SYSTEMATIC APPLICATION OF MICROBICIDES 141

five microorganisms. Pseudomonas aeruginosa and Aerobacter aerogenes,

as mentioned before, are common inhabitants of aqueous cooling systems,
so the effect on these two species is of particular interest in screening bio-
cides. Bacillus myocoides is a 'spore-forming bacterium not often of any
significance in cooling systems. Desulfovibrio desulfuricans, an anaerobic
sulfate-reducer, is of some concern, particularly in cooling systems on non-
chromate treatments. Aspergillus niger, a rather resistant mold, is some-
times encountered in cooling systems, although whether it does any harm
is a matter of discussion. For eradicating this mold, incidentally, 2,2-di-
bromo-3-nitrilopropionamide is superior to any of the biocides listed in
Table 6.16.

5.4 Chlorination
Chlorine is favored as a biocide for large cooling systems, primarily
because it is inexpensive. It does have disadvantages, however, the most
serious being its deleterious effect on wooden towers, especially when the
pH is over seven. Moreover, regulatory agencies are regarding chlorine in
discharged water with increasing disfavor, so it probably will become
necessary to dechlorinate, or else abandon chlorine entirely in streams dis-
charged to public waters. In most places where chlorine is used it is fed
into. the suction of the recirculating pumps at a residual not exceeding 0.8
ppm in the warm return water. Comeaux and Tyler(33) recommend that
chlorine be added directly to the basin at the point most remote from the
pump suction, but not many do this as the gas tends to dissipate through
the fan stacks causing odor complaints in populated areas. Control can be
maintained by the usual o-tolidine method, or by measuring the oxidation
potential of the recirculating water. Damage to tower wood is less severe
if chlorine is used intermittently, but even so, occasional shock treatment
with high concentration is likely to damage the wooden structure perma-
nently.
When chlorine gas is bubbled into water hypochlorous acid, hydrogen
ion, and chloride ion are formed:
C12 + H20 = HClO + H' + C1- (6.10)
If the water contains weak bases, such as CaC03 or HCOB-,hydrogen ion
reacts with them more readily than does the weak hypochlorous acid.
Thus, the hydrolysis is favored by the presence of weak bases, which, in
effect, make chlorine more soluble.
 TABLE 6.16

Minimum Inhibiting Concentrations of Toxicants

Toxicant (ppm)

Pseudomonas Aerobacter Bacillus Desulfovibrio Aspergillus

Toxicant Active (%) aeruginosa aerogenes mycoides desulfuricans niger
~~ 0
Q
A 100 - 150 50 - 40
B 10 25 45 20 20 25
C 35 30 30 4 2 5
D 10 20 20 10 15 60
E 100 - 200 4 - 25

A = Acrolein
B = Chloroethylene bisthiocyanate
C = Dodecylguanidine hydrochloride
D = Methylene bisthiocyanate
E = Pentachlorophenol
 SYSTEMATIC APPLICATION OF MICROBICIDES 143

Undissociated hypochlorous acid is the active toxicant in chlorination.

Hypochlorite ion has no bactericidal properties, and it is for this reason
that chlorine becomes rapidly ineffective as pH increases above 7. Ridge
and Little(34) have investigated the equilibria in hypochlorite solutions and
have calculated the fraction of undissociated HClO in the pH range from 1
to 10.
Cooling waters under pH control contain only small concentrations of
weak bases, so the pH falls rapidly as chlorine is added. For instance, 2
ppm of chlorine added to a cooling system initially at pH 6.0, lowered the
pH to 4.4. The effect varies, of course, with the buffering capacity of the
recirculating water, the number of cycles of concentration, the cleanliness
of the system, and other factors. In normal operating practice the acid
injection is shut off and the pH is allowed to rise to 6.5-7.0 before chlori-
nation is started. The rate of addition of the gas is then regulated so that
the pH does not fall below 5.5.
As mentioned in Chapter V, chlorine is incompatible with many water-
treating chemicals. It adds readily to a number of nitrogen-containing
compounds, notably to ammonia, which is present as an impurity in some
formulations of polyacrylate; to polyacrylamide; and to natural extrac-
tives in wood. Lignin is oxidized to a mixture of aldehydes and acids,
ferrocyanide to ferricyanide, and 2-mercaptobenzothiazol is converted to
the corresponding disulfide. In the presence of aminomethylenephospho-
nate and low pH, chlorine dissolves copper alloys; the cupric ion formed
attacks iron.
Although Bringn~ann,(~’)many years ago, showed by electron photo-
micrographs that chlorine causes no visible changes in the cell walls of bac-
teria, it is still alleged by some that chlorine “burns up” microorganisms.
Chlorine, in fact, is ineffectual against masses of algae and slime, for it has
little penetrating capability, although occasionally after chlorination there
is a substantial increase in plate count. This seems to be caused by a loos-
ening, or stirring up of accumulations that brings into solution many bac-
teria previously sessile. Dosage should be such that the “total residual
chlorine,” as measured by reaction with ortho-tolidine for three minutes,
is not more than 2 ppm, and the “free available chlorine,” as measured by
reaction with the reagent for 5 s is 0.5-0.8 ppm. If the water treatment is
compatible with chlorination the free available chlorine residual recom-
mended should be attained within one to two hours, after which it should
be maintained at 0.5-0.8 ppm for an additional hour.
To introduce chlorine into cooling water safely, a chlorinator is needed,
144 THE MICROBIOLOGY OF COOLING WATER

the size of which depends upon the maximum recirculation rate of water
through the system.

Capacity (lb/24 h) = Recirculation rate (gpm) X ppm dosage X 0.012

(6.9)
Thus, for a cooling system recirculating at 50,000 gpm, the capacity needed
to give 1-2 ppm of chlorine in the water is calculated by Eq. (6.9).

Chlorination rate, lb/24 h Chlorine Concentration (pprn)

600 1.o
900 1.5
1200 2.0

From these values it can be seen that if chlorination proceeds for two hours
m13thirty minutes at the rate required to give 2.0 ppm total residual chlo-
rine, ~~. + h t of chlorine added is 1200 X (2.5/24), or 125 lb. Chlorinat-
ing every wirer day, a one-ton cylinder lasts about a month. Excessive
chlorine demand may indicate contamination of the cooling water by am-
monia, monoethanolamine, or reducing agents.

5.5 Flocculant-Surfactant-Chlorine Dioxide Program

It is now possible to develop an economical program for microbiological

control based on the principles discussed in the preceding sections of this
chapter. In Section 1 of this chapter, it was noted that large numbers of
bacteria adhere to surfaces within a recirculating system in the form of
sticky films that tend to collect all manner of debris suspended in the
water flowing over them. Sessile, adherent bacteria, of course, are not
counted in viable plate counts made on samples of the recirculating water.
Moreover, they are not accessible to most commercial microbicides until
dislodged from the surfaces and dispersed as invisible flocs in the water.
This can be done by adding a small amount of a cationic polyamine* having
a molecular weight of 30,000-50,000, to the system each day.
Dixon and Z i e l ~ k ( have
~ ~ ) investigated the flocculation of bacteria by
polymers, measuring their effects on filtration rates, electrophoretic mobil-
ity, and light transmission and scattering. Polymers evaluated include poly-
acrylamide (nonionic) with molecular weights of 120,000-3,000,000,
* Magnifloc 521 CH, manufactured by the American Cyanamid Company, is suitable.