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Ozonation kinetics of
ammonia and nitrite
removal from aqueous
solution
a a
S. H. Lin & Y. L. Yen
a
Department of Chemical Engineering , Yuan
Ze Institute of Technology , Neili, Taoyuan,
320, Taiwan, ROC
Published online: 15 Dec 2008.

To cite this article: S. H. Lin & Y. L. Yen (1996) Ozonation kinetics of ammonia
and nitrite removal from aqueous solution, Journal of Environmental Science
and Health . Part A: Environmental Science and Engineering and Toxicology:
Toxic/Hazardous Substances and Environmental Engineering, 31:4, 797-809,
DOI: 10.1080/10934529609376389
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 J. ENVIRON. SCI. HEALTH, A31(4), 797-809 (1996)

OZONATION KINETICS OF AMMONIA AND NITRITE REMOVAL

FROM AQUEOUS SOLUTION
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Keywords : Ammonia and nitrite removal, ozonation, oxidation kinetics

S. H. Lin and Y. L. Yen

Department of Chemical Engineering
Yuan Ze Institute of Technology
Neili, Taoyuan 320, Taiwan, ROC

ABSTRACT
he rates of ammonia and nitrite removal were determined in terms of the pH,
temperature and initial nitrite or ammonia concentration. The ammonia removal was
found to follow fairly well a first-order oxidation kinetics with a constant activation
energy and exponential pH-dependent frequency factor. But a zero-order oxidation kine-
tics with constant activation energy and frequency factor described well the nitrite
removal. The effect of initial ammonia concentration on the ammonia removal was not as
strong as those of the pH and temperature. But the effect of initial nitrite concentration on
the nitrite removal was rather significant.

INTRODUCTION
Aquaculture is an important business in many countries around the world. Traditi-
onal aquacultural activities were conducted in large ponds with low fish density. Such
activities required considerable amount of land and water resources. Therefore, they are
becoming relatively uneconomic due to increasing cost and decreasing availability of
these resources. A recent trend tends to employ high density aquaculture which requires
significantly less amount of land and water resources (1-4). Regardless of its strong
economic advantage, the high density aquaculture incurs a new problem. An increase in
fish density in a limited aquatic space would lead to a rapid degradation of the water
quality. Hence, the aquacultural water needs to be treated to maintain proper water

797

Copyright © 1996 by Marcel Dekker, Inc.

 798 UN AND YEN

quality required for such a activity (1-4). It is crucial that the water quality problem be
efficiently resolved before high density aquaculture can yield much real benefit.
A major issue to be addressed first in connection with the aquacultural water qua-
lity is the high ammonia and nitrite concentrations. Ammonia and nitrite in the aqua-
cultural ponds are generated primarily by fish excretion and decomposition of uncon-
sumed fish foods. In sufficient amounts, both ammonia and nitrite are toxic to marine
fishes. The acceptable levels of these two chemical compounds in the aqueous solution
for a normal aquacultural activity are quite low, being no more than 0.5 mg/I (1-4). The
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water quality of a high fish density and untreated aquacultural pond can deteriorate fairly
rapidly and fall below an acceptable level. Water treatment thus has become necessary if
the water quality is to be sufficiently maintained for a normal aquacultural activity. The
treatment methods proposed by the previous investigators included nitrification by
biological methods and activated carbon absorption and suspended solids (SS) removal by
sedimentation (1-4). In recent years, removal of nitrogeneous compounds by ozonation
has received increasing amount of attention (1-5). Ozonation of the aquacultural water is
capable of efficiently converting toxic ammonia and nitrite to non-toxic nitrate, reducing
excess algae growth, disinfecting water and increasing the dissolved oxygen (DO) con-
centration of the aqueous solution. In comparison, no other biological, chemical or
physical methods can accomplish the same objective in a single treatment. However, the
previous investigations (1-5) provided only qualitative assessment of aquacultural water
by ozonation. Singer and Zilli (6) and Haag (7) conducted experiments examining the
kinetics of ammonia removal by ozonation. A first-order kinetics for the ammonia remo-
val was obtained. However, several important aspects not considered previously include
the temperature effect on ammonia removal, effect of the presence of nitrite on the am-
monia removal kinetics and the the nitrite removal kinetics. The purpose of the present
work is to conduct experimental investigations to address these issues. Experimental re-
sults obtained here provide more quantitative information on understanding the removal
kinetics of nitrogenous compounds from aqueous solution by ozonation.

MATERIALS AND METHOD

The experimental schematic is shown in Fig. 1. Ozone generation system consisted
of two major portion. A pressure swing adsorption (PSA) apparatus was used to processe
the incoming air for the ozone generator. The PSA unit which consists of two ion exchan-
ge resin columns is capable of cleaning and drying (to a dew point below - 55°C) the
ambient air and elevating its oxygen content to over 80%. Dry and enriched air was then
fed to the Sumitomo ozone generator (Model SG-PSA-01A, Sumitomo Electric, Osaka,
Japan). With the operating conditions of 1.2 A current and 4 1/min air flow rate, the ozone
generator put out 10.2 g/hr of ozone in the exit ozone/air mixture. The ozone/air mixture
from the ozone generator was passed to the bottom distributor of the packed bed reactor.
 OZONATION KINETICS OF AMMONIA AND NITRITE REMOVAL 799

Thermocouple O3 Outlet
Exhaust

KÏ Absorber
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Pressire Swing
Adsorstion

Air Exhaust

Ozone
Generator
KI Absorber

Fig. 1. Experimental Schematic.

The gas effluent exiting the packed bed reactor passed through a potassium iodide (KI)
trap before being vented to the atmosphere.
The packed bed reactor was a Pyrex glass column of 6 cm in diameter and 1 m
long. The packing material in the reactor consisted of several structured cylindrical ele-
ments of 20 cm long and 6 cm in diameter. Cylindrical elements were made of SS 316
stainless steel strips of 2 cm wide. These thin stainless steel strips, which had many
punched holes of 0.1 mm in diameter, were twisted and bundled togather to form a cylin-
drical element which looked much like a conven-tional static mixer. Four of these pack-
ing elements were inserted into the the reactor resulting in a 0.8 m total packing length.
For temperature control, an electric heating tape was wound around the packed section of
the reactor. The packed bed temperature was continuously monitored by a thermocouple
and the measured temperature signal was employed for controlling the applied current to
the heating tape. The temperature of the packed bed reactor was controlled to within an
accuracy of ±0.3°C.
At the beginning of each experimental run, the packed bed reactor was filled with
2.2 liters of prepared aqueous solution containing 5 mg/1 nitrite or 20 mg/1 ammonia or
both. The aqueous solutin was sufficient to cover the packing materials in the packed bed
reactor. The aqueous solution was prepared by dissolving appropriate amount of reagent
grade ammonium chloride (NH4C1) or sodium nitrite (NaNO2) in deionized water.
 800 LIN AND YEN

The major variables considered in the present study included pH, temperature and
initial solute concentration. ForpH control, buffer solution containing boric acic (H,BO,)
and sodium borate (Na2B4O7) was employed. With the buffer solution, the pH of the
aqueous solution was controlled to within an accuracy of ±0.2 during each experimental
run. The nitrite and ammonia concentrations were determined by the diazotization and the
Nesslerization methods, respectively (8).

RESULTS AND DISCUSSION

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Ammonia Removal by Ozonation

Ammonia oxidation by ozonation can be represented by the following equation
NH 4 + + 4 0 , > NO," + 4 O2 + H2O + 2 H+ (1)
According the above equation, four moles of ozone are required for complete oxidation of
one mole of ammonia had shown that the molar ratio of ozone consumption exceeded the
theoretical value of the above equation due to ozone self-decomposition. Those authors
also presented the kinetic data based on the above equation. A test run was performed
here so that the ammonia removal and nitrate production could be compared between the
present experimental results and those of Singer and Zilli (6). Fig. 2 displays such a com-
parison. Significantly faster ammonia oxidation of the present experimental work (solid
line and solid triangles/cycles) is observed here than that of Singer and Zilli (6) (dashed
line and open triangles/cycles). The faster ammonia oxidation of the present study is due
mainly to the difference in the type of reactors employed (bubble column of Singer and
Zilli (6) vs. packed bed reactor of the present study) and the capacity of ozone generator,
the present ozone generator being having larger capacity than that of Singer and Zilli (6).
The same faster ammonia removal is also revealed in Fig. 3 which shows the ammonia
removal as a function of pH and time. For instance, at pH 9, the ammonia removal in 30
minutes by ozonation as obtained by Singer and Zilli (6) was less than 76% while in the
present study, over 82% ammonia removal was achieved.
Temperature plays an important role in the ammonia oxidation reaction. Figs. 4
and 5 show the ammonia removal as a function of temperature for pH 8 and 9, respective-
ly. Strong dependence of the ammonia removal on temperature is apparent here. In fact,
such a strong temperature dependence was also observed for other pHs. Fig. 5 reveals that
at pH 9, close to complete ammonia removal was achieved when ozonation was perform-
ed at a temperature higher than 36°C for 30 minutes.
The effect of initial ammonia concentration on the ammonia removal is demonstra-
ted in Fig. 6 for a particular case with pH 9 and at 28°C. The ammonia removal appears
to be slightly higher for 10 mg/1 initial ammonia concnetration than other cases at or
above 20 mg/1. Regardless of the initial ammonia concentration, over 80% of ammonia
removal were achieved after 30 minutes of ozonation. In general, the effect of initial am-
monia concentration on the ammonia removal is observed here to be significantly smaller
than those of the temperature and pH.
 OZONATION KINETICS OF AMMONIA AND NITRITE REMOVAL 80!

12 12

NHj-N+NtV-N
11-10
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10 20 30
Time, min
Fig. 2. Comparison of the Present Results with Those of Singer and Zilli.

100

a : pH= 7.5
o : pH= B.O
D : pH= 8.5
. : pH= 9.0

10 20
Time, min
Fig 3. The pH Effect on the Ammonia Removal at 30.5°C.
 802 UN AND YEN

100
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10 20
Time, min
Fig. 4. The Temperature Effect on the Ammonia Removal at pH 8.

uu -
pH= 9.0

80-

60-

40-
ffi / ^ \ •• 14.5°C

/ / •* o : 30.2"C
20- / / / ^ o : 36.0"C
. : 40.1*C

OH r 10 20
. : 45.1'C

30
Time, min
Fig. 5. The Temperature Effect on the Ammonia Removal at pH 9.
 OZONATION KINETICS OF AMMONIA AND NITRITE REMOVAL 803

100
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0 10 20
Time, min
Fig. 6. The Effect of Initial Concentration on the Ammonia
Removal at pH 9 and 28.5»C.

According to Singer and Zilli (6), the ammonia removal can be represented by a
first order reaction
C
ln( ) = -kt (2)
Co
where C is the ammonia concentration (mg/1) at time t (min), C„ the initail ammonia con-
centration and k the first-order reaction rate coefficient (min-1). A plot of ln(C/C0) vs t
yields a straight line, as shown in Fig. 7, with the slope being the reaction rate coefficient
k. Similar fit could be performed for other pHs also. The temperature dependent reaction
rate coefficient k follows the Arrhenius equation
AE
k = k o exp( ) (3)
RT
where k,, is the frequency factor (min-1), AE the activation energy (kcal/mol), R the gas
constant (kcal/mol-K) and T the temperature (K). Plots of ln(k) vs 1/T for various pHs are
displayed in Fig. 8. It is of interest to note that all straight lines have essentially the same
slope. The activattion energy calculated using eq. (3) for all pHs was found to be 12.8
 804 LIN AND YEN

1.4

1.2 -

1.0 -
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Ö0.4-
1—4
I
0.2 -

0.0
10 20 30
Time, min
Fig. 7. The First-Order Kinetics of Ammonia Oxidation at pH 8.

3.0 3.1 3.2 3.3 _ 3.4 3.5

Fig. 8. The Arrhenius Plot of the Ammonia Removal.

 OZONATION KINETICS OF AMMONIA AND NITRITE REMOVAL 805

kcal/mol. The frequency factor k,, obtained from Fig. 8 is exponentially pH dependent, as
demonstrated in Fig. 9. The exponential relationship can be represented by
k,,= 134.8 exp(1.5188pH) (4)
Nitrite Removal by donation
Ozonation experiments were also conducted using 5 mg/1 sodium nitrite solution.
The same H1BO:t/Na2B4C)7 buffer solution was employed to control the pH to within the
accuracy of ±0.03. As will be seen in the following figures, the nitrite removal by ozona-
tion was considerably faster than the ammonia removal, implying much less amount of
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ozone required for the nitrite removal than for the ammonia removal. Hence all nitrite
oxidation experiments were conducted with an ozone production rate at about 1.0 g/hr by
properly lowering the current input into the Sumitomo ozone generator.
The pH effect on the nitrite removal is demonstrated in Fig. 10 for a constant
temperature of 28°C. The figure clearly shows a zero-order kinetics for the nitrite removal
by ozonation which was characteristically quite different from the first-order kinetics of
the ammonia removal. It is apparent that the pH effect on the nitrite removal was margi-
nal, unlike that on the ammonia removal. Approximately, 90% nitrite removal were achie-
ved in just 5 minutes for all pHs.
Fig. 11 shows the temperature effect on the nitrite removal for pH 8. As anticipat-
ed, the nitrite removal become increasingly better as the temperature increases. The same
strong temperature effect was observed for other pHs also.
The initial nitrite concentration was varied in Fig. 12 to test its effect on the nitrite
removal with pH 8 and at 28°C. It is of interest to note that it took 4 minutes to reach
about 21% nitrite removal. But the time to achieve approximately the same nitial removal
was reduced by a minute as the initial nitrite concentration was increased from 5.03 to
10.58, 20.2 and 31.89 mg/1, respectively.
The rapid nitrite oxidation follows the chemical reaction
NO2- + O, > NO,- + O 2 (5)
According to the above reaction, only one mole of ozone is required to completely oxidi-
ze one mole nitrite. The zero-order oxidation kinetics observed above can be represented
by
AE
C o - C = k t = k,,exp( )t (6)
RT

where C is the nitrite concentration (mg/1) at time t, Co the initial concentration (mg/1), k
the zero-order reaction rate coefficient (mg/l-min), k,, the frequency factor (mg/l-min), t
the reaction time (min), AE the activation energy (kcal/mol), T the temperature (K) and R
the gas constant (kcal/mol-K). The straight lines of (Co-CyC,, vs t yielded the reaction
 806 LIN AND YEN

iv.u -

18.5 -

18.0 -
1

c 17.5
a -

ô 17.0 -
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16.5 - /

16.0 -

15.5 -
7.0 7.5 8.0 8.5 9.0 9.5
PH
Fig. 9. The Frequency Factor as a Function of pH.

100

fi : pH= 7.5
o : pH= 8.0
• : pH= 8.5
. : pH= 9.0

2 3 4 5
Time, min
Fig. 10. The pH Effect on the Nitrite Removal at 27.5°C.
 OZONATION KINETICS OF AMMONIA AND NITRITE REMOVAL 807

100
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1 2 3 4 5

Time, min
Fig. 11. The Zero-Order Kinetics of the Nitrite Oxidation at pH 8.

LUV

pH= 8.0

80- A : 5.03 ppm /

»—< o : 10.58 PPm /
CO
lemov

• : 20.20 ppm /
60- . : 31.89 Ppm / -

40-
i
o
20-

0H
0 1 2 3 4 5 6
Time, min
Fig. 12. The Effect of Initial Nitrite Concentration on the Nitrite Removal at 28»C.
 LIN AND YEN

0.4

0.2 -

S 0.0 -
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S-,0.2-

£-0.4 H

-0.6
2.9 3.0 3.1 3.2 3.3„ 3.4 ,3.5 3.6
( l / T ) * 10 3 , K"1
Fig. 13. The Arrhenius Plot of the Nitrite Removal.

rate coefficient k. The logarithmic k vs 1/T, in rum, gave the activation energy (AE) and
the frequency factor (k,,). Fig. 13 displays the Arrhenius plot of ln(k) vs 1/T for various
pHs. The data fell within ±5% of the straight line. The activation energy and the frequen-
cy factor were found to be 1.74 kca/mol and 0.00117 mg/l-min, respectively.

CONCLUSIONS
Ammonia and nitrite removal by ozonation was investigated. Experiments were
conducted to examine the effects of pH, temperature and initial ammonia or nitrite con-
centration on the removal efficiencies. A first-order and zero-order kinetics were found to
represent well the ammonia and nitrite removal, respectively. The activation energies for
both ammonia and nitrite oxidations were constant. The frequency factor for the ammonia
removal was exponentially pH-dependent while that for the nitrite removal was essential-
ly a constant. The effect of initial concentration on the ammonia removal was significant-
ly smaller than that on the nitrite removal. In general, ozonation was found to be capable
of efficiently removing ammonia and nitrite from the aqueous solution.

ACKNOWLEDGMENTS
The authors are grateful to the National Science Council, Taiwan, ROC for the
financial support (under the grant NSC85-2214-E155-005) of this project.
 OZONATION KINETICS OF AMMONIA AND NITRITE REMOVAL 809

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2. Orte, G. and Rosenthal, H. Management of Closed brackish Water System for High
Density Fish Culture by Biological and Chemical Water Treatment. Aquaculi. 1979;
18, 169.
3. Rosenthal, H. and Kruner, G. Treatment Efficiency of an Improved Ozonation Unit
Applied to Fish Culture Situation. Ozone Sci. Eng. 1986; 7, 179.
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4. Bovendeur, J., Eding, E. H. and Henken, A. M. Design and Performance of a Water

Recirculation System for High Density Culture of the African Catfish. Aquaaili. 1987;
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5. Honn, K. and Chavin, W. Utility of Ozone Treatment in the Maintenance of Water
Quality in a Closed Marine System. Mar. Biol. 1976; 34, 201.
6. Singer, P. C. and Zilli, W. B. Ozonation of Ammonia in Wastewater. Wat. Res. 1975;
9,127.
7. Haag, W. R. Improved Ammonia Oxidation by Ozone in the Presence of Bromide Ion
during Water Treatment. Wat. Res. 1984; 18, 1125.
8. APHA Standard Methods for Water and Wastewater Examination, 17th ed. Washing-
ton , D.C: Am. Public Health Assoc, 1992.

Date Received: November 17, 1995

Date Accepted: January 5, 1996