BULLETIN OF THE POLISH ACADEMY OF SCIENCES

TECHNICAL SCIENCES, Vol. 65, No. 2, 2017

DOI: 10.1515/bpasts-2017-0016

Cobalt adsorption on the nano-hydroxyapatite matrix:

isotherm and kinetic studies
V.N. NARWADE1,2 and R.S. KHAIRNAR1*
1
School of Physical Sciences, Swami Ramanand Teerth Marathwada University, Nanded, 431-606 Maharashtra, India.
2
University of Maribor, Institute for Engineering Materials and Design, 17 Smetanova St., SI-2000 Maribor, Slovenia

Abstract. Cobalt radionuclide is one of the prime contaminants generated during operation of pressurized heavy water. The paper reports the
study of cobalt adsorption on hydroxyapatite (HAp) nanoceramic. A modified wet chemical precipitation method is used for HAp synthesis. The
HAp nano-material is characterized by XRD, FTIR, TG/DTA, AFM, SEM, and EDAX. Experiments are performed in batches to observe the
effect of cobalt adsorption on HAp matrix. The adsorption of cobalt on HAp is examined at room temperature. The isotherm and kinetic studies
showed that the Freundlich isotherm and pseudo-second order model are the best choices to describe the nature of adsorption.

Key words: hydroxyapatite, cobalt, adsorption, XRD, SEM.

1. Introduction reverse osmosis, etc. [8‒10]. It was reported that apatite-group

minerals with special crystal characteristics are the most prom-
Revelation of heavy metals to man, which are discharged into ising materials in the treatment of wastewater containing fluo-
bodies of water via industrial operations, human practices, ride and heavy metals [11]. Moreover, as a member of apatite
etc. even at trace levels, is believed to be a great risk with its mineral family, hydroxyapatite (Ca10(PO4)6(OH)2, HAp) is
long-term effects [1]. Heavy metals are not biodegradable and an ideal material for the discarding radioactive contaminants
tend to accumulate in living organisms, causing various dis- having long life because of its elevated sorption capacity for
eases and disorders [2]. When their hostile effects and toxicity heavy metals, low water solubility, availability, low cost, and
are considered, it is critical to remove heavy metal ions from high stability under oxidizing and reducing conditions. The
water resources. There has been a rising interest and hard work sorption mechanisms of heavy metals are diverse and mainly
put to improve the efficiency of conventional techniques of include processes such as ion exchange, dissolution/precipita-
treating metal-contaminated effluents. Among the conventional tion, and formation of surface complexes [12, 13].
physico-chemical methods, adsorption has been extensively
employed because of its ease of use and effectiveness [3, 4].
Cobalt, a natural element present in certain ores of the Earth’s 2. Experimental
crust, which exists in the form of various salts, is essential to
life in trace amounts due to being an essential component of Materials and methods. Calcium nitrate tetrahy-
Vitamin B12. It has also recently been identified as an inte- drate (Ca(NO3)2.4H2O), di-ammonium hydrogen
gral part promoting blood cell production. Pure cobalt is an phosphate ((NH4)2HPO4) and cobalt nitrate
odourless, steely-gray, shiny, stiff metal [5]. Cobalt has both (Co(NO3)2.6H2O) standard samples were purchased from
advantageous and detrimental effects on health. Cobalt may Merck specialties Pvt. Ltd. Am- monia (25%) was used
occur with oxidation levels from –1 to +4, but in nature it oc- for adjusting the pH of the mixture. The cobalt solution
curs usually as a di-valent cation Co2+ (cobalt compounds). In was prepared from the nitrate salt (AR) grade.
erosive environment it easily undergoes oxidation from Co2+ to
Co3+ and creates the complex anion [6]. According to interna- Synthesis of HAp. The synthesis of HAp is performed
tional standards, the allowed restrictions for amounts of cobalt according to the literature previously reported in
in irrigation water and livestock watering is 0.05 mg dm –3 [5]. Mahabole et al. using the wet chemical method [14].
Cobalt may cause mutations in living cells where, as its ionizing Pure grade calcium nitrate, di-ammonium hydrogen
radiation, it is associated with an increased risk of developing phosphate, and ammonium hy- droxide were used as the
cancer [7]. Therefore, their optimal removal from wastewater starting chemicals. The stoichiometry of the calcium
is a foremost important global issue for preserving ecology. nitrate and di-ammonium phosphate solutionsis adjusted
Generally, the techniques employed for heavy metal removal so as to get the theoretical (Ca/P) molar ratio close to
include ion exchange, adsorption, filtration, electrodeposition, 1.67 [15]. The precipitation is performed by slow
addition of di-ammonium phosphate solution (0.6 M) to
calcium nitrate solution (1 M) under continuous and
*e-mail: [email protected] gentle stirring at 80°C. The pH of the reaction mixture is
adjusted by the addition of NH4OH. As a result of
reaction, milky precipitate is obtained. In the wet chemical
Bull. Pol. Ac.: Tech. 65(2) 2017 131
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 process, the precipitate is continuously stirred

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 V.N. Narwade and R.S. Khairnar

for 5 hours using a magnetic stirrer. The resulting white pre-

cipitate is washed thoroughly three times with double-distilled 3000
water, dried in an oven at about 100°C for 2 hours and further
kept in a high-temperature furnace at 1000°C.

Intensity (A.U.)
Characterization. The synthesized hydroxyapatite pow- 2000
ders are characterized by X-ray diffraction (XRD),
atomic force microscopy (AFM), Fourier transform
infrared spectros- copy (FTIR), thermal 1000
gravimetric/differential thermal analysis (TG/ DTA),
scanning electron microscopy (SEM) and energy
dispersive x-ray diffraction (EDAX). X-ray diffraction
0
pat- terns are obtained with an X-ray diffractometer with
CuKα (λ = 1.543 Å) incident radiation. The XRD peaks 0 30 40 50
are recorded in the 2θ range of 20°– 60°. AFM is used to 2 Theta (degree)
observe the topog- raphy of samples at nanoscale
resolution with variable magnifi- cation in the range of 1
μm– 400 nm. FTIR spectrophotometer is
used for identification of functional groups present in the HAp Fig. 1. XRD pattern of the synthesized HAp nanopowder displaying
ceramic. The samples are scanned from 3700 cm–1 to 400 cm–1 sharp diffraction peaks
with the average of 45 scans. Thermal methods are based on
the measurement of dynamic relationship between temperature
and some properties of the system such as mass, heat of reaction 3. Results and discussion
or volume. Hence, the thermal properties of HAp are verified
with the help of TG/DTA analyzer system. Scanning electron XRD study. Figure 1 shows that the characteristic peaks of
microscopy was used to visualize surface topography, while HAp are at 2θ angle of 32.41, 33.58, 26.79, 50.25, 47.32, 34.71,
energy-dispersive X-ray analysis used for elemental analysis. 40.57 etc. From this, it can be observed that most of the peaks
The Co-HAp samples, which are obtained after sorption exper- fit well with hexagonal hydroxyapatite phase, which represents
iments, are characterized by FTIR, AFM, SEM, and EDAX. the lattice parameters: a = b = 9.42 Å, c = 6.88 Å [18]. The
phase analysis of crystalline HAp shown was carried out with
Batch adsorption experiments. The adsorption experi- the help of JCPDS data card no. 09‒0432. The grain size D of
ments of Co2+ are performed according to the batch HAp is calculated, which turns out to be 24 nm, as calculated
method. Various conical flasks containing varied amount by Scherrer formula, which is expressed as [14]:
of HAp adsor- bent and 20 ml of cobalt solution with the
initial pH of 5.8 ±0.1
are placed in a constant air bath oscillator to vibrate at room kλ
D= , (3)
temperature. After a certain, fixed period of time, the HAp is βcosθ
separated from the solutions using a filter paper. The initial and
final metal concentrations are determined by a UV-Vis spec- where: λ is the X-ray wavelength in nanometers (nm), β is the
trometer at a wavelength of 511 nm. The removal percentage peak width of the diffraction peak profile at half its maximum
of cobalt by hydroxyapatite is calculated by the following for- height in radians, and k is a constant related to crystallite shape,
mula [16]: normally taken as 0.9.
Ci − C e AFM study. AFM experiments are conducted in non-
% removal = ∗∙ 100, (1)
Ci con- tact mode using a glass probe. An AFM image
shows detailed topography of the nano-sized porous
where: Ci and Ce are the initial and final cobalt concentrations surface. Fig. 2 shows HAp
in mg l–1, and cobalt adsorption capacity of hydroxyapatite at
equilibrium is observed by [17]: (b)
(a)
V
qt = (Ci − Ce), (2)
W
where: qt is the adsorption capacity of an adsorbent in mg g–1
at time t, V is the volume of adsorbate in litres, and W is the
mass of adsorbent in grams. After the removal of Co is com-
plete, the HAp samples are separated by filtering and dried.
FTIR, AFM, SEM and EDAX analyses are carried out on the
dried samples to examine the changes in the HAp matrix after
the adsorption process. Fig. 2. AFM of the synthesized HAp nanopowder at magnification
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 (a) 1 μm and (b) 400 nm

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 Cobalt adsorption on the nano-hydroxyapatite matrix: isotherm and kinetic studies

phosphate species. The absorption band appearing 3572 cm–1

(a) (b) corresponds to the stretching vibration mode of the hydroxyl
group. The absorption bands at 1032 cm–1 and 1092 cm–1 are
¡
caused by ν3 stretching of the phosphate group (PO43 ). Along
with these peaks, the fractional replacement of Ca2+ by Co2+
results in the formation of a new phosphate peak at 903 cm–1.
The intensity of the newly developed peak decreases with the
increase in cobalt concentration [13].

TG/DTA study. TG/DTA graph of HAp is displayed in

Fig. 5. The slightly sloped TGA curve indicates thermal
sta- bility of the material. During heating up to 1000°C,
Fig. 3. AFM of HAp after Co sorption at magnification (a) 1μm and the HAp material undergoes a weight loss of 16%,
(b) 400 nm obviously attributed to desorption of water and CO2
molecules. Corresponding to the changes in TGA, there
are changes in DTA. The exothermic

surface composed of smooth-faceted grains with uniform di-

6.5 5
mensions. It can be seen that the size of pores varies in the range
DTA
of 100 nm–200 nm for the HAp matrix. Fig. 3 shows the AFM 0
of HAp after Co sorption. Fig. 3(b) is a magnified portion of 6.4
Fig. 3(a), which clearly denotes the dotted spot, which is a clear –5
indication of Co sorption on HAp surface.
Weight (%)

6.3 –10

DTA (μV)
TGA
3.3 FTIR study. FTIR spectra given in Fig. 4 reveal the chem- –15
ical composition of the HAp and HAp powder after Co sorp- 6.2
tion. The spectra indicate a presence of a phosphate group and –20

a hydroxyl group in HAp. The IR spectra of HAp indicate the –25

6.1
absorption bands at 3572 cm–1 and 3433 cm–1, corresponding
to the stretching mode of the hydroxyl group. The hydroxyl –30
libration mode is found to be present at 632 cm–1. The band 6.0
at 1622 cm–1 reveals ν3 vibrations of the hydroxyl group. The 0 200 400 600 800 1000
band at 963 cm–1 and 974 cm–1 are caused by the ν1 mode Temperature (°C)
of (PO43¡) [14]. The FTIR spectra of HAp after cobalt sorp-
tion show the presence of individuality bands of hydroxyl and Fig. 5. TG/DTA curve of the synthesized HAp nanopowder

and endothermic peaks are present due to the removal of the

hydroxyl group and breakdown of the residual CaCO3 group.
Above 1000°C HAp decomposes into tetra calcium phosphate
and α-TCP according to the following reaction [19]:

Ca10(PO4)6(OH)2 → Ca(PO4)2 + 2αCa(PO4)2O + H2O

% Transmittance

Thus, it is confirmed that HAp is thermally stable up to 1000°C.

SEM and EDAX analysis. The SEM image of synthe-

sized HAp nanopowder indicates a porous nature
throughout the HAp matrix. The porous nature directly
relates to higher availability of adsorption sites. The
average pore size is about
0.5 micron and the particles are seen to agglomerate exhib-
iting high porosity, which is an ideal property for the material
to be used as an efficient adsorbent. The elemental analysis
Wavenumber (cm–1) of HAp was done using EDAX. It indicates the elemental
composition of materials. HAp constitutes mainly of calcium
Fig. 4. FTIR spectra of the (a) synthesized HAp nanopowder and and phosphate groups which are indicated in EDAX spectra.
(b) HAp after Co sorption The weight percentages of Ca, P, O, and C are found to be
21.57%, 12.58%, 54.98%, and 10.87%, respectively. The

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 V.N. Narwade and R.S. Khairnar

SEM image of HAp after cobalt sorption is shown in FIG. 150 mg

After cobalt sorption, the porous nature of HAp is collapsed, 100 200 mg
showing adsorption of cobalt on the HAp matrix, while EDAX 300 mg
spectra show the characteristic peak of cobalt. The weight
percentages of Ca, Co, P, O, and C are 16.95%, 6.06%, 9.44%,
80
60.77%, and 6.78%, respectively. The elemental analysis also
reveals that Ca2+ undergoes ion exchange with Co2+ during

% Removal
the shaking process.
60

(a) (b) Spectrum1

40

20
10 20 30 40 50 60 70 80

0 2 4 6 8 10 Time (min)
Full Scale 6701 ds Cursor: 0.000 keV

Fig. 6. (a) SEM image and (b) EDAX spectra of synthesized HAp Fig. 8. Effect of the contact time on cobalt adsorption by HAp nano-
nanopowder powder at given conditions: Ci = 870 mg l–1 with different adsorbent
HAp concentrations

(a) (b) Spectrum1

metal solution are placed in an air bath shaker. After separation,

the residual metal concentrations in the solutions are measured.
At lower HAp doses, the percentage of sorption is low. As the
HAp doses are increased, the HAp tends towards equilibrium.
It is seen that HAp doses achieve their maximum removal effi-
ciency after 200 mg l–1. The maximum removal efficiency was
0 2 4
Full Scale 6701 ds Cursor: 0.000
6 8 10
keV
found to be as high as 87%.

Fig. 7. (a) SEM image and (b) EDAX spectra of HAp after Co sorption

from the
Effect of initial metal concentration. Sorption
isotherms were obtained by equilibrating HAp with metal
solutions of different initial concentrations – 0.02‒0.07
mol, i.e. from 270 mg l–1 to 1890 mg l–1 – for 120 min.
The obtained data was used to predict the nature of
adsorption isotherms.

Effect of contact time. The effect of contact time on

each metal sorption was studied in different time
intervals, ranging from 10 min to 70 min with the initial
fixed cobalt metal con- centration (Ci) of 0.03 mol i.e.
870 mg l–1. After the completion of the reaction, the
conical flasks were taken out and the HAp adsorbents
were separated, followed by the determination of the
residual metal concentrations. Fig. 8 shows the
percentage removed by different adsorbent
concentrations viz. 150 mg l–1, 200 mg l–1, 300 mg l–1.
Here it is observed that as the con- centration of HAp
sorbent is increasing, the cobalt sorption efficiency also
increases. For the HAp dose of 300 mg l–1, the removal
efficiency is nearly 87%, while for 150 mg l–1 and 200
mg l–1 HAp, it is 84% and 85% respectively, for a
contact duration of 30 min.

Effect of HAp dosage. The suspensions containing dif-

ferent amounts of HAp – 50 mg l–1 to 300 mg l–1 –
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 80
Fig. 9. Effect of the HAp doses on cobalt adsorption at given condi-
tions: Ci = 870 mg l–1

% Removal
60

Effect of pH. The pH of solution is an influential factor

which affects the adsorption phenomena. The percent
40
removal increases as the pH increases, and maximum
adsorption occurs at a pH around 6. Here, at higher pH,
20
heavy Co ions tend to form precipitation. Therefore, the
50 100 150 200 250 250 pH study observed valuesup to pH 7.
HAp dosage (mg)

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 Cobalt adsorption on the nano-hydroxyapatite matrix: isotherm and kinetic studies

83 where: qe (mg g–1) is the amount adsorbed on HAp at equilib-

rium, and qmax (mg gm–1) is the maximum adsorption mono-
82
layer capacity. kL is the Langmuir constant related to the affinity
81 between the adsorbate and the adsorbent, and is related to the
free energy of adsorption. Ce (mg L–1) is the concentration of
% Removal

80 cobalt in liquid phase at equilibrium.

79

78

77 1.8

76
3 4 5 6 7
pH 1.6

log qe
Fig. 10. Effect of pH on cobalt adsorption at given conditions: Ci
= 870 mg l–1
1.4

At lower pH, various types of reactions take place as shown

below. During these reactions, depending on the solution condi- 2.7 2.8 2.9 3.0 3.1 3.2 3.3 3.4
tions, some different sites can be formed on the mineral surface.
log Ce
¡
= OH + => H+ OH+ 2
3¡ ¡ Fig. 11. The Freundlich isotherm plot for cobalt adsorption onto
= PO => HPO HAp nanopowder
4 4

= HPO4 + H+ => H2PO¡4

¡

= Ca2+ + OH¡ => CaOH

= PO 34¡ + Ca2+ => PO4Ca 32

= HPO4 + Ca2+ => HPO4Ca2+

¡
28
qe /ce

These reactions explain the generation of anionic and cationic

charges on the surface. At lower pH the surface tends toward 24
the positively charged surface sites.
20
Adsorption isotherms. The Langmuir and Freundlich
equations are commonly used for describing adsorption
16
equi- librium of adsorbate onto the adsorbent. The 500 1000 1500 2000
Langmuir isotherm is applicable to monolayer
chemisorptions, while the Freundlich isotherm is used to ce(mgL)
describe adsorption on surfaces having het- erogeneous
energy distribution: Fig. 12. The Langmuir isotherm plot for cobalt adsorption onto
The linear equation for Freundlich is given by [20]: HAp nanopowder

1
log qe = log Ce + log kf , (4)
n Table 1
Various parameters of Freundlich and Langmuir isotherms
where: Kf (L mg–1) and 1/n are the Freundlich empirical con-
stants related to the total adsorption capacity of the solid, and Isotherm Freundlich Langmuir
the Freundlich exponent, respectively. kf = 0.3019 qmax = 140
And for Langmuir it is given by [21]:
Parameters 1/ = 0.6982 kL = 0.000366
Ce 1 Ce n
q = k q +q , (5)
R2 = 0.78
R2 = 0.97
e L max max

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Bull. Pol. Ac.: Tech. 65(2) 2017 135

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 V.N. Narwade and R.S. Khairnar

Kinetic modeling. Knowledge of the kinetic constituents

0.40
of adsorption is the first step in the investigation of the
possi- bility of using an adsorbent for a particular 0.35

t/qt (min*gm/mg)
separation task. In this study, the first-order kinetic model
0.30
and pseudo-second order kinetic model was used to
elucidate the adsorption mechanism. The first-order 0.25
kinetic model is given as [22]: 0.20
1 k1 1 1
= + , (6) 0.15
qt q1 t q1
0.10

where: q1 and qt are the amounts of cobalt particles adsorbed on 0.05

10 20 30 40 50
the adsorbent at equilibrium (in mg g–1) and at various time t,
respectively, and k1 is the rate constant (min–1) of the first-order Time (min)
model for the adsorption process. Values of k1 are calculated
from the slope of the plots of 1/qt against 1/t. Fig. 14. The second order kinetic model of cobalt adsorption onto HAp
The pseudo-second-order kinetic model is expressed as [21]: at room temperature

t 1 t
= + , (7) The correlation coefficient values (R2) range between zero
qt k2q2 2
q2 and one. The R2 value nearing to unity shows the best fitted
model [22]. Here, the value of R2 (0.99) for the second-order
where: q2 is the maximum adsorption capacity (mg g–1) for the kinetic model is much higher than first-order (0.87) kinetic
pseudo-second order adsorption, qt is the amount of cobalt ad- model, indicating that pseudo second order model is the most
sorbed at equilibrium (mg g–1) at time t (min) and k2 is the rate suitable for Co adsorption.
constant of the pseudo-second order adsorption (g mg–1 min–1).
Values of k2 and q2 are calculated from the plot of 1/qt versus t.
Table 2 describes various parameters of the first-order ki- 4. Discussion
netic model and pseudo-second order kinetic model.
HAp (Ca10(PO4)6(OH)2) contains the Ca2+, (PO4)6, and (OH)2
Table 2 groups. These groups are ion-exchangeable. The Ca2+ cation
Parameters of the first- and second-order kinetic models is easily ion-exchangeable with various divalent metals. The
mechanisms of metal cations retention by HAp include ion ex-
Kinetic model First order Pseudo-second order
change, adsorption, dissolution-precipitation, and substitution
k1 = 0.2382 k2 = 0.02635 of Ca2+ ions in mineral structure. Here in our study, Ca has
a cationic radius of 0.99 Å and Co has a cationic radius 0.745 Å.
Parameters q1 = 126.74 4 q2 = 127.06
Moreover, both cations have the same oxidation state of 2. So,
R2 = 0.87 R2 = 0.99 it is expected that Co gets ion-exchanged with Ca easily. The
adsorption of ions on HAp could be a combination of two
mechanisms. The first one is ion exchange between Co ions
0.00808
contained in the contaminated solution and the Ca 2+ cations
present in the HAp. This ion exchange process is done through
the dissolution of apatite followed by precipitation, according
0.00804 to following equation:
1/qt (gm/mg)

0.00800
Ca 10(PO4)6(OH)2 + x Co2 →
→ Ca 10xCox(PO4)6(OH)2 + x Ca 2+
0.00796
The second mechanism is that of surface adsorption of Co on
HAp. The third mechanism is possibly caused by the forma-
0.00792 tion of complexing of the Co ions with the HAp matrix. This
complexing happens due to the dissolution of HAp, followed
0.02 0.04 0.06 0.08 0.10 by precipitation of Cobalt phosphate according to the following
1/t (min ) –1 two equations:

Fig. 13. The first order kinetic model of cobalt adsorption onto HAp
Ca 10(PO4)6(OH)2 + 12 H+ →
at room temperature → 10 Ca2+ + 6H2PO4¡ + 2OH¡ (dissolution)

136 Bull. Pol. Ac.: Tech. 65(2) 2017

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 Cobalt adsorption on the nano-hydroxyapatite matrix: isotherm and kinetic studies

10 Co2+ + 6H2PO4 + 2OH →

¡ ¡
[7] EPA United States Environmental Protection Agency, www.epa.
gov/airtoics/hlthef/cobalt.html, (2015).
→ Co10(PO4)6(OH)2 + 12 H+ (precipitation) [8] H.S. Lim, W. Lim, J.Y. Hu, A. Ziegler, and S.L. Ong, “Com-
parison of filter media materials for heavy metal removal from
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5. Conclusion Manage. 147, 24‒33 (2015).
[9] S. Zhang, M.H. Peh, Z. Thong, and T.S. Chung, “Thin film in-
In this study, the adsorption potential of HAp nanopowder terfacial cross-linking approach to fabricate a chitosan rejecting
is investigated for the removal of cobalt from contaminated layer over poly (ether sulfone) support for heavy metal removal”,
aqueous solutions. The effect of contact time, initial cobalt Ind. Eng. Chem. Res. 54 (1), 472‒479 (2014).
concentration, and adsorbent doses on the cobalt adsorption [10] R. Sitko, P. Janik, B. Zawisza, E. Talik, E. Margui, and I. Qu-
by HAp nanopowder are evaluated. The kinetic equilibrium eralt, “Green approach for ultratrace determination of divalent
study of the adsorption of cobalt onto HAp nanopowder is also metal ions and arsenic species using total-reflection X-ray
revealed with variation in cobalt concentration and contact time. fluorescence spectrometry and mercapto-modified graphene
The following results are obtained: oxide nanosheets as a novel adsorbent”, Anal. Chem. 87 (6),
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removal occurs at pH = 6. The Freundlich isotherm model is best property of hydroxyapatite ceramic”, Bull. Mater. Sci. 28 (6),
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