Ecotoxicology and Environmental Safety 131 (2016) 22–29

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Ecotoxicology and Environmental Safety

journal homepage: www.elsevier.com/locate/ecoenv

Effective removal of tetracycline from aqueous solution using activated

carbon prepared from tomato (Lycopersicon esculentum Mill.) industrial
processing waste
Hasan Sayğılı a, Fuat Güzel b,n
a
Department of Chemistry, Institute of Science and Technology, Dicle University, 21280 Diyarbakir, Turkey
b
Department of Chemistry, Faculty of Education, Dicle University, 21280 Diyarbakır, Turkey

art ic l e i nf o a b s t r a c t

Article history: Activated carbon (TAC) prepared under optimized conditions with ZnCl2 activation from a new pre-
Received 12 February 2016 cursor; tomato industrial processing waste (TW), was applied as an adsorbent to remove tetracycline
Received in revised form (TC) from aqueous solution. The factors (TAC dosage, initial TC concentration, contact time, ionic strength
3 May 2016
and solution temperature) affecting the adsorption process were examined at natural pH (5.7) of TAC-TC
Accepted 4 May 2016
system in aqueous solution. Kinetic data was found to be best complied by the pseudo-second order
model. The isotherm analysis indicated that the equilibrium data could be represented by the Langmuir
Keywords: model. The maximum adsorption capacity was identified as 500.0 mg g
1 at 308 K.
Tetracycline antibiotic & 2016 Elsevier Inc. All rights reserved.
Tomato industrial processing waste
Activated carbon
Adsorption
Waste water treatment

1. Introduction
Tetracycline (TC), as its cost effect, high quality and desirable
antimicrobial activity, due to having the stable naphthol ring as its
main structure, is widely applied in livestock industry and human
therapy. It has become one of the most extensively used antibiotic
all over the world (Zhang et al., 2015; Xu and Li, 2010). It has a high
aqueous solubility and a long environmental half-life (Lin et al.,
2013). In recent years, residues of TC discharged from municipal
wastewater treatment plants and agricultural runoff are frequently
detected in various environment matrices (Lian et al., 2013). In
addition, even little amount of TC can cause serious environmental
pollution. The continuous release of TC into aquatic environment
increases the potential for antibiotic resistance among microbial
populations, and the degradation by-products have been proven
even more toxic than the parents. Therefore, it is urgent to develop
efficient and economical technologies to remove TC from surface
and wastewater. There are many technologies available for TC re-
moval including oxidation, photochemical degradation, and ad-
sorption. The adsorption process is a practical method for the re-
moval of TC from wastewater in situ (Liu et al., 2013).
Adsorption by porous materials is effective in removing
n
Corresponding author.
E-mail addresses: hasan.saygili33@gmail.com (H. Sayğılı), fguzel@dicle.edu.tr,
guzelfuat@gmail.com (F. Güzel).
antibiotics from aqueous solution because of its low energy cost,
high adsorption capacity as well as environmental friendliness
(Liao et al., 2013). Carbon-based adsorbents possess large surface
areas and abundant pore structures and have shown great po-
tential in the removal of undesirable organic pollutants from
aqueous solutions (Zhu et al., 2014). However, commercially
available carbon-based adsorbents are very expensive. Therefore,
in recent years, various kinds of activated carbons (AC) have been
prepared from low-cost precursor materials, which are pre-
dominantly biomass wastes. (Güzel and Sayğılı, 2016). Until now,
the study on TC adsorption using AC produced from tomato pro-
cessing wastes (TW) has not been reported in literature. Tomato is
a very abundant and inexpensive material in Mediterranean
countries. According to the records of the United Nations Food and
Agriculture Organization (FAO), tomato is the most widely grown
product in fresh vegetables around the world with a production of
145.6 million tons. Turkey ranks fourth with the production of 10
million tons of tomato in the world (Sarısaçlı, 2007). TWs are
continuously disposed as solid waste, causing environmental
problems.
In this study, the new activated carbon (TAC) prepared under
optimum production conditions from TW with ZnCl2, that it was
chosen due to the increase of the pore structure in the carbon
adsorbent and carbon yields as noted in several literature, acti-
vation was adopted for TC adsorption. The impacts of some para-
meters (i. e. TAC dosage, initial TC concentration, contact time,
ionic strength and solution temperature were studied. Adsorption

http://dx.doi.org/10.1016/j.ecoenv.2016.05.001
0147-6513/& 2016 Elsevier Inc. All rights reserved.
 H. Sayğılı, F. Güzel / Ecotoxicology and Environmental Safety 131 (2016) 22–29 23

kinetics, isotherms and thermodynamics were also evaluated and
reported. Furthermore, before and after TC adsorption of the TAC,
were compared with scanning electron microscopic (SEM) and
Fourier transform infrared spectroscopic (FT-IR) analysis to
brighten the corresponding adsorption mechanisms.
2. Materials and methods
in the absorbance range of 0.2–0.9 was obtained prior to measurements. Unknown
TC concentrations were determined from the linear equation (A ¼ 0.0326.C
þ0.0626) obtained from calibration curve. The amount of adsorption, qt (mg g
1),
at time t (min), and TC amount, qe (mg g
1) removed at equilibrium onto per gram
of TAC. Each experiment was repeated three times under identical conditions and
the values were averaged.
To select the best kinetic and isotherm models were evaluated the determi-
nation correlation coefficient (R2) and normalized standard deviations Δq (%) va-
lues, which were calculated through the relation shown in Eq. (1).

⎡ q ⎤2
2.1. Materials and reagents ( )
⎣ e,exp − qe, cal / qe,exp ⎦
Δq (%) = 100 ∑ (1)
N−1
TAC was prepared with ZnCl2 activation using TW as a precursor, collected from
1
where N is the number of data points, qe, exp and qe, cal (mg g ) are the experi-
a local tomato paste factory in Adana, Turkey. Its preparation, effects of preparation
mental and calculated adsorption capacities, respectively.
parameters, physical and chemical properties was discussed in our previous study
Regeneration studies were studied to test the reusability of TAC. For this, re-
(Sayğılı and Güzel, 2016). Some physicochemical properties are given in the Table 1.
covery of TC from TC-loaded TAC was performed with NaOH solution. Initially,
TC (Molecular formula: C22H24N2O8; Molecular weight: 444.43 g mol
1; CAS no:
10 mg of the TAC were added to 100 mg L
1 of TC solution and agitated for 1 h. The
60-54-8; λmax: 360 nm) was purchased from Sigma-Aldrich Co., Ankara, Turkey.
adsorbed amount was calculated and then, it was washed with distilled water and
Stock TC solution was prepared by dissolving 0.5 g of TC in 1 L of double distilled
added to 0.05 mol L
1 NaOH, solution for 1 h. This adsorption-desorption cycle was
water. Synthetic experimental solutions of desired concentrations were prepared
repeated five times.
by diluting the stock solution.

2.2. Instrumentation
3. Results and discussions
Batch adsorption experiments were performed in a water bath shaker (Daihan-
WSB-30, Korea). The pH of aqueous solutions was measured by a pH meter (model 3.1. Optimization of TC adsorption conditions
Hanna pH meter 211). The concentration of TC in the solution before and after
adsorption was determined by using a UV–vis spectrophotometer (Perkin Elmer-
Lamda 25, USA) at maximum wavelength (λmax) of 360 nm. The surface physical 3.1.1. Dosage effect
morphology was identified by using SEM technique (JEOL JSM-6335 F, USA). FT-IR To observe the effect of TAC dosage on TC adsorption, different
spectra was collected with Attenuated Total Reflectance Fourier transform infrared amounts of TAC (varying from 10 to 50 mg) were respectively
(ATR-FT-IR) spectroscopy, Perkin-Elmer Spectrum 100 spectrometer, in the range
added into initial concentration of 100 mg L
1 TC solution. The
650–4000 cm
1, using a resolution of 4 cm
1 and 20 scans.
mixtures were shaken in 100 mL stoppered Erlenmeyer at 298 K
2.3. Batch adsorption and regeneration studies for 1 h at nature pH (figure not shown). From the experimental
results, amount of TC adsorbed onto the TAC decreased from 92.5
Experiments were performed with the TAC in a 100 mL Erlenmeyer flask to 73.7 mg g
1 as the TAC dosage was increased from 10 to 50 mg
containing 50 mL TC solution. To optimize the experimental conditions, the effects 50 mL
1. This decrease may be due to a reduction in the total
of various operating parameters, TAC dosage (10–50 mg), initial TC concentration adsorption surface area available to TC, resulting from overlap or
(200–400 mg L
1), agitation time (5–480 min) and temperature (288–308 K) on
adsorption at natural pH (5.7) level in aqueous solution of TC were studied by aggregation of adsorption sites. Based on these results, optimum
varying the parameters under study and keeping other parameters constant. After dosage for further studies was chosen as 50 mg.
each adsorption process, the samples were centrifuged (5000 rpm, 10 min) for
solid-liquid separation, and the residual TC concentration in solution was analyzed 3.1.2. Effects of initial concentration/contact time and kinetic
with UV–vis spectrophotometer at a maximum wavelength of 360 nm. For this
purpose, by using standard TC solutions of known concentrations, A (absorbance at
modeling
360 nm) vs. C (molarity of TC) calibration curve (correlation coefficient, R2 ¼0.9996) The adsorption of TC at different initial concentrations was
studied as a function of contact time in order to determine the
Table 1 necessary adsorption equilibrium time. To examine the effect of
Some physicochemical characteristics of TAC (Güzel and Sayğılı, 2016). initial TC concentration, 50 mL solution of initial concentrations of
200, 300 and 400 mg L
1 were shaken in 50 mL with 10 mg of
Parameter Value Parameter Value
TAC. In this case, the solution pH was kept natural without any pH
Proximate analysis (dry basis, wt%) Ultimate analysis (dry basis, wt%) adjustment (Fig. 1). As seen this figure, the TC adsorption was
rapid in the beginning, and then slight increase occurs till the
Moisture 9.22 Carbon 79.38
adsorption reached equilibrium. The rapid adsorption at the initial
Ash 25.56 Hydrogen 1.76
Volatile matter 11.30 Nitrogen 1.70 contact time can be attributed to the availability of active sites on
Fixed carbon 53.92 Oxygena 17.06 the surface and the slow rate of adsorption is probably due to the
Yield 38.20 Sulfur 0.10 slow pore diffusion of the adsorbate molecule into the bulk of the
Burn-off 62.80
adsorbent (Chen et al., 2010). The equilibrium was attained at
280 min when the maximum adsorption was reached and it is
Pore characteristics Surface functional groups (meq g
1) selected as equilibrium contact time for further adsorption ex-
SBET (m2 g
1) 1093 Carboxylic 0.52 periments. It was also seen that adsorption capacity at equilibrium
VT (cm3 g
1) 1.569 Phenolic 0.13 (qe) increased from 243.5 to 315.3 mg g
1 with an increase in the
Vmic (cm3 g
1) 0.129 Lactonic 0.52 initial TC concentrations from 200 to 400 mg L
1. This may be
Vmes (cm3 g
1) 1.440 Total acidity 1.17
attributed to an increase in the driving force of the concentration
Vmic (%) 8.22 Total basicity 1.04
Vmes (%) 91.78 CEC 0.95 gradient with the increase in the initial concentration of adsorbate
Dp (nm) 5.92 pHpzc 6.17 (Nasuha et al., 2010; Wang, 2012).
The kinetic data in Fig. 1 were analyzed using two kinetic
SBET: BET surface area; Vtot: Total pore volume; Vmic: Micropore volume; Vmes:
models: pseudo first-order (Lagergren, 1898) and pseudo second-
Mesopore volume; Vmic(%): Micropore contribution; Vmes(%): Mesopore contribu-
tion; DP: Average pore diameter; CEC: Cation exchange capacity; pHpzc: Point of order (Ho and McKay, 1998) kinetic models. The linearized forms
surface zero charge. of pseudo first-order and pseudo second-order kinetic equations
a
By difference. are given as follows, respectively:
24 H. Sayğılı, F. Güzel / Ecotoxicology and Environmental Safety 131 (2016) 22–29

kinetic model. Meanwhile, the qe, cal values calculated by pseudo-

second order kinetic model are much closer to the qe, exp than
fitting by other kinetic model. Therefore, the pseudo-second order
kinetics model is more appropriate to describe the adsorption
behavior of TC onto TNC. Furthermore, the k2 values decreases
with the increasing initial TC concentration and surface loading.
Higher surface loadings would result in less diffusion efficiency
and a high competition of TC molecules for a fixed reaction sites,
consequently a lower k2 values were observed (Kumar and Ahmad,
2011).
Since the kinetic models mentioned above cannot identify a
diffusion mechanism, the intra-particle diffusion model was ap-
plied to the kinetic data. This model can be defined by Eq. (3)
(Weber and Morris, 1963):

qt = kid t1/2 + C (4)

Fig. 1. Adsorption kinetic curves at different initial TC concentration onto TAC
(initial concentration: 200, 300 and 400 mg L
1, dosage¼ 10 mg 50 mL
1;
temperature¼ 298 K).
ln (qe − qt ) = ln qe − k1t
t 1 t
= +
qt k2 qe qe
where qe and qt (mg g
1) are the amount of dye adsorbed at
equilibrium and at time t, respectively, and k1(min
1) and k2
(g mg
1 min
1) are the pseudo first-order and the pseudo sec-
ond-order rate constant, respectively. Least-squares regression
analysis was used to fit these models to kinetic data.
The kinetic parameters, correlation coefficients, R2, and nor-
malized standard deviations, Δq(%) obtained from the linearized
kinetic plots of pseudo-first order (ln(qt
qe) vs. t) and pseudo-
second order (t/qt vs. t) (not shown) drawing by evaluating in the
Eqs. (2) and (3) are given in Table 2. The applicability of the kinetic
model is compared by evaluating R2, and Δq (%), and the agree-
ment between the calculated qe (qe, cal) and the experimental qe
(qe, exp) values. The R2 values of pseudo-second order kinetic model
are higher than the other kinetic model, while the Δq (%) values of
pseudo-second order kinetic are much lower than the other

1
1/2
where, kid (mg g min ) is the intra-particle rate constant and
C (mg g
1) is a constant that gives an idea about the thickness of
the boundary layer, where a value of C close to zero indicates that
diffusion is the only controlling step of the adsorption process
(Ahmed and Theydan, 2012). If the mechanism of adsorption
process follows the intra-particle diffusion, then the plot of qt vs.
t1/2 would be a straight line and the kid and C can be calculated
from the slope and intercept of the plot, respectively.
(2)
Intra-particle diffusion plots (not shown) drawing by evaluat-
ing in the Eq. (4) of the kinetic data in Fig. 1 were not linear over
time, which indicates that more than one mode of adsorption was
involved in the TC adsorption for TAC. However, they did not pass
(3)
through the origin. These results indicated that intra-particle dif-
fusion was present, but was not the only rate controlling step, and
that some other mechanisms may have been involved (Chen et al.,
2010). The values of kid and C obtained from the second linear
portion are listed in Table 2. As seen in this table, kid values in-
creased with an increase in initial concentration. This was due to
an increase in the driving force with initial concentration and
adsorption through meso- and micropores. In addition, the C va-
lues were larger than zero and increased with increasing initial TC
concentration. This fact confirmed that the rate-limiting step in
the adsorption process might contribute to boundary layer diffu-
sion, not intra-particle diffusion (Gao et al., 2013).
3.1.3. Effect of temperature, isotherm modeling and thermodynamic
analysis
To observe the effect of temperature, the experiments were

Table 2
Kinetic and isotherm parameters for TC adsorption onto TAC.

Kinetic parameters

Models: Pseudo-first order Pseudo-second order Intra-particle diffusion

Co qe, exp qe, cal k1  10
4 R2 Δq qe, cal k2  10
6 R2 Δq C kid R2 Δq

200 244.5 125.0 1.36 0.985 7.12 250.0 1.71 0.993 0.30 48.9 14.71 0.986 0.43
300 281.7 207.6 1.31 0.971 3.51 294.1 1.52 0.996 0.59 100.7 13.53 0.990 0.69
400 316.6 224.8 1.21 0.982 3.88 320.6 1.44 0.989 0.25 104.8 12.44 0.970 0.31

Isotherm parameters

Models: Langmuir Freundlich D-R

2 2
T qm b R Δq RL KF 1/n R Δq qD-R E R2 Δq

288 370.4 0.031 0.986 0.61 0.059 99.5 0.230 0.636 1.78 351.1 3.36 0.916 1.39
298 416.7 0.032 0.989 0.60 0.058 117.4 0.217 0.629 1.77 389.2 3.73 0.916 1.45
308 500.0 0.035 0.992 0.59 0.054 128.1 0.208 0.717 1.57 464.5 3.08 0.976 1.09

C0: mg L
1; qe, exp: mg g
1; qe, cal: mg g
1; k1: min
1; k2: g mg
1 min
1; kid: mg g
1 min
1/2; C: mg g
1; T: K; qm: mg g
1; b: L mg
1; KF: (mg g
1) (L mg
1)1/n; qD-R:
mg g
1; E: kJ mol
1; Δq: %.
 H. Sayğılı, F. Güzel / Ecotoxicology and Environmental Safety 131 (2016) 22–29
Fig. 2. Adsorption isotherms of TC onto TAC at different temperatures (tempera-
ture: 288, 298 and 308 K; dosage¼ 10 mg 50 mL
1; contact time: 5 h; pH¼ 5.7).
studied by determining the adsorption isotherms at three different
temperatures (288, 298 and 308 K) with different concentrations,
where all other effects such as TAC dosage, contact time and agi-
tation speed remained constant while the solution pH was original
without any adjustment (Fig. 2). As seen this figure, the adsorption
capacity increased from 332.6 to 439.8 mg g
1 by increasing so-
lution temperature from 288 to 308 K, indicating that the ad-
sorption is endothermic process. This was likely due to the in-
crease in the rate of molecular diffusion and the decrease in so-
lution viscosity with increasing temperature, facilitating adsorbate
molecule diffusion across the external boundary layer into the
internal pores of the adsorbent (Chen et al., 2013).
Three isotherm models namely, Langmuir (Langmuir, 1916),
Freundlich (Freundlich, 1906) and Dubinin–Radushkevich (DR)
(Dubinin and Radushkevich, 1947; Fu et al., 2008) isotherm models
were fitted to the equilibrium data in Fig. 2.
The linear form of the Langmuir isotherm model is given by the
following equation:
Ce 1 1
= + Ce
qe qm b qm (5)

1
where Ce (mg L ) is concentration of TC at equilibrium. qm
(mg g
1) is the Langmuir maximum adsorption capacity of TC per
unit mass of TAC, b (L mg
1) is the Langmuir constant related to
the adsorption equilibrium.
The Langmuir parameters can also be used to predict the ad-
sorption process is favorable or unfavorable (Cengiz et al., 2012). In
order to describe this, the dimensionless equilibrium constant
must be calculated by using the equation below:
1 form cation species (pH o3.3), zwitterion species (3.3 opH o 7.68)
RL =
1 + qm C0 (6)

1
where b is the Langmuir isotherm constant (L mg ) and C0 is the
initial dye concentration (mg L
1). It was stated that RL 4 1 re-
presents unfavorable, RL ¼1 represents linear, 0 oRL o 1 re-
presents favorable and RL ¼0 represents irreversible characteristic
of process (Kadirvelu and Namasivayam, 2003).
The linear form of the Freundlich isotherm model is given by
the following equation:
25
1
ln qe = ln KF + ln Ce
nF (7)

1
1 1/n
where KF ((mg g ) (L mg ) ) and n are Freundlich constants
which give a measure of adsorption capacity and intensity, re-
spectively. If 1/n o1, the adsorption process is favorable; the ad-
sorption capacity increases and new adsorption sites appear. If 1/
n 41, the adsorption process is unfavorable; the adsorption bonds
become weak and the adsorption capacity decreases (Isa et al.,
2007).
Dubinin–Radushkevich isotherm can be defined by the fol-
lowing equation:
ln qe = ln qD − R − Bε2 (8)
where qD-R (mg g
1) represents the maximum adsorbed amount. ε
is Polanyi potential (RT ln(1 þ(1/Ce)), B a constant related to ad-
sorption energy, R and T are the gas constant and temperature (K).
The mean energy of adsorption (E) can be calculated from the B
value using the following equation (Apiraticul and Pavasant,
2008):
B−1/2
E=
2 (9)
The value of E can give information about the adsorption nat-
ure. If the magnitude of E is between 8 and 16 kJ mol
1, the ad-
sorption process is supposed to proceed via chemisorption, while
for values of Eo8 kJ mol
1, the adsorption process is of physical
nature (Ahmed and Theydan, 2013; Tuzen and Sarı, 2010).
The isotherm parameters and correlation coefficients, R2, ob-
tained from the plots of Langmuir (Ce/qe vs. Ce), Freundlich (lnqe vs.
lnCe) and D-R (lnqe vs. ln(1 þ1/Ce)2) (not shown) drawing by
evaluating in the Eqs. (5), (7) and 8) of the equilibrium data at
studied temperatures are tabulated in Table 2. As observed from
this table, Langmuir isotherm model fits better than other iso-
therm models used, as confirmed by the high R2 values (40.986)
and the low Δq (%) values (˂0.059) in case of Langmuir isotherm
model, which shows that the adsorption of TC on TAC takes place
as monolayer adsorption on a surface that is homogenous in ad-
sorption affinity. The Langmuir constants, b, increased when the
temperature is increased, indicating that the adsorption density
was higher at higher temperatures. The maximum adsorption
capacity, qm obtained from the Langmuir equation was found as
500.0 mg g
1 at pH 5.7 and 308 K. This high adsorption capacity
also depends on the surface chemical properties as well as the
high mesoporosity and large average pore diameter owned of TAC.
The mesopore contribution and average pore size of TAC is 91.78%
and 5.92 nm (Table 1). The molecular size of the TC is 0.475 nm (Ji
et al., 2011). These data clearly demonstrate that the TC very easily
enters the pores of TAC. In addition, the point of surface zero
charge (pHpzc) of the TAC is 6.17 (Table 1). At pH˂pHpzc, the ad-
sorbent surface has a net positive charge, while at pH˃pHpzc the
surface has a net negative charge (Al-Degs et al., 2000). That is to
say, the surface of the TAC is positively charged at pH o 6.17 while
it is negatively charged at pH 46.17. TC in aqueous solutions, three
groups can undergo protonation-deprotonation reactions and
or anion species (pH 47.68) (Parolo et al., 2008). According to this,
at studied pH also indicates that TAC has mainly a positively
charge surface generated by protonation of the hydroxyl and car-
boxyl groups in weak acidic medium as well as negative acidic
groups, and TC is the form of the zwitterion. Hence, adsorption
mechanism can contribute for TC adsorption in this condition as
such surface complexation (e.g., H-bonding), since the zwitterion
molecule is predominant in this pH ranges (3.3 opH o 7.68)
(Martins et al., 2015). In the H-bonding formation, the functional
26 H. Sayğılı, F. Güzel / Ecotoxicology and Environmental Safety 131 (2016) 22–29

Table 3
Comparison of the adsorption capacity for TC by various adsorbents reported in literature (SWCN: Single-walled carbon nanotube; MWCN: Multi-walled carbon nanotube;
AC: Activated carbon).

Adsorbent Experimental conditions qm (mg g
1) References

pH Co (mg L
1) T (K)

Tomato processing waste-AC 5.7 200–800 308 500 Present study

Iris tectorum-AC 4.4 350–800 295 625 (Li et al., 2013)
Macadamia nut shells-AC 7.0 250–800 – 455 (Martins et al., 2015)
Grape processing waste-AC 5.7 200–800 308 625 (Güzel and Sayğılı, 2016)
Graphene oxide 3.6 8–167 298 313 (Gao et al., 2012)
SWCN 5.7 1.5–91.4 298 340 (Ji et al., 2009)
MWCN 5.8 1.5–91.4 298 100 (Ji et al., 2009)
Sorbo commercial AC 4.0 100–1000 298 375 (Rivera-Utrilla et al., 2013)
Merck commercial AC 4.0 100–1000 298 471 (Rivera-Utrilla et al., 2013)
Smectite 5.8 100–3000 298 462 (Li et al., 2010a)
Kaolinite 4.0 48–480 298 4 (Li et al., 2010b)
Rectorite 4.0 50–100 298 140 (Chang et al., 2009a)
Palygorskite 8.7 50–800 328 99 (Chang et al., 2009b)

groups such as –CH3, –OH, –NH2 and N-H in the TC molecule the
binding of TC onto TAC may act as H acceptor interacting with the
O-containing groups such as C ¼O, –COOH in the surface by
H-bonding. Similar adsorption mechanism was observed in our
previous study (Güzel and Sayğılı, 2016). Furthermore, RL values
are in the ranges of 0.054–0.059 at 288–308 K and confirmed that
the TAC is favorable for adsorption of TC under conditions studied.
Also, as the adsorption temperature increased from 288 K to
308 K, the RL values were found to decrease, indicating that the
adsorption of TC was more favorable at higher temperature. This
can also concluded from the Freundlich model fitting results
shown in Table 2. The increase of Freundlich constant, KF, values at
higher temperatures suggests that the adsorption process was
favorable at higher temperatures. The values of 1/n obtained at
temperatures studied in the present study were less than unity,
indicating the favorable adsorption of TC onto TAC. Furthermore,
the magnitudes of E (
5.89,
6.42 and
7.35 kJ mol
1 at 288,
298, and 308 K, respectively) are lower than 8 kJ mol
1 under
studied experimental conditions (Table 2), indicating that ad-
sorption nature of TC onto TAC is physisorption. Table 3 offers a
comparison of the maximum adsorption capacities of various ad-
sorbents for TC.
Thermodynamic behaviors were interpreted by the thermo-
dynamic parameters including the change in standard Gibbs free
energy (ΔG0), standard enthalpy (ΔH0), and standard entropy
(ΔS0). These parameters are calculated by the following equations
(El-Sayed, 2011):
ΔGo = − RT ln K
ΔGo ΔH o ΔS o
ln K = − = − +
RT RT RT
where K equals to qm. b, the equilibrium constant of the adsorption
process. R (8.314 J mol
1 K
1) and T (K) are gas constant and ab-
solute temperature, respectively. Thermodynamic parameters
were determined from Eqs. (10) and (11), respectively. The plot of
lnK as a function of 1/T (figure not shown) yields a straight line (R2
¼ 0.994) from which ΔHo and ΔSo were calculated from the slope
and intercept, respectively.
The negative values of ΔGo (
5.89,
6.42 and
7.35 kJ mol
1
at 288, 298, and 308 K, respectively) suggested that the adsorption
process was spontaneous. However, the increase in absolute values
of ΔGo with increasing temperature shows an increase in feasi-
bility of adsorption at higher temperatures. In addition, the values
of ΔGo in this study were within the ranges of
20 and
0 kJ mol
1, which indicated that the adsorption mechanism was
mainly a physical adsorption (Feng et al., 2011). The positive value
of ΔHo (11.40 kJ mol
1) indicates the endothermic nature of the
adsorption processes. The positive ΔHo is an indicator of en-
dothermic nature of the adsorption process and also its magnitude
gives information on the type of adsorption, which can be either
physical or chemical. The enthalpy of adsorption, ranging from
2.1 to 20.9 kJ mol
1 corresponds to a physisorption (Anayurt et al.,
2009). The ΔHo value of TC adsorption onto TAC is in range of
physisorption. Therefore, the ΔHo value shows that the adsorption
process was taken place via physisorption. The positive value of
ΔSo (60.34 J mol
1 K
1) showed the affinity of TAC for TC and the
increasing randomness at the solid-solution interface during the
adsorption process.
3.1.4. Effect of ion strength
Ionic strength of the solution is a factor that controls both
electrostatic and non-electrostatic interactions between the ad-
sorbate and the adsorbent surfaces (Xue et al., 2009). To determine
whether the adsorption process was affected by salt, it was con-
ducted at 0–0.5 mol L
1 NaCl, with a constant initial TC con-
centration of 100 mg L
1, pH of 5.7, and TAC dosage of 10 mg and
contact time of 1 h (not shown). From the experimental results,
the adsorbed amount of TC increased from 132.4 to 172.7 mg g
1
as the concentration of NaCl increased from 0 to 0.5 mol L
1. This
increase may be caused cannot access to adsorption sites in the
pores of TAC of large TC molecules aggregated at the high ionic
strength wherein hydrophobic interaction between the TC mole-
(10) cules may overcome the attractive electrostatic interaction, which
favours aggregation of the TC molecules. Similar results were ob-
served for TC adsorption on other adsorbents (Turku et al., 2007;
Chang et al., 2009a; Figueroa et al., 2004; Li et al., 2010a).
(11)
3.2. SEM and FT-IR analysis of TC adsorption
SEM micrographs of TAC before and after TC adsorption are
shown in Fig. 3(a). As can be seen from this figure, the external
surface of the TAC is full of cavities and the pores were at different
sizes and shapes. It is clear that TAC appears to have numbers of
pores where, there is a good possibility for TC molecule to be
trapped and adsorbed into these pores. SEM images showed bright
dark color on the surface. The surface after adsorption was turned
to light color. This may be due to the adsorption of TC on the
surface.
The FT-IR spectra of the TAC before and after TC adsorption are
shown in Fig. 3(b). Evaluation of the differences in the peak in-
tensity, peak shifting and peak appearance indicates the type of
 H. Sayğılı, F. Güzel / Ecotoxicology and Environmental Safety 131 (2016) 22–29 27

Fig. 3. SEM images (a) and FT-IR spectra (b) of TAC before and after TC adsorption.

interaction between surface functional groups and adsorbed TC. In

the spectra of TAC, the broad peak located in the region of
3100–3400 cm
1 related to O–H stretching vibrations. The band at
1581.45 cm
1, which could be attributed to (C ¼C) vibration in
aromatic rings. The band at 1228.21 cm
1 is due to the C-O
stretching vibration of phenol group (Lua and Yang, 2005). More
significance changes in the FT-IR spectra of the synthesized carbon
from tomato residue occurred after adsorption of TC. It was ob-
served a clear shift in peaks from 3368 to 3196, 1581–1573 and
1228–1219, corresponding to the stretching vibrations of the O–H,
C ¼C and C–O groups respectively. Additionally, new specific peaks
were also detected in fingerprint region (500–1500 cm
1) after
adsorption. These observations confirm the interaction between
TAC and TC.
Fig. 4. Effect of regeneration cycles on the adsorption capacity of TC onto TAC.
28 H. Sayğılı, F. Güzel / Ecotoxicology and Environmental Safety 131 (2016) 22–29
3.3. Reusability of TAC
Regeneration studies are essential to evaluate the reusability of
adsorbents for practical applications due to stringent ecological
and economic demand for sustainability (Sun et al., 2011). In this
study, the reusability of TAC was investigated by conducting the
adsorption-desorption process for five cycles for TC (Fig. 4). As
seen in Fig. 4, the adsorption capacity of TAC decrease for each
new cycle after desorption with five cycles. The original adsorption
capacity of TAC for TC is 98.57 mg g
1. After five cycles, the ad-
sorption capacities of adsorbent drop down to 53.80 mg g
1. The
results showed that TAC could be regenerated and repeatedly used
in water treatment.
4. Conclusions
The following conclusions can be drawn from the present
study:
 Adsorption of the TC increased with increase in contact time,
initial TC concentration and solution temperature and ionic
strength while it decreased with increase in TAC dosage.
 The equilibrium between the TC ions in the solution and on the
TAC surface was practically achieved in 3 h.
 The adsorption kinetic data were well described by the pseudo-
second order model.
 The diffusion mechanism was rather a complex process and the
intra-particle diffusion was not the only rate-controlling step.
 Equilibrium adsorption data of TC onto TAC at different tem-
peratures were well represented by Langmuir isotherm, show-
ing maximum capacity of 500.0 mg g
1.
 The separation factors, RL values of Langmuir isotherm were in
the range of 0–1, and the Freundlich constant, 1/n values were
smaller than 1, which indicated that the TC adsorption process
is favorable. E values obtained from D-R isotherm for the TC
adsorption process were found to range from 3.36 to
4.48 kJ mol
1 indicating that the mechanism of adsorption of
TC onto TAC is physical in nature.
 Thermodynamic study showed that the adsorption processes
were spontaneous and endothermic under studied conditions.
 TAC was proven to be an effective adsorbent for TC removal as
compared to the other ones reported in literature studies.
In conclusion, TAC could be employed as an adsorbent as al-
ternative to commercial ones for the removal of TC from water and
wastewater.
Acknowledgments
The authors acknowledge the Scientific Research Fund of Dicle
University for financial support (Project no: 12-ZEF-95).
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