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by KENNETH J . FICEK, manager-Technical Services, M a r k e t i n g D e p a r t m e n t
JOHN E. BOLL, Senior Technical Service Representative, M a r k e t i n g D e p a r t m e n t ,
C a r u s Chemical C o m p a n y , 1500 Eighth Street, L a Salle, Illinois 61301. 815/223-1500
Summary: Significant changes in water treatment practices are now being considered as a result of the passage of the National
Interim Primary Drinking Water Regulations. Potassium permanganate, a strong oxidant. is being investigated in order to define
the role it may play in helping water treatment plant operators meet the new Total Trihalomethane standards.
This paper summarizes some of the currently available laboratory and field data on the use of potassium permanganate as a
substitute for prechlorination. The discussion centers around the relocation of the point of prechlorination to reduce TTHM
concentrations; and the use of permanganate as an alternate oxidant to control taste and odors, oxidize manganese, control algae,
slime and marine growths. and to oxidize THM precursors.
The oxidation of phenol with KMnO, is discussed as a possible explanation for some of the increases in TTHM concentrations
found when permanganate was applied together with free chlorine.
Resume: Des modifications significatives dans les procedes de traitemem de leau sont actuellement A letude depuis le vote du
Reglement national interimaire de leau potable primaire. Le permanganate de potassium, oxydant energique, est etudie en vue de
definir le rBle quil pourrait jouer en aidant les exploitants des stations de traitemem de Ieau a atteindre les nouvelles normes du
trihalomethane total.
Le rapport resume quelques unes des donnees de laboraroire et dexploitation acquises sur Iemploi du permanganate de
potassium comme substitut de la prechloration. La ditcussion e5t centree sur la redefinition du point de prechloration pour require les
teneurs en TTHM, et sur Iemploi du permanganate comme oxydant alternatif pour lutter contre les g o h et odeurs, pour oxyder le
manganese, pour lutter contre les algues. les dep6tc vicqueux et les animaux marins, et pour oxyder les precurseurs du THM.
Loxydation du phenol par KMnO, est discutee comme explication possible de Iaugmentation des teneurs en TTHM constatee
quand le permanganate etait utilise en meme tempc q u e du chloce Itbre.

Introduction However, by applying an oxidant other than chlorine, these

The passage of the National Interim Primary Drinking Water problems can be prevented without the production of THMs.
Regulations now limits the concentration of Total Trihalo-
methanes (TTHMs) in drinking water to 0. IO milligrams/liter An alternate oxidant-potassium permanganate
(100 parts per billion) on a running annual average. This The application of an alternate oxidant, while not a complete
requirement has led treatment plant supervisors to consider substitute for prechlorination, can solve some of the problems
major changes in water treatment practices ( I ) . Most notable created by the chlorine relocation. One of the oxidants worthy
of the changes is the elimination of raw surface water treatment of consideration is potassium permanganate.
with free chlorine. This chlorination technique has been shown As a result of the TTHM regulation, the use of permanganate
to be the main reason for the formation of trihalomethanes. as a substitute for prechlorination is seriously being investi-
The chemical interaction between chlorine and the commonly gated at many locations. For example, C. Blanck, in an article
present, natural humic substances (the precursors) produces published in the Journal of the American Water Works
chloroform and the other haloform compounds (2). Association, reported that a 76% reduction in finished water
Many studies have now shown that by altering the point of TTHMs was achieved by a twofold treatment where the point
chlorine addition and improving the coagulation step, a of chlorination was moved from the raw water, and potassium
marked reduction in T T H M formation can be achieved. For permanganate was substituted (5).
example, in Cincinnati, Ohio, a reduction in TTHMs from 300 But such treatment schemes are not new. Potassium
ppb to 20-50 ppb was reported by Superintendent Richard permanganate has been applied in this manner for twenty
Miller, when they stopped chlorinating the influent to the pre- years. Before 1960, it was being used to solve specific taste and
settling basins (2). In Huron, South Dakota, Harms and odor problems. Later, its main application was for the
Looyenga reported a 75% reduction in chloroform concen- oxidation of iron and manganese, where the permanganate
tration by changing the prechlorine application point (3). was used on ground waters in conjunction with pressure
Further experimenting showed that by substituting chloramine filters using manganese treated greensand (6). As permanga-
treatment for free chlorine, the TTHM concentration was nate was used at more and more treatment plants, it was seen
reduced from an average of 154 ppb in the finished water to that it would better solve many of the problems that were
37 ppb (4). originally controlled by free chlorine. In many cases where
These examples illustrate two of the many techniques under potassium permanganate was applied for taste and odor
investigation that can be employed to lower the finished water control, a reduction in chlorinous odors in the finished water
concentration of TTHMs: first, the elimination of prechlori- was noticed (7). Research based upon finished water threshold
nation, or alternately, the application of chloramines. odor numbers showed that permanganate was particularly
However, delaying the point of chlorination must be con- effective when applied before any chlorination. With the
sidered very carehlly before imp!emen:ation, since all benefits advent of :he chlorinated organic problem, the study of
of prechlorine treatment would be lost. In addition to permanganate as an alternate pre-oxidant to reduce TTHM
disinfection, these include algae/slime control, tastdodor formation was initiated.
control, or ironlmanganese oxidation. By altering the point of These years of practical experience coupled with the new
prechlorination and not providing a substitute oxidizing data generated through trihalomethane research clearly show
chemical, serious problems, unrelated to the TTHM problem, that permanganate will be important for: the oxidation of
can occur. Some of these can be solved by chlorinating later in THM precursors; some pre-disinfection; control of slimes,
the treatment, or by installing granular activated carbon algae, etc. . .; control of taste and odor; and the oxidation of
filters, but these solutions may not: manganese (8, 9).
1) prevent algae and slime from growing in intake lines,
2) oxidize and coagulate the manganese in the raw water, Permanganate oxidation of THM precursors
3) keep the sludge from going sour in the settling basin, The use of KMnO, to oxidize the precursors of the trihalo-
or methanes was first studied by the U.S. EPA in Cincinnati,
4) provide adequate taste and odor control. Ohio. Their work was limited in scope to laboratory tests on
Aqua No. 1. 1980
Marlborough Publishing Lid. 1980. Printed in England 0153
Ohio River water. They found a 5-20% reduction of TTHM together (no coagulation or filtration) the final T T H M concen-
concentrations when KMnO, was added in dosages of 0.7 to tration was increased to 99 ppb, higher than that produced by
5.0 mg/l, followed by chlorination after any excess KMnO, chlorination of the raw water alone. This test indicated that
was reduced. With permanganate treatment under extreme thepermanganate should be added, the water coagulated, and
conditions ( I O mg/l KMnO, at pH 11.5 for 21 hours), followed only then should the water be chlorinated t o produce the best
by chlorination, a 40% reduction in TTHM concentration was results (14).
achieved (IO). One explanation for the TTHM increase in the previously
O t h e r laboratory and field studies substantiated the mentioned case might be found in the work done by the
oxidation of precursors with KMnO, and showed reductions in Russian scientist, V. N. Bobkov (15). In his work on the
TTHM concentrations of 5-40'70, attributable to permanga- oxidation of phenol by potassium permanganate, Bobkov
nate application ( I I). showed that some of the intermediate oxidation products were
Singer e l a / , studied the application of potassium humic substances. Production of humic substances was
permanganate in waters collected in North Carolina. He greatest at a permanganate to phenol weight ratio of 4: 1.
reported that when these waters had been pretreated with 2 to The permanganate oxidation of phenol t o carbon dioxide
10 mg/l KMnO, before chlorination, less chloroform was and water is shown below. The weight ratio for this reaction is
produced, compared to the same waters treated with chlorine 15:7 parts KMn0,:I part phenol, the theoretical maximum.
only (12). (See Figs. 1-2.) The potassium permanganate
treatment (at the dosages tested) did not oxidize all of the
3 C,H,OH + 28 KMnO, + 5 H,O
+ 28 MnO,
-. 18 CO, + 28 KOH

precursors, and its application alone, without moving the

point of chlorination, would not reduce the THM concen- According to Bobkov, where permanganate was added at
tration to required levels. The combined treatment changes, less than the 4: 1 ratio, the humic substances increased. Beyond
however, along with improved coagulation would result in the 4: I ratio, the humic substances began to decrease until they
finished water that met the TTHM regulation. are completely undetectable at the ratio of about 15:l (See
Fig. 3 . ) Other oxidation products were identified at various
I 1 I I I I ratios of KMnO, to phenol. These included formic acid, oxalic

H ^ ^ ^II
I acid, tartaric acid, and carbon dioxide. (See Fig. 4, 5 . 6 . )
These oxidation products and the ratios are important
because, if indeed humic substances are produced as a result of

inadequate oxidant additions, chlorination of these oxidation

products could produce high concentrations of TTHMs. In
other words, chlorination of phenol might only produce
chlorophenol, which may be objectionable due to its dis-
agreeable odor. But the partial oxidation of phenol by
permanganate and subsequent chlorination could produce a
substantial trihalomethane concentration This theory is to be
studied in more detail in our laboratory and in the field.
The information available at this point indicates that, when
' 0 1 2 3 4 5 6 7
using permanganate, the most effective means of minimizing
the formation of trihalomethanes is to:
Fig. 1. 1) add the permanganate to the raw water, and allow it t o
react completely,
r I I I I I I I 1
2) coagulate and settle turbidity and suspended solids, and
3) chlorinate before or after filtration, depending upon
TURBIDITY 6 4NTU bacterial properties of the water and local regulation
regarding chlorine contact time.
Tastes, odor, slime, algae
It has long been recognized that chlorination of raw surface
water has provided some degree of taste and odor control, as
well as keeping intake lines and basins free of algae and slime.
At times, chlorination of raw water also could intensify taste
and odor problems by forming odorous, chlorinated organics,
I I as is the case with phenol. Many plants in the early 1960s
5 6
I minimized or eliminated prechlorination in favor of per-
CHLORINE CONTACT TIME - DAYS manganate treatment to control these taste and odor problems.
Excellent odor control was achieved at a Virginia supply when
Fig. 2. 1.75 mg/l KMnO, was substituted for 6 mg/l CI,. The finished
threshhold odor number was reduced from a 6 TON (chlor-
A report from the Frankfurt Water Plant in West Germany inous) t o a 1.2 TON, which was not considered objectionable
indicated a n overall reduction of 50% in haloform generation when post-chlorinated (7).
due to a shift in the point of chlorination, and raw water The application of permanganate prior to chlorination in
permanganate addition. Further work is being conducted on a many cases reduced the chlorine demand, indicating that the
combination of permanganate and biological treatment to KMnO, was reacting with contaminants in the raw water.
completely replace chlorination and further suppress T T H M Without KMnO,, these products would probably have reacted
formation (13). with CI,-possibly being oxidized, but more than likely simply
Studies of permanganate raw water addition and chlorine being chlorinated. In the early 1960s the technical expertise
relocation conducted by Carus personnel in the field, verified was not available t o detect these chlorinated products.
the reduction of final T H M concentrations, but showed that However, odor tests and consumer acceptance of water pre-
the lower levels were mainly due to the elimination of raw treated with KhlnO, supported its successful application.
water chlorination. In addition, an increase in T T H M In those cases where prechlorination is providing oxidation
concentration was noted on several occasions when KMnO, of the taste- and odor-producing organics, the elimination of
and free CI, were present simultaneously. this step, without substitution of another oxidant, could lead to
In one such test in California, chlorination of the raw water inadequate control. The water may be low in TTHM concen-
produced a concentration of 83 ppb TTHM. By eliminating tration, but unacceptable because of tastes and odors.
prechlorine, adding KMnO,, coagulating, filtering, and then Permanganate oxidation along with other treatment tech.-
post-chlorinating, the final T T H M concentration was reduced niques, such as the addition of activated carbon, may help
t o between 30 and 40 ppb. By adding KMnO, and chlorine in some of these situations. It is, however, not a cure-all, and

Fig. 3.


404 1 \
00 \ 0 0
\ 0
I ,
1 I 9
2 6 10 14
m KMn0,l m C,H,O m KMn0,l m CH

Fig. 5. Fig. 6.

1.2 I

m KMn0,l m CH
, m KMn0,l m CH

Figs. 3-6: The composition of the reaction by-products, when phenol; c) formic acid; d) oxalic acid; e) tartaric acid; and
phenol is oxidized by potassium permanganate at different f) carbon dioxide. From V. N. Bobkov. Study of the
ratios of the initial reactants-a) humic substances: b) oxidized Oxidation of Phenol by Potassium Permanganate. (1975).
Manganese oxidation
combination treatments should be studied to achieve the
optimum in quality and economy. The application of permanganate for the oxidation of soluble
In addition to the oxidation of taste- and odor-producing manganese is well documented and widely used. Whether
organic contaminants, KMnO, is being used to solve some of treating surface or ground water, most manganese is
the other previously mentioned problems. A water plant using controlled with permanganate dosages from 0.25 mg/l to 2.5
Lake Michigan water continuously feeds a dosage of 0.25 mg/l mg/l. Chlorine can also be used to oxidize manganese, but the
of KMnO, to the raw water at the intake, which is several miles necessaiy conditions are more critical, and a high pH is usually
from the plant. This low dosage completely controls the slime required.
and algae build-up in the line. Prior to the KMnO, treatment, Research and field work has indicated that the formation of
CI, had been applied to keep the line free of growths (16). trihalomethanes is pH-dependent. As the p H of a water to be
Another case is in Alabama, where KMnO, is added every chlorinated increases, the tendency to produce trihalo-
spring to rid a raw water line of the Asian clam, Corbicula. methanes also increases. I f a pH of greater than nine is
The permanganate, at a dosage of 4 mg/l, is introduced required for the oxidation of manganese by chlorine, the
primarily for taste and odor control at the intake structure, conditions become more favorable for high TTHM formation.
approximately 1 % miles from the treatment plant. Shortly The oxidation of manganese by permanganate is also
after the KMnO, is started every spring, the clams begin to somewhat p H dependent. The reaction rate is faster at higher
slough off and within two to three weeks, the line is free of pHs, but under normal treatment plant conditions (pH 7-8) it
the Corbicula and a corresponding increase in flow rate of is already extremely fast. Therefore, manganese removal with
about 9-10Vo is ,achieved. The superintendent claims that if permanganate oxidation in place of chlorination will minimize
they fed KMnO, at 20 mg/l, he could accomplish the tasks trihalomethane formation, due to the pH change alone.
more quickly, but they would have a problem with the excess This was verified at a plant in West Virginia where these two
residual permanganate in the plant. Similar results (i.c. manganese oxidation techniques were studied (18). In separate
ridding the line of the clam) can be achieved with chlorine, but tests, pretreatment with free chlorine was compared to per-
they prefer permanganate for the taste and odor control (17). manganate oxidation and chlorination just ahead of the filters.
In addition to complete manganese control, the following
TTHM results (See Fig. 7) were obtained:

TTHM Concenirations data strongly indicates that potassium permanganate addition
Range Average should be considered as one of the alternatives t o prechlori-
nation treatment.
Chlorination Only 50-330 ppb 127 ppb
KMnO, & Chlorination 43-82 ppb 56 PPb References
1. USEPA. National Interim Primary Drinking Water
WEST VIRGINIA WATER Regulations. 44 Fed. Reg., 231:141.12 (29 November
PRE-CI, vs KMnO, FOLLOWED BY CI, 2. DALLAIRE, GENE, assoc. ed. Arecities Doing Enough
to Remove Cancer-Causing Chemicals From Water?,
FINAL T T H M CONCENTRATION Civil Engineering-ASCE. (September 1977), p. 88-94.
Adjustment to Reduce Chloroform Formation, Journal
11-1 -
American Water Works Association. (Huron, South
11-2 115 ppb Dakota: May 1977), p. 258-263.
11-6 330 4. NORMAN, T. S., HARMS, L. L., LOOYENGA, R. W.
11-8 148 The Use of Chloramines To Prevent Trihalomethane
11-9 130 Formation, JournalAmerican Water WorksAssociation.
11-13 (Huron, South Dakota: March 1980), p. 176-180.
11-16 5. BLANCK, C. A. Trihalomethane Reduction in Oper-
11-17 ating Water Treatment Plants, Journal American Water
I 1-20 Works Association. (September 1979), p. 525-528.
11-21 6. FICEK, K. J. Potassium Permanganate for Iron and
11-21 -
Manganese Removal and Taste and Odor Control. In
1 1-24 90 Water Treatment Plant Design For the Praciicing Engineer.
11-27 86 Sankes, R. L., ed. (Michigan: Ann Arbor Science 1978),
11-28 86 461-479.
11-29 78 7. WELCH, W. A. Potassium Permanganate in Water
11-30 53 Treatment, Journal American Water Works Association.
12-1 78 (Reprint-June 1963), p. 735-741.
12-4 150 8. FLETCHER, W. H. C. In Golden, Colorado-One
12-5 94 Answer to Slime Problems in Coagulation, Water Works
12-6 157 and Wastes Engineering. (March 1965).
12-7 99 9. MUCHMORE, C . B. Algae Control in Water-Supply
12-12 123 Reservoirs, JournalAmerican Water WorksAssociation.
12-13 162 (May 1978). p. 273-279.
AVERAGE 127 ppb 10. STEVENS, A. Personal Communication. U S E P A ,
Cincinnati, Ohio.
Figure 7. 11. Potassium Permanganate Reduces Trihalomethanes,
Public Works. (January 1979), p. 107.
Conclusion J. M. Effects of Permanganate Pretreatment On Tri-
Test work in the laboratory and the field has now shown that halomethane Formation In Drinking Water. Presented
by relocating the point of prechlorination, or by substituting at 98th Annual Convention, American Water Works
chloramine treatment, TTHMs can be substantially reduced. Association. (June 1979).
By doing so, however, a variety of problems, unrelated to 13. MACK, E. Personal Communication. T h . Goldschmidt
trihalomethanes, may occur. A.G., Mannheim, West Germany (August 1979).
Potassium permanganate, while not the ultimate answer to 14. Personal Communication. Carus Chemical Company.
all of these problems, can be used effectively in combination 15. BOBKOV, V. N . Study of the Oxidation of Phenol by
with other treatment techniques to produce a water, not only Potassium Permanganate. (1975). CA86:215 1511.
low in T T H M concentration, but also free of manganese and 16. Personal Communication.
taste and odor producing compounds. It can also be beneficial 17. Personal Communication.
in controlling algae, slime, and other marine growths. The 18. Personal Communication.

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