Removal of Ammoniacal Nitrogen from contaminated water using bio-waste of papaya peel bio- Commented [U1]: Add authors

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Ammoniacal nitrogen (AN) is one of the harmful pollutants in the wastewater. High level of this ada buat adsorption publications which you refer to. Tlg
check if those journals are scopus cites, indexed in web of
species can give a negative impact towards environment especially to aquatic life. In this study, science, which tier and what impact factor. Lets target Q1
journal and free (not paid journal or open access)
papaya peel, a fruit waste was used to produce an environmental friendly activated carbon
adsorbent to remove ammoniacal nitrogen from the aqueous solution through biosorption This paper needs to be vetted through for english. After u
edit it, send for proof reading.
techniques. Papaya peel was activated using potassium hydroxide (KOH) as chemical activating Commented [U2]: Must add research gap
agent to enhance the adsorption capacity of papaya peel and its removal efficiency. The
adsorbents were characterized using FTIR, FESEM, XRD and BET. The adsorption process was
carried out in batch mode considering different control parameters of initial pH (4-9), dosage of
adsorbent (0.01-0.3 g), contact time (5-120 min), initial (NH4+) ion concentration (10 -150 mg/L)
and temperature (25-65). The final concentrations of ammoniacal nitrogen was determined by
using Nessler method (Spectrophotometer DR 6000). The best condition with highest removal
(42 %) was obtained at pH 7, 50 mg dosage of adsorbent, 100 mg/L (NH4+) concentration at 30
minutes and 25. Desorption and regeneration studies were additionally conducted to evaluate
the reusability of the adsorbent. The experimental isotherm and kinetics data were evaluated with
Langmuir, Freundlich and Temkin isotherm models and pseudo first order and pseudo second
order kinetic models to relate the mechanism of adsorption ion by papaya peel powder. The data
fitted well with Freundlich model and Pseudo second order kinetic model. In addition,
thermodynamic parameters such as enthalpy change (H), free energy change (G) and
entropy change (S) were calculated. The result shows that the reaction was happenoccurs
spontaneously under atmospheric condition. High percentage removal of ammoniacal nitrogen
using carica papaya activated carbon (CPAC) in compared to other agricultural waste confirms
that papaya peel potentially can be used as an alternative adsorbent for ammoniacal nitrogen
removal.
 1. Introduction

Majority of industries will produce a large volume of highly polluted wastewaters

containing heavy metals, organic and inorganic pollutants. Ammoniacal nitrogen (AN) is one of
the major common inorganic pollutants in wastewater. Industries dealing with chemicals such as
petrochemical, textile, electroplating and metal finishing contributes to ammoniacal nitrogen
pollution and release of AN to the environment through their wastewater discharges (Liang and
Ni, 2009). Runoff and leachate from agricultural field, high consumption of chemical fertilizer,
use of chemical reagents for housekeeping such as detergent and soap are also considered as the
main sources of ammoniacal nitrogen in municipal wastewater. Malaysia environmental quality
standard for surface water defines the level limit of ammoniacal nitrogen concentration for
effluent releasing in river as of 10mg/L by standard A and 20mg/L by standard B (DOE, 1979).
But currently the ammoniacal nitrogen concentration is higher than the threshold level due to
extensive water discharge from industrial and domestic municipal wastewater.

Ammoniacal nitrogen (AN) can be detected at a very low concentration as it may cause
unpleasant odour due to its release in the air and this is the main problem associating with the
AN in Malaysia. In addition, high concentration of ammoniacal nitrogen in water makes it unsafe
for drinking purpose, may harm vegetation and more seriously it can be very toxic to aquatic life
(Copcia et al., 2010). Besides, ammoniacal nitrogen can contribute to corrosion and fouling of
some certain metals and reduce the amount of dissolved oxygen due to nitrification process
(Halim et al., 2013).

Therefore, the removal of ammoniacal nitrogen from surface water and wastewater has
been given great consideration. There are numerous removal techniques that have been
developed and applied to remove ammoniacal nitrogen including biological and physicochemical
methods. However, biological techniques have their own disadvantages over the successful
removal. For Hhigh concentration of AN pollutant, direct biological treatment has low removal
efficiency since high concentrations of ammoniacal nitrogen is toxic and inhibit nitrification
process (Aziz et al., 2004). Hence, physiochemical treatment such as ion exchange, adsorption,
membrane filtration, chemical precipitation, coagulation and flocculation and lastly
electrochemical treatment are more promising with higher removal efficiency compared to
biological treatment techniques. However, some physiochemical treatments such as membrane
filtration, chemical precipitation, coagulation and electrochemical treatment have their own
drawbacks like complex process, produce large volume of sludge and high operational cost.
Among various existing physicochemical methods for ammoniacal nitrogen removal, ion
exchange and adsorption have gained tremendous popularity among scientific community and
researcher because of their high removal efficiency (Copcia et al., 2010; Halim et al., 2011).
Removal of ammoniacal nitrogen by using ion exchange such zeolite shows good adsorption
capacity and high percentage removal. In spite of its high removal potential, this process requires
pre-filtration, caused interference of completion cations in wastewater, and has low-temperature
resistance of organic (resin) ion exchanger. It also needs high initial capital investment, high Commented [U3]: X faham ayat ni.

maintenance cost, and needs high energy to perform the process and produce toxic sludge.
These cause disadvantageousness disadvantages that have encouraged researchers to find new
alternatives (Jorgensen and Weatherley, 2003; Saltali et al., 2007).

Among the possible techniques for wastewater treatments, adsorption process using solid
adsorbents has been considered as an effective, efficient and more economical procedure.
Simplicity of the design and involving low production cost of the adsorbent cost are the main
advantages of adsorption treatment methodology (Rashed, 2013). In facts, for adsorption
process, activated carbon is actively used for wastewater treatment due to its good adsorptive
ability (Carotenuto et al., 2015).

An alternative method to remove any inorganic pollutant in the wastewater is adsorption

using agricultural waste products that is much more preferable since utilization of such materials
also has many advantages like cheap price, readily available, low cost and simple application
(Fang et al., 2015; Hossain et al., 2012). The main contents in agriculture waste are
hemicellulose, lignin, lipids proteins, simple sugar, water, hydrocarbon starch containing variety
of functional group which shows the potential of ion binding capacity (Bailey et al., 1999).
There are currently only limited study on the use of agro-waste material to remove ammoniacal
nitrogen e.g. bamboo charcoal (Li et al., 2012) and coconut shell (Boopathy et al., 2013) due to
low removal percentage of ammoniacal nitrogen from aqueous solution, which the removal is
below than 30%. Therefore, to overcome the low percentage removal, chemical surface
modification of activated carbon iswa as recognized as andan attractive approach to improve its
adsorption properties through thesuch enhancenhancement ofing the surface area to increase the
active site and formation of new functional groups of adsorbent (Chen et al., 2003; Demirak et
al., 2015).

Agro waste of papaya peel, is discarded all over the world as useless material. According
to the Department of Agricultural Malaysia (DOA, 2013), papaya has been proved as the main
locals fruits in Malaysia and it was the most cultivated fruits compare to the other types of fruits.
The production of papaya for year 2013 are 31,748.3 metric tons, and it will generates large
amount of wastes as well as peel due to the high rate of consumption in Malaysia. The other
parts of papaya such as leaves, seed, root, seed and pulp can contribute for towards medical
benefit (Aravind et al., 2013). However, theThere are increasing usage of papaya wastes such as
utilization of its leaves and seeds., Hhowever, the peel still remains as waste . Despite of this
significant, there have beenand there are onlyvery few publications on the utilization of papaya
peel. Currently, utilization of papaya peel as adsorbent to remove heavy metals and dyes from
wastewater has successful been conducted by Manjusha et al. (2012), Teja et al. (2013) and,
Abbaszadeh et al. (2016) to remove chromium (VI), methylene blue and lead respectively.
However, the study by using papaya peel to remove ammoniacal nitrogen has not been
investigated yet and this is the main motivation for the current study since it is expected that
papaya peel has such potential for ammoniacal nitrogen removal and at the same time it is a good
practice to reduce the waste.

In the present work, the adsorption of ammoniacal nitrogen from aqueous solution using
carica papaya activated carbon (CPAC) was investigated in for the batch process which
considering the pH of the solution, dosage of adsorbent, contact time, initial concentration of
(NH4+) and temperature. The experimental data obtained were evaluated and fitted using
equilibrium isotherm, kinetics and thermodynamics model. The results was confirmed its papaya
peel as potential as good alternative adsorbent for future wastewater treatment.
2. Materials and Methods
2.1 Reagents
For pH adjustment throughout the experiment, 0.1M sodium hydroxide, NaOH (MERCK,
99%) or 0.1M Sulphuric acid, H2SO4 (PC,99%) were used as necessary. In order to activate the
surface of the adsorbent, 0.1M Potassium hydroxide, KOH (HMBG, 85%) was used and
Ammonia chloride, NH4Cl (QREC) wasere used for the preparation of stock (NH4+) solution in
distilled water.

2.2 Preparation of Adsorbate

Standard stock solution of ammonia chloride (1000 mg/L) was prepared by dissolving
3.819 g of solid ammonium chloride (NH4Cl) in distilled water. The solutions with various Commented [U4]: Why this weird number?

concentrations was obtained by diluting the stock solution with distilled water (Liu et al., 2010).

2.3 Preparation of Adsorbent (Carica Papaya Activated Carbon)

The papaya were bought at the local market and peeled. The peel was dried using oven
(Constance,FCH 9036A, Germany) for 24 hours at 105 until they become crisp. Then the
crisp was grinded using blender (waring, MX 800S, USA) to provide papaya peel powder. This
powdered peel was labeled as carica papaya raw (CP-raw). CP-raw was heated up to 400 in
the furnace (Heattemp, Type S, Malaysia) for 30 minutes to make relative charcoal and labeled
as CP-char. To prepare carica papaya activated carbon (CPAC), 0.1M Potassium Hydroxide was
used as activating agent in contact with CP-char for 2 days to modify the surface characteristic.
After 48 hours, the mixture was filtered, then the adsorbent was washed with chemicals either of
1% NaOH (MERCK, 99%) followed by distilled water to neutralized the adsorbent. Then the
oxidized powder is kept in the furnace for another 2 hours (Ahmida et al., 2015). The dried
CPAC was sieved to get 0.5mm particles (using 500 micron mesh) and the final product kept in
an air tight bottle for future experiments.
2.4 Surface Characterization
The surface morphology of the adsorbents (CP-raw, CPAC before adsorption and CPAC
after adsorption) were done using Field-Emission Scanning Electron Microscope (JEOL JSM-
6701F) coupled with Energy Dispersive X-ray Analysis, EDX (S-3400N HITACHI) in
identifying the elemental composition of the materials. The functional groups of the adsorbents
were also identified through Fourier Transform Infrared spectroscopy (Perkin Elmer, USA) with
the spectra range 500 - 4000 cm-1. In addition, the crystalline properties of papaya peel
adsorbents with particle size of 500 micron was determined by using X-Ray Diffractometer
(Bruker, D8 Advance) and the surface area and pore size of the adsorbent powder was analyzed
using BET (Thermo Fisher Scientific).

2.5 Equilibrium Batch Experiments

The effect of adsorbent pH, adsorbent dosage, initial concentration of NH4+ solutions,
contact time and temperature were investigated through several batch experiments to determine
the suitable operating parameter for efficient ammoniacal nitrogen removal. The effect of pH on
the removal of ammoniacal nitrogen was studied by adding 0.3 g of CPAC powder into 50 mLl
solution containing 10 mg/L at different pH solution (pH 4 - 9). The solution and the powder
was agitated using digital orbital shaker (Labwit ZHWY- 334, China) for 2 hour. The pH of
solution was adjusted by using either sodium hydroxide (NaOH) or sulphuric acid (H2SO4) and
measured by digital pH meter (Milwaukee MW102 pH, Germany). After that, the adsorbent and
the solution wereas separated by centrifugation (Hettich Zentrifugen, Germany) and filtration
(Smith filter paper 150 mm and Nylon 0.45m syringe filter). The filtrated solution was analysed
by Nessler method using spectrophotometer (DR6000 Hach, US) in order to determine the
concentration of ammoniacal nitrogen after it has been adsorbed by CPAC (Demirak et al.,
2015). The same spectrophotometric method was used in the subsequent experiments. The
adsorption NH4+ study was conducted to consider the effect of adsorption parameters i.e pH of
the solution (4 - 9), adsorbent dosage (10 - 300 mg), contact time (5 - 120 minutes), initial
concentration of NH4+ in the solution (10 - 150 mg/L) and temperature (25 to 65 ). The
optimum parameters obtained were used to fit with the adsorptions isotherm, kinetics and
thermodynamic study. Each experiment was carried out in triplicate and the average results are
presented in this work. The amount of adsorption at equilibrium, (mg/g) and the removal
efficiency of ammoniacal nitrogen will be calculated by using Equations 1 and Equation 2
respectively (Hadi et al., 2011):

= ( ) (1)

0
Percentage Removal (%) = 100% (2)

Where 0 (mg/L) is liquid-phase concentration of concentration ammoniacal nitrogen at initial,

(mg/L) is the concentration of ammoniacal nitrogen at equilibrium, V (L) is volume of the
solution and M (g) is mass of CPAC used.

3 Results and Discussion

3.1 Surface Characterization

Surface characterization was conducted to compare the characteristic of the developed

adsorbent after chemical modification and also after the adsorption of Ammoniacal Nitrogen.
The morphology and the nature of the surface structure for raw papaya peel, before and after
adsorption are presented on the FESEM image in Figure 1 (a - c). Figure 1 (a) shows the
morphology of the raw papaya peel, which is rough and without any clear pores on the surface.
This will make the adsorption rate of the raw papaya peel very slow. To help the adsorption of
ammonium ion, the surface of the peel should be modified in which the aim of the modification
is to increase the surface area and enhance the pores of the adsorbent (Ferreira et al., 2012).
After treatment using alkali (KOH, 0.1M) as a modifier, the structure was modified and pores
were formed on the surface of the papaya peel (Figure 1(b)). These pore structures will enhance
the adsorption of ammonium ion. After adsorption of the ammonium ion, the pore structure of
CPAC was covered with another image in which it is shown that the ammonium ion has been
adsorbed into the CPAC (see Figure 1(c)). From elemental analysis (see Table 1), the presence
of nitrogen confirms that ammonium ion was adsorbed by the CPAC. BET results reveals that
the surface area increases from the raw peel and after activation (26.559 m2/g). The surface area
of raw papaya peel has been studied by Abbaszadeh et al. (2016) and it shows the surface area of
raw-PP as 9.63 m2/g. The results was are shown in Table 1.

FTIR analysis was carried out to identify the functional group on the surface of papaya
peel. The presence of some certain functional groups can control the adsorption process of
ammoniacal nitrogen where functional group such as hydroxyl and carboxyl acts as proton
donors. Hence, deprotonated hydroxyl and carboxyl may further involved in coordination with
the adsorbed ion. Figure 2 presents the FTIR spectra of two adsorbents, the raw papaya peel
powder and the spectra of the Carica Papaya Activated Carbon (CPAC) after adsorption. The
spectra was measured within the range of 500 4,000 cm-1 where the change in the identified
functional groups on the powder surface can be seen clearly. From the comparison of these two
adsorbents, the variations in the spectra appear different in intensity. The change in intensity is
due to the peaks, which represent the oxygenated group change after the adsorption process and
in turn leads to the existence of the amine group, which is believed to originate from the
ammonium ion. It can be seen that the broad peak falls within the range of 3,1003,400 cm-1 (see
Figure 2 (a)) attributed to the O-H stretching and adsorbed water molecules due to the
intermolecular hydrogen bonding of polymeric compounds such as alcohols or phenols in pectin,
hemicellulose, cellulose, and lignin (Iqbal et al., 2009). The broad peaks in the range of 3,300
3,500 cm-1 show a slight difference after adsorption had occurred showing that the amine groups
(N-H) have emerged. The peak in the range of 2,8002,950 cm-1 is due to C-H stretching (Gin et
al., 2014). Besides that, the peak in the range of 1,6001,700 cm-1 is due to the carbonyl (C = O) Formatted: Superscript
-1 -1
stretch. The peak in the range 1,6701,820 cm range shifted to 1,600 cm due to the exchange Formatted: Superscript

of C = O to N-H (amine) where it can be seen that the ammonium ions are embedded. The last Formatted: Superscript

peak falls within the range of 1,0201,040 cm-1, which is due to the C-O stretch. Formatted: Superscript

In this study a non-crystalline pattern by XRD analysis for CPAC before and after
adsorption is observed as presented in Figure 3. The pattern shows that the adsorbent was in
amorphous solid form and possesses a heterogeneous surface as a broad diffused peaks were
observed at low angles. In this analysis, the diffraction peaks of crystalline carbon was not
observed. Amorphous means the powder pattern contains no crystalline diffraction peaks and it
was happened when the x-ray were scattered in many direction leading to a large bump
distribution in a wide range (2 Theta) instead of high intensity narrower peaks (Danish et al.,
2011). Organic materials are expected to have an amorphous structure rather than crystalline
since the organic materials do not exhibit any minerals (Mafra et al., 2013).

(a) (b)

(c)
Figure 1 FESEM image for papaya peel powder. (a) Carica Papaya raw (CP-raw), (b) Carica
Papaya Activated Carbon (CPAC) before adsorption of ammonium ion, (c) Carica Papaya
Activated carbon (CPAC) after adsorption of ammonium ion.

Table 1: Elemental analysis and BET characterization of the adsorbents

Adsorbent/Element Carbon, Oxygen, Potassium, Nitrogen, Surface Cumulative
C (%) O (%) K (%) N (%) Area pore Commented [U5]: Any unit?
 (m2/g) Formatted: Superscript
CP-raw 66.76 33.24 - - 9.63 0.0169
CPAC Before 65.23 28.20 6.57 - 26.559 0.0858
Adsorption
CPAC After 59.95 23.46 0.52 16.07 18.685 0.0897
Adsorption

Figure 2 FTIR spectra of papaya peel powder: (a) Carica Papaya (CP) raw; and (b) Carica
Papaya Activated carbon (CPAC) after adsorption of ammonium ion.
 Figure 3 X-ray Diffractogram of CPAC before and after adsorption

3.2 Batch Adsorption of Ammoniacal Nitrogen

Adsorption capacity with the percentage removal were studied through batch experiments
and five parameters as effect of pH, dosage of adsorbent, contact time, initial concentration of
ion in solution and temperature were eveluated.

3.2.1 Effect of pH
Optimisation of solution pH is very important since pH is not only affects the surface
charge, but also controls the degree of ionization of adsorbate during reaction. For pH value
below 7, ammonium comes mainly as NH4+ and in pH >7, NH4+ will be replaced by NH3.
According to Bronsted - Lowry acid base reaction given in equation 3, the removal should be
greater at lower pH and smaller at higher values if the cation exchange mechanism occurs only
by means of the ammonium ions.

NH3 + H2O NH4+ + OH- (3)

The effect of pH in this study was evaluated via a batch mode process using a pH range
from 4 to 9 at room temperature (25 2 ) and the results are shown in Figure 4. The results
reveal that as the solution pH increased from 4 to 7, the removal efficiency of ammonium
increased gradually and reached the maximum uptake. Thereafter, the ammonium uptake
decreased steadily from pH 8 to pH 9. The result shows that the removal of ammoniacal nitrogen
was best achieved at pH 7 where the developed adsorbent was able to remove 0.522 mg/g of
ammonium ions with an adsorption efficiency of 31.33%. Due to high competition of H+ and
ammonium ions over the adsorption sitesd, the removal amount was decreased at pH < 7 (Liu et
al., 2010). On the other hands, at pH > 7, ammonium ions are transformed to aqueous ammonia
(Demirak et al., 2015). Thus, less adsorption capacity was observed at pH > 7 which is probably
due to an increase in percentage of molecular ammonia which reduces the ion-exchange
potential. Thus, the adsorption reaction of CPAC can be described as a chemical reaction
including sharing or exchanging of electrons through valence forces between the negatively
charged adsorbent sites and ammonium ions. The results effect on the pH results showed a
similar trend as per the study of Liu et al. (2010) and Li et al. (2012), which proved that the
highest pH in the removal of ammonium ion using Boston ivy leaf powder and using bamboo
charcoal modified with nitric acid, respectively, was at a pH of 7.

Formatted: Indent: First line: 0"

Figure 4 Effect of pH on the removal of ammonium ion

3.2.2 Effect of Adsorbent Dosage

The effect of biosorbent dosage on the removal of ammonium was investigated at 10
mg/L ammonium concentration, a pH of 7, and at room temperature (25 2) and the results
are shown in Figure 4.10. The effect of adsorbent dosage was evaluated using 0.01, 0.02, 0.03,
0.04, 0.05, 0.1, 0.2, and 0.3 g of adsorbent dosage. From the results, it can be observed that by
increasing adsorbent dosage, the removal efficiency initially increases. As adsorption progressed
and after reaching the equilibrium, the removal efficiency declines. However, the ammonium
uptake capacity is inversely proportional to the dosage amount. The percentage removal of
ammonium ion increased from 16.67 % to 33.67 % when the adsorbent dosage increased from
0.01 g to 0.05 g, respectively. However, by increasing the dosage to 0.1g, the percentage of
removal drops to 33.00 % and further increase of dosage up to 0.3 g of CPAC resulted in only a
marginal removal of ammonium. Increasing the dosage from 0.01 g to 0.05 g offered more
available active sites, providing for higher removal efficiency. However, a further increase of
adsorbent dosage was not favourable as it decreased the uptake slightly. However, the
adsorption capacity (qe) showed an opposite trend in which it decreased from 8.333 mg/g to
3.367 mg/g as the amount of dosage increased from 0.01 g to 0.05 g. In fact, the number of
active sites increased with the increase in adsorbent dosage, providing more chances for the
ammonium ion to adsorb at the adsorbents surface. But tThis trend occurred due to the
unsaturation of adsorption sites through the adsorption process overlapping or partial
accumulating among the available active binding sites (Hossain et al., 2012; Ofomaja et al.,
2009). In addition, the amount of ammonium ion adsorbed per unit mass of CPAC adsorbent
reduced with the higher adsorbent dosage, which led to a decrease in qe value.

Figure 5 Effect of adsorbent dosage on the removal of ammonium ion

3.2.3 Effect of Contact Time
Contact time indicates the time needed for adsorbent to be in contact with the adsorbate
until it reaches equilibrium or maximum adsorption achieved by the adsorbent. A shorter contact
time practically more preferable in order to minimise the operating cost and optimise the
adsorption process. From the results in Figure 6, it can be observed that the kinetic of reaction
was faster with an adsorption percent removal of 42.67 % and an adsorption capacity of 4.267
mg/g. After 1 h, the adsorption process onto CPAC has reached equilibrium state, and from this
point onwards, the removal efficiency started to decline. The increase in the adsorption capacity
in the first 30 minutes is due to the availability of active sites, providing good chances for the
ammonium ion to bind onto the CPAC surface. After one hour of reaction, the percentage
removal declined. This maybe due to the ammonium ion at the surface which were not totally
adsorbed onto the CPAC have been desorbed. After 30 minutes, there are no more available
sites for the adsorption to occur, hence, it is not favourable to increase the time of reaction to
more than 30 minutes for the removal of ammonium using papaya peel (CPAC). Therefore, it
can be concluded that the optimum contact time is affected by the ratio of the number of
adsorption sites to the number of ion in the solution. It also depends on the nature of adsorbent
which are responsible for the time needed to reach equilibrium (Babel and Kurniawan, 2004).

Figure 6 Effect of contact time on the removal of ammonium ion

3.2.4 Effect of Initial Concentration of Ion in the Solution
It is observed forom Figure 7 that the percentage removal was inversely proportional to
the adsorption capacity of the adsorbent. Increasing the initial concentration of solution showed
an increase in adsorption capacity but a decline in the removal percentage of ammonium ion.
Using an initial concentration of 10 mg/L, the highest percentage removal of ammonium ion was
achieved (42.67 %) while a minimum adsorption capacity of 4.267 mg/g was observed.
However, as the initial concentration increases up to 150 mg/L, the lowest percentage removal of
ammonium was achieved (8.667%) but at this initial concentration, the adsorption capacity was
the highest (17.33 mg/g). The reason for this trend is that the ion mechanism is particularly
dependent on the initial NH4+ ion concentration. The decrease in the percentage removal (%)
with the increase in initial concentration is due to the fact that all the adsorbents have a fixed
number of active sites and at higher concentrations, the active sites become saturated and
exchange sites are filled (El-Ashtoukhy et al., 2008; Omar et al., 2011). However, the adsorption
capacity (qe) is increased with the increase in initial concentration, which is due the initial
concentration acting as the driving force to overcome mass transfer resistance of ammonium ions
between the aqueous and the solid phase (Akpomie et al., 2015; Li et al., 2012).

Figure 7 Effect of initial concentration of ions on the removal of ammonium ion using CPAC

3.2.5 Effect of Temperature

 Temperature is one of the important parameters in determining the thermodynamic
property of an adsorption process. The results presented in Figure 8 show the effect of
temperature on the adsorption capacity and adsorption efficiency of CPAC. From the plot in
Figure 8, both results show decreasing values of adsorption capacity and the efficiency as the
temperature is increased. It can also be seen that the removal percentage decreased from 41.7 %
to 30.3% when the temperature was increased from 25 to 65 . It can therefore be concluded
that this process is exothermic in nature and energy is released during the adsorption process.
This is due to the tendency of the adsorbed ions to escape from the liquid phase to the bulk phase
for which the ion binding power might be weakened with increasing temperature of the solution.
Hence this process is suitable and economical since it can also be progressed at room
temperature.

Figure 8 Effect of temperature on the removal of ammonium ion

3.3 Adsorption isotherm

Adsorption isotherm represents the equilibrium in the adsorption system. It is represented
by the distribution of the adsorbed material between adsorbed phase and the solution phase at
equilibrium (Inglezakis and Poulopoulos, 2006). There are three different isotherm models that
are commonly used to evaluate the adsorption equilibrium, which are the Langmuir, Freundlich
and Temkin models. The Langmuir model shows that the adsorbent behaviour supposedly
contains fixed individual sites, which adsorb only one molecules, forming a monolayer adsorbate
on the outer surface of the adsorbent and after that no further adsorption will takes place
(Hameed et al., 2009). There are three assumptions used in Langmuir isotherm model. Firstly,
the surface of adsorbent is in contact with the solution that contains the adsorbate, which is
strongly attracted to the surface. Secondly, the surface has specific number of sites where the
solute molecules can be adsorbed. Lastly, the adsorption involves the attachment of only one
layer of molecules to the surface, also known as monolayer adsorption (Bansal and Goyal, 2005).
Freundlich model is commonly used to describe the adsorption characteristics for a
heterogeneous surface. These data often fit the empirical equation proposed by Freundlich
(Zhang et al., 2009). It also has been used to describe non-ideal and reversible adsorption
phenomena, specifically for complex solids with non-uniform distribution in terms of adsorption
energy and affinity such as activated carbon (Achak et al., 2009). Temkin isotherm model
defines a factor of adsorbent-adsorbate interaction by ignoring the extremely low and large value
of concentrations and the model assumes that the heat of adsorption (function of temperature) of
all molecules in the layer decreases linearly (Dada et al., 2012).

A linear equation of Langmuir, Freundlich and Temkin models are expressed as Equation 3, 4
and 5 respectively.

Langmuir Model: = + (3)

1
Freundlich Model: = + log (4)

Temkin Model : : =
ln +
ln (5)

Where is the saturation concentration of ammoniacal nitrogen (mg/L) is, is the amount of
ammoniacal nitrogen adsorbed at equilibrium conditions (mg/g), is the maximum
monolayer adsorption capacity (mg/g) and is the sorption equilibrium constant (L/mg), which
is related to the energy of adsorption. The performance of the adsorbent was determined by
in which a good adsorbent will obtain high . The value of and was calculated

from the slope and intercept of the plotted graph ( ) from the result of isotherm

experiments. is the characteristic constants related to the adsorption capacity (mg/g) while n
is adsorption intensity or degree of favorability of adsorption. A larger value of n denotes a
stronger interaction between ions and adsorbent particles. and 1/n was calculated from slope
and intercepts of the graph ( vs log ) respectively. and b is Temkin isotherm constant
of adsorption affinity (L/mg) and Temkin isotherm constant of heat sorption (kJ/mol)
respectively. Commented [U6]: If you want to submit to JCLEPRO, do
not use the word respectively.

The essential characteristic of the Langmuir isotherm model can be explained in terms of
dimensionless constant separation factor (RL) which defined by Equation 6.

= (6)
+

Where b is the Langmuir constant and is the initial concentration of ion. The indicated that
the type of Langmuir isotherm is either irreversible ( =0), favourable (0< <1), linear ( = 1)
or unfavorable ( >1) (Hameed et al.,2009).

In validating the experimental value with the theoretical value of the model, root mean square
error (RMSE) and chi-squre test ( 2 ) were used as expressed in Equation 7 and 8 respectively.

1
RMSE = 2
=1[ ]2 (7)

( )2
2 =
=1
(8)

is the adsorption capacity at equilibrium from the experimental value and was
estimation from isotherm model and N is the number of data points. Smaller RMSE and 2
makes the estimation of more accurate (Abbaszadeh et al., 2016).

Table 2 shows all the parameter for the Langmuir, Freundlich and Temkin isotherm
which calculated from the plotted graphs from isotherm experiment results (Figure 9 (a) (c)). In
conclusion, all these three models are favourable for this study, however, the best correlation
coefficient must still be selected to describe the adsorbent-adsorbate relation. The model was
chosen based on the highest value of correlation coefficient (R2). Highest correlation coefficient
R2 demonstrates better explanation of experimental data with the Freundlich isotherm model as
shown in Table 2. In addition, the error analysis from RMSE and chi-square test ( 2 ), shows the
Freundlich model gives the smallest value out of all the thers. So, it can be concluded that the Commented [U7]: What is this?

ammoniacal nitrogen adsorbed onto heterogeneous surface of CPAC and the value of n > 1
denotes that the adsorption of ammoniacal nitrogen using Carica Papaya Activated Carbon
(CPAC) is favourable.

Figure 9 (a) Langmuir isotherm plot model Figure 9 (b) Freundlich isotherm plot model

Figure 9 (c) Temkin isotherm plot model Commented [U8]: Please make sure all the fonts are
readable for all Figures. Not less than pt 8 if possible
Table 2: Langmuir, Freundlich and Temkin parameter for the adsorption of Ammoniacal
Nitrogen.
Langmuir Freundlich Temkin
Q max = 21.552 mg/g

= 0.015 L/mg = 1.316 L/g = 0.193 L/mg

= 0.401 n = 2.079 = 583.659 kJ/mol
2 = 0.7872 2 = 0.9447 2 = 0.8111
RMSE=1.224 RMSE= 0.048 RMSE= 1.947
X2 = 1.304 X2 = 0.011 X2 = 1.875

3.4 Adsorption Kinetic

Adsorption kinetic depends on the adsorbate-adsorbent interaction and one of the
important elements in the adsorption process is the reaction rate. The residence time required in
completing the adsorption process can be determined by solute uptake rate, which can be
estimated from the kinetic analysis (Ho, 2004). In order to investigate the controlling mechanism
of the adsorption processes such as mass transfer and chemical reaction, the pseudo-first-order
and pseudo-second-order equations are applied to model the kinetics for the adsorption of
ammoniacal nitrogen onto CPAC

The linear form of pseudo-first-order rate equation (see Equation 9) is given as

ln ( )= ln qe - 1 (9)

Where and are the amount adsorbed (mg/g) at time, t, and at equilibrium respectively and
1 is the rate constant of the pseudo-first-order adsorption process (min-1). Straight line plots of
ln ( - ) against t were used to determine the rate constant, 1 , and adsorption capacity at
equilibrium . In addition, the correlation coefficients, R2 also was determined from the plotted
graph.

A pseudo second order can be expressed as shown in Equation 10.

1
= + (10)
2 2
Where 2 is the equilibrium rate constant (g/mg.min). This model is expressed by a plotted
1 1
graph ( vs t) to form a slope of and intercept of .
2 2

In addition, to validate the kinetic models, normalized standard deviation (NSD) and average
relative error (ARE) are evaluated as shown in Equation 11 and 12 respectively:

2
1
NSD = 100
=1 [ ] (11)
1

100
ARE=
=1 | | (12)

Where and (mg/g) are experimental and calculated value for adsorption capacity of
ammoniacal nitrogen at time, t while N is the number of data points. Smaller NSD and ARE
values are better since they indicates a closed estimation of values (Pezoti et al., 2016;
Abbaszadeh et al., 2016).

The model mentioned previously was plotted graphically in the Figure 10 (a) and 10(b).
It is observed that the data was fitted well with the pseudo-second order model. The value of 2
and calculated was 1.138 g/mg.min and 3.734 mg/g respectively. Calculated (from plotted
model) was nearest with the experimental value (4.267 mg/g). In addition, correlation
coefficient of R2 for this model is high and nearest to one and the value of NSD (23.726) and also
ARE (17.228) value are smaller compared to value from pseudo-first order model. Therefore,
pseudo-second model was the best model to describe the kinetic process for adsorption of
ammoniacal nitrogen onto CPAC. It indicates that chemical sorption takes place in the
adsorption process which may partly due to the hydrogen bonding between the hydroxyl
functional group of the CPAC and the ammonium ion (Achak et al., 2009). All the parameter for
the Pseudo- first order and pseudo-second order was listed in Table 3.
Figure 10 (a) Pseudo-first order plot model Figure 10(b) Pseudo-second order plot model
Using CPAC using CPAC

Table 3: Kinetic parameter of Pseudo-first order and Pseudo-second order for the adsorption of
ammoniacal nitrogen.
Kinetic Model Constant parameter Results
Pseudo-First Order (meas)(mg/g) 4.267
1 min-1 0.0082
(calc)(mg/g) 1.2663
R2 0.2245
NSD 230.109
ARE 139.605
Pseudo-second Order 1 g/mg.min 1.138 3
(calc)(mg/g) 3.7341
R2 0.9763
NSD 23.726
ARE 17.228

3.5 Thermodynamic
 Spontaneity of a process can be determined by thermodynamic parameters such as
enthalpy change (H), free energy change (G) and entropy change (S). A spontaneous
process will show a decrease in G and H values with increasing temperature (Achmad et
al., 2012). Gibbs free energy (), change in enthalpy () and the change in entropy () can Commented [U9]: Betul ke ejaan nama ni?

be correlated with the isotherm constant in the estimation of thermodynamics parameters. Gibbs
free energy () is the fundamental criterion to determine if a process occurs spontaneously and
at a given temperature, a phenomenon is considered to be spontaneous if the has a negative
value. In this study, the shows a negative results and the value is decreases as temperature
increased. The exothermic and endothermic nature of adsorption can be determined by using
value of . A negative value of showed that the adsorption process was exothermic, while
the positive value of H showed endothermic process. A positive value of shows the
increase in randomness at the solid solution interfaces (Gueu et al., 2007). The thermodynamic
parameters and the influence of temperature on the uptake capacity on CPAC for the adsorption
of ammonium ion are illustrated in Table 4 and graphically plotted (Vant Hoff plot) in Figure
11. From the results, it can be concluded that this process was occur spontaneously when
showing shows negative value and negative H (-9.627 kJ/mol) value indicates that the process
occur under exothermic conditions while positive (34.812 J/mol K) values shows the increase
in randomness at solid solution interfaces.

Figure 11: Vant Hoff plot for the adsorption of ammonium ion onto CPAC
Table 4 Thermodynamic constant from the adsorption of ammonium onto CPAC
Temperature Equilibrium Ln Kc G H S
(K) Constant (kJ/mol) (kJ/mol) (J/mol K)
(Kc)
298.15 1.410 0.343 -0.851
308.15 1.513 0.414 -1.060
318.15 1.688 0.524 -1.385 -9.627 34.812
328.15 1.793 0.584 -1.593
338.15 2.311 0.838 -2.355

3.6 Desorption and regeneration study

Desorption of ammonium ion and regeneration of the CPAC are important in determining
the reusability of the adsorbent for the evaluation of the efficiency and feasibility of ammonium
ion removal. The capability of the adsorbent to be regenerated and reused in the adsorption
process is one of the criteria in order to choose a low-cost adsorbent and environmentally
friendly adsorbent. Hydrochloric acid and sodium hydroxide were chosen in the first place due
to their high removal percentage and low cost as reported in the literature (Iqbal et al., 2009;
Kulkarni and Kaware, 2014). Figures 12 and 13 shows the results for percentage removal while
by using 0.1 M HCL and 0.1M NaOH, respectively. From the Figure 12, the performance of the
new CPAC is found to be good and a percentage removal of 44% was achieved. However, after
the first cycle of desorption and regeneration, the performance dramatically declined to 10%
percentage removal and worsen in the next cycle. However, as seen in Figure 13, the
performance of the adsorbent when alkaline was used as the desorbing agents showed a slight
differencet in percentage removal of ammonium ion between the first cycle (44%), second cycle
(40%) and third cycle (36%). Therefore, it can be concluded that the high removal of
ammonium ion is acceptable even when with the CPAC having have been regenerated up to
three times. In comparison, both desorbing agent showed a decline in percentage removal with
an increase in the concentration of acid and alkaline (desorbing agents). Increasing the
concentration of desorbing agents might reduce the performance due to the destructive effect of
the high concentration of desorbing agents, negatively affecting the performance of adsorbents.
This result is significant and this will help point towards the right concentration of the desorbing
agent for the desorption process (Kulkarni and Kaware, 2014). Hence, sodium hydroxide (0.1M)
proves as better medium for desorption process.

Figure 12 Desorption using 0.1M HCl Figure 13. Desorption using 0.1M NaOH

4 Conclusion

The current study emphasizes on the ability of papaya peel activated carbon (CPAC) to
adsorb ammoniacal nitrogen from aqueous solution. The determined surface area and pore size
of the adsorbent before and after activation by BET analysis demonstrated significant increase
from 9.63 to 26.559 m2/g with the pore having micropore of 0.7546 nm. This pore size was
suitable and sufficient to adsorb ammonium ion because the ammonium size was the same as the
micropore structure. In batch mode studies, the adsorption was evaluated consoidering the
effects of solution pH, adsorbent dosage, contact time, initial concentration of NH4+ in solution
and temperture. According to the results, the removal of ammoniacal nitrogen were best
achieved at a pH = 7, 30 minutes of contact time, 0.05 g of adsorbent dosage, and 100 mg/L
initial concentration of ion in the solution at 25 .These conditions enabled the adsorbent to
remove 4.27 mg/g of ammonium with a maximum percentage removal of 42.667%.
The adsorption isotherm data were correlated with lagmuirLagmuir, Ffreundlich and
Ttemkin models. Comparing the three models in the equilibrium isotherm study, the data of
experiment was found to fit well with the Freundlich model, which describes the multi-layer
adsorption behavior of ion onto the adsorbent. The kinetic study suggests that the order of the
adsorption process followsed by pseudo second order and it shows that the adsorption of
ammonium onto CPAC was controlled by more than one-step. Thermodynamic study was
performed in confirming the spontaneity of the reaction. The results reveal that this process
occur spontaeously since (G) shows a negative value. P and positive entrophy change (S=
34.812 J/mol K) indicates an increase in randomness at the solid-solution interface. The negative
enthalpy (H= -9.627 kJ/mol), indicates that the process is exothermic where increasing the
temperture decreases the adsorption capacity of ammonium ion.
Desorption process was done by using two desorbing agents of HCl and NaOH. The
results confirmed that NaOH works better as desorbing agents compared to HClL. This is due to
the regeneration capacity of CPAC after being desorbed with NaOH (0.1M), which was
obeserved to have 40% to 36% and 32% removal of ammonium for the first, second and third Commented [U10]: Should this be a comma?

cycle, respectively. Therefore, in conclusion, a high removal of ammonium ion was achieved
even though the CPAC was regeneratedcycle up to three cycle times without significant loss in
removal efficiency.
Therefore, it can be proved that papaya peel can be used as an environmental friendly and
inexpensive locally available agro-waste to develop an alternative adsorbent in removal of
ammonium ion from aqueous solution. However, it is recommended for the future works to
undergo another surface modification which will enhanced the adsorption capacity of CPAC for
the removal of ammonium ion.

Acknowledgement Commented [U11]: Add acknowledgement to the GUP

grant for ammoniacal nitrogen
Formatted: Indent: First line: 0"
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