Aquacultural Engineering 30 (2004) 1–13

Strategies for alkalinity and pH control

for ozonated shrimp pond water
Niwooti Whangchai a , Veronica P. Migo b ,
Catalino G. Alfafara b , Henry K. Young c ,
Nakao Nomura d , Masatoshi Matsumura d,∗
a Department of Fisheries Technology, Faculty of Agricultural Production,
Maejo University, Chiangmai 50290, Thailand
b National Institute of Molecular Biology and Biotechnology (BIOTECH),

University of the Philippines Los Banos, Laguna, Philippines

c Aqua-Ecotechnology Research Inc. (AERI), Quezon City, Philippines
d Laboratory of Bioprocess Engineering, Institute of Applied Biochemistry,

University of Tsukuba, Tsukuba 305-0006, Japan

Received 10 July 2002; accepted 28 November 2002

Abstract

In order to derive the full benefits of ozonation technology for the destruction of toxic metabolites
in 1shrimp grow-out ponds, strategies to supplement and control high alkalinity loss during ammonia
oxidation in a model ozonation system were studied. Alkalinity loss and pH profiles were investigated
in the ozonated model system containing artificial seawater and ammonia, and alkalinity compen-
sation ability of supplements such as calcium carbonate-based limes, hydrated limes and sodium
bicarbonate were evaluated. In some experiments, application of these supplements during ozona-
tion were combined with other treatments like recarbonation (external CO2 supply). Results showed
that calcium carbonate-based limes were not anymore effective for alkalinity supplementation when
ozonation is applied to seawater containing ammonia. Although recarbonation improved the effec-
tiveness of CaCO3 as an alkalinity supplement, application in large ozonated grow-out ponds were
considered not practical. The effective alkalinity supplements for ozonated seawater containing am-
monia were the more soluble materials, high purity sodium bicarbonate and hydrated lime applied at
a proper dosage. Sodium bicarbonate and hydrated lime would be more appropriate alkalinity control

∗ Corresponding author. Tel.: +81-0298-53-6624.

E-mail address: aquacel@sakura.cc.tsukuba.ac.jp (M. Matsumura).

0144-8609/$ – see front matter © 2003 Elsevier B.V. All rights reserved.
doi:10.1016/j.aquaeng.2002.11.001
2 N. Whangchai et al. / Aquacultural Engineering 30 (2004) 1–13

strategies for in situ1 ozonated shrimp grow-out ponds; however, for application of hydrated lime, the
problem of overdosage should be taken into consideration.
© 2003 Elsevier B.V. All rights reserved.

Keywords: Alkalinity control; Ozonation; Lime materials; Black tiger shrimp

1. Introduction

Effective strategies for pathogenic control and the maintenance of good water quality
(particularly low levels of toxic metabolites like ammonia, hydrogen sulfide, etc. and other
optimum environmental parameters such as DO, alkalinity, pH) have been an active area of
research in shrimp aquaculture. There have been many attempts to find methods for effective
disinfection and improvement of water and sediment quality in shrimp ponds. Among these,
UV irradiation, application of formalin and sodium hypochlorite, and bioremediation have
been widely used (Liltved et al., 1995; Lazarova et al., 1999; Boyd and Massaut, 1999). One
of the emerging technologies available for marine shrimp cultivation is ozonation. Ozone,
a powerful oxidizing agent, has been used in aquaculture for disinfection and improvement
of water quality (Summerfelt and Hochheimer, 1997). Ozonation has been successful in
the inactivation of protozoa, oxidation of toxic metabolites in freshwater and also in the
improvement of water quality in recirculating rainbow trout culture system (Colberg and
Lingg, 1978; Summerfelt et al., 1997). In seawater, ozone reacts rapidly with bromide
ions to produce hypobromous acid (HOBr) which is an effective oxidant and disinfectant.
Ozonation in seawater was found to be effective in reducing shrimp pathogenic bacteria
such as Vibrio harveyi and the white spot syndrome baculovirus at ozone doses of 2.3 mg/l
for 30 s and 0.5 mg/l for 10 min, respectively (Matsumura et al., 1998; Chang et al., 1998).
In our previous work, we described the use of an ozonation process coupled with a novel
system for efficient recirculation and aeration in shrimp grow-out ponds. From our results,
it was found that both water quality improvement and disinfection can simultaneously be
done. Although it was effective for the removal of ammonia and pathogens, it was found to
decrease alkalinity and pH during the oxidation of ammonia by ozone (Whangchai, 2001).
Decrease in alkalinity and pH fluctuation in the pond were observed in in situ ozonated
shrimp pond (Matsumura et al., 2001). At the start of cultivation, alkalinity in the ex situ2
and in situ ozonation ponds were almost the same with an initial value of 100 mg/l (as
CaCO3 ). After 2 months of cultivation, however, alkalinity in the in situ ozonated pond
tended to decrease, even with the application of local liming materials such as hydrated
lime, dolomite and agri-lime. In contrast, maintenance of alkalinity was observed during
cultivation in ex situ ozonated pond. The decrease in alkalinity during ozonation has been
attributed to reactions involving the oxidation of ammonia with ozone (Matsumura et al.,
2001).

1 Ozonation inside grow-out pond.

2 Ozonation outside grow-out pond.
 N. Whangchai et al. / Aquacultural Engineering 30 (2004) 1–13 3

Due to the reaction of ozone with bromide in seawater, hypobromous acid (HOBr) is
produced (Eqs. (1) and (2)) and further reacts with free ammonia producing hydrogen ions
(Eq. (3)) (Haag and Hoigne, 1984; Tanaka et al., 1999).
O3 + Br − → OBr − + O2 (1)
H+ + OBr − ↔ HOBr (2)
3HOBr + 2NH4 + + 2OH− → N2 + 3Br − + 3H+ + 5H2 O (3)
HCO3 − + H+ ↔ CO2 + H2 O (4)
Alkalinity loss during ozonation of ammonia-containing seawater was due to the reaction
of the hydrogen ion with bicarbonate (Eq. (4)). Low alkalinity gives low buffering capacity
to pond water (Boyd, 1989), leading to high pH fluctuations and has negative effects on the
shrimp (Chanratchakul et al., 1995). Thus, in order to derive the full benefit of the ozonation
process in shrimp grow-out ponds, the importance of incorporating a good method to control
and compensate lost alkalinity was emphasized.
In order to investigate more about the decrease in alkalinity during ozonation, and to
establish good alkalinity supplementing strategies for application in in situ ozonated shrimp
grow-out ponds, experiments in an ozonated model system containing artificial seawater
and ammonia were conducted and the results are presented in this paper.

2. Materials and methods

2.1. Seawater and nitrogen components used

The model experiments were conducted using artificial seawater (ASW; Marina Com-
pany, Japan), containing 55–60 mg/l bromide ions. The composition is shown in Table 1.
Salinity was between 28 and 30 ppt. Ammonia was supplied as NH4 Cl (15 or 100 mg/l) and
nitrite was supplied as NaNO2 (25 mg/l).

2.2. Ozonation system

The batch reactor used for the alkalinity control experiments in an ozonated model system
was a 5-l rectangular vessel. A small, one-UV lamp model of an ozone generator (Asian
Laboratory Systems, Japan), with a similar ozone generation principle as those in grow-out
ponds was used. The mean inlet ozone concentration of the gas phase was 255 ppm (v/v)
with a gas flow rate of 1 l/min. Ozone was bubbled into the reactor by a gas sparger. The
experiments were conducted at 25 ◦ C.

2.3. Alkalinity control experiments

The effect of addition of liming materials on alkalinity profiles during the ozonation of
artificial seawater (containing ammonia) was studied. The effect of ozonation on alkalinity
in artificial seawater containing nitrite was monitored as well. These treatments were done
in combination with or without other treatments such as recarbonation. The materials used
4 N. Whangchai et al. / Aquacultural Engineering 30 (2004) 1–13

Table 1
Composition of artificial seawater (Marina Company, Japan) in 1 l of water
Composition Amount

NaCl (g) 21.9

MgCl2 ·6H2 O (g) 10.0
CaCl2 ·6H2 O (g) 1.4
Na2 SO4 (g) 3.7
KCl (g) 0.63
NaHCO3 (g) 0.18
KBr (mg) 90
Na2 B4 O7 ·10H2 O (mg) 36
SrCl2 (mg) 13
NaF (mg) 3
LiCl (mg) 1
KI (g) 70
MnCl2 ·4H2 O (␮g) 0.8
CoCl2 ·6H2 O (␮g) 0.2
AlCl3 ·6H2 O (␮g) 8
FeCl3 ·6H2 O (␮g) 5
Na2 WO4 ·2H2 O (␮g) 0.2
(NH4 )6 Mo7 O24 ·4H2 O (␮g) 20

were mainly lime-based (chemical grade CaCO3 ; Wako Chemical Company, Japan), marble
dust, coral sand, agri-lime, local hydrated lime (from Philippines), chemical grade Ca(OH)2
(Wako Chemical Company, Japan), sugar mill hydrated lime (from Philippines) and one
soda-based NaHCO3 (from Australia and China). All liming materials were in powder
form. Addition of the chemicals was done directly into the reactor vessel before the start
of ozonation or at the start of recarbonation. All experiments were performed in the batch
mode. Carbon dioxide was supplied at concentration of 1% at a flow rate of 10 ml/min
together with the air supply line. Air was supplied at 1 l/min of flow rate in all experiments.

2.4. Analytical methods

The pH in the ozonation tank during alkalinity control experiments was measured by a
pH meter (TOA Electronics Ltd., Japan), which was installed in the reactor and connected
to a recorder. Total alkalinity and nitrite were analyzed according to Standard Methods
(APHA, 1992). Total ammonia was determined using an ammonia test kit (Wako Chemical
Company, Japan). Ozone concentration in the gas phase was measured by a gas detection
tube (Kitagawa Company, Japan).

3. Results and discussion

3.1. Evaluation of locally available carbonate-based liming materials as alkalinity

supplements in ozonated seawater containing ammonia

Initially, the decrease in pH and alkalinity profiles during the oxidation of ammonia by
ozone were checked in the ozonated model system (i.e., 5 l reactor containing artificial
 N. Whangchai et al. / Aquacultural Engineering 30 (2004) 1–13 5

Fig. 1. Changes in (a) alkalinity and total ammonia–nitrogen (NH4 –N) and (b) pH in control (without ozonation)
and ozonated artificial seawater with 0.41 mg-O3 /l and 1 l/min flow rate, using 100 ppm NH4 Cl as ammonia source.
Each plot represents the mean ± S.D. of three replicate experiments.

seawater and ammonia as ammonium chloride). Also, the total alkalinity changes during
the ozonation of nitrite (instead of ammonia) were investigated.
The total alkalinity, total ammonia–nitrogen (NH4 –N) concentration and pH profiles in
the ozonated model system are shown in Fig. 1a and b. The effectiveness of ozone in the
removal of ammonia was confirmed. Likewise, the accompanying decrease in alkalinity
and pH were also observed. Using nitrite alone, the time courses in Fig. 2 showed that
nitrite could be effectively removed by ozone in seawater without a decrease in alkalinity.
Because the reaction of nitrite with ozone produced nitrate without H+ liberation, therefore,
the oxidation of nitrite by ozone had no effect on alkalinity (Eq. (5)).
O3 + NO2 − → NO3 − + O2 (5)
During ozonation in seawater, the conversion of ammonia to nitrogen gas is very fast. Ni-
trate formation is very low compared to nitrogen gas formation. Nitrate formed by ozonation
6 N. Whangchai et al. / Aquacultural Engineering 30 (2004) 1–13

6.00 250

Alkalinity (mg/L as CaCO3 )

5.00
Nitrite (mg NO 2 -N/L )

200
4.00
150
3.00
100
2.00

1.00 50

0.00 0
0 30 60 90 120 150 180
Time (min)

Fig. 2. Time course of: (䊏) nitrite and (䊉) alkalinity during ozonation in artificial seawater with 0.41 mg-O3 /l
ozone dosage and 1 l/min gas flow rate, using NaNO2 as nitrite source.

is less than 1% (Kobayashi et al., 1993). In this study, ozone concentration used in experi-
ment was relatively low concentration (0.41 mg-O3 /l). Hence, it is expected that amount of
nitrate formed was negligible.
Strategies to maintain good alkalinity levels in the ozonated model system (with am-
monia load) were then made by application of alkalinity supplements. Although there are
many kinds of liming materials that were used, initially, calcium carbonate-based limes,
which have been commonly used in conventional (non-ozonated) grow-out ponds, were
investigated.
Using chemical grade CaCO3 as the benchmark carbonate-based liming material, the pH
and alkalinity time courses in the ozonated model system (artificial seawater with NH4 Cl as
ammonia source) were investigated. An ozonated model system without CaCO3 was used
as control. The results in Fig. 3 show alkalinity declines for both control and CaCO3 -treated
experiments. Chemical grade CaCO3 was not effective in reducing the decline in alkalinity
levels during ozonation. The rate of alkalinity loss in the CaCO3 -treated ozonated sys-
tem (15 mg/l as CaCO3 per day) were almost the same as the untreated ozonated system
(16.7 mg/l as CaCO3 per day).
From the values of the slopes of the time courses of alkalinity and ammonia–nitrogen
concentrations, the “alkalinity consumption coefficient” for the removal of ammonia by
different liming materials during ozonation was calculated by taking the ratio of the al-
kalinity consumption rate and the ammonia–nitrogen removal rate. Results are shown in
Fig. 4. For chemical grade CaCO3 , this was about 3.2 ppm alkalinity (as CaCO3 ) per ppm
ammonia–nitrogen removed. With this value for chemical grade CaCO3 as the benchmark,
the alkalinity coefficients of other commercially available liming materials during ammonia
oxidation in the ozonated model system were investigated. The graph in Fig. 4 shows that
the commercially available liming materials had alkalinity consumption coefficients similar
to chemical grade CaCO3 . When these values are compared with the alkalinity consumption
coefficient under unlimed conditions (4.2 ppm alkalinity lost/ppm ammonia removed), only
a small improvement in alkalinity compensation is obtained.
 N. Whangchai et al. / Aquacultural Engineering 30 (2004) 1–13 7

140

120
(m g/L as CaCO3)

100
Alkalinity

80

60

40

20

0
0 48 96 144
Time (hour)

Fig. 3. Time course of total alkalinity in ozonated artificial seawater containing ammonia (100 ppm NH4 Cl) with
addition of chemical grade CaCO3 (100 ppm) and 0.41 mg-O3 /l ozone dosage and 1 l/min gas flow rate: (䊏)
without ozonation; (䊐) with ozonation + NH4 Cl; (䊊) with ozonation + NH4 Cl + CaCO3 .

By experience and observation, alkalinity compensation in limed but unozonated ponds

does not pose a serious difficulty since the rate of alkalinity loss is not severe and could be
balanced by the rates of dissolution of solid CaCO3 and subsequent alkalinity formation
toward equilibrium concentrations. However, for the case of ozonated ponds, alkalinity
compensation due to natural mechanisms of the carbonate system equilibria is disrupted,
and becomes dynamically unbalanced. The reaction rate of ammonia destruction by ozone
can be considered a very fast reaction (Tanaka et al., 1999). Hence, the corresponding rate of
H+ ion formation and alkalinity loss (Eqs. (3) and (4)) will be much faster than alkalinity loss

Marble dust 3.4

Coral sand 3.1

Agri-lime 3.2

No liming 4.2

0 1 2 3 4 5
Alkalinity consumption
mg/L as CaCO3 per 1 ppm NH3-N

Fig. 4. Alkalinity consumption coefficients of commercially available liming materials during ozonation
(0.41 mg-O3 /l) of seawater containing ammonia (as 100 ppm NH4 Cl).
8 N. Whangchai et al. / Aquacultural Engineering 30 (2004) 1–13

occurring in natural unozonated systems. Alkalinity compensation by natural mechanisms

of the carbonate equilibria in this case will not be anymore sufficient. This is compounded
by the fact that CaCO3 is only sparingly soluble in water; hence, the rate of mass transfer of
CaCO3 to the liquid phase will be very small, because the driving force for mass transfer is
also very small. The small difference in the rate of alkalinity loss between the limed ozonated
system and unlimed ozonated system (control) (as described above), is an indication that
alkalinity compensation using CaCO3 in the ozonated system was only minimal, almost
insignificant. It is likely that the rate of mass transfer of CaCO3 from the solid phase to
the bulk liquid phase (solubilization rate) is limiting and would make CaCO3 an ineffective
supplement for alkalinity control.

3.2. Effect of recarbonation in combination with carbonate-based alkalinity

supplements

Increasing the solubilization of CaCO3 by carbon dioxide (recarbonation) could increase

the driving force for increasing the mass transfer rate to the liquid phase, according to the
reaction:
CaCO3( s) + CO2( aq) + H2 O → Ca2+ + 2HCO3 − (6)

Also, this reaction would supply additional alkalinity directly from solid CaCO3 .
Carbon dioxide can be produced by respiration of organisms and could provide a way
to improve CaCO3 as an alkalinity supplement. Thus, experiments were done to determine
the effects of CO2 gas on alkalinity and pH in the model ozonation system containing
ammonia. The experiments in the model system attempted to simulate the shrimp pond
water that contained a critical level of ammonia (0.4 mg/l NH3 equal to 5.32 mg NH4 –N at
pH 8) (Boyd, 1982) and with 40 ppm of commercial hydrated lime/agri-lime (as a dose of
lime application).
Using ASW containing 15 mg/l NH4 Cl and an initial alkalinity of 120 mg/l (as CaCO3 ),
ozonation was carried out and then recarbonation by sparged CO2 –air mixture as described
in the Materials and Methods. The time courses for alkalinity for the recarbonated system
are shown in Fig. 5. Liming and recarbonation were simultaneously done after 48 h of
ozonation. The alkalinity profile which normally decreases during ozonation quickly shot
up when recarbonation and liming were done. About more than 90% of the initial alkalinity
was compensated within a short period of time and gradually increased to more than 100%
of initial value when recarbonation was continued. Thus, in the model ozonation system,
recarbonation maintained a low pH and increased the effectiveness of CaCO3 as an alkalinity
supplement according to Eq. (6).
Initially we expected that the increased CO2 levels in the shrimp grow-out pond during
the latter period of cultivation would similarly show improved levels of alkalinity in in situ
ozonated shrimp pond. However, as shown in our previous work (Matsumura et al., 2001),
no improvement in alkalinity levels was obtained during this period in the in situ ozonated
ponds. The reason is that alkalinity, produced from the reaction of “natural recarbonation”
with CaCO3 , is not sufficient. In the model system used in the experiment, the CO2 dose
is much higher than is produced in actual system. Hence alkalinity improvement could not
be observed. However, in order to realize the beneficial effect of recarbonation in an actual
 N. Whangchai et al. / Aquacultural Engineering 30 (2004) 1–13 9

140
Ozonation Recarbonation
Alkalinity (mg/L as CaCO 3)

130 Liming

120

110

100
0 24 48 72 96 120
Time (hour)

Fig. 5. Changes in alkalinity during ozonation (0.41 mg-O3 /l) and recarbonation (1% CO2 ) in the model ozonated
artificial seawater containing ammonia (15 ppm NH4 Cl) system with: (䊏) 40 ppm commercial hydrated lime
and (䊊) 40 ppm agri-lime as alkalinity supplements. Each plot represents the mean ± S.D. of three replicate
experiments.

shrimp pond would require additional input of CO2 ; this may not be practical from the
points of view of cost and negative effects of excess CO2 on shrimps.

3.3. Alkalinity control by more soluble alkalinity supplements

To find more suitable methods for alkalinity control in ozonated seawater containing
ammonia, the use of alkalinity supplements which were more soluble than CaCO3 were
evaluated. Here, the materials tested were NaHCO3 , and sugar mill hydrated lime which
has a higher purity of Ca(OH)2 compared with the commercially available one. Evaluation
of these materials were done with and without recarbonation. Recarbonation experiments
were done especially for sugar mill hydrated lime to see if the potential alkalinity in the
CaCO3 (major impurity in sugar mill hydrated lime) could also be tapped, in a similar
mechanism described in the preceding section. Liming was done after 48 h of ozonation,
and recarbonation in the recarbonation experiments were done also simultaneously at this
time.
The results shown in Fig. 6a show that both NaHCO3 and sugar mill hydrated lime
were effective alkalinity supplements in the model ozonated system, which contain 15 ppm
NH4 Cl. Liming and recarbonation were done after 48 h ozonation. Alkalinity levels were
restored to slightly more than 100% of initial values before the start of ozonation.
The pH time courses were observed in Fig. 6b, only NaHCO3 showed a stable value
before and after supplement addition (without recarbonation) during ozonation. The pH
for the sugar mill hydrated lime (without recarbonation) initially shot up to about 10.0,
before decreasing to a stable value of about 8.5. This could be a consequence of a shift
in alkalinity species to predominantly bicarbonate/carbonate. Because of a high initial pH
rise when sugar mill hydrated lime was used, this may not be good for shrimps in the
grow-out pond. Caution and careful addition of the right dosage of hydrated lime may be
necessary.
10 N. Whangchai et al. / Aquacultural Engineering 30 (2004) 1–13

200
Ozonation
Alkalinity (mg/L as CaCO3)

180
Liming
160

140

120

100

80
0 24 48 72 96 120
(a) Time (hour)

12.0
Ozonation
11.0
Liming
10.0
pH

9.0

8.0

7.0

6.0
0 24 48 72 96 120
(b) Time (hour)

Fig. 6. Changes in (a) alkalinity and (b) pH during ozonation of artificial seawater containing 15 ppm NH4 Cl: (䊊)
non-recarbonation with 40 ppm sugar mill hydrated lime; (䊐) non-recarbonation with 40 ppm sodium bicarbonate;
(䊉) recarbonation (2% CO2 ) with 40 ppm sugar mill hydrated lime; (䊏) recarbonation (2% CO2 ) with 40 ppm
sodium bicarbonate. Each plot represents the mean ± S.D. of three replicate experiments.

Although the total alkalinity was not affected by recarbonation for both materials, the pH
changes may reflect changes in the predominant alkalinity species (more dissolved CO2 ).
Recarbonation also caused a sharp decline in pH for both sugar mill hydrated lime and
NaHCO3 , to values slightly less than 7. This pH, alkalinity and water temperature produced a
dissolved CO2 concentration of 167 mg/l. Thus, recarbonation using these soluble alkalinity
materials is not recommended.
The results of this study showed that NaHCO3 and sugar mill hydrated lime, were much
better alkalinity supplements in ozonated seawater containing ammonia, compared with
CaCO3 . For practical application of these strategies, a system for the addition of these
supplements will be necessary especially from the viewpoint of preventing too high pH
values during the addition of these supplements. This is especially important in the case of
sugar mill hydrated lime.
 N. Whangchai et al. / Aquacultural Engineering 30 (2004) 1–13 11

9.0

8.8

8.6
pH

8.4

8.2

8.0
0 10 20 30 40
Concentration of alkalinity supplements (mg/L)

Fig. 7. Relationship between pH and concentration of different types of sodium bicarbonate (NaHCO3 ) and
hydrated lime: (䊊) sodium bicarbonate (Australia); (䊐) sugar mill hydrated lime; (䉱) sodium bicarbonate (China);
and (䉫) local hydrated lime. Each plot represents the mean ± S.D. of three replicate experiments.

Fig. 7 shows a relationship between pH and concentration of the alkalinity supplement

for two types of NaHCO3 and two types of hydrated lime. The graph shows that NaHCO3
has a very stable pH (about 8.1) over the range of concentrations indicated (0–40 ppm).
This pH value (which is expected when bicarbonate alkalinity is predominant) was stable
and indicated that the NaHCO3 materials used were almost pure. In contrast, hydrated
limes showed an increasing pH (from 8.1 to 8.9 for sugar mill hydrated lime, and from 8.1
to 8.2 for local commercial hydrated lime) over the same concentration range. Although
hydroxide alkalinity should be the main alkalinity for pure hydrated lime (pH about 10), the
commercially available limes have CaCO3 impurities which result in a mixture of hydroxide,
carbonate and bicarbonate alkalinities with a pH > 8. The higher and steeper slope of the line
for sugar mill hydrated lime compared to the locally available hydrated lime also indicates
a higher purity of sugar mill hydrated lime. The pH profile of the local commercial lime
showed that it may have more of calcium carbonate impurities. In order to confirm the
purity of the materials, the alkalinity dose factors for each of the alkalinity supplements
were determined from the slope of the plot of the concentration of supplement (x-axis) and
its alkalinity (y-axis) (data not shown). The summarized results are shown in Fig. 8. The
theoretical alkalinity factors which were obtained by the ratio of the gram equivalent weight
of CaCO3 over the gram equivalent weight of alkalinity supplement were compared with
actual values in Fig. 8. Theoretical alkalinity doses (in ppm alkalinity as CaCO3 per ppm
supplement) for NaHCO3 and hydrated lime are about 0.6 and 1.3, respectively. The results
confirmed that both types of NaHCO3 were relatively pure, while commercial hydrated
lime may be predominantly carbonate (only 12% pure). Sugar mill hydrated lime had an
estimated purity of about 75%.
Calcium carbonate-based liming materials which are commonly used for effective alka-
linity supplementation in conventional (non-ozonated) shrimp grow-out ponds, were found
to be ineffective for alkalinity compensation in in situ ozonated grow-out shrimp ponds
12 N. Whangchai et al. / Aquacultural Engineering 30 (2004) 1–13

Sodium bicarbonate (China) 0.62

Sodium bicarbonate (Australia) 0.64

Local hydrated lime 0.16

Sugar mill hydrated lime 0.98

0 0.2 0.4 0.6 0.8 1 1.2

Alkalinity dose factor
mg/L as CaCO3 per 1 ppm lime

Fig. 8. Alkalinity dose factors of different types of sodium bicarbonate (NaHCO3 ) and hydrated limes. Each plot
represents the mean ± S.D. of three replicate experiments.

(Matsumura et al., 2001), as well as in the ozonated model system. This could be traced to
the imbalance between the speed at which alkalinity is consumed when ammonia is oxidized
by ozone, and the slow solubilization of CaCO3 which severely limits its rate of alkalinity
compensation. Although recarbonation (by external CO2 supply) was found to improve the
effectiveness of CaCO3 as an alkalinity supplement in the model system, its application for
large grow-out ponds may not be practical from the viewpoint of cost and potential negative
effects on the shrimp.
The best alkalinity supplement during ozonation of seawater containing ammonia would
be high purity NaHCO3 . Its high solubility provided effective alkalinity supplementation
at an acceptable and stable pH and is difficult to over dose (Bisogni and Timmons, 1991),
NaHCO3 is the preferred additive for increasing alkalinity because it is inexpensive, dis-
solves rapidly and safe to handle (Loyless and Malone, 1997). Reasonably, high purity
hydrated lime to some extent would also make a good alkalinity supplement however, the
sudden increase in pH during its addition in water makes it important to have a proper
dosage for application.

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