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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).
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.
concentrations was obtained by diluting the stock solution with distilled water (Liu et al., 2010).
= ( ) (1)
0
Percentage Removal (%) = 100% (2)
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.
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
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.
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.
Figure 7 Effect of initial concentration of ions on the removal of ammonium ion using CPAC
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
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.
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
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.