War. Res. Vol. 30, No. 3, pp.

715-721, 1996
~ Pergamon 0043-1354(95)00208-1
Copyright© 1996ElsevierScienceLtd
Printed in Great Britain,All rights reserved
0043-1354/96 $15.00+ 0.00

E L E C T R O C H E M I C A L R E M O V A L OF NITRITE A N D
AMMONIA FOR AQUACULTURE
S. H. LIN *@ and C. L. WU
Department of Chemical Engineering, Yuan Ze Institute of Technology, Neili, Taoyuan 320, Taiwan,
Republic of China

(First received March 1994; accepted in revised form August 1995)

A~traet--Electrochemical nitrite and ammonia removal from aqueous solution was investigated.
Operating variables of the electrochemical method including the current input, pH, conductivity, buffer
solution and initial nitrite and ammonia concentrations were considered to determine their respective effect
on the efficiency of nitrite and ammonia removal. The experimental results indicated that the time for
complete nitrite removal and power consumption decrease with an increase in conductivity. For nitrite
removal, the electrochemical process was found to consume less power when utilizing a current input larger
than 2 A. The pH effect on the nitrite removal was observed to be significantly smaller than those of
conductivity and current input. While the acidic environment favored the nitrite removal, the alkaline
environment appeared to be beneficial to the ammonia removal. The ammonia removal was found to be
a much slower process than the nitrite removal.

Key words--electrochemical method, nitrite and ammonia removal, aquacultural water

INTRODUCTION unconsumed fish foods. Nitrite and ammonia are

Aquaculture is an important business in many
countries around the world. Traditional aquacultural
activities are conducted in large ponds with low fish
density. Such activities require a large amount of
land and water resources. Due to increasing cost
and decreasing availability of these resources, the
traditional aquacultural activities are becoming
relatively uneconomic. An emerging recent approach
is to employ high density aquaculture which requires
significantly less amount of land and water resources
than the conventional method (Liao and Mayo, 1972;
Otte and Rosenthal, 1979). The economic advantages
of this approach are enormous. However, the high
density aquaculture incurs a new problem. An increase
in fish density in a limited aquatic space would lead
to a more rapid degradation of the water quality.
Hence, treatment of aquacultural water to maintain
high water quality required for such an activity
becomes increasingly crucial (Liao and Mayo, 1972;
Otte and Rosenthal, 1979). It is important that the
water quality problem be resolved efficiently before
high density aquaculture can yield real economic
benefit.
A major difficulty of high density aquacultural
system stems from the rapid nitrite and ammonia
accumulations in the water. The problem is caused
primarily by the fish excretion and decomposition of
*Author to whom all correspondence should be addressed
[Tel.: (886) 3 463 8910; Fax: (886) 3 455 9373].
toxic to marine fishes and the tolerable concentration
levels of those compounds for an aquacultural system
are quite low, usually being much less than 1 mg-l-'
(Liao and Mayo, 1972; Otte and Rosenthal, 1979;
Poxton and Allhouse, 1982). The water quality of a
high density and untreated aquacultural pond can
deteriorate fairly rapidly and fall below the acceptable
level. External water treatment units are therefore
necessary if the water quality is to be sufficiently main-
tained for a normal aquacultural activity (Kruner and
Rosenthal, 1983; Bovendeur et al., 1987). Treatment
methods proposed by the previous investigators
included nitrification/denitrification using fixed film
or fluidized bed biological reactors, adsorption by
activated carbon and suspended solids removal
by sedimentation (Liao and Mayo, 1972; Otte and
Rosenthal, 1979; Poxton and Allhouse, 1982; Kruner
and Rosenthal, 1983; Bovendeur et al., 1987). In
recent years, nitrification by ozonation has received
increasing attention (Anon., 1972; Blogoslawski et al.,
1975; Honn and Chavin, 1974; Otte and Rosenthal,
1979). Ozonation of the aquacultural water is capable
of efficiently converting the toxic nitrite and ammonia
to non-toxic nitrate at a relatively higher cost than
the other methods. A method that has not been
considered for nitrification is the electrochemical
method. This method has been successfully employed
to deal with various industrial wastewaters (Beck et al.,
1974; Biwyk, 1980; Matis, 1980; Ramirez, 1981;
Cenkin and Belevtsev, 1985; Lin and Peng, 1994).
Hence it would be of significant academic and

715
716 S.H. Lin and C. L. Wu
practical interest to test whether the electrochemical
oxidation method is a potential alternative for the
nitrite and ammonia removal from aqueous solution.
The purpose of this study is to conduct experimental
investigations to address this issue. A bench-top
electrolytic apparatus was assembled to perform the
simulation tests. Several aspects regarding the effects
of current, type of electrodes, conductivity, pH, buffer
solution and initial nitrite and ammonia concentra-
tions on the nitrite and ammonia removal efficiencies
are explored. As will be seen later, the electrochemical
method is at least as effective and promising as the
other treatment methods.
EXPERIMENTAL
The batch experimental apparatus is shown in Fig. 1.
Two pairs of anodic and cathodic electrodes situated approx.
1.5 era apart to each other and dipped in the prepared
sample solution containing nitrite and/or ammonia. The
current input was controlled by an ammeter and the total
power consumption was integrated and registered by a
power integrator. In each run, approximately 1 1 of sample
solution was placed in the electrolytic cell. The sample
solution (single component or mixture) was prepared by
dissolving an appropriate amount of reagent grade sodium
nitrite or ammonium chloride (E. Merck, Inc., Germany) in
deionized water. Single component sample solution contained
either sodium nitrite or ammonium chloride only whereas
mixture sample solution contained both components. The
total effective surface area of electrodes was 22.6 cm 2. The
initial pH of the sample solution in the electrolytic cell was
adjusted to around 7 except for those samples intended to
investigate the pH effect on the nitrite or ammonia removal
efficiency.
The conductivity of the freshly prepared sample doluyion
was very low, generally no more than 70 # mho-cm -t. At
such a low conductivity, the current that could be applied
to the electrodes was very low indeed which was insufficient
2
1
['~--]wh
o
I I ..... II
5
4!
+i
I
o{9
Fig. 1. Experimental setup.
to initiate and maintain normal nitrite and ammonia oxid-
ation. To overcome this difficulty, a small amount of table salt
was added to the sample solution to raise its conductivity to
over 1500 # mho-cm-~ for all experimental runs. The nitrite
and ammonia concentrations were determined, respectively,
by the standard photometric and Nessler methods (APHA,
1992) using a Hitachi u,v. spectrophotometer (Model U3410,
Hitachi, Inc., Japan).
In the initial experimental tests, the cast iron electrodes
were employed to investigate the efficiencies of nitrite and
ammonia removal from the aqueous solution. The removal
efficiencies turned out to be rather low, being no more than
20% for a 2-h test run. Moreover, the cast iron electrodes
turned from light grey into black, presumably due to
oxidation on the electrode surface. Search for replacement
electrodes resulted in choosing the high purity graphite rod
as anodes and titanium dioxide as cathodes. Such electrode
pairs, which had a surface area of 22.6 cm2, performed well
for the present nitrite and ammonia removal experiments.
RESULTS AND DISCUSSION
The mechanism of electrochemical oxidation
process in aqueous systems is inherently complex
(Pletcber and Walsh, 1990). It is generally believed that
there are two possible mechanisms involved in the
process: electro-flotation and electro-oxidation. Oxid-
ation and reduction o f the electrochemical process
occur, respectively, at the anode and cathode of the
electrodes (Pletcher and Walsh, 1990). With sufficient
power supply, the nitrite or ammonia molecules
are oxidized at the anode to nitrate. Electro-flotation
is caused by the hydrogen gas generated during the
electrochemical process. In the present study, the
hydrogen gas did not generate much electro-flotation
effect due primarily to that there were no suspended
or dissolved solids in the present aqueous solution,
unlike the ordinary industrial wastewaters.
1. D. C. Power Supply
2. Digital Ammeter
3. Power Integrator
4. Parallel Graphite Anodes
5. Parallel Titanium Dioxide Cathodes
6. Magnetic Bar-Stirrer
7. Sampling Valve
8. Electrolytic Cell
9. Digital Magnetic Stirring Controller
 Aquacultural nitrite and ammonia removal 717
,00 --¢ • 5000 --
I I 100,O....o'•~O~
80 r d" _,,o" 'E 4000
,Y
- -

?
6o0 // 0
E 3000 -

.~ •
I /
~"~ 2000
-o
~ / / Initial concentration (mg-I-I )

20 l•/ 1000
/
I ] I I I f I 1 I
0 10 20 30 40 50 60 0 1000 2000 3000 4000
Time (min) Salt concentration (mg-l -I)
Fig. 2. Effect of initial nitrite concentration on the nitrite re- Fig. 4. Conductivity of the aqueous solution as a function
moval with 1.5 A current and 2000 mg-1-~ salt concentration. of salt concentration.

The effect of initial nitrite concentration on the
nitrite removal is demonstrated in Fig. 2. An initial
nitrite concentration of 10mg-1 -~ or less shown in
this figure is about the maximum nitrite concentra-
tion level that could be found in an untreated, high
density fish hatchery (Liao and Mayo, 1972; Otte and
Rosenthal, 1979; Poxton and Allhouse, 1982; Kruner
and Rosenthal, 1983; Bovendeur et al., 1987). It
appears that at I mg-1-~ initial nitrite, complete nitrite
removal is achieved in just about four minutes. As
the nitrite concentration was elevated to 5 mg-l -~,
the time for total nitrite removal increased rapidly to
more than 30 min, as demonstrated in Fig. 3 which
reveals a linear relationship between the time for total
nitrite removal and the initial nitrite concentration.
As mentioned earlier, the sample solution prepared
by dissolving sodium nitrite or ammonium chloride in
deionized water consistently had a conductivity of no
more than 70 p mho-cm -~ which is too low for an
effective electrochemical treatment. Addition of 1.5 g
concentration of 1500 mg-1-1 ) raised the conductivity
to slightly over 2000 # mho-cm- 1, as shown in Fig. 4.
The conductivity was further elevated to over 4000 V
mho-cm- l by maintaining a 3000 mg-l- ~ of salt con-
centration. According to Krstajic and Nakic (1987),
the added chloride ion in the aqueous solution will be
converted anodically to chlorine which is further
converted to hypochloric acid. The reaction sequence
can be represented by
2 CI----, C12 + 2 e -
C12 + H20----~HC1 + HOC1.
The hypochloric acid (HOCI) is a strong oxidant
which oxidizes nitrite to nitrate according to
NO~- + HOCI --* NO~- + CI-.
This oxidation reaction enhances the electrochemical
nitrite removal process. This may account for the
strong influence of the conductivity on the nitrite

1oo80/y
of table salt to l 1 of sample wastewater (with a salt removal as seen in Fig. 5. Here the current input was

80 -

E
"d
60 --
O
E

40
e.

Z, 40 o m
-I-')

20 •
20
v-
• j
I I I
0 2 4 6 8 10 12 0 10 20 30 40
Initial NO2-N concentration (rag-1 -I) Time (rain)
Fig. 3. Time for total nitrite removal vs initial nitrite concen- Fig. 5. Effect of salt concentration on the nitrite removal
tration with 1.5 A current and 2000 mg-l- t salt concentration. with 1.5 A current and 5 mg-l-~ initial nitrite concentration.
718 S. H. Lin and C. L. Wu
1o0 50-- -- 35
?2.0 ~n'| / O,, ' ' ' I / !

v
E
80 Time
40
0
- 25
> 60
"~ 30
Z 40 Current O
I cq
0
/ O -- IS

20

L I I L I 10 I I L 5
10 20 30 40 50 1000 2000 3000 4000
Time (min) NaCl(mg-1 -I)
Fig. 6. Effect of current input on the nitrite removal with Fig. 8. Time for total nitrite removal and power consump-
5 mg-1- ~ initial nitrite concentration and 2000 rag-l- ~ salt tion vs salt concentration 5 mg-I -~ nitrite concentration and
concentration. 1.5 A current input.

kept at 1.5 A for the three test runs. The time for total
nitrite removal was seen to be virtually cut in half
as the salt concentration was increased from 1500 to
3000 mg-l- ~. Beyond the 3000 rag-l- ~ level, the effect
of salt concentration on the time for total nitrite
removal was significantly reduced. Hence 3000 mg-l-
of salt concentration with a corresponding conduc-
tivity around 4000/~ mho-cm-~ would be the optimal
value. The present conclusion confirms that observed
in our previous report for electrochemical treatment
of textile wastewater (Lin and Peng, 1994).
By employing an initial 2000 rag-1 ~ salt concen-
tration in the sample solution, the curent input was
varied between 1 and 2.5 A to examine its effect on
the nitrite removal. As seen in Fig. 6, the effect of
current input was as significant as that of conductivity.
An increase in the current input considerably enhances
the oxidation power of the anode, leading to an
increase in the nitrite removal or a shorter time for
complete nitrite removal. The time for total nitrite
removal as a function of current input is demonstrated
in Fig. 7, Also shown in this figure is the power
consumption pertaining to the current input. The
curve dearly demonstrates a steady increase in power
consumption as the current input increases from 1 to
2 A. Beyond that, the power consumption decreases
with increasing current due to a rapid decrease in the
time for total nitrite removal. Hence, in terms of
power consumption, an applied current input larger
than 2 A is strongly recommended.
A similar figure for the time of total nitrite removal
and the power consumption vs the salt concentration
is displayed in Fig. 8. The rapid decrease in the time
for complete nitrite removal is due primarily to
enhanced anodic oxidation by hypochloric acid at
higher salt concentration. Unlike that of Fig. 7, the
power consumption in this figure is seen to decrease
monotonically with increasing salt concentration.
This, however, may not be construed that the salt
concentration can be much further increased in order

60 -- 30 I00 - o i ° ~.,Oa 0

Time
Time ~e .y
_ .p"
s0
80 - / ~ ¢,~"
Powor
40 -- 20

"~ 60 '°t/;7
Initial pH
30 -
f,/ oS7
20 -- -- 10 L4°°z
50 /7' .9
10 --

L I 0 I L L L
l 2 3 0 10 20 30 40
Current (A) Time (min)
Fig. 7. Time for total nitrite removal and power consump- Fig. 9. Effect of pH on the nitrite removal with 5 mg-1-
tion vs current input with 5 mg-1- ~nitrite concentration and initial nitrite concentration, 2000 mg-1-~ salt concentration
2000 mg-l-~ salt concentration. and 1.5 A current input.
 Aquacultural nitrite and ammonia removal 719

to achieve a greater power consumption efficiency 100

because presence of excessive amount of chloride

ions in the aqueous solution will not be ideal for the
treated wastewater.
The initial pH of the sample solution in the previ-
ous figures was adjusted to 7 before the experimental
run started. Figure 9 shows the effect of initial pH
on the nitrite removal. The pH chosen here covers the
actual pH range realizable in an aquacultural effluent.
Although the initial pH effect on the nitrite removal
is seen to be still significant, it is not of the same
magnitude as those of conductivity and current input,
This figure also indicates that the acidic pH range
favors the nitrite removal and seems to have a
stronger effect on the nitrite removal than the alkaline
pH range.
The pH of the sample solution was observed to
decrease from 7 to less than 5 during the electro-
chemical process of a typical test run. This was due
to conversion of nitrite to nitrate, the latter being a
much stronger acid. Hence it would be of practical
interest to see whether pH control during the electro-
chemical process will benefit the nitrite removal.
Hence, experimental runs were conducted with and
without boric acid/sodium borate buffer solution.
The buffer solution was capable of controlling the
pH to between 7 and 6 during the electrochemical
process, which is much narrower than that of the
unbuffered case. The results in Fig. 10 clearly indicate
that control of the pH in the aqueous solution during
the process has an adverse effect on the nitrite
removal. This is in line with what was observed in
Fig. 9 that the more acidic environment of the
unbuffered case is favored when compared to that of
the buffered case.
The above experiments were performed using
sample solution containing nitrite only. In many
practical situations, both nitrite and ammonia will be
present simultaneously in the aqueous solution.
Figure 11 compares the nitrite removal of a single-
80
j•j•J•J•
> 60
Q
E
i Z 40
©
Z
20 • Nitrite-ammonia
I E I f
0 10 20 30 40
Time (rain)
Fig. 11. Comparison of nitrite removal for nitrite and
nitrite-ammonia solutions with 5 rag-1 1 initial nitrite and
20 rag-l- t initial ammonia concentration.
component (nitrite) system and that of a two-
component (nitrite-ammonia) system. Presence of
ammonium ion is seen to strongly retard the nitrite
removal. As noted by Benefield et al. (1982), oxid-
ation of ammonium ion in the aqueous solution is
a two-step process. In the first step, ammonium ion
is oxidized to nitrite which then is further oxidized to
nitrite in the second step. Hence, during the electro-
chemical oxidation process, certain amount of nitrite
was generated in the first stage ammonia oxidation
for the two-component system. The actual amount of
nitrite existing in the aqueous solution would be more
than that derived from the initial nitrite. This results
in a significant slowdown of the nitrite removal, as
shown in this figure.
Because of the two-step nature of its electro-
chemical oxidation, ammonia removal will be expected
to be slower than that of nitrite. Figure 12 demon-
strates the ammonia removal as a function of time for
two different pHs. In comparison with that of Fig. 9

100 80

80

>
Q
60
/ p
40
E Buffer

'C
z
I

z
20

0 10 20 30
Time (min)
40
I
50
z~ 2o

0
J I
I0
I
20
I
30
Time (rain)
I
40
]
50
I
60

Fig. 10. Effect of buffer solution on the nitrite removal with Fig. 12. Effect of pH on the ammonia removal with
5 mg-1-~ initial nitrite concentration and 2000rag-l- t salt 20 mg-I-~ initial ammonia concentration, 2000mg-I-~ salt
concentration. concentration and 2.5 A current input.
720 S. H. Lin and C. L. Wu
lOO(~l)-l(ql~,)~,~,, 7, ammonia existing in its un-ionized form (NH3) also
increases. This accounts for the favorable effect of the
'~ 80 - -
alkaline pH range on the ammonia removal shown in
Fig. 12.
The ammonia removal for the single-component
60-- (ammonia) and the two-component (ammonia-nitrite)
systems by electrochemical oxidation is compared in
.,'~ Temperature
(°(3) \~mk~ Fig. 14. The current input was only 1.5 A which is
Q 40 -- • 16 ~.~\t~\ lower than the 2.5 A current employed in the single
component case shown in Fig. 12. The ammonia
20 - o 28
removal is seen to be considerably lower in the
present case, Essentially linear ammonia removal was
observed for both single-component and mixture
0 I I I I cases. A much higher ammonia removal for the single
8 9 10 11
component case than that of mixture is anticipated
pH because part of the power input was utilized for
Fig. 13. Percent of un-ionized ammonia (NH3) existing in nitrite oxidation in the latter.
the aqueous solution as a function of pH and temperature.
CONCLUSIONS

which shows total nitrite removal in the neighbor-
hood of 30min, that of the ammonia removal in
Fig. 12 is about 40% or less for the same time period
and the removal is essentially linear for that period.
Comparison of these two figures also reveals that
while acidic pH range is beneficial to the nitrite
removal, the ammonia removal shows an opposite pH
trend. According to Emmerson et al. (1980), ammonia
in aqueous solution can exist in either un-ionized
form (NH3) and/or ionized form (NH~-). Of these
two forms of ammonia, the un-ionized one is much
easier to oxidize (Benefield et al., 1982). For a given
pH and temperature, these two forms of ammonia
establish an equilibrium following the equation
(Emmerson et al., 1980)
NH3 + H 2 0 ~ N H ~ +OH-.
The percentage of ammonia existed in ionized form
as a function of pH and temperature is shown in
Fig. 13. It is apparent that as the pH increases above
20 --
Ammonia
Electrochemical method has been employed in the
present study to investigate nitrite and ammonia
removal from aqueous solution. Several aspects, such
as the sample solution conductivity, pH, current
input and type of electrodes, are explored to determine
their respective effects on the electrochemical removal
efficiency. The iron electrodes were found to be un-
suitable for the present process due to its low removal
efficiency. Pairs of graphite anode and titanium
dioxide cathode considerably elevate the removal
efficiency and were adopted for the present study.
Among the three major operating variables exam-
ined here, conductivity and current input were found
to exert much stronger influence on the nitrite and
ammonia removal efficiency than the pH. While a
current input larger than 2 A was observed to yield
lower power consumption than that below, the power
consumption decreases steadily with increasing con-
ductivity in the aqueous solution. It is also seen in the
experimental results that the nitrite and ammonia
removal is enhanced, respectively, in the acidic and
alkaline environments. Although the pH of the
aqueous solution decreases significantly during the
electrochemical process, pH control appears to exert
a negative effect on the nitrite removal. Presence of a

1015_ second component in the aqueous solution was found

to adversely affect nitrite and ammonia removal.

Acknowledgements--The authors wish to sincerely thank

the Yuan Ze Memorial Foundation for the financial support
/ Ammonia-nitrite (under the grant DRA 83001) of this project.

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