Materials Today: Proceedings xxx (xxxx) xxx

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Adsorptive removal of phosphate from aqueous solution using waste

chicken bone and waste cockle shell
Nor Zalina Kasim ⇑, Nur Afiqah Amni Abd Malek, Nur Syuhada Hairul Anuwar, Nur Hazimah Hamid
Environmental Engineering Technology Section, Malaysian Institute of Chemical and Bio-Engineering Technology, University Kuala Lumpur, Bandar Vendor Taboh Naning, 78000
Alor Gajah, Melaka, Malaysia

a r t i c l e i n f o a b s t r a c t

Article history: The removal of phosphates from surface water is crucial to avoid water pollution problems such as
Received 16 October 2019 eutrophication and algae blooms. There are many established methods that normally used to remove
Received in revised form 25 September phosphates such as by chemical precipitation, biological processes and physicochemical by sedimenta-
2020
tion. On the other hand, calcium carbonate (CaCO3) is recognised as an efficient phosphorus (P) binder
Accepted 27 September 2020
Available online xxxx
in lake sediment which contribute to the permanent burial of P in the sediments. Therefore, this paper
studies the potential of raw cockle shells (RCS), calcined cockle shells (CCS), raw chicken bone (RCB)
and calcined chicken bone (CCB) in phosphates removal from aqueous solutions. The collected chicken
Keywords:
Phosphate removal
bone waste and cockle shells waste were washed, boiled, sundried and oven dried for raw sample and
Natural adsorbent calcinated at high temperature for calcined sample before been grinded into granular size between 1
Waste cockle shell and 2 mm. The dosage of 0.1 g, 0.2 g, 0.3 g, 0.4 g, 0.5 g, 0.6 g, 0.7 g, 0.8 g, 0.9 g and 1.0 g of the adsorbent
Waste chicken bone were applied into the artificially prepared phosphate solution. The result indicated that the maximum
removal of phosphate was achieved at 0.1 g (90.02% phosphate removal) for CCS, 0.2 g (58.78% phosphate
removal) for RCB, 0.1 g (30.40% removal efficiency) for CCB and 0.1 g (26.69% removal efficiency) for RCS.
As a general conclusion, phosphate species seem to be efficiently removed from solutions using cockle
shell compared to chicken bone as natural adsorbent. In addition, the waste from the adsorption process
can be recycle and used as fertilizer for acidic soils.
Ó 2020 Elsevier Ltd. All rights reserved.
Selection and Peer-review under responsibility of the scientific committee of the 4th International Con-
ference on Green Chemical Engineering and Technology: Materials Science.

1. Introduction bon [7], alum and aluminium oxide [8,9], iron and iron oxide
[10,11], laterite [12], slag [13] and red mud [14,15].
Phosphorus as phosphate is a very important compound that is Calcium carbonate (CaCO3) has a long history and well known
used in many industrial applications mainly in fertilizer, detergent, in healthcare industries as it is used as phosphate binder to control
pharmaceuticals and personal care products [1]. The extensive use blood phosphate level for patients with hypertension [16,17] and
of phosphates increase waste containing phosphates in the chronic renal failure [18]. Other application of CaCO3 was in the
wastewater effluent, which with the improper treatment will Baltic Lake where the content of CaCO3 successfully inhibit the
resulted to water pollution problems such as eutrophication and phosphate release from the sediment and reduce the eutrophica-
algae blooms. Removal of phosphates from the wastewater is cru- tion altogether [19]. Waste cockle shell and waste chicken bone
cial to avoid these problems. However, due to the operational dis- contains CaCO3 [20,21]. Therefore, the objective of this work was
advantages and economic drawbacks, phosphorus removal was not to study the potential of waste cockle shell and waste chicken bone
widely adopted. Phosphate treatment and removal can be done in as an adsorbent for phosphate removal from aqueous solution.
many ways such as physical [2,3], chemical [4,5] and biological [6]
methods. Besides that, adsorption method was also one of the 2. Materials and method
methods that has a successful story in phosphate removal. The fol-
lowing are among the adsorbent evaluated such as activated car- 2.1. Adsorbent

⇑ Corresponding author. Waste cockle shell and waste chicken bone collected from
E-mail address: [email protected] (N.Z. Kasim). nearby restaurant were thoroughly washed, boiled, sundried and

https://doi.org/10.1016/j.matpr.2020.09.687
2214-7853/Ó 2020 Elsevier Ltd. All rights reserved.
Selection and Peer-review under responsibility of the scientific committee of the 4th International Conference on Green Chemical Engineering and Technology: Materials

Please cite this article as: Nor Zalina Kasim, Nur Afiqah Amni Abd Malek, Nur Syuhada Hairul Anuwar et al., Adsorptive removal of phosphate from aqueous
solution using waste chicken bone and waste cockle shell, Materials Today: Proceedings, https://doi.org/10.1016/j.matpr.2020.09.687
Nor Zalina Kasim, Nur Afiqah Amni Abd Malek, Nur Syuhada Hairul Anuwar et al. Materials Today: Proceedings xxx (xxxx) xxx

oven dried at 70 °C for 24 h to become raw sample. Calcined sam- 3. Results and discussions
ple was prepared after the raw sample undergo the thermogravi-
metric analysis (TGA) to determine the suitable temperature for 3.1. Calcination temperature of waste cockle shell (WCS) and waste
the calcination process and calcined using the furnace. After heat- chicken bone (WCB)
ing, the sample were cooled to room temperature and stored in air-
tight container. The WCS and WCB were decomposed at temperatures ranging
from 30 °C to 900 °C for 2 h by using thermogravimetric analysis
(TGA). It can be seen on Fig. 1 that the rapid changing of WCS
2.2. Adsorbate weight occurred at the temperature between 700 °C and 900 °C
where the decomposition begins to take place. It was assumed that
Artificial phosphate solutions were used throughout the after 900 °C most of the sample was changed to CaO. On the other
adsorption tests. 100 ppm of stock solutions were prepared by dis- hand, WCB weight loss observed in the temperature range between
solving certain amount of anhydrous potassium phosphate (KH2- 30 °C and 150 °C due to the removal of incorporated water (Fig. 2).
PO4) in distilled water. Certain volume from the stock solution Continuous weight loss from 250 °C to 500 °C was occurred might
was diluted to prepare the phosphate solution at the desired be due to the removal of the organic portion such as collagen and
experimental concentration. protein [22]. No significant weight loss has been observed after
600 °C confirming the complete removal of the organic substances.

2.3. Characterization
3.2. Fourier transform infrared (FTIR) spectroscopy analysis
Raw cockle shell (RCS), calcined cockle shell (CCS), raw chicken
bone (RCB) and calcined chicken bone (CCB). Fourier transform FTIR analyses was done to confirm the presence of the CaCO3 in
infrared spectra of the samples was recorded by FTIR spectroscopy raw sample and CaO in calcined sample. Based on the result
(NICOLET iS10 Thermo Scientific) using potassium bromide (KBr) obtained in Fig. 3 and Fig. 4, the results are consistent with other
as reference. UV–Vis Spectrophotometer (Perkin Elmer UV–Vis studies as listed as Table 1. FTIR analyses revealed the presence
Lambda EZ201) was used for obtaining concentrations of the phos- of carbonate groups in both cockle shell and chicken bone samples.
phate solutions before and after adsorption to determine the The FTIR spectra of the raw samples shows the characteristic bands
amount of phosphate removal. Standard method in phosphate of commercial calcium carbonate structure at 1554 cm1,
determination by APHA was referred. 1743 cm1, 2858 cm1 and 2928 cm1 for chicken bone and at
706 cm1, 860 cm1, 1084 cm1, 1790 cm1, 2523 cm1 for cockle
shell. By comparing the FTIR spectra of Figs. 3(b) and 4(b), new
2.4. Adsorption studies peaks at 1797 cm1 and 3641 cm1 were found to be the character-
istic frequency of CaO bond vibration in calcined cockle shell sam-
2.4.1. Effect of variation in dosage ple. Moreover, a new strong absorbance band at 1216 cm1
Adsorption experiments were carried out by adding a fixed showed in Fig. 4(a) confirms the CaO formation in calcined chicken
amount of adsorbent from 0.1 g to 1.0 g of raw chicken bone, raw bone sample. In general consideration, the existence of calcium
cockle shell, calcined chicken bone and calcined cockle shell to a oxide founds in both samples shows that both calcined samples
series of Erlenmeyer flask filled with 50 mL of 10 ppm phosphate have great affinity toward phosphate and suitable to be used as
solutions with pH 3, pH 5 and pH 8. The Erlenmeyer flasks were the adsorbent.
placed on a hotplate at constant temperature. The removal effi-
ciency (E) of phosphate on different adsorbents, the sorption
capacity, (q) and distribution ratio (Kd) were calculated from Eqs. 3.3. Effect of variation in dosage
(1)–(3):
Different adsorbent dosages starting from 0.1 g to 1.0 g were
Ci  Cf added into the 50 mL of aqueous solution containing phosphorus
Eð%Þ ¼  100 ð1Þ
Ci concentration of 10 mg/L to study the effect of adsorbent dose to
the percentage of phosphorus removal. Fig. 5 shows the effect of
VðCi  Cf Þ dosage on RCB and CCB adsorption with error bars showing the
q¼ ð2Þ value of standard deviation (SD). The experimental data obtained
m
is more reliable because almost all data shows small SD bar which
  means that the data is low spread and are clumped around the
amountofphosphateinadsorbent V L mean. Furthermore, the trend of the percentage removal shows
Kd ¼  ð3Þ
amount of phosphate in solution m g in Fig. 5 is fluctuate and decreasing when different dosing is
applied for both raw and calcined samples. It was assumed that
where Ci and Cf are the initial and final concentrations of phosphate the maximum removal efficiency was achieve at an adsorbent
(mg/L) in aqueous solution, respectively, V is the volume of the dosage of 0.2 g for RCB with percentage removal 59.59% and
solution (L) and m represents the weight of the adsorbent (g). 0.1 g for CCB with percentage removal 50.82%. The highest value
of percentage removal shows that more phosphorus is attached
on the adsorbent surface at that particular dosage.
2.4.2. Effect of variation in pH Fig. 6 show the percentage phosphorus removal by different
The effect of pH on the removal of phosphate species, through dosage of the RCS and CCS. The graph plotted clearly shows that
adsorption onto calcite, was examined in the pH 3, pH 5 and pH 8. the percentage removal fluctuates for each of raw and calcined
The tests were carried out at constant experimental conditions sample. The findings contradicted with the study by Kini & Sridevi
with an initial solution concentration 10 ppm in phosphate and [28] where the percentage removal of the phosphorus increases as
0.1 g adsorbent for all sample except 0.2 g for RCB. All the tests the raw and calcined sample increases. Besides, error bars for phos-
were carried out at constant retention time, fixed at 20 min. phorus removal of raw cockle shells are slightly larger than cal-
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Nor Zalina Kasim, Nur Afiqah Amni Abd Malek, Nur Syuhada Hairul Anuwar et al. Materials Today: Proceedings xxx (xxxx) xxx

Fig. 1. Decomposition of waste cockle shell.

Fig. 2. Decomposition of waste chicken bone.

Fig. 3. Calcium carbonate (CaCO3) in (a) RCB; (b) RCS.

cined cockle shells because each reading for the triplicate test of 3.4. Effect of variation in pH
raw cockle shells is slightly far from the mean of the data [29].
Adsorption capacity is also been studied in the research. From According to Xiuyun [30], pH of the solution involved is one of
Fig. 7, it is shown that 0.1 g of RCS, CCS, RCB and CCB had a higher the important parameter in the adsorption process. Therefore, the
adsorption capacity. Thus, this investigation can be assumed that effect of pH has been studied by varying the adsorption experiment
at a lower concentration, the adsorbent has a stable number of in pH 3, pH 5 and pH 8. The effect of pH on removal of phosphate is
the active adsorption site which means the adsorption site can shown in Fig. 8. The optimum pH value for phosphate adsorption
adsorb more metal ions. On the other hand, the active sites can was found to be pH 8. The percentage removal was observed up
become saturated as the concentration became increased which to 99.65%, 69.07%, 64.36% and 44.94% for CCS, RCS, RCB and CCB
resulting to lower adsorption capacity. It can be concluded that respectively. This is maybe because of the adsorbent is alkaline
surface saturation is one of the sorption characteristics that can by nature. Therefore, the equilibrium pH tends to be alkaline
influence the initial metal ions concentration in the solution. [31]. Furthermore, Liu et al. [32] identifies that phosphate species

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Nor Zalina Kasim, Nur Afiqah Amni Abd Malek, Nur Syuhada Hairul Anuwar et al. Materials Today: Proceedings xxx (xxxx) xxx

Fig. 4. Calcium oxide (CaO) in (a) CCB; (b) CCS.

Table 1
Infrared absorption bands for calcium carbonate (CaCO3) and Calcium Oxide (CaO).

Phase FTIR absorption band References

1 1
Calcium Carbonate (CaCO3) 1390 cm , 866 cm [23]
1083 cm1, 861.93 cm1 [24]
712.64 cm1, 700.10 cm1
2646 cm1, 2423 cm1 [25]
1833 cm1, 1782 cm1
Calcium Oxide (CaO) 3643 cm1, 1417 cm1 [26]
3640 cm1 [23]
3656 cm1, 3822 cm1 [27]
3388 cm1, 1444 cm1

Fig. 6. Effect of variation in dosage on phosphate removal for RCS and CCS.

Fig. 5. Effect of variation in dosage on phosphate removal for RCB and CCB.

can exist as H3PO4, H2PO 2 3

4 , HPO4 and PO4 depending on the solu-
tion pH. The authors further expressed that at pH 3, the predomi- Fig. 7. Phosphate adsorption capacity.
nant species of phosphate is H3PO4 which is weakly attached to
adsorption sites. In addition, for solution pH within range 4–10
the dominant species are H2PO 2
4 and HPO4 which can promptly 4. Conclusion
adsorbed. Supported by other studies by Yao et al. [33] indicated
that electrostatic attraction play the main interaction between As a general conclusion, phosphate species seem to be effi-
the positively charged surface in the adsorbents and the negatively ciently removed from solutions using calcite as natural adsorbent.
charged phosphate species at low pH while the precipitation and Waste cockle shells have high potential as a phosphate binder
surface deposition of phosphate would present onto the adsor- compared to waste chicken bone. Based on the result, waste cockle
bents at high pH. Therefore, the results showed that the precipita- shells had achieved up to 90.02% removal efficiency of phosphorus.
tion and surface deposition at high pH made significant affect to Therefore, this research can be used for further study to develop a
the effectiveness of adsorption of phosphate on the adsorbents. new green technology in order to treat water that contaminated

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Nor Zalina Kasim, Nur Afiqah Amni Abd Malek, Nur Syuhada Hairul Anuwar et al. Materials Today: Proceedings xxx (xxxx) xxx

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