ISSN 1066-3622, Radiochemistry, 2013, Vol. 55, No. 1, pp. 101107. Pleiades Publishing, Inc., 2013.

Published in Russian in Radiokhimiya, 2013, Vol. 55, No. 1, pp. 6873.

Adsorption of 60Co on Natural and Dithizone-Modified Chitin1

H. A. Omar
Radiation Protection Department, Nuclear Research Centre, Atomic Energy Authority,
P.O. Box 13759, Cairo, Egypt; e-mail: hodaatom@yahoo.com

Received March 12, 2012

AbstractImmobilization of dithizone onto natural biopolymer chitin to enhance the ability of chitin to adsorb
60
Co was performed. Natural and dithizone-modified chitin was characterized using surface area analyzer and
infrared spectroscopy. The sorption was studied in relation to the contact time, pH, initial 60Co concentration,
and adsorbent dosage. Batch adsorption models based on the assumption of the pseudo-first-order, pseudo-
second-order, and intraparticle models were applied to examine the adsorption kinetics. The results showed that
kinetic data followed closely the pseudo-first-order model. The Freundlich, Langmuir, and RedlichPeterson
isotherms were used for the mathematical description of the adsorption equilibrium, and the best fitting was
attained using the Freundlich model. Sorption studies were also performed at different temperatures to obtain
the thermodynamic parameters of the process. The quantity G0 decreases with an increase in temperature,
indicating that the sorption is more favorable at higher temperatures. The positive value of H0 indicates that
the sorption is endothermic.
Keywords: chitin, dithizone, cobalt-60, chemical treatment, immobilization, adsorption

DOI: 10.1134/S1066362213010207

Nuclear reactors, research centers, and isotope pro-
duction laboratories produce various liquid radioactive
wastes. Such wastes require adequate treatment in ac-
cordance with the radionuclidic composition and rele-
vant regulations, so as to decrease the activity level to
the permissible discharge limit [1]. Among the ra-
dionuclides usually present in radioactive waste solu-
tions, 60Co is of major importance because of its radio-
logical hazard determined by relatively long half-life,
5.27 years [2]. High levels of cobalt may cause several
health troubles such as paralysis, diarrhea, low blood
pressure, lung irritation, and bone defects [3]. Biosorp-
tion has recently received a great deal of attention due
to low cost of the materials used and to their environ-
mentally friendly nature. In recent years, much atten-
tion has been paid to the adsorption of metal ions on
various kinds of biomass, such as natural and synthetic
adsorbents; their potential uses for metal removal has
been reported [4, 5]. Among these natural polymers,
alginic acid, cellulose, chitin, and chitosan have been
examined [69].
skeleton, insects cuticles). Its annual production is
estimated to be almost as high as the production of
cellulose. The chemical structure of chitin is similar to
that of cellulose, with the hydroxy group at C-2 re-
placed by acetamide group. The empirical formula is
(C6H9O4NHCOCH3)n, and the pure compound contains
6.9% N [10, 11].
The main methods that have been used to remove
metal ions from wastewaters include chemical precipi-
tation, ion exchange, electrolytic extraction, membrane
process, and adsorption. Adsorption is an efficient way
to remove contaminants from wastewater [12]. In this
work, the sorption of 60Co from dilute aqueous solu-
tions by natural and dithizone-modified chitin was
studied in detail. Batch experiments were performed to
study the feasibility of practical application, and the
factors that affect the removal such as equilibration
time, solution pH, and dosage were examined. Adsorp-
tion isotherms were obtained, and the effect of tem-
perature was studied.

Chitin is the second most abundant biopolymer on EXPERIMENTAL

the Earth after cellulose, and it is found in the structure
Chemicals and materials. Metal salts of analytical
of a wide range of invertebrates (crustaceans exo-
grade and dithizone (1,5-diphenylthiocarbazone) of
1
The text was submitted by the author in English. reagent grade were purchased from Merck. Chitin was

101
102 OMAR
isolated from shrimp exoskeleton. Organic solvents
were of reagent grade and were used as received. All
the solutions were prepared using double-distilled wa-
ter, and the required pH values were adjusted with
buffer solutions.
Preparation of chitin. Chitin was isolated from
shrimp exoskeleton using modified method of No et al.
[13] and involving deproteination and demineraliza-
tion. Deproteination of the shrimp shells was carried
out by heating 50 g of shrimp shells with 500 ml of
3.5% NaOH (w/v) for 2 h at 65C. The mixture was
cooled, and the product was washed with water to neu-
tral reaction and dried. The deproteination is carried
out so as to prevent formation of chitosan. Deminerali-
zation was carried out by mixing 30 g of the residue
with 450 ml of 1.0 M HCl and stirring for 30 min at
room temperature. The mixture was then filtered, and
the solid obtained was washed with water as described
above and dried at 60C to yield chitin. The deminer-
alization was carried out so as to remove any adsorbed
minerals from the chitin surface. According to [8],
Ca3(PO4)2 and CaCO3 are the most common minerals
found as impurities in chitin. On adding HCl, these
minerals pass into the solution. The reaction was per-
formed at room temperature to avoid depolymerization
of chitin.
Immobilization of dithizone on chitin. To prepare
dithizone-modified chitin, 40 g of chitin prepared as
described above was added to 80 ml of toluene and
mixed with 10 g of dithizone in a 500-ml flask. The
mixture was refluxed and stirred for 4 h at 70C. The
product was filtered off, and the mixture was washed
consecutively with toluene, ethanol, and water several
times. The dithizone-modified chitin was then dried in
an oven at 60C for 12 h and sieved through a 200-
mesh sieve. The dithizone-modified chitin obtained
had brown color. Before adsorption study, the charac-
teristics of the modified polymer were determined
[14].
Radioactive tracer 60Co was produced by irradia-
tion of highest purity grade CoCl2 in the Second Egyp-
tian Research Reactor (ERR-2) at Inshas. The irradi-
ated CoCl2 sample was dissolved in concentrated HCl
and was used as tracer.
Batch adsorption technique. To examine the ef-
fect of various parameters on the sorption, 0.1 g of
natural (Ch) or dithizone-modified (Di-Ch) chitin was
mixed with 10 ml of a cobalt solution spiked with
60
Co, and the mixture was shaken for 3 h at ambient
temperature (27 1C) and pH varied in the range 2
10 (adjusted with HCl or NaOH solution, measured
with a pH meter).
After attaining the equilibrium, the samples were
separated by centrifugation, and the supernatant was
radiometrically analyzed using a NaI scintillation de-
tector connected to a multichannel analyzer (Giene
2000, USA). The removal percent (R) of 60Co was cal-
culated (here and hereinafter, the designation 60Co re-
fers to labeled Co and not to the pure isotope).
Sorption kinetics and isotherms. The kinetics of
60
Co sorption on Ch or Di-Ch was studied using batch
technique. The 60Co sorption isotherm was determined
in the concentration range from 5 104 to 102 M.
The amount of 60Co adsorbed onto two adsorbents, qe
(mg g1), was calculated by the following equation:
qe = (Ce C0)V/W,
where Ce and C0 are the initial and equilibrium concen-
trations of 60Co in solution (mg l1), respectively, V is
the aqueous solution volume (l), and W is the weight
(g) of Ch or Di-Ch.
Characterization of the biopolymer. The Ch and
Di-Ch samples were characterized by surface area
measurements using a Nova SA 3200 device. The IR
spectra were recorded with a Pye Unicam Maltson
1000 IR spectrometer in the range 4000400 cm1.
RESULTS AND DISCUSSION
The specific surface area of Ch and Di-Ch was
found to be 1.50 and 2.20 m2 g1, respectively. Thus,
the Di-Ch porosity is high enough for efficient adsorp-
tion of Co ions.
The IR spectra of Ch and Di-Ch are shown in
Fig. 1. Both spectra contain characteristic chitin bands
(cm1) 3438 [(OH)aliph], 3268 and 3108 (asymmetric
and symmetric stretching vibrations of acetamide N
H, respectively). 2931 [(CH) of CH3 group], 1381
[(CH) of CH3 group], 1659 [(C=O) in acetamide],
1315 (in Ch) and 1317 (in Di-Ch) [(CN) in
acetamide], 1558 (in Ch) and 1559 (in Di-Ch) [(NH)
in acetamide] [15], 1156 (in Ch) and 1158 (in Di-Ch)
[(CO) in polysaccharide], 1028 (in Ch) and 1031
(in Di-Ch) [COC) in glucosamine].
Effect of pH. The initial pH of the adsorption me-
dium is one of the most important parameters affecting
the adsorption. 10 ml of a 5 104 M aqueous Co solu-
tion was brought in contact with 0.1 g of Ch or Di-Ch
RADIOCHEMISTRY Vol. 55 No. 1 2013
 ADSORPTION OF 60Co ON NATURAL AND DITHIZONE-MODIFIED CHITIN 103

Fig. 1. IR spectra of (a) Ch and (b) Di-Ch samples.

at room temperature for 3 h, after which the adsorbents ate kinetic models should be used to describe the sorption
was separated. Figure 2 shows how the adsorption of dynamics [21]. We have considered three simplified ki-
Co on Ch and Di-Ch samples depends on pH. As can netic models: pseudo-first-order, pseudo-second-order,
be seen, the Co adsorption increases with pH, reaching and WeberMorris intraparticle diffusion models.
a maximum at pH 6 for Ch and 7 for Di-Ch, after
which it decreases. This is due to protonation of the
active sites at low pH values, preventing the adsorption
of Co2+ ions, and by possible hydrolysis of Co2+ at
high pH values [16]. Figure 2 also shows that Di-Ch
adsorbs more 60Co than Ch does. This may be due to
the appearance of various types of active sites (N,
NH, and SH) upon dithizone immobilization onto
the chitin surface [1719].
Fig. 2. Effect of pH on the removal of 60Co by (1) Ch and
Dosage of biopolymers. The dependence of the (2) Di-Ch.
degree of 60Co removal on the adsorbent amount was
studied by varying the adsorbent amount from 0.01 to
0.3 g, keeping the other parameters (cobalt solution
volume, pH, temperature of 27 1C, and contact
time) constant. Figure 3 shows that the degree of 60Co
removal gradually increases with an increase in the
adsorbent amount, apparently owing an increase in the
amount of exchangeable sites. However, at the adsorb-
ent amounts exceeding 0.2 g, the degree of removal
ceases to increase further [20].
Effect of contact time. Figure 4 shows the effect of Fig. 3. Effect of adsorbent dosage on the removal of 60Co
by (1) Ch and (2) Di-Ch.
contact time on the removal of Co ions at room tem-
perature. As can be seen, the amount of Co adsorbed
increases rapidly during the first 90 min, reaching 44
and 72% for Ch and Di-Ch, respectively. After that,
the growth decelerates, and in 180 min the adsorption
reaches 60 and 96% for Ch and Di-Ch, respectively,
with no noticeable further growth. Therefore, further
sorption experiments were performed for 3 h.
Kinetic models. The characteristics and diffusion
resistance of the sorbent surface strongly affect the sorp- Fig. 4. Effect of contact time on the removal of 60
Co by
tion rate and the overall transport of the solute. Appropri- (1) Ch and (2) Di-Ch.

RADIOCHEMISTRY Vol. 55 No. 1 2013

104 OMAR

Table 1. Kinetic models for Co sorption by biopolymers

Pseudo-first-order model Pseudo-second-order model Intraparticle diffusion model
Biopolymer
k1, min1 r2 k2, g mg1 min1 r2 kd, mg g1 min1/2 r2
Ch 0.017 0.982 0.0148 0.926 0.11 0.94
Di-Ch 0.018 0.985 0.0192 0.983 0.16 0.94

Pseudo-first-order model. The Lagergrens rate
equation is one of the most widely used rate equation
for describing the adsorption of an adsorbate from the
liquid phase [22]. The linear form of pseudo-first-order
equation is given as
log(ae at) vs. t plots, we determined the first-order
rate constants k1, compiled in Table 1 along with the
correlation coefficients (r2).
Pseudo-second-order model. The kinetics was also
described as pseudo-second-order process [23]:

log (ae at) = log ae k1t/2.303, t/qt = 1/(k2qe2) + t/qe,

where ae and at (mg g1) are the amounts of cobalt ad-
sorbed at equilibrium and at time t, respectively, and k1
is the pseudo-first-order rate constant. Figure 5 shows
the corresponding plots. From the slopes of the
where qe and qt are the amounts of Co (mg g1) ad-
sorbed at equilibrium and at time t, respectively, and k2
is pseudo-second-order rate constant. The correspond-
ing plots are shown in Fig. 6, and the values of k2 and
r2 are listed in Table 1. The more recent pseudo-
second-order model has been extensively used in the
same field [24].
WeberMorris model. The kinetic data were further
analyzed using the intraparticle diffusion model based
on the theory proposed by Weber and Morris [25];
qt = kdt1/2,

Fig. 5. Lagergren first-order plot for 60Co sorption. (1) Ch
and (2) Di-Ch; the same in Figs. 6 and 7.
Fig. 6. Pseudo-second-order plot for 60Co sorption by bio-
polymers.
where qt is the amount of cobalt adsorbed at time t, and kd
is the intraparticle diffusion rate constant (mg g1 min1/2).
In this case, the plot of qt vs. t1/2 should be linear with
slope kd. However, as seen from Fig. 7, the quality of
approximation is poor, and the straight line does not
pass through the origin. The correlation coefficients r2
are less than 0.99, suggesting that the sorption occurs
in two or more steps.
Adsorption isotherms. The effect of the initial
concentration was studied in the interval from 5 104
to 102 M at 27, 35, and 45C. The results are shown in
Fig. 8. As can be seen, the cobalt adsorption increases
with temperature.
The data obtained were interpreted using the Lang-
muir, Freundlich, and RedlichPeterson isotherms. The
Langmuir isotherm corresponds to the monolayer cov-
erage of the sorbent surface by the sorbate. It suggests
the surface homogeneity. The linear form of the Lang-
muir isotherm is as follows:
Ce/qe = 1/(q0b) + Ce/q0,

Fig. 7. Intraparticle diffusion plot for 60

Co sorption by where Ce is the equilibrium concentration of Co ions,
biopolymers. mg l1, qe is the amount of Co ions sorbed on Ch or

RADIOCHEMISTRY Vol. 55 No. 1 2013

 ADSORPTION OF 60Co ON NATURAL AND DITHIZONE-MODIFIED CHITIN 105

Table 2. Parameters of the Langmuir, Freundlich, and RedlichPeterson isotherms of Co sorption by Ch and Di-Ch
Langmuir isotherm Freundlich isotherm RedlichPeterson isotherm
Biopolymer T, C
q0, mg g1 r2 KF, mg g1 1/n r2 bR, mg l1 r2
27 12.38 0.960 0.35 1.8 0.991 0.469 2.35 0.986
Ch 35 14.71 0.999 0.407 1.4 0.992 0.459 1.98 0.987
45 27.25 0.987 0.379 1.5 0.991 0.348 2.20 0.988
27 26.52 0.960 1.599 2.1 0.974 0.445 0.76 0.977
Di-Ch 35 30.21 0.944 1.934 2.1 0.977 0.476 0.51 0.966
45 30.58 0.965 2.86 2.3 0.966 0.362 1.26 0.940

Di-Ch at equilibrium, mg g1, and q0 and b are the ln (kCe/qe 1) = ln bR + ln Ce,

Langmuir constants related to the sorption capacity
and energy of adsorption, respectively. Plotting Ce/qe where K, bR, and (0 < < 1) are the Redlich
vs. Ce gives straight lines (Fig. 9). Their parameters are Peterson parameters. For = 1, the RedlichPeterson
given in Table 2. The Langmuir constants q0 and b in- equation transforms to Langmuir form. When K and bR
crease with temperature. An increase in the adsorption
capacity with temperature suggests an increase in the
amount of adsorption sites [26].
The Freundlich isotherm, one of the most widely
used mathematical descriptions, usually fits the experi-
mental data over a wide concentration range. The
Freundlich isotherm gives an expression encompassing
the surface heterogeneity and the exponential distribu-
tion of active sites and their energies. The logarithmic
form of the Freundlich model is as follows:
log qe = log KF + n1 log Ce,

where KF and n are Freundlich constants related to the

Fig. 8. Effect of initial concentration on the adsorption of
adsorption capacity and adsorption intensity, respec- 60
Co by (a) Ch and (b) Di-Ch. Temperature, C: (1) 27,
tively; qe and Ce have the same meaning as above. The (2) 35, and (3) 45; the same in Figs. 911.
plots of logqe against logCe for the 60Co adsorption at
different temperatures are shown in Fig. 10, and the
calculated Freundlich constants are given in Table 2. It
is clear that the Langmuir model does not fit all the
experimental data well, as the correlation coefficients
(r2) at different temperatures are generally lower than
for the Freundlich model. The maximum capacity q0
increases with temperature, reaching at 318 K 27.25
and 30.58 mg g1 for Ch and Di-Ch, respectively. The
increase in the sorption equilibrium constant with tem-
perature suggests chemical interaction between the
adsorbent and adsorbate.
Then we analyzed the cobalt adsorption data using
the RedlichPeterson isotherm. It contains three pa-
rameters and incorporates the features of the Langmuir
and Freundlich isotherms. The RedlichPeterson iso-
therm in the linearized form can be described as fol- Fig. 9. Langmuir isotherm for adsorption of 60Co by (a) Ch
lows: and (b) Di-Ch.

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106 OMAR

Table 3. Thermodynamic functions for Co sorption by Ch and Di-Ch

H0, kJ mol1 S0, J mol1 K1 G0, kJ mol1
Concentration, M T,
Ch Di-Ch Ch Di-Ch Ch Di-Ch
300 11.77 18.70
5 104 308 0.259 0.85 1.42 3.68 12.50 19.95
318 13.62 23.56
300 10.77 14.54
1 103 308 0.295 0.48 1.49 2.28 11.88 15.69
318 12.72 17.53
300 9.10 12.64
5 103 308 0.40 0.34 1.76 1.74 10.01 13.59
318 11.42 14.91
298 8.37 10.97
1 102 308 0.45 0.3 1.85 1.52 9.32 12.09
318 10.05 12.95

are much greater than unity, the equation can trans-
form into Freundlich form. Plotting ln [(kCe/qe) 1]
against ln Ce yields a straight line of slope and inter-
cept bR (Fig. 11). As seen from Table 2, the three-
parameter RedlichRedlich model adequately de-
scribes the adsorption of cobalt by the biopolymer.
Thermodynamic functions. The temperature de-
pendence of cobalt adsorption was studied at Co ion
concentrations of 5 104, 103, 5 103, and 1
102 M and temperatures of 300, 308, and 318 K, with
60
Fig. 10. Freundlich isotherms for adsorption of
(a) Ch and (b) Di-Ch.
the other parameters kept constant. An increase in tem-
perature leads to an increase in the amount of Co ions
sorbed on Ch and Di-Ch. This may be due to attrition
of the particles at higher temperature, thus increasing
the surface area available for ion exchange [27]. The
enthalpies (H0) and entropies (S0) were calculated
from the linear dependences of ln Kd on 1/T (Fig. 12):
ln Kd = S0/R H0/(RT),
where T is the absolute temperature (K), and R is the
gas constant (kJ K1 mol1).
The values of H0, S0, and G0 for the two sam-
ples are given in Table 3. The positive values of H0
indicate that nonlocalized adsorption takes place on the
adsorbent surface. The G0 values are negative and
decrease with an increase in temperature, i.e., the reac-
tion becomes more favorable at higher temperatures.
Thus, we have isolated high-purity chitin from
shrimp skeleton shells. Organic ligand dithizone can be
Co by
ln Kd

ln Kd

Fig. 12. Variation of ln Kd with 1/T for 60Co sorption by

Fig. 11. RedlichPeterson isotherm for adsorption of 60Co (a) Ch and (b) Di-Ch. Co concentration, M: (1) 5 104,
by (a) Ch and (b) Di-Ch. (2) 1 103, (3) 5 103, and (4) 1 102.

RADIOCHEMISTRY Vol. 55 No. 1 2013

 ADSORPTION OF 60Co ON NATURAL AND DITHIZONE-MODIFIED CHITIN
immobilized onto the surface of the isolated chitin by
refluxing in toluene. The dithizone immobilization on
chitin enhances the selectivity and capacity in adsorp-
tion of Co ions. The kinetic study showed that the
sorption rate is best described by the pseudo-first-order
equation. According to the evaluation using Langmuir
equation, the monolayer sorption capacity obtained
was 12.38, 14.71 and 27.25 mg g1 for chitin, and
26.52, 30.2, and 30.58 mg g1 for dithizone-modified
chitin at 27, 35, and 45C, respectively. The thermody-
namic functions of the adsorption were determined.
The sorption is spontaneous and endothermic, and the
process becomes more favorable at higher tempera-
tures.
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