aqueous environment. Yet, the
studies of polymer degradation in general may give some leads and may help
explain impurities in the drinking water. Decomposition of a polymer can be
accomplished by (1) thermal degradation, (2) chemical degradation, (3) bio-
degradation, (4) photodegradation, and (5) mechanochemical degradation  or,
through a combination of these processes. Modifications are made to the main
polymer chains, the side-chain functional groups, or both. Primary valence
bonds may be broken, leading to molecular weight reduction, crosslinking, and
cyclization. If secondary valence bonds within a chain are broken, conformational
changes result. Monomers may also be degraded: they may undergo biological or
chemical reactions such as hydrolysis and polymerization.
Polyelectrolytes are commercially available as solids or liquids. Solid
polyelectrolytes can normally be stored in unopened containers for 12 months:
most liquid polyelectrolytes can be stored in unopened containers for only 6
months. After these periods, the polyelectrolytes will probably be degraded
and become less effective coagulant aids.
95

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6.1 Thermal Degradation
Thermal decomposition products of polymers vary from one material to
another. Their structures depend on the nature of the polymer and the
reaction temperature and time: the products may be monomers, oligomers,
or polymers with low molecular weight.
Thermal degradation is usually accomplished by a free radical mechanism.
A typical degradation process involves an initiation step which takes place
by either random or chain-end scission. Random scission can be expressed
as
H
H
H
H

H
H
H
H
i
I
I
I
Heat^
i
I
i
t
C
- C
- C -
c
		
I
- C * + ^
1
X
C
- c 
|
1
H
1
X
1
H
1
X

1
H
1
X
H
0
a
-H, -CH3, -C2H5 , - CI, -CN, - C - NH2, etc.
While chain-end scission can be expressed as
HHHH	HH HH
I I I l	Heat til)
c - C - C - CH		>- ^ C - C * + HC - C
I l i I	II I'
H XHX	HX HH
The initiation step is followed by a depropagation step.
H
H
H
H
H
H
H
H
I
C
i
- C
1
- C
1
- C 
1
Heat>- v^C
1
I
C  +
t
C =
I
I
C
|
I
N
1
X
l
H
1
X
1
H
i
X
1
H
X
In this step the polymer decomposes to small fragments stepwise along the chain.
After the depropagation step, the polymer may undergo transfer processes that
involve intra- and intermolecular reactions, namely,
96

-------
H
1
H

H
|
H
|
H
|
1
c
1
1
- C
1
- C
- C

- C
1
X
1
H
X
V
H
1
X
H
I
H
|
H
H
|

C  +
1
C =
i
C
1
- C
- CX
I
1
X
1
H
1
X
I
H
H
and
H
t
H
i
H
I
H
I
H
i
H
I
H
1

H H
i 1
c  + ^
1
w c
t
- C
i
- C
i
- c vW
i
	vw CH
i
+ w C
1
- C =
i
C + C
 I
X
H
X
H
X
X
H
X
H X
During the last step, polymers may combine or disproportionate with others
to terminate the degradation reaction. These processes are depicted as follows:
HHH	HHH	HHHHHH
III	lii	i I i l i I
H
1
H
1
H

1
C
1
- C -
1
C

H
1
X
1
H
C-C-C  + * C - C - C wt 	c-C-C-C-C-C
ill	i I <	i i l i i i
HXH	HXH	HXHHXH
and
HHH	HXH	HHH	HXH
ill	III	1 l l	>11
C - C - CH	+ C = C - C wv	C-C-CH	+ C = C-C
i I I	lii	lii	ill
HXH	HXH	HXH	HXH
Among the various means of polymer degradation, thermal degradation is the
least complicated.
The thermal degradation products of some additional oolvmers are listed
in Table 6-1. ^ The first twelve polymers undergo chain-scission
reactions; the others lose substituents while their main chains regain intact.
For most of the polymers the thermal degradation takes place at a measurable
rate at high temperature. The degradation products and the ranges of temperatures
(2)
required to degrade some polymers are listed in Table 6-2. Note that the
thermal degradation temperatures of polymers are well above 100C. For example,
polyacrylamide and its solutions degrade at temperatures of 175-300C. The
97

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TABLE 6-1
PRODUCTS OF THERMAL DEGRADATION OF SOME
ADDITION POLYMERS
Polymer
Mciliyl mcllia-
crylatc (and
mcthacrylatci
generally ex-
cept tertiary
esters)
Structure
COOCH,
C.H,

Hto , of
Polymet izction
(kealfmolc)
10-13

17
Products of
Degradation
monomer yield
> 90%
monomer vicld
>90%
monomer yield
eco/
 00 /o
very high
mononuT
>icl(U
monomer yield
65% with
dimer, irimrr,
and ictramer
CIV
*~CH
d:H-
COOCHj
CH,
		CH. D3u
hydrogen
chloi ide in
yields > s)5%
uuDutcne ii
! quantitative
, yield
98

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Table 6-2. Temperature Ranges for Thermal Degradation of Polymers
(2)
Polymer
Polyaery1ami de
Temperature
Range (C)
175-300
> 300
Degradation Products
NH^ and imidized polymer.
H2, CO, NH3, and imidized polymer.
Cellulose
Cellulose (oxidized)
Polymethacrylonitrile
Poly(acrylic acid)
Methyl ester
250-397	H2O with smaller amounts of CO2 and CO and a
tar containing principally levoglucosan.
180-331	Mainly H0 and CO2, smaller amounts of CO,
formaldehyde, methanol, acetic acid, ethanol,
and acetaldehyde, and very little tar.
Cellulose triacetate	250-310
Product fraction volatile at 25 C contains
acetic acid, CO2, CO, Cl^ Hj, acetaldehyde
and acetone. Heavier fractions do not
contain levoglucosan acetate.
<200	No volatile material, coloration through
yellow, orange, and red.
220-270	50-100%' monomer depending upon pretreatment
and purity of polymer.
292-339	26% of products are volatile at 25 C, mainly
methyl alcohol and carbon dioxide with
traces of monomer and methyl methacrylate
and C^-Cg oxygenated compounds. 74% of
products are larger chain fragments involatile
at 25C.
Tert-butyl ester	>160
a-bromo-, methyl ester 110-150
a-cyano-, methyl e9ter >180
86% isobutylene, 11% water, 3% carbon dioxide.
Methyl bromide, hydrogen bromide.
Non-volatile yellow material and some
monomer formed.
ct-chloro-, sec-butyl
ester
Polyacrylonitrile
190	Sec-butyl chloride, butylene, hydrogen
chloride.
<200	No volatile material, coloration through
yellow, orange, red, and black.
250-280	12% of products are volatile at 25C, con-
sisting of hydrogen cyanide, acrylonitrile,
and vinyl acetonitrile. 88% of products are
involatile at room temperature.
99

-------
Table 6-2. (Continued)
Polymer
Temperature
Range (C)
Poly(methyl vinyl ketone) 270-360
Poly(ethylene tereph-
thalate)
Polyformaldehyde
Polyisobutene
283-306
222
288-425
up to
1,200
Degradation Products
H2O, 3-methyl-2-cyclohexene-l-one and
other six membered ring ketones.
Acetaldehyde major gaseous product with CO2,
CO, C2H4, H2O, CH4, benzene, 2-methyl-
dioxolane, terephthalic acid, and more
complex chain fragments.
100% monomer.
18.1% monomer together with methane, isobutane
and C5 and higher saturated and unsaturated
hydrocarbons.
As temperature is increased the yields of
fragments smaller than monomer increase at
the expense of larger fragments.
100

-------
degradation products are ammonia and imidized polymer. At temperatures of 300C
and above, hydrogen gas and carbon monoxide can also be released as degradation
becomes more extensive.
During the coagulation process, polyelectrolytes will dissolve in water and
will experience temperatures close to the ambient temperature. At such low
temperatures, very little, if any, thermal degradation of polyelectrolytes is
expected. If necessary the thermal degradation of polyacrylamide in aqueous
(4)
solution can be inhibited by adding sodium sulfite.
.6.2 Chemical Degradation
Polymers react with many chemicals under various conditions. In the
water treatment process, polyelectrolytes dissolved in water may be hydrolyzed
or may react with chlorine, acids, alkaline substances, ozone, and many
other chemicals. The number of possible reactions is vast and complex;
a complete discussion is beyond the scope of this report. This pre-
sentation is restricted to general concepts and a few typical examples.
Studies concerning hydrolysis of starch and cellulose are not new. Recent
investigations have been made of hydrolysis of synthetic polymers. Hydrolytic
degradation may occur through main-chain scission of the functional interunits in
condensation polymers or through side-chain scission.
Polyacrylamides can be hydrolyzed by alkalies to yield the corresponding
salts of polyacrylic acid. The negative charge on the polymer depends upon the
number of acrylamide groups hydrolyzed to form acrylic acid groups. The
partially hydrolyzed polycrylamide has the following form:^
-ch2-ch
I
C
NH
m
-ch2-ch
-0
Polyacrylamide can be hydrolyzed in an acidic environment much more rapidly.(13)
101

-------
Polyacrylamide can be imidized when treated with acids whose dissociation
constants are greater than 1x10"^. The products have the following general
(3)
structure:
-ch2 - CH - ch2 - CH - ch2 - CH - ch2
I		l
C=0

NH0
0=C
N
I
H

C=0
CH
I
C=0
I
NH0
Imidization can decrease the water solubility of the polymer and reduce its
effectiveness as a coagulant aid.
There are many other possible chemical reactions of polyacrylamide which can
take place only under particular conditions. Some reactions will proceed only in
the presence of catalysts. For example, polyacrylamide may react with formaldehyde
with the aid of basic catalysts to yield methylolpolyacrylamide. Other reactions
require either high temperature or the addition of chemicals which are not expected
to appear in the water treatment process. For example, sodium sulfomethyl groups
may be added to polyacrylamide by reaction with formaldehyde in sodium bisufite.
The likelihood of this reaction occurring during the treatment of drinking water
is very small.
Residual monomers of a polyelectrolyte may react with other polyelectrolytes
and their residual monomers when two or more coagulant aids are used together.
For example, epichlorohydrin may react with ethylenimine in the presence of sodium
hydroxide in the following manner:^
2H2C - CH2	CH2 - CHCH2CL
V + "V + Na0H 	
1
H
ethylenimine	epichlorohydrin
H2C - CH2	H,C - CH,
N - CH2CHOHCH2 -V	+ NaC1 + H2
1,3-diethylenimino-propanol
Another example is the reaction of an amine with polyacrylamide and formaldehyde
to yield an amino-methylated polyacrylamide.
102

-------
6.3 Biological Degradation
Polymers may be degraded when attacked by bacteria, fungi, algae, protozoa,
rotifers, crustaceans, and viruses. These biological degradation processes are
complex and intricate. Basically, polymers are degraded with the aid of enzymes
which are organic catalysts produced by microorganisms. The function of an enzyme
is represented by the following equation:
Enzyme + polyelectrolyte
enzyme-	~]
polyelectrolytel-> products + enzyme,
complex	I
Enzymes efficiently convert a substrate to its end products. The activity of
enzymes is substantially affected by pH and temperature; as well as polymer
concentration. The susceptibility of a polyelectrolyte to microbial attack
generally depends on the availability of an enzyme and the number of available
sites in the polyelectrolyte for enzymatic attack.
Pure synthetic polymers are generally resistant to microbial attack. However,
commercial polyelectrolytes may contain components such as residual monomers,
solvents, and antioxidants that are susceptible to microbial attack. Natural
polymers generally are less resistant to microorganisms and undergo degradation
by enzymatic action. Starch can be degraded by bacteria and fungi. For
example, upon the attack of Bacillus polymyxa, starch may be converted to dextrin.
Industrial gums such as guar gum can be hydrolyzed by microorganisms very easily.
Cellulose is known to be subject to attack by biological agents through enzymatic
hydrolysis.^
Monomers can also be biodegraded by microorganisms in water. Studies of the
biodegradability of acrylamide have been reported by Croll:^^ acrylamide monomers
at concentrations ranging from 0.06 to 0.17 ppm were degraded by sewage micro-
organisms within 16 days.
6.4 Photodegradation
Recently developed sources of powerful light are capable of cleaving chemical
bonds of polymers. The mechanism of photodegradation is similar to that of
thermal degradation which involves four steps: initiation, propagation,
transfer, and termination.
103

-------
Special attention has been given to the initiation step in which chemical
bonds are attacked by radiative energy; the weakest bonds tend to be broken first.
This is illustrated by the following example: the carbon-nitrogen single bond in
the amide functional group (-C-N-) is the weakest one in the polyamide chain and
(I I
0 H
requires 53 Kcal/mole for its cleavage. The energy required to break a carbon-
carbon bond is MJO Kcal/mole. Thus the amide bonds should be cleaved first. If
the chain of polyamide is exposed to light with wavelength of 410 nm which has
an energy of 70 Kcal/mole, the C-N bonds may be cleaved while C-C bonds remain
intact. Chain scission and cross-linking are two common results of photodegrada-
tion. Polyacrylamide can be cross-linked by the visible light controlled photo-
(31
reduction in the presence of the bichromate ion. '
Monomers can be photopolymerized by radiation. Acrylamide absorbs light in
the ultraviolet region from 200-280 nm, which is below the cutoff point for
radiation from the sun at the earth's surface. Aqueous solutions of acrylamide
will not polymerize on exposure to UV light, but acrylamide and N,N'-methylene
bisacrylamide mixtures may be photopolymerized by visible light in the presence
of a sensitizer or catalyst, such as riboflavin, various silver salts, various
metal oxides, sulfides, etc.^ Hydrogen peroxide has also been used to cause
(9)
photosensitized polymerization of aqueous solutions of acrylamide. y Monomers
can also be photolyzed to produce lower molecular weight compounds. The chief
products of photolysis of ethylenimine are hydrogen, nitrogen, and ethylene.^
Because monomers can sometimes be polymerized or degraded to other low molecular
weight compounds by photochemical radiation, such processes may be employed to
(9)
detoxify drinking water.	Irradiating UV or visible light on toxic contaminants
may provide a way to degrade them to non-toxic substances that pose no threat
to human health.	Further study is needed to determine the effectiveness
of removing toxic contaminants by UV or visible radiation.
6.5 Mechanochemical Degradation
It has been known for many years that textile fibers break under physical
stress. This can be explained by the fact that the stresses from intermolecular
interactions among macromolecules exceed the intramolecular chemical bond energies.
The breaking of fibers is thus the result of the mechanical cleavages of the
polymers at chemical bonds.	The work required to break one C-C bond is
104

-------
0.6x10"^ erg. Because of the nonuniform force distribution over a macromolecule,
chemical bonds of a polymer can often be broken even under very small external
mechanical stress.
Mechanical influences can also weaken a chemical bond. The activation energy
required to chemically destroy a bond is lowered when there is a mechanical stress
on the bond. Chemical reactions can therefore be accelerated by mechanical influences.
Most commercial polyelectrolytes should not be subjected to vigorous agitation
in the mixing tank before entering into the clarifier. During the coagulation
process, the manufacturer-recommended mixing rates should be lower than 450 rpm
to prevent breakdown of the polymer structure by mechanical stress. This mechanical
breakdown of the polymer chain may reduce the average molecular weight of the
polymer and its ability to act as a coagulant aid.
REFERENCES
1.	Grossie, N., "Chemistry of High Polymer Degradation Process," Inter-
Science publishers, Inc., New York (1956).
2.	Brandrup, J., and Immergut, E,H,, "Polymer Handbook," 2nd ed., New York,
Wiley Interscience (1975).
3.	"Chemistry of Acrylamide," American Cyanamide Company. Process Chemicals
Department (1969).
4.	Pye, D.J., U.S. Patent No. 2,960,486 (1960).
5.	O'Melia, C.R., "A Review of the Coagulation Process," Public Works, 100,
87 (May 1969).
6.	Dermer, O.C., and Ham, G.E., "Ethylenimine and Other Aziridines,"
Academic Press, Inc., New York (1969).
7.	Reich, L., and Stivala, S.S., "Elements of Polymer Degradation,"
McGraw-Hill, New York (1971).
8.	Croll, B.T., Arkell, G.M., and Hodge, R.P.J., "Residues of Acrylamide
in Water," Water Res., 8(11):989 (1974).
9.	Dainton, F.S., and Tordoff, M., "The Polymerization of Acrylamide in
Aqueous Solution. Part 3 - The Hydrogen Peroxide Photosensitized
Reaction at 25C," Trans. Faraday Soc., 53:499 (1957).
10.	Berglind, L., Gjessing. E., and Johansen, S.E. "Removal of Organic Matter
from Water by UV and Hydrogen Peroxide." in Kiihn, ITJ and Sontheimer, H
edited "Oxidation Techniques in Drinking Water Treatment, Drinking Hater
Pilot Project Report ZA, Advanced Treatment Technology, EPA-570/9-79-020,
510 (1979).
11.	Neiman, M.B., "Aging and Stabilization of Polymers," Consultants Bureau,
New York (1965).
105

-------
7. ESTIMATES OF POLYELECTROLYTE CONCENTRATIONS IN DRINKING WATER
Few studies have been conducted in the area of polymer toxicity because
polymers are generally regarded as chemically inert. But the products of
polymer degradation and the contaminants present in commercial synthetic
polyelectrolytesresidual monomers, solvents, etc.may be harmful to human
health. Thus it is important to determine the concentrations of both
contaminants and polymers in the finished drinking water.
It is helpful to estimate the concentrations of contaminants and polymers
before the actual concentrations are measured analytically. Good estimates
can serve as a preliminary guideline to identify potential hazards and to
select the appropriate analytical methods with the needed detection limits.
Polyacrylamide is the most popular coagulant aid used in potable water
treatment. An estimate of the overall human exposure to polyacrylamide
through water consumption is given in Table 7-1. An individual's daily water
consumption is a function of temperature, humidity, body size, physical
activity, and other factors. The average amount of water consumed per person
per day in the United States is estimated at 2 liters. EPA uses this amount
to calculate the current interim standards.	One mg/1 is the maximum
dosage of the powder polyacrylamide recommended by EPA for use in potable
(2)
water treatment.	If 100% of the polyacrylamide added in the coagulation
process were present in treated drinking water, the daily intake of
polyacrylamide would be 2 mg. This is equivalent to 730 mg/year. If
polyacrylamide accumulated in the human body, this figure would be striking.
However, in the actual process, most polyacrylamide coagulated with the
colloidal particles and remains in the settling basin. The rest might be
filtered out during the filtration step. The actual concentration of
polyacrylamide in the finishing water is unknown and varies with different
treatment olants. However, if there is 0.01% of the polyacrylamide remaining
in the final product, the intake per person would be 0.073 mg/year.
Investigations should determine if this amount affects human health.
106

-------
Table 7-1. Estimation of Annual Intake of Polyelectrolytes in Drinking Water
Polyelectrolyte
Active
Incredients
Maximum
Concentrat ion
Recommended
(mg/Jl)
Estimated Annual Intake per Person*
(mg/year)

a
b
c
MAGNIFLOC 845A
Polyaerylamide
1
7.3xl02
7.3
7.3xl0~2
HAMACO 196
Potato starch
5
3.7xl03
3.7X101
3.7xlO-1
KELGIN W
Sodium alginate
2
1.4xl03
1.4X101
1.4xl0-1
MAGNIFLOC 521C
Copolymer of
more methylamine
& epichlorohydrin
10
7.3x10?
(1.4x10 )**
7.3x10^
(1.4x10 )**
7.3xl0~*
(1.4x10 )**
SUPERCOL
GUAR GUM
Guar gum
10
7.3xl03
7.3x10
7.3xl0-1
CARBOXYMETHYL-
CELLULOSE
Carb'oxymet hy 1
cellulose
1
7.3xl02
7.3
7.3xl0~2
NALCOLYTE 8113 |
Polyethylenimine
10
7.3xl03 *
7.3X101
7.3X10"1
*a, b, and c represent 100%, 1%, and 0.01% of Dolvmers passing through the potable water treat-
ment processes, respectively.
(y\
**Active ingredients amount based on 19.3% solution produced by the American Cyanamid Company.v

-------
To determine the actual concentration of polyacrylamide in drinking
water, analytical methods must be used. Methods of measuring trace amounts
of polyacrylamide in water are described in detail in Appendix II.
The annual intake of other polyelectrolytes in drinking water per person
can also be estimated by assuming that a certain percentage of the polymers
pass through the water treatment processes. A few typical polyelectrolytes
and the estimated annual intake per person are listed in Table 7-1. Most
of these polyelectrolytes are in solid form but some, the copolymer of mono-
methylamine and epichlorohydrin for example, are liquids dissolved in water.
The amount of active ingredient contained in formulations of liquid polyelec-
trolytes is generally not released by the manufacture. A process to produce
the copolymer of monomethylamine and epichlorohydrin was discussed in
Section 5. In this method, American Cyanamid produced this copolymer with
19.3% of active ingredient. It is important to know the amounts of active
ingredient in the polyelectrolytes before the estimation can be made. The
actual concentration of the polyelectrolyte in the final product of drinking
water must be measured using analytical methods. The maximum allowable
concentration of the polyelectrolyte in water can be set with the help of the
health effect studies described in Section 5.
The concentration of acrylamide monomer in drinking water can also be
estimated. From Section 5 the residual acrylamide retained in polyacrylamide
ranges between 0.004 and 0.05% (upper limit). If 1 mg[I of polyacrylamide is used
in drinking water, the amount of acrylamide added would be between 0.00004 and
0.0095 mg/fc. If all the residual acrylamide in the polyelectrolytes
dissolves and passes through the water treatment process, the concentration
of acrylamide in drinking water would be 0.04-0.5 ppb. The annual exposure
of acrylamide per person would then be between 0.3 and 3.5 mg, based on the
average drinking water consumption of 2 liters/day. The actual concentration
of acrylamide in drinking water can also be determined by analytical methods
described in Appendix II.
The intake of monomer through drinking water cannot be estimated without
knowing the amounts of residual monomer in the polymer. This information is
not usually available. Estimated annual intake of some monomers is shown in
Table 7-2. The amount of residual monomer in the polymer is assumed to be
0.05%. The amounts of annual monomer intake should then be less than 1 mg/year/
person. Since the amount of monomer intake will depend on the amount of
108

-------
Table 7-2. Estimation of Annual Intake of Monomers in Drinking Water
Monomer
Active
Ingredient
Maximum
Concentration
Recommended
(mg/il)
Estimated
Residual
Monomer in
Polymer
Estimated Annual Intake per Person*
(mg/year)

a
b
c
Acrylamide
Polyacrylamide
1
0.05%
3.7xlO_1
3.7xl0~2
3.7xl0-3
Monomethylamine
Copolymer of
monomethylamine &
epichlorohydrin
10
0.05%
3-7 1
(7.1x10 )**
3.7xl0~*
(7.1x10 )**
3.7xl0~?
(7.1x10 )**
Epichlorohydrin
Copolymer of
monomethylamine &
epichlorohydrin
10
0.05%
3'7 -1
(7.1x10 )**
3.7xl0~*
(7.1x10 )**
3.7x10"!?
(7.1x10 )**
*a, b, and c represent 100%, 10%, and 1% of monomers passing through the potable water treatment processes,
respectively.
**Active ingredient's amount based on 19.3% solution produced by the American Cyanamid Company.

-------
water consumed, the type of coagulant aids used, the effort to remove monomers
in the water treatment processes, the amount of residual monomer in the
polymer, the dosage of the polyelectrolyte, and many other factors, analytical
techniques should be developed to determine the actual intake of specific
monomers. Studies of health effects could be conducted to ensure that the
concentrations of these monomers in the drinking water pose a minimal
risk to human health.
110

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REFERENCES
1.	Safe Drinking Water Committee, "Drinking Water and Health," National
Academy of Sciences, Washington, D.C. (1977).
2.	"Report on Coagulant Aids for Water Treatment," EPA (April 1979).
3.	Nagy, D.E., U.S. Patent No. 3, 755, 159; (1973).
Ill

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8. PRODUCTION AND MARKET
The most significant development in the field of coagulation is the
combination of inorganic coagulants with organic coagulant aids for more
effective removal of suspended solids in water. Both types will continue to
be used, although the demand for coagulant aids will probably grow more rapidly.
The attractive features of using coagulant aids in treating drinking
water are threefold. First, they are effective in clarification and sludge
handling at very low dose levels, generally in the ppm range. The inorganic
coagulants, most often alum or various iron salts, generally require large
dosage levels. Consequently, the use of inorganic coagulants, although initially
inexpensive (in 1977, a typical price for alum was 6.5 cents per pound), is
becoming increasingly costly because of the disposal of the sludge. Ocean
dumping of sludge, once common, is generally prohibited by environmental
regulations. Similar regulations have also greatly increased the cost of
sludge disposal in landfills. Organic coagulant aids, on the other hand,
produce far less sludge because of the mechanism by which they operate. Thus,
the cost of using coagulant aids is greatly reduced because lesser amounts are
required (from 1/3 to 1/2 as much as inorganic coagulants, depending on the
constituents of the raw water) and much less sludge is generated. Secondly,
organic coagulant aids, such as synthetic polyelectrolytes, can easily be tailor-
made to meet specific requirements, while inorganic coagulants have no such
flexibility. Finally, coagulant aids are not particularly corrosive, and little
danger is associated with the handling of these materials.
There are, however, some negative factors which have to be considered
here as well. There is a definite concern about using chemicals for cleaning
water, when these very same chemicals can be classified as pollutants or
contaminants. The price of organic chemicals has risen sharply. For example,
some increases during 1973-75 were on the order of 100-200%, and more. In such
instances, users are compelled to seek cheaper substitutes.
112

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The market for water treatment chemicals, in general, has recently been
reviewed and analyzed by Gross. ^ The use of coagulants and coagulant aids
in 1970 was reported in the following proportions, on a weight basis:
municipal water treatment, 30%, and industrial water treatment, 31%, municipal
waste water treatment, 31%; and industrial waste water treatment, 8%. Gross
also predicts that corresponding figures for 1980 would be 22, 32, 33 and 13 %
respectively. The above figures indicate that municipalities,, as a whole, still
use more coagulants than industries do, and therefore, more coagulants are
used for potable water than for sewage treatment. However, industrial
treatment is growing more rapidly than municipal treatment. Liquid waste treat-
ment is expected to grow more rapidly than potable water clarification.
Among the direct additive chemicals used in drinking water treatment,
coagulant aids are used in the least amount. An estimate of the usage of all
direct additives for drinking water is illustrated in Figure 8-1.
The estimates for coagulant aid usage for 1978 are from 4 to 5 million
pounds per year (approximately 2,000 ton/year). This estimate is consistent
with our calculation from other sources. The production and sales of organic
flocculants in the United States for 1975-1977 has been reported by the
International Trade Commission. A summary of this report can be seen in Table
8-1. Furthermore, the consumption pattern of organic flocculants has been
analyzed by the Stanford Research Institute as the following: Coagulant aids
- 7% stabilizing and suspending agents and dispersants - 25%, thickeners -
23%, film-forming agents - 17%, water-retention agents - 12%, colloids - 6%,
lubricants and friction reducers - 5%, and other functions - 5%.
113

-------
S
Hl|:
j'
4'*
iv'l-A'i., TO
iU
\ffy
4,vfi
igg
6^48
RWv>x5r

y0-
HHi
i a ,--&
'* r-s-;-rp
its?
W;S:
Chemical
Lima
Alum
Chlorine
Soda Ash
Iron Salts
Pluorida
Activated Carbon
Caustic Soda
Corrosion Control
Coagulant Aids


Ifjfef;


f-- '?


^ "'"'JV


; S

V,l" r>*,
Vs., -.

,< /V .
'/-I V>

'j'" '
Estimated Use - 1978
In tons x 1000 per year
1,630
450
304
231
60
S3
18
8-15
5
2
T.TMB
Estimates
ALUM CHLO-
RINE
SODA
ASH
IRON
SALTS
FLUOR-
IDE
ACTCV.
CARBON
CAUSTIC CORK. CO AG.
SODA CONTROL AIDS
Figure 8-1
of Direct Additive Cheaiicals Used for Drinking Water Treatment, 1978.
114

-------
TABLE 8-1; U.S. Production and Sales of Organic Flocculants
(Quantities in thousands of pounds; value in thousands of dollars)



Percentage

Percentage

Percentage



change

change

change
Item
1974
1975
1975 from
1976
1976 from
1977
1977 from



1974

1975

1976

Production Quantity
Organic flocculants:







Polyacrylamide
29,217
26,276
-10.0
41,507
58.0
45,319
9.2
Other
(1)
22,764
-
27,242
19.7
26,069
-4.3
Total
(1)
49,040
-
68,749
40.2
71,388
3.8


Sales quantity
Organic flocculants:







Polyacrylamide
30,844
25,581
-17.1
36,829
44.0
37,244
1.1
Other
(1)
15,777
-
21,620
37.0
23,241
7.5
Total
(1)
41,358
-
58,449
41.3
60,485
3.5

Sales value
Organic flocculants:







Polyacrylamide
25,849
25,665
-0.7
41,479
38.1
40,916
1.4
Other
(1)
13,994
-
14,697
4.8
18,368
20.0
Total
(1)
39,659

56,176
29.4
59,284
5.2
^ Not available.
Source: U.S. International Trade Commission.

-------
The combination of these two sets of data indicate that annual
production levels of organic coagulant aids are 3.4 M lb for 1975,
4.8 M lb for 1976; and 5.0 M lb for 1977. The annual usage of
coagulant aids can also be estimated, based on a 7% consumption rate,
as follows: 2.9M lb for 1975; 4.1M lb for 1976; and 4.2M lb for 1977.
Although about 400 commercial coagulant aids are on the market,
this large number can be grouped into categories according to the
monomeric classification. These are polyacrylamide, starch, sodium
alginate, quarternary ammonium, polyamine, and cellulose and gum. The
number of coagulant aids in each category with known formulation are
listed In decreasing order as follows: polyacrylamide (131), quaternary
ammonium (69), polyamine (22), starch (19), cellulose and gum (9), and
sodium alginate (3).
The largest market share of coagulant aids is taken by the
polyacrylamide category. It accounts for 62% of their total production
and usage throughout 1975-77 (Table 8-1). It is also interesting to
note that an intense competitive struggle for markets has developed
over the past few years among natural and synthetic products. The
natural products, such as starch, cellulose and gum, gradually have lost
ground to the synthetic polyelectrolytes because the natural products
have higher BOD (biological oxygen demand) which could cause stream
pollution. These natural polyelectrolytes have found application in
pharmaceuticals, foods, cosmetics, beverages, adhesives, mining, textile
processing, and as suspension agents in paints, ceramics, and pesticides.
The annual level of usage for each individual coagulant aid could not be
estimated since coagulant aids are only a small segment of the polyelectrolvte
industry.
116

-------
Prices of coagulant aids are now in the $0.50 - 3.00/lb.
range. Like other specialty chemicals, the individual price will
vary according to volume purchased and transportation costs.
Polyacrylamides, the most important coagulant aids in the market
today, had a unit price of $1.10/lb. in 1977 (Table 8-1).
The major manufacturers of coagulants aids include American
Cyanamid, Dow, Nalco, Mugul, Calgon, Drew, Hercules, and Betz
Laboratories. The steady growth of coagulant aid production can
be expected to continue so long as high quality of water and sludge-
handling continue to be primary concerns of the water treatment
industry.
117

-------
REFERENCES
1.	"Synthetic Organic Chemicals", International Trade Commission,
ITC Publication (1977).
2.	Gross, A. C., "The Market for Water Management Chemicals,"
Environmental Science and Technology 13(9):1050 (1979).
3.	Frank Bell, EPA, personal communication (1979).
4.	Stanford Research Institute, "Chemical Economics Handbook."
Menlo Park, California (1976).
118

-------
9. CONCLUSIONS AND RECOMMENDATIONS
1.	Coagulant aids have found Increasing application in the treatment of
drinking water. The main function of coagulant aids is to improve the
removal of suspended solids in water and, hence, to reduce the turbidity of
water, and to dewater the sludges.
2.	There are more than 400 commercial coagulant aids available on the market
for drinking water treatment. This large number of products can be
classified in six groups based on their major chemical components, i.e.,
polyacrylamide, quaternary ammonium salts, polyamines, starch, cellulose
and gum, and sodium alginate.
3.	The advantages of using coagulant aids include
	effectiveness at very low dosage, generally in the parts
per million level (in conjunction with inorganic
coagulants). .
	formation of dense-sludge for minimizing handling and
disposal problems, and
	non-corrosiveness of the chemicals.
4.	Currently, between four and five million pounds of coagulant aids are used
for drinking water treatment. Polyacrylamide, which makes up about 62% of
the market share, is the most frequently used coagulant aid.
5.	The possible contamination of drinking water resulting from the use of
some coagulant aids might pose a potential public health problem. Care
must be taken to ensure that the use of coagulant aids does not adversely
affect human health.
6.	Possible contaminants associated with aid usage include
	the polyelectrolyte itself, such as polyacrylamide;
119

-------
o contaminants present in the polyelectrolyte including
residual monomers, initiators, solvents, catalysts,
plasticizers, emulsifiers, chain-transfer agents, anti-
microbial agents, and oligmers; and
 degradation products formed during storage and use of
the polyelectrolyte.
7.	At present, quantitative formulations of most coagulant aids are not
available to us, as they are considered proprietary. Therefore, the
identity of components, including possible contaminants and degradation
products of polyelectrolytes, cannot be fully assessed without an extensive
amount of work.
8.	Polyalectrolytes may react with disinfectants, such as chlorine and ozone, in
the water treatment process. These reactions should be studied more
extensively to identify the reaction products.
9.	Five monomers have been identified for future study based on premliminary
toxicity data. There five monomers are acrylamide, epichlorohydrin,
methylamine, dimethylamine, and ethylenimine. Detailed literature review
and laboratory tests are recommended to study the effects of long-term
exposure at very low levels of these compounds.
10.	Criteria for re-evaluating currently approved coagulant aids or approving
new coagulant aids should be established by EPA.
11.	The maximum allowable dosage levels of commercial coagulant aids are
recommended by EPA and are listed in Appendix 1. These dosage levels
range from 1 ppm to as much as 180 ppm. More careful examination and re-
evaluation of such maximum allowable dosage levels should be performed by
EPA in order to incorporate the most current toxicological information.
120

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121

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Press, New York (1969).
122

-------
"Dow Chemicals Schedules Epichlorohydrin Project." Chem. Mark. Rep. 208:1,
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123

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Gosselin, R.E., Hodge, H.C., Smith, R.P., and Gleason, M.N., "Clinical
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124

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125

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126

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APPENDIX I
Recommended Dosage Levels of Available
Coagulant Aids
ii Name
EPA Recommended Maximum Concentratlon-ppm
(decreasing order)
~ 86
180
RCO-FLOC
150
inmite ZC-301
130
M0GUL-6913A
125
GUL-7913A
125
M0GUL-9013A
125
GNIFLOC 584-C
100
GNIFLOC 586-C
100
GNIFLOC 588-C
100
GNIFLOC 590-C
100
BRENCO 870
100
ENCO 880
100
Cat-Floe R
100
ta Lyte (TM) 2C
100
" ta Lyte 23C
100
GUL-6923N
100
GUL-7923N
100
MUGUL-9023N
100
llfloc 686
100
Wallfloc 688
100
llfloc 690
100
^"t-Floc A
80
.GNIFLOC 593-C
80
127


-------
APPENDIX I
Recommended Dosage Levels of Available
Coagulant Aids
u Name
EPA Recommended Maximum Concentration-ppm
(decreasing order)
zm-130
80
-621
80
ZT-623
80
-627
80
lcolyte 8104
75
GNIFLOC 589-C
70
GUL-9050C
70
wallfloc 689
70
ta Floe (R) WA Special
70 *(20)
Cat-Floe
66.7
GNIFLOC 513C
65
** llfloc 623
65
ta Lyte (TM) 3C
65
t-Floc 121
60*(6)
amERFLOC 10
50
uafloc 401
50
Aquafloc 408 (liquid)
50
yfloc 901
50
" tz DK-724
50
t-Floc T
50
t-Floc T-l
50*(5)
t-Floc 21
50*(15)
. 462 KLeer-Floc
50
No. 482 Kleer-Floc
50
128


-------
APPENDIX I
Recommended Dosage Levels of Available
Coagulant Aids
i Name

EPA Recommended Maximum Concentratlon-ppm
(decreasing order)
.GNIFLOC 515C

50
.GNIFLOC 583-C

50
MAGNIFLOC 585-C

50
GNIFLOC 587-C

50
.GNIFLOC 591-C

50
GUL-CO-983

50
iGUL-CO-984

50
GUL-9021C

50
.LCO 7852

50
NALCO 8852

50
lcolyte 8102

50
Nalcolyte 8103

50
ilcolyte 8142

50
lcolyte 8792

50
_JRCHEM 550

50
PERFLOC C587

50
TIDE-TRO B

50
llfloc 615

50
illfloc 685

50
illfloc 687

50
illfloc 691

50
-
-------
APPENDIX I
Recommended Dosage Levels of Available
Coagulant Aids
i Name
EPA Recommended Maximum Concentratlon-ppm
(decreasing order)
""GUL-6921C
40
GUL-9070C
40
GUL-PC-1913C
40
wallfloc 617
40
ta Lyte 7C
40
Zeta Lyte 43C
40
ta Lyte 53C
40
-""-616
40
-626
40
t-Floc S
33.3
i-cta Floe (R) WA 3000
33.3
.GNIFLOC 594-C
33
MAGNIFLOC 596-C
33
-137
33
"TERFLOC 435
30
iERFLOC 440
30
ERFLOC 445
30
wjuafloc 411
30
:tz Entec 600
30
NO. 460 Kleer-Floc
30
lcolyte 8106
30
Pnly-FloC 3
30
-625
30
,GNIFLOC 598-C
28
130


-------
APPENDIX I
Recommended Dosage Levels of Available
Coagulant Aids
id Name
EPA Recommended Maximum Concentration-ppm
(decreasing order)
betz Polymer 1190
25
i :z Polymer 1290
25
Betz Polymer 2890
25
! tz Polymer 3390
25
rt-Floc C
25
1 3NIFL0C 592-C
25
1 3NIFL0C 595-C
25
"roly-Floc AD
25
1 .CO 600SS 1-0
23.5
ALCO-FLOC #8
20
, ERFL0C 485
20
. "ERFL0C 490
20
tz DK-720
20
tz Entec 610
20
2
20
-84
20
D-67
20
. 458 Kleer-Floc
20
NO. 461 Kleer-Floc
20
GN1FL0C 570-C
20
SNIFLOC 571-C
20
GNIFL0C 572-C
20
3NIFL0C 573-C
20
MAGNIFLOC 575-C
20
GNIFL0C 577-C
20
131


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APPENDIX I
Recommended Dosage Levels of Available
Coagulant Aids
it Name
EPA Recommended Maximum Concentration-ppm
(decreasing order)
1__ 3NIFL0C 579-C
20
] 3NIFL0C 581-C
20
MOGUL-PC-1914C
20
] 3UL-9032C
20
NALCO 600-SS1
20
] .CO 8850
20
]" Lcolyte 8100
20
1 Lcolyte 8101
20
] Lcolyte 8105
20
OLIN 5108
20
: LYHALL 347
20
POLYHALL 351
20
: RBO
20
1 PERFL0C C577
20
1 Llfloc 672
20
1 Llfloc 673
20
Wallfloc 675
20
1 Llfloc 677
20
Wallfloc 679
20
1 Llfloc 681
20
r ta Floe (R) WA
20
L.-622
20
: -624
20
ZT-628
20
: -684
132
20

-------
APPENDIX I
Recommended Dosage Levels of Available
Coagulant Aids
d Name
EPA Recommended Maximum Concentration-ppm
(decreasing order)
686
20
i -IT
19
Coagulant Aid #18
15
I asol
10
AMERFLOC 2
10
P. IRFLOC 420
10
C 66
10
C-Floe B
10
C LOC (R) 6000
10
Drewfloc 922
10
P eg el
10
GOTHOFLOC 283 PWG
10
G RTEC F
10
G RTEC SJ
10
I^co 1 FA 313
10
M NIFLOC 521-C
10
MOGUL-CO-940
10
M UL-CO-941
10
MOGUL-PC-1911C
10
M UL-6903C
10
WUL-7903C
10
Mw-UL-9003C
10
N :olyte 8103
10
Nalcolyte 8104
10
:olyte 8143
10
133


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APPENDIX I
Recommended Dosage Levels of Available
Coagulant Aids
lc Name
EPA Recommended Maximum Concentration-ppm
(decreasing order)
Nalcolyte 8114
10
' B Floe
10
r"IN 5109
10
FORD-HYDRO-FLOC
10
rfectamyl A5114/2
10
SUPERCOL Guar Gum
10
perfloc 16228
10
T0LFL0C 534
10
llfloc 621
10
" ta Lyte (TM) 4C
10
Ca Lyte (TM) 5C
10
-680
10
zeta Floe WCF-312
8
DE-TRO
7
TOLFLOC 333
7
yFloc 901
5
idfloc No. 1-101
5
rtonite #78
5*(.25-.5)
agulant Aid //961
5
Drewfloc 4
5*(1)
ewfloc 21
5
DynaFloc 631
5
naFloc 664
5
" 'naFloc 693
5
oc-Aid 1038 134
5

-------
APPENDIX I
Recommended Dosage Levels of Available
Coagulant Aids
d Name
EPA Recommended Maximum Concentration-ppm
(decreasing order)
F-Loc-Aid 1063
5
GBiafloc PWS
5
Gamlose W
5
G ilen Wisprofloc 20
5
C hofloc 383 PWG
5
F iaco 196
5
E cofloc 863
5
Ryarofloc 225
5
N^ 116 Kleer-Floc
5
No. 483 Kleer-Floc
5
ene Coagulant P-6
5
N "".colyte 11 OA
5
f .colyte 8142
5
Qpi 5110
5
Percol LT-24
5*(1)
PBrcol LT-25
5*(1)
Polyhall 355
5
ULyhall 357
5
P^yhall 361
5
PPLymer M-502
5
I ifloc C31
5
IxJE-TRO B-l
5
Vflsprofloc P
5
Formula 720-CL
5
AKRFLOC 2265 x
4

-------
APPENDIX I
Recommended Dosage Levels of Available
Coagulant Aids
d Name
EPA Recommaided Maximum ConcenCraClon-ppm
(decreasing order)
Betz Polymer 1115 LP
4
] :z Polymer 1215 LP
4
B^tz Polymer 2815 LP
4
] :z Polymer 3315 LP
4
( -97
4
L^LOC (R) 5500
4
i lafloc Nl-702
4
L-650E
4
j 575
4*(1)
MAGN1FL0C 1848-A
4
1 3NIFL0C 1849-A
4
1 3NIFL0C 1985-N
4
] jNIFLOC 1986-N
4
3UL-CO-985
4
MOGUL-PC-1905A
4
: jUL-PC-1950
4
MOGUL-9035A
4
: 3UL-9036N
4
Llfloc 2849
4
...llfloc 2986
4
ta Lyte (TM) 1A
4
Zeta Lyte 2N
4
-649
4
ZT-669
4
136

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APPENDIX I
Recommended Dosage Levels of Available
Coagulant Aids
d Name
EPA Recommended Maximum Coneentration-ppm
(decreasing order)
1		STATE NO. 2
3
I swfloc 3
3*(1)
Craig-FKCA-100
2*(1)
I irfloc 4943
2
FLOCCULITE 550
2
1 .gin W
2
I .cosol
2
~_^uar MRL-22A
2*(1)
o
o
rH
2
ZT-637
2
J -643
2
ZT-650
2
2 -656
2
T~ -660
2
1 jul Co-982
1.5
i jASEP-PWG-11
1
ATLASEP-PWG-44
1
i jASEP-PWG-77
1
ATLASEP-PWG-1010
1
i jASEP-PWG-255
1
/".STATE NO. 6
1
i. srfloc
1
- SRFLOC 265
1
AMERFLOC 275
1
i SRFLOC 307 237
1

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APPENDIX I
Recommended Dosage Levels of Available
Coagulant Aids
i Name
EPA Recommended Maximum Concentration-ppm
(decreasing order)
Aquafloc 409


1
lafloc 411


1
P.z
Entec 620

1
:z
Entec 622

1
:z
Polymer
1100P

1
betz
Polymer
1110P

1
:z
Polymer
1120P

1
Betz
Polymer
113QP

1
:z
Polymer
1160P

1
tz
Polymer
12 OOP

1
tz
Polymer
1205P

1
tz
Polymer
1210P

1
aetz
Polymer
1220P

1
tz
Polymer
1230P

1
Betz
Polymer
1260P

1
tz
Polymer
2800P

1
tz
Polymer
281 OP

1
tz
Polymer
2820P

1
tz
Polymer
28 3 OP

1
&etz
Polymer
2860P

1
tz
Polymer
3300P

1
Betz
Polymer
3310P

1
tz
Polymer
3320P

1
tz
Polymer
3330P
138
1

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APPENDIX I
Recommended Dosage Levels of Available
Coagulant Aids
iae Name
EPA Recommended Maximum Concentration-ppm
(decreasing order)
Betz Polymer 3360P
1
C 75
1
CA-95
1
C 96
1
C 98
1
C~-99
1
C boxymethylcellulose
1
:~gulant Aid it233
1
Z gulant Aid //243
1
Coagulant Aid #253
1
: LOC (R) 4500
1
5YNAFL0C 632
1
) kFLOC 633
1
) tfLOC 634
1
. AFLOC 661
1
)' ^FLOC 691
1
)YNAFL0C 692
1
n :CULITE 551
1
iXOCGEL SN
1
T :gel A
1
'( IULA 740AP
1
'C IULA 74OA
1
'( [ULA 763N
1
'ORMULA 764N
1
139


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APPENDIX I
Recommended Dosage Levels of Available
Coagulant Aids
i Name
EPA Recommended Maximum Concentration-ppm
(decreasing order)
Hereofloc 812 FWG
1
1 reofloe 815 PWG
1
Hercofloc 818 PWG
1
] cofloc 1018 PWG
1
1" reofloe 1021 PWG
1
1 reofloe 1031 PWG
1
1 Irofloc 40
1
Hydrofloc 45
1
1 Irofloc 62
1
Hvdrofloc 65
1
] IIFLOCK PA-322'
1
r~lIFL0CK PA-331
1
1 .102 Kleer-Floc
1
1 .104 Kleer-Floc
1
No. 109 Kleer-Floc
1
1 ,119 Kleer-Floc
1
No. 12Q Kleer-Floc
1
] . 1702 Kleer-Floc
1
1 , 1707 Kleer-Floc
1
1 5NIFL0C 843-A
1
1 JN1FL0C 844-A
1
MAGNIFLOC 845-A
1
1 JNIFLOC 846-A
1
MAGNIFLOC 847-A '
1
1 JNIFLOC 848-A 140
1

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APPENDIX I
Recommended Dosage Levels of Available
Coagulant Aids
i Name
EPA Recommended Maximum Concentration-ppm
(decreasing order)
] JNIFLOC 860-A
1
I'";NIFLOC 971-N
1
1 ;NIFLOC 972-N
1
1 JNIFLOC 985-N
1
1 INIFLOC 990-N
1
1 HJL-9001A
1
M0GUL-9025N
1
] JUL-9043N
1
MDGUL-9044A
1
] JUL-904 5C
1
] JUL-9046C
1
1 JUL-PC-1901A
1
: 3UL-PC-1921N

M0GUL-PC-1943N
1
: 3UL-PC-1945C
1
MnGUL-PC-l946C
1
i Lcolyte 671
1
i Lcolyte 7870
1
L._lcolyte 8181
1
Lcolyte 8182
1
Nalcolyte 8184
1
Lcolyte 8770
1
Nalcolyte 8771
1
Lcolyte 8775
1
lcolyte 8781
1
141

. _lcolyte 8783
1

-------
APPENDIX I
Recommended Dosage Levels of Available
Coagulant Aids
c Name
EPA Recommended Maximum Concentration-ppm
(decreasing order)
f colyte 8784
1
F "colyte 8170
1
f.	colyte 8171
1
J colyte 8172
1
Nalcolyte 8173
1
J colyte 8174
1
Nalcolyte 8175
1
f colyte 8180
1
C'N 4500
1
CN 4502
1
C N 4515
1
OLIN 4517
1
I col LT-20
1
Percol LT-22
1
I col LT-22S
1
I col LT-26
1
I col LT-27
1
1 col LT-28
1
Polyhall M-295-P.W.
1
I ifloc A22
1
Purlfloc A23P
1
I ifloc A23P-S
1
F ifloc N17-S
1
I ifloc N20-S
1
 >aran AP30
1
142


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APPENDIX I
Recommended Dosage Levels of Available
Coagulant Aids
d Name
EPA Recommended Maximum Concentration-ppm
(decreasing order)
S .iaran AP30-S
1
 aran AP273-P
1
Separan AP273P-S
1
S aran NP10P
1
Separan NP10P-S
1
35 7817.00 (exp. Polymer)
1
IT 'lfloc 944
1
fc lfloc 945
1
K lfloc 946
1
Wallfloc 947
1
K lfloc 1085
1
Wallfloc 1090
1 4
Z a Lyte (TM) 2A
1
Z-'-mite ZT-600
1
Z mite ZT-601
1
Z mite ZT-603
1
Zi-636
1
Z 644
1
ZT-651
1
Z 657
1
l" 661
1
Z LAR 110 PW
1
Z LAR 220 PW
1
ZUCLAR 990 PW
1
' COn 143
0.5

-------
APPENDIX I
Recommended Dosage Levels of Available
Coagulant Aids
d Name
EPA Recommended Maximum Coneentration-ppm
(decreasing order)
Formula 741 A
0.5
r< nula 742A
0.5
Formula 743A
0.5
?i nula 748A
0.5
nula 7 60N
0.5
Formula 765N
0.5
" nula 766N
0.5
raguar WPB
0.5
J jar WST
0.5
Svlar 110 PW
0.5
I cules SP944
0.25
k several cases there were discrepancies with regard to the EPA recommended
naximum concentration. In these instances, information received from the manufacturers
t mselves indicated different values from those reported in April, 1979, by the Office
3j. Drinking Water, EPA. Where such discrepancies did occur the data was presented as
E lows:
Trade Name EPA Maximum Recommended Concentration, *(Manufacturer's Value)
April 1980
144

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APPENDIX II
PROTOCOL TESTS FOR POLYACRYLAMIDE AND ACRYLAMIDE
The concentration of polyacrylamlde in water can be measured by various
existing analytical methods. Two methods developed by Dow Chemical Company
involve converting the polyacrylamide to other compounds and measuring the
(1 2)
absorbance of samples in a spectrophotometer. ' American Cyanamid Company
has developed two simple and convenient methods to determine the concentration
(3)
of polyacrylamide in the diluted acrylamide solution. Both methods require
the construction of a calibration curve from instrument readings for a series
of solutions containing known amounts of added low-molecular-weight poly-
acrylamide. The Hach Turbidimeter is used to measure turbidity and the Klett-
Summerson Colorimeter to measure the color of polyacrylamide solutions. Procedures
and calibration curves for these methods are shown in Figures II-l and II-2.
T 15
U
R
B
I
D '0
1
T
Y
U 5
N
I
T
S







H
ich Turbidime
er










50	i00	150
PPM Polymer Solution Basis
200
PROCEDURE FOR HACH METHOD
1.	Pipet 4 mis of filtered sample into a 25 ml volumet-
ric flask containing 2 mis ethanol and mix.
2.	Add 5 mis n-butanol, mix well and let stand
5 minutes.
3.	Make to volume with n-butanol. mix well and
transfer to the Hach cell.
4.	After the bubbles have dissipated, insert the cell
into the meter which has been set on 10 with the
10 FTU Standard on the 0-10 scale.
5.	Read the turbidity. Subtract a blank prepared by
using 4 mis sample and diluted to 25 mis volume
with water.
6.	Refer to the calibration curve for ppm polymer.
Figure II-l. Calibration Curve of the Hach Method
145

-------









/










PROCEDURE FOR KLETT METHOD
1.	To a 25 ml volumetric flask, add 4.0 mis of filtered
sample and 2 mis of 3-A alcohol and mix.
2.	Add 5.0 mis of n-butanol. Mix well and let stand
5 minutes.
3.	Dilute to volume with n-butanol. Mix well.
4.	Read the absorbance on a Klett Summerson Color-
imeter (40 mm cell. No. 42 filter) which has been
Hanked using 4.0 mis of sample made to 25 mis
with water.
5.	Determine ppm soluble polymer from the calibra-
tion curve.
100	200	300 J00
PPM Polymer Soluiion Basis
500
Figure II-2. Calibration Curve of the Klett Method
It should be noted that, although these methods have been used to measure
the concentration of polyacrylamide in water, their sensitivities may be too
low to be used for the determination of trace amounts of polyacrylamide in
finished drinking water. An extraction procedure may be used to first adsorb
polyacrylamide with a resin and then elute it with a solvent. This procedure
would concentrate the concentration of polyacrylamide in solvent to a measurable
level.
The concentration of the acrylamide monomer in the water can be monitored
using the various analytical techniques discussed in Section 5. Most are not
sensitive enough to measure the trace amounts of the acrylamide in finished
drinking water.
The minimum detectable concentration is reported to be 3.2 x 10 ^ mg/
(4)
which was measured with an electron-capture chromatograph. In this method,
acrylamide is first brominated to 2,3-dibromopropionamide which can be extracted
easily from aqueous solutions with ethyl acetate after salting out with sodium
sulfate. The concentration of 2,3-dibromopropionamide can then be determined
by means of gas-liquid chromatography. The yields of bromination product
146

-------
-3
are 85.2 + 3.3 and 83.3  0.9% at fortification levels of 1.0 x 10 and
_3
5.0 x 10 mg/t respectively. A calibration curve can be constructed to
calculate the actual concentration of acrylamide in the aqueous solution.
The bromination procedures and the analysis conditions of a gas-liquid
chromatograph are given below:
Bromination
1.	Dissolve 7.5 g of potassium bromide in 50 ml of sample.
2.	Add two or three drops concentrated hydrobromic acid to adjust the pH
to between 1 and 3.
3.	Add 2.5 ml saturated bromine water and allow the mixture to stand for
1 hour in the dark at 0 C.
4.	Decompose the bromine that remains with 1 M sodium thiosulfate solution.
5.	Add 15 g of anhydrous sodium sulfate and stir vigorously.
6.	Extract the aqueous solution with two 10-ml portions of ethyl acetate
for 2 minutes, using a mechanical shaker.
7.	Dry the organic phase with 1 g of anhydrous sodium sulfate and transfer
it into a 25-ml calibrated amble-glass flask.
8.	Rinse the solid phase with three 1.5 ml portions of ethyl acetate and
combine the rinsings with the organic phase.
9.	Add exactly 100 yg of dimethyl phthalate and fill the 25 ml flask with
ethyl acetate up to the mark of 25 ml.
10. Inject 5-vil portions of this solution into the gas-liquid chroma to graph.
Gas-liquid chromatograph
Column: 2m x 3mm glass column
Packing: 5% free fatty acid polyester on 60-80 mesh acid-washed
chromosorb W.
Carrier gas: nitrogen at a flow rate of 40 ml/min
Column temperature: 165C
Injection temperature: 180C
Detector temperature: 185C
Detector: electron-capture
A high performance liquid chromatographic (HPLC) method which can avoid
the bromination and extraction procedures is also recommended for the measurement
of the acrylamide concentration in aqueous solution. Although the detecting
147

-------
limit of this method is 0.1 mg/-, the sample can be concentrated. A
calibration curve is made by measuring the peak height of the standard
solutions of acrylamide in water with a high performance liquid chromatograph.
The concentration of the acrylamide in the sample solution can be determined
by comparing the peak height to the standard. The analysis conditions of a
high performance liquid chromatograph are given below:
Analytical column: 2.5m x 4.6mm reverse-phase column
Guard column: 60 x 2.1mm to protect analytical column
Water eluant: pumped at 2 ml/min, a pressure of 1600 psig
Detector: variable wavelength detector at 208 nm
Injection volume: 20 yl
148

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REFERENCES
1.	Crummet, W.B., and Hummel, P.A., Jour. AWWA, 50:209 (1963).
2.	Dow Chemical Company, "Separan Polymers, Settle Process Problems,"
No. 192-404-77 (1975).
3.	American Cyanamid Company, "Handling and Storage Procedures of Acrylamide-50,"
Process Chemicals Department, (October 1977).
4.	Hashimoto, A., "Improved Method for the Determination of Acrylamide
Monomer in Water by Means of Gas-Liquid Chromatography with an Electron-
Capture Detector," Analyst, 101:932 (1976).
5.	Skelly, N.Z., and Husser, E.R., "Determination of Acrylamide Monomer in
Polyacrylamide and in Environmental Samples by High Performance Liquid
Chromatography," Anal. Chem. 50(14):1959 (1978).
149

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APPENDIX III
RECOMMENDATIONS REGARDING APPLICATION FOR APPROVAL OF NEW PRODUCTS INTENDED
FOR USE AS COAGULANT AIDS FOR THE TREATMENT OF DRINKING WATER
Due to the possibility of a high risk associated with the use of coagulant
aids in the treatment of drinking water, chere must be sufficient evidence pre-
sented to ensure that a particular coagulant aid poses minimal danger to human
health. Consideration must include both low-exposure long-term use as well as
high-exposure short-term use under various environmental, health, and age
conditions.
Specific information is needed for the review and ultimate acceptance or
rejection of those chemicals intended for use as coagulant aids. Recommendations
for the content of this information are outlined below in Sections I and II. That
information which may be of a proprietary nature should be indicated as such, with
an understanding that this material will be treated as confidential.
Any data presented in reference to studies involving experimental
animals should indicate how the results may be projected to man. It is
suggested that this data represent no less than one year of study in order
to be considered valid. Concentration levels in water (or other suitable
media), which are administered to animals over a prolonged period of
time, should include: the concentration recommended for that use, 10
times that concentration, and 100 times that concentration. Section
III lists recommendations for toxicologic studies. Investigations should
be designed to produce information pertinent to the question of long-term
safety of the use of the coagulant aids in the treatment of drinking water.
I CHEMICAL PROPERTIES
A. Composition
1.	monomeric components, structures and quantities
2.	physical and chemical properties of ingredients
3.	for polymers: monomeric content (%), methods utilized to
characterize the product, molecular weight distribution
4.	analytical methods for determination of residues (monomer & polymer &
toxic ingredients) in water (including accuracy & precision data)
6. Impurities
1.	chemical structures, names, classes
2.	amounts
150

-------
C.	Stability in storage
D.	Data reflecting uniformity of product & quality control processes
E.	Reaction in water
1.	possible changes at elevated temperatures
2.	changes at pH values from 5.0 to 11.0
3.	degradation products
F.	Possible reaction with other chemicals
1.	water treatment chemicals (disinfectants^ etc.)
2.	known water contaminants
G.	Residues of monomer and polymer remaining after treatment
1.	additional water treatment used
2.	no other treatment used
H.	Trade and proprietary names
I.	Label of product as sold
J. Possible use in other edible materials (include amounts approved by
other agencies)
II.	USAGE CONDITIONS
A.	Recommended levels of dosage
B.	Application methods
1.	hazards
2.	safe handling practices
III.	TOXICITY DATA
The following are recommendations for experiments designed to produce
data relative to the question of toxic effects on human health. Not all
procedures listed below are required to Judge the acceptability of a
product. Decisions as to which methods shall be used should be made by
a competent investigator. Emphasis, however, should be placed on those
studies which indicate high sensitivity, high specificity, and clinical
relevance.
In cases where the product is a polymer, experiments should be
designed to include both the monomer as well as the polymer. All information
151

-------
should be presented in appropriate statistical format. Pertinent toxicologic
and epidemiologic data that has been previously reported can be substituted in
lieu of duplicating such experiments.
Any pertinent data on occupational and/or environmental human exposure should
-lso be submitted. Information on the uses of coagulant aids will indicate areas of
oncern for human toxicity. Production and process information is useful in
assessing occupational exposure.
Acute toxicity (single dose) experiments should be designed to establish the
.D-50 by oral and other routes in animals thereby indicating toxic levels. Emphasis
ihould be placed on type, time of onset, severity and duration of toxic signs and
".ymptoms. A dose-response curve should be established to permit an estimation of
tafe doses. Metabolism studies should be performed to identify the degree of
absorption, extent of distribution, routes of excretion and metabolites. Chronic
:oxicity (oral) experiments should be designed to produce data for the evaluation of
substances that may be Ingested by man. Data resulting from chronic toxicity
ixperiments should reveal information concerning potential hazards associated with
.ong-term exposure and direct emphasis toward establishing a "no-effect" dosage.
This "no-effect" dosage shall be used to determine a safety margin. Tests should
:over a duration of one to two years, using a minimum of three concentration levels,
and a control.
Recommendations for additional studies include oncogenicity, mutagenicity, and
teratogenicity experiments. Information regarding possible oncogenic effects,
genetic mutations, effects on fertility, size of litters and litter survival can
support existing data on toxicity and possible human health effects resulting from
the use of coagulant aids.
In the event that the application is being submitted solely for the purpose of
changing a trade name or repackaging a product, the following guidelines are
recommended:
When repackaging one previously approved product, a written testimony from the
manufacturer and/or distributor should be submitted in assurance that the product is
the same (in composition) as the one previously approved. A label of the product
should be enclosed with this testimony along with recommeded levels of dosage for
the new product.
152

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When repackaging a combination of more than one previously approved product,
the aforementioned procedure should be followed along with an indication that the
repackaging process does not alter the chemical properties of the product in any
way. It is suggested that data be submitted with reference to the uniformity of
the new combination and to the acute toxicity potentiation of the components.
153

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