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Chemical Engineering Journal 217 (2013) 119–128 Contents lists available at SciVerse ScienceDirect Chemical

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Chemical Engineering Journal

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Journal journal homepage: www.else vier.com/locate/cej Preparation, characterization and adsorption potential of

Preparation, characterization and adsorption potential of the NH 4 Cl-induced activated carbon for the removal of amoxicillin antibiotic from water

Gholamreza Moussavi a , , Ahamd Alahabadi a , Kamyar Yaghmaeian b , Mahboube Eskandari a

a Department of Environmental Health Engineering, Tarbiat Modares University, Tehran, Iran b Center for Water Quality Research (CWQR), Institute for Environmental Research (IER), Tehran University of Medical Sciences, Tehran, Iran

(IER), Tehran University of Medical Sciences, Tehran, Iran highlights " NH 4 Cl-induced activated carbon (NAC)

highlights

" NH 4 Cl-induced activated carbon (NAC) was prepared from a waste biomass.

" The prepared NAC was a mesoporous material with a BET surface area of 1029 m 2 /g.

" NAC had a high density of hydroxyl, carbonyl, carboxylic, and carboxylate surface functional groups.

" NAC had an amoxicillin adsorption rate of up to 4.3 times greater than the standard AC.

" NAC had an amoxicillin adsorption capacity of 2 times of that of the standard AC.

article info

Article history:

Received 29 October 2012 Accepted 14 November 2012 Available online 29 November 2012

Keywords:

Waste biomass

Activated carbon

Chemical activation

Amoxicillin

Adsorption

abstract

The preparation, characterization and application of NH 4 Cl-induced activated carbon (NAC) for amoxicillin removal from the contaminated water were studied. The prepared NAC had a specific surface area of 1029 m 2 /g and a mean pore volume of 2.46 nm. Over 99% of 50 mg/L amoxicillin (AMX) was adsorbed using 0.4 g NAC/L at the optimum solution pH of 6; while standard activated carbon (SAC) could only adsorb around 55% of AMX under similar experimental conditions. Kinetic analysis revealed that adsorption exper- imental data for both NAC and NAC were best fitted by the pseudo-second-order model, with the greater rate for NAC than for SAC. Results of equilibrium experiments indicated that adsorption of AMX onto SAC and NAC were better described by the Langmuir model. The maximum adsorption capacity of AMX onto SAC and NAC was 262 and 437 mg/g, respectively. AMX adsorption onto SAC increased from 76.8% to 92% with increased temperature from 10 to 35 C. However, a further increase of temperature to 50 C led to declining AMX removal to 78.1%. Overall, these results indicate that developed NAC was an efficient adsorbent that presents an attractive adsorbent method for application in treating contaminants in water. 2012 Elsevier B.V. All rights reserved.

1. Introduction

Pharmaceuticals present class of health care products that are intensively used worldwide to promote human health and well being as well applications in animal care and agriculture. Among pharmaceuticals, antibiotics are the most widely used drug for the prevention or treatment of bacterial infections in humans, ani- mals and plants [1] . Antibiotics are released into bodies of water mainly through effluent of municipal wastewater treatment plants, as well as through effluent from pharmaceutical manufacturing plants. Pharmaceuticals are gaining recognition as being environ- mental contaminants, classified as recalcitrant bio-accumulative

Corresponding author. Tel.: +98 21 82883827; fax: +98 21 82883825. E-mail address: moussavi@modares.ac.ir (G. Moussavi).

1385-8947/$ - see front matter 2012 Elsevier B.V. All rights reserved.

compounds and are thus regarded as hazardous chemicals. The re- lease of pharmaceuticals into the environment thus results in con- tamination of aquatic or terrestrial ecosystems [2] . Effluent containing antibiotics needs to be treated chemically or physically to prevent the adverse effects from contaminated water. Although chemical processes, especially advanced oxidation processes, can often degrade and decompose antibiotics’ molecules into simple compounds and/or mineralize them, these processes are very expensive and difficult to operate for complete elimination of re- calcitrant compounds including antibiotics. Physical techniques re- main the most appropriate treatment option and adsorption is among the most efficient of these techniques for removing organic compounds from industrial effluent [2,3] . Adsorption is efficient, simple to design and operate and it is unaffected by toxicity as well as being inexpensive [4] . Adsorption therefore presents an efficient

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G. Moussavi et al. / Chemical Engineering Journal 217 (2013) 119–128

and economical technique widely used to accumulate organic compounds from contaminated streams onto solid material [2] . A saturated adsorbent is easily separated from a treated stream for regeneration or disposal in an environmentally acceptable way. The performance of an adsorption process is affected by an adsor- bent’s characteristics as well as by the composition of a waste stream (mainly by the structural properties of the contaminant(s) and the composition of the waste stream) [5] . Several materials including activated carbon, waste material and minerals either plain or modified have been examined so far as adsorbents for organic contaminants. Due to its porosity and very high specific surface area and capacity, activated carbon is the most widely used adsorbent to remove various classes of com- pounds from contaminated streams [6] . However, the main disad- vantages of activated carbon are high production and regeneration costs [5] . Interestingly, it has been found that adsorption of antibi- otics onto activated carbon is significantly influenced by character- istics of the activated carbon [7] . Therefore, the method of carbon activation aimed at improving its adsorption capability and thus reducing the rate of activated carbon consumption to reduce the cost of activated carbon adsorption making more it cost-effective. Several chemicals have been used in the process of microwave assisted activation of carbon, and the best activation has been obtained with the presence of alkaline hydroxide of KOH [8] . However, the main challenge with this technique of microwave- assisted modification of activated carbon using metal salts is the metal compound formed during the activation process [8] . These metal compounds are deposited in the internal structure and pores of the activated carbon, thereby reducing its pore volume and specific surface area. Accordingly, non-metal hydroxides might be used as an alternative chemical to activate carbon. This study was set up to examine the NH 4 Cl-induced activation of carbon prepared from pomegranate wood, an agricultural waste, to compare the capability of NH 4 Cl-induced activated carbon (NAC) with that of standard activated carbon (SAC) in adsorption of amox- icillin (AMX) as a model of an antibiotic, from contaminated water. AMX, a b -lactam antibiotic, is the drug of choice prescribed for the treatment of a number of human bacterial infections, as a growth promoter for animals and in agriculture to prevent infections [9] . Influences of the following basic variables were evaluated in the tests on adsorption of AMX; pH of the solution, activated carbon con- centration, AMX concentration, reaction time and solution temper- ature. The equilibrium, kinetic, mechanism and thermodynamics of AMX adsorption onto SAC and NAC were also evaluated.

2. Materials and methods

2.1. Material

Analytical grade AMX (chemical formula: C 16 H 19 N 3 O 5 S, molar mass: 365.4 g/mol) was purchased from Sigma Aldrich Co., and used as received. As stated above, two types of activated carbon were used in this study, NAC and SAC. The NAC was prepared from pomegranate wood waste according to the procedure explained in the following sec- tion. Activated carbon obtained from Merk Co. was used as the SAC to make a comparison with and to highlight the adsorption potential of the NAC prepared in this study. The contaminated water used in the experiments was prepared from mixing aliquots of AMX stock solu- tions (1000 mg/L) with distilled water. A stock solution of AMX was made by dissolving 1 g of analytical grade AMX in distilled water.

2.2. Activated carbon preparation and characterization

Dried pomegranate wood was used as the base material for the preparation of activated carbon. The pomegranate wood was ob- tained from a local farm as discarded agricultural waste and was

first debarked, then crushed into small parts and ground. The wood particles were carbonized at 700 C for 1 h in an oven under a N 2 gas stream. The carbonized granules were then soaked in the NH 4 Cl solution with different concentrations (NH 4 Cl to char ratio was 0–10 w%); each solution was shaken for 24 h at room temperature. The mixture was then sieved to separate the char, and the sepa- rated char was then oven-dried at 105 C for 24 h. Pre-treated char was finally activated by oven-heating at various temperatures ranging from 500 to 900 C and activation time between 0.5 and 2.5 h under N 2 atmosphere. Accordingly, the prepared NH 4 Cl-in- duced activated carbon (NAC) was ground to particles according to a mesh size of 20/16 for use in the adsorption experiments. The SAC and NAC were characterized for surface morphology, specific surface area, pore volume and size, pH of point of zero charge (pHpzc) and surface functional groups. The surface mor- phology of the adsorbent was observed using the scanning electron microscopy (SEM) technique (Philips-XL30 Electron Microscope). Evaluations for BET (Brunauer–Emmett–Teller) specific surface area and pore volume and size were determined by a nitrogen gas adsorption analyzer (BELSORP-miniII instrument). The pHpzc of adsorbents was determined according to the pH drift procedure. Surface functional groups of the selected adsorbents were deter- mined using Fourier Transform Infrared (FTIR) spectroscopy with a Nicolet spectrometer.

2.3. Adsorption experiments

2.3.1. Parametric and kinetic experiments Parametric experiments were conducted in the stirred (100 rpm) glass reactor in a temperature-controlled incubator. In each test, 50 mL of contaminated water containing given concen- trations of AMX was transferred into the reactor, its pH was regu- lated (with 0.1 N HCl or NaOH) at the desired level, the predetermined amounts of activated carbon (NAC or SAC) were added to the reactor and the suspension was mixed at 100 rpm. When the predetermined mixing time was up, the suspension was filtered using a cellulose acetate filter with 0.2 l m pore size and the filtrate was analyzed for residual AMX. The concentration of AMX in a solution was measured using a Knauer HPLC (C18 ODS column; 250 4.6 5) with a UV detector 2006 at a wavelength of 190 nm. The mobile phase was a mixture of buffer phosphate with pH = 4.8 and acetonitrile with a volumetric ratio of 60/40 with an injection flow rate of 1 mL/min. The pH level of samples was mea- sured using a pH meter (Sense Ion 378, Hack). The temperature of solutions was measured using a mercury thermometer. Parameters at this stage were as follows; water pH (2–9), initial AMX concen- tration (10–100 mg/L), solution temperature (10–50 C), and reaction time (0.3–100 min) in kinetic experiment and 6 h in equilibrium tests). Experimental runs and conditions are given in Table 1 . All tests were performed in duplicate to ensure reproduc- ibility of the results; the mean of these two measurements was ta- ken to represent each evaluation. Calculations of amounts of adsorption of AMX onto prepared NAC and SAC were based on re- moval percentages (Eq. (1)) and adsorption capacity (Eq. (2)).

Amoxicillin removal

ð %Þ ¼ ð C 0 C t Þ 100

C

0

Adsorption capacity ðmg= gÞ ¼ V ð C 0 C t Þ

m

ð

1Þ

ð 2Þ

where C 0 and C t represent AMX concentration at initial and time t of the contact time, respectively. V is the volume of the AMX solution and is the mass of adsorbent added.

G. Moussavi et al. / Chemical Engineering Journal 217 (2013) 119–128

Table 1 The experimental runs and conditions.

121

Run Experiment

AMX concentration (mg/L) pH

Adsorbent

Contact time (min) Temperature ( C)

 

concentration

(g/L)

SAC a

NAC b

1 Adsorption potential of NAB activated under different conditions 50

Natural (6.8) –

0.4

10

25

2 Effect of solution pH

50

2–9

0.8

0.4

10

25

3 Effect of AMX concentration and contact time

10–100

6

0.8

0.8

0.3–100

25

4 Equilibrium adsorption

50–500

6

0.8

0.8

360

25

5 Effect of temperature

50

6

0.8

0.4

10

10–50

a Standard activated carbon.

b NH 4 Cl-induced activated carbon.

2.3.2. Adsorption equilibrium experiments and isotherm modeling

Test to evaluate an adsorption equilibrium onto prepared NAC and SAC were done by adding a given mass of 0.04 g SAC or NAC into a series of Erlenmeyer flasks, containing 50 mL of various con- centrations, in the range of 50–500 mg/L, with a pH of 6 (optimum

pH). Flasks were then stirred for 6 h at a constant temperature (25 C) to attain equilibrium, after which the suspension was ana- lyzed as described in Section 2.3.1 . The equilibrium adsorption of AMX onto prepared SAC and NAC was modeled using isotherm models Langmuir, Freundlich, and Dubinin-Radushkevich by fitting results from the experiment on to the models.

2.3.3. Adsorption thermodynamic and modeling

The thermodynamics of AMX adsorption onto the prepared NAC and SAC was evaluated using adsorption experiments performed by an Erlenmeyer flask, containing 50 mL of 50 mg/L solution with the optimum pH of 6 into which amounts of 0.04 g SAC or NAC were added and shaken in a temperature-controlled shaker incubator. This experiment was conducted at various temperatures between 10 and 50 C. At the end of each test the suspension was analyzed as described in Section 2.3.1 . The thermodynamics of AMX adsorp- tion onto NAC and SAC was analyzed using an estimated change in adsorption free energy ( D G ), adsorption enthalpy ( D H ), and adsorption entropy ( D S ) as shown in the following equations [10] .

3. Results and discussion

3.1. The effect of activation conditions on the adsorption potential of NAC

At the beginning of the study, in order to obtain the optimum activation conditions, the effect of NH 4 Cl to carbon ratios,

conditions, the effect of NH 4 Cl to carbon ratios, Fig. 1. The effect of NH

Fig. 1. The effect of NH 4 Cl concentration in activation process on the adsorption potential of prepared carbon (activation temperature and time was 800 C and 2 h, respectively).

activation temperature, and activation time was evaluated on the activation process. The activation performance index for each acti- vation condition was the capability of the prepared activated carbon in adsorption of AMX tested under experimental conditions given in Table 1 (run 1). Fig. 1 shows the effect of NH 4 Cl to char ratio ranging from 0 to 10 wt% on the adsorption potential of the produced carbon activated at 800 C for 2 h. As seen in Fig. 1 , carbon activated without NH 4 Cl induction removed only 56% of the AMX under the selected conditions. The percentage of AMX removal increased when the amount of NH 4 Cl was increased to 2% at which around 87% removal of AMX was observed. However, a further increase of NH 4 Cl to 10 wt% resulted in decreasing the amount of AMX that was removed. This can be attributed to destruction of the carbon texture likely due to generation of the excessive gas from the NH 4 Cl combustion. Over- all, it is seen that the when the activation of char was induced with NH 4 Cl at optimum ratio of 2 wt%, the prepared activated carbon had an AMX adsorption potential considerably (31%) greater than the carbon activated without NH 4 Cl induction. This finding confirms the efficacy of the selected method of carbon activation. The effect of activation temperature ranging from 500 to 900 C on the quality of the prepared carbon is indicated in Fig. 2 . Accord- ing to the results given in Fig. 2 , the carbon activated at 800 C at- tained the highest AMX adsorption. Fig. 3 depicts the results of the effect of activation time between 0.5 and 2.5 h on the quality of the prepared activated carbon. It is observed in Fig. 5 that the carbon activated for 2 h at 800 C achieved the highest AMX removal of 86.6%. Accordingly, the optimum conditions for the activation of prepared carbon in these tests were found to be a NH 4 Cl to carbon ratio of 2 wt%, temperature of 800 C, and activation time of 2 h was selected as the optimum activation temperature for the rest of experiments.

º
º

Fig. 2. The effect of activation temperature (500–900 C) on the adsorption potential of prepared carbon (NH 4 Cl concentration and activation time was 2% and 2 h, respectively).

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G. Moussavi et al. / Chemical Engineering Journal 217 (2013) 119–128

et al. / Chemical Engineering Journal 217 (2013) 119–128 Fig. 3. The effect of activation time

Fig. 3. The effect of activation time (0.5–2.5 h) on the adsorption potential of prepared carbon (NH 4 Cl concentration and activation temperature was 2% and 800 C, respectively).

3.2. Activated carbon characterization

The FTIR spectra of NAC and SAC are shown in Fig. 4 , indicating several intense peaks revealing the presence of a number of impor- tant functional groups on the surface of the carbon. An absorption band is observed at wave numbers between 3200 and 3600 cm 1 for both SAC and NAC (with maximums of 3425 and 3443 cm 1 for SAC and NAC, respectively), which is representative of hydroxyl functional groups on the surface [11–13] of the selected activated carbons. Absorption at wave numbers of 2929 cm 1 for SAC and 2922 cm 1 for NAC are attributed to aliphatic C A H interaction with the surface of the adsorbent [13,14]. Absorption at wave number of 2350 cm 1 is attributed to C @ O asymmetric stretching vibration of CO 2 [15] . Absorption at wave number of 1604 cm 1 observed at FTIR spectra of SAC is attributed to C @ O stretching vibration of car- bonyl groups [16] . NAC had no absorption at 1594 cm 1 . The strong absorption bands at wave numbers of from 1420 to 1090 cm 1 is also observed in the FTIR spectra of both SAC and NAC, demonstrating that oxygen was functioning to stretch car- boxylic groups and that carboxylate groups were present on the surface of the activated carbon [17,18] . According to Fig. 4 , the FTIR spectrum of NAC shows lower transmission (thus higher absorp- tion) percentages at all observed bands compared to SAC, implying greater density of functional groups on the surface of NAC than on SAC.

of functional groups on the surface of NAC than on SAC. Fig. 4. The FTIR spectra

Fig. 4. The FTIR spectra of NAC and SAC.

Textural characteristics of SAC and NAC are given in Table 2 . As seen in Table 2 , the activated carbon prepared in this work (NAC) had a high BET specific surface area of 1029 m 2 /g, which is close to that of SAC supplied by Merck Co. ( Table 2 ). Both SAC and NAC are mesoporous materials. However, the total volume and size of pores in NAC were around 10% greater than those in SAC. The larger pore volume and size of NAC compared with SAC can be re- lated to the generation and release of gases due to the evaporation and volatilization of ammonium impregnated onto carbon at a high activation temperature (800 C). Overall, it was demonstrated that NAC prepared from pomegranate wood chips had comparable textural characteristics with the high-grade standard carbon. The pHpzc of SAC and NAC were 7.4 and 6.6, respectively; the surface of carbons would be positively charged at pH below pHpzc and negatively charged at solution pH greater pHpzc.

at pH below pHpzc and negatively charged at solution pH greater pHpzc. Fig. 5. The SEM

Fig. 5.

The SEM images of (a) NAC and (b) SAC.

G. Moussavi et al. / Chemical Engineering Journal 217 (2013) 119–128

123

Table 2 The main properties of the NAC and SAC.

Parameter

Unit

Value

 

SAC a

NAC b

BET (m 2 /g) Total pore volume ( P / P 0 = 0.990) V m (monolayer volume) BET constant C Mean pore diameter Pores structure

m 2 /g cm 3 /g cm 3 /g – nm – –

1024

1029

0.572

0.633

235.3

236.4

691.8

1088.7

2.23

2.46

Mesopore

Mesopore

pH pzc

7.4

6.6

a Standard activated carbon.

b NH 4 Cl-induced activated carbon.

The surface morphology of NAC was compared to that of SAC in terms of SEM images as shown in Fig. 5 a. As can be seen in Fig. 5 a, NAC has a fibrous structure composed of a series of long parallel similar shaped channels with a smooth surface. Ioannidou et al. [14] also reported similar morphology for activated carbon pre- pared from rapeseed stalks using steam activation. Fig. 5 b shows the SEM image of SAC, indicating a smooth surface with scattered cavities of various sizes on the surface of the carbon. The difference in surface morphology of NAC and SAC can be attributed to specific base materials as well as to the activation procedure. Accordingly, preparation of the mesoporous activated carbon with high pore volume and specific surface area from low/no cost agricultural bio- mass presents an economically viable application to control water pollution with appropriate benefits to the environment.

3.3. Parametric experiments

3.3.1. Effect of solution pH and adsorption mechanism To find the optimum pH for maximum adsorption of AMX onto SAC and NAC, the effect of AMX solution pH level ranging from 2 to 9 was investigated under the conditions given in Table 1 (run 2). The adsorption experiments for each adsorbent at each pH were carried out in duplicate and the average results are presented in Fig. 6 . As seen in Fig. 6 , the maximum AMX adsorption was ob- tained at solution pH of around 6 for both SAC and NAC adsorbents. According to Fig. 6 , the percentage of AMX adsorption onto SAC in- creased from 53.9% to a maximum of 73% when the pH was raised from 2 to 6. However, AMX removal percentage decreased consid- erably with a further increase of pH to 9. The same trend was ob- served for adsorption of AMX onto NAC, although with greater percentages, while lower NAC concentration (half of SAC) was

percentages, while lower NAC concentration (half of SAC) was Fig. 6. The effect of solution pH

Fig. 6. The effect of solution pH (2–9) on the adsorption of amoxicillin onto NAC and SAC (see Table 1 for the experimental conditions).

used. Based on data plotted in Fig. 6 , the adsorption of AMX onto NAC improved from 76.8% to over 91% when the solution pH was increased from 2 to 6. A further increase of pH to 9 resulted in a reduction of AMX to 75.4%. The relationship between effects of the selected adsorbents in AMX adsorption and solution pH can be explained by considering both the surface charge of the adsorbent and the dissociation con- stant (p K a ) of AMX. Since the pHpzc of SAC and NAC were 7.4 and 6.6, respectively, a positive charge developed on their surfaces at pH below pHpzc. AMX has p K a of 2.4 (carboxyl), 7.4 (amine), and 9.6 (phenol) [19] . Therefore, in an acidic solution (pHs 2–6), the carboxyl group ( A COOH) present in the AMX molecule is dissoci- ated into carboxylate ( A COO ) [20] . Accordingly, electrostatic attraction between the AMX (anionic) molecules (through COO functional group) and the surface of the activated carbons (posi- tively charged at pHs below 7.4 for SAC and 6.6 for NAC) was most likely the predominant adsorption mechanism [21] . However, the reduced AMX removal with an increased pH beyond 6 can be jus- tified by an increase of OH formation in the solution and subse- quent competition with the COO anions on AMX molecules for active adsorption sites on the surface of the activated carbon. The reduction of AMX adsorption at alkaline solution pH (pH > pHpzc) can be related to a negative charge on the surface of the carbon and thereby activating electrostatic repulsion of the anions to adsorb on the adsorption sites, onto the activated carbon [22] . Putra et al. [23] reported the maximum adsorption of AMX onto a commercial activated carbon at adsorbent pHpzc (around

4.9), although they tested the limits of levels of solution pH (only

2, 5, and 7). Therefore, the pH of 6 was selected as the optimum va-

lue of pH in the next experiments. As stated above, although NAC concentration used in this exper- iment was half that of SAC, the percentages of AMX adsorption onto NAC was considerably greater than that onto SAC. For in- stance, MAX removal by NAC was 18.1% greater than that by SAC in optimum pH (6) and similar contact time. This indicates the greater adsorption potential of prepared NAC compared with SAC. The greater performance of NAC than that of SAC relates to the surface characteristics of adsorbents, which is discussed later in this text.

3.3.2. Dynamic of AMX adsorption and its kinetic modeling The effect of various concentrations of AMX (10, 50, and 100 mg/L) on its adsorption onto SAC and NAC was investigated under conditions given in Table 1 (run 3). Data obtained from the experiment were evaluated based on both removal efficiency and adsorption kinetics. Fig. 7 shows removal efficiency at various con- centrations of AMX using adsorption onto SAC and NAC as a func- tion of contact time; significantly greater adsorption percentages

and rates were recorded for NAC than for SAC for all tested concen- trations. As can be seen in Fig. 7 , the complete adsorption of 10 mg/

L AMX onto NAC was obtained at a contact time of 2 min. More-

over, the complete removal of medium (50 mg/L) and high (100 mg/L) concentrations of AMX were obtained by adsorption onto a small dosage of NAC (0.8 g/L) at contact times of 20 and 40 min, respectively. In comparison, SAC could only completely re- move 10 mg/L AMX in 30 min contact time. Extending the contact time for adsorption of medium (50 mg/L) and high (100 mg/L) con- centrations of AMX onto SAC up to 100 min achieved 95.1% and 98.1% removal percentages, respectively. These findings reveal the high affinity of prepared NAC to adsorb AMX molecules indi- cating that the adsorption of AMX onto NAC is a rapid process occurring within a wide rage in a reasonable contact time. The ra-

pid AMX adsorption onto NAC can be attributed to surface mass transfer that will be addressed below. Kinetics of adsorption of various concentrations (10, 50 and 100 mg/L) AMX onto NAC and SAC was analyzed by fitting data

124

G. Moussavi et al. / Chemical Engineering Journal 217 (2013) 119–128

(a)
(a)
(a) (b)
(b)
(b)
(a) (b)

Fig. 7. The adsorption of various concentrations of amoxicillin (10–100 mg/L) onto (a) NAC and (b) SAC as a function of contact time (see Table 1 for the experimental conditions).

from the tests of this step with pseudo first order (PFO) and pseudo second order (PSO) models.

PFO

PSO

equation :

equation :

lnð q e q t Þ ¼ ln q e k 1 t

t ¼

q

t

1

þ t

q

e

k 2 q 2

e

ð

ð

3Þ

4Þ

where k 1 and k 2 are constants of adsorption rate, q t is adsorption capacity at time t, q e is adsorption capacity at equilibrium condition. The determination coefficient ( R 2 ) and the standard deviation relative error ( D q ) were used as criteria of goodness of fitness. The D q was calculated according to the Eq. (6) as reported by Basha et al. [24] .

Table 3 The kinetic information of amoxicillin adsorption onto NAC and SAC.

Dq ¼

ffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffi

s

P ½ðq exp q model Þ = q exp 2

n 1

ð

5Þ

where q exp and q model are the experimental and model estimated adsorption capacities, respectively, and n represents the number of the tests. Information on the kinetics of AMX adsorption onto NAC and SAC is given in Table 3 . The higher values of R 2 and lower values of D q for PSO model than for PFO one for adsorption of all the tested concentrations of AMX onto both NAC and SAC indicates that results were best described with the PSO kinetic model. Avail- able literature on adsorption of AMX is limited. Putra et al. [23] also reported the better fitness of adsorption of AMX onto both commercial activated carbon and bentonite to the PSO model. The better fitness of data from the experiment to the PSO model implies that the rate of AMX adsorption onto SAC/NAC was affected mainly by the availability of active adsorption sites on the adsor- bent rather than the concentration of the AMX in the solution [25,26]. It is also reconfirmed that adsorption of AMX onto both SAC and NAC is attained through the electrostatic attraction be- tween carboxyl anions in the structure of antibiotic molecules and positively charged functional groups (adsorption sites) on the cationic surfactant of the adsorbent. A similar conclusion was made by Shaarani and Hameed [27] for adsorption of 2,4-dichloro- pheno onto ammonia-modified activated carbon. Two important points can be derived from the information on kinetics given in Table 3 . Firstly, values of k 2 for adsorption of all tested concentrations of AMX onto NAC are greater (between 2.7 and 4.3 times) than those onto SAC, verifying the higher affinity of NAC than SAC for interaction with AMX that resulted in a higher adsorption potential, which means higher removal percentages were obtained using NAC in a shorter contact time ( Fig. 7 ). The higher affinity of AMX toward NAC than toward SAC (at similar experimental conditions) was related to the surface characteristics of carbons to the greater number of functional groups on the sur- face of NAC than SAC (see Fig. 4 and Section 3.2 ). The greater num- ber of surface functional groups means a greater number of adsorption active sites and a higher interaction of AMX molecules with the surface of the adsorbent surface thus a higher adsorption rate. Secondly, values k 2 for AMX adsorption onto NAC decreased with an increased concentration of AMX. Decreasing k 2 values with an increase of AMX concentration in the adsorption onto NAC de- picts that there has not been any limitation to adsorption sites

and that adsorption is limited by the concentration of AMX [8] and thus by the mass transfer rate. Indeed, the increase of initial AMX concentration resulted in increase of driving force [28] , there- by improving the mass transfer rate. The two main steps involved in mass transfer in the adsorption of organic molecules onto adsorbents are the liquid phase mass transport (film diffusion) and the intra particle mass transport (pore diffusion or intraparticle diffusion) phase [29] . To deduce whether adsorption of AMX onto NAC has been limited by film

Adsorbent

Amoxicillin concentration (mg/L)

q exp (mg/g)

Pseudo first order kinetic

 

Pseudo second order kinetic

 
 

R 2

q e (mg/g)

k 1 (min 1 )

D q

R 2

q e (mg/g)

k 2 (g/mg min)

D q

SAC a

10

12.3

0.931

3.6

0.185

0.70

0.999

12.7

0.122

0.370

50

54.9

0.871

30

0.083

0.39

0.999

58.8

0.008

0.650

100

110.6

0.983

83.3

0.044

0.59

0.998

125

0.001

1.170

NAC b

10

12.5

0.958

1.55

1.064

1.005

0.999

12.8

2.035

0.092

50

62.5

0.912

12.85

0.311

0.827

0.999

63.3

0.078

0.212

100

126

0.961

40.29

0.099

0.626

0.999

126.6

0.013

0.472

a Standard activated carbon.

b NH 4 Cl-induced activated carbon.

G. Moussavi et al. / Chemical Engineering Journal 217 (2013) 119–128

125

Table 4 The film diffusion and intraparticle diffusion information of amoxicillin adsorption onto NAB and SAC.

Type of diffusion

SAC a , amoxicillin concentration (mg/L)

 

NAC b , amoxicillin concentration (mg/L)

 

10

50

100

10

50

100

Film diffusion R 2 k fd (min 1 )

0.896

0.891

0.938

0.914

0.988

0.965

0.11

0.032

0.018

0.608

0.264

0.095

Intraparticle diffusion R 2 k id (g/mg h) C

0.64

0.813

0.912

0.87

0.854

0.818

1.26

4.01

8.97

1.227

3.939

9.377

7.54

27.6

31.89

10.86

45.56

69.46

a Standard activated carbon.

b NH 4 Cl-induced activated carbon.

diffusion or by intra particle diffusion, adsorption data from the experiment was fitted with the intra particle diffusion model [30] and the liquid film diffusion model [31] , given in Eqs. (6) and (7) , respectively.

lnð 1 q t = q e Þ¼ K fd t

ð

6Þ

q t ¼ K id t 0 : 5 þ C

ð

7Þ

where K fd and K id represent constants of liquid film diffusion and in- tra particle diffusion, respectively. Constants of the fitted models are given in Table 4 . As seen in Table 4 , R 2 values of the film diffusion model for adsorption of AMX particularly onto NAC at all of the tested concentrations was higher than those of the intra particle diffusion model. This finding suggests that diffusion through the boundary liquid layer surrounding the NAC particles was the main step controlling the rate of AMX adsorption [29] . A greater initial AMX concentration causes a greater concentration gradient thus a higher rate of AMX molecules diffuse through the boundary layer around the adsorbent, which in turn stimulates a higher rate of adsorption.

3.3.3. Equilibrium of AMX adsorption and its isotherm modeling The equilibrium of adsorption of various concentrations of AMX onto SAC and NAC was investigated under experimental conditions given in Table 1 (run 4). Results are shown in Fig. 8 . According to plots shown in Fig. 8 , the adsorption efficiency and capacity of AMX was considerably greater for adsorption onto NAC that onto SAC particularly at higher AMX concentrations, reconfirming the better performance of NAC to adsorb AMX compared with SAC. Re- moval of AMX at the initial concentration of 50 mg/L by SAC and NAC was 100% and 99.3%; removal efficiencies decreased to 41.7% (by SAC) and 68.3% (by NAC) when the initial AMX concen- tration was increased step wise to 500 mg/L. In contrast, adsorp- tion capacity in the tests increased with increased concentration of AMX and reached 260.4 and 426.9 mg/g for SAC and NAC, respectively, under the similar conditions. Considering that the concentration of adsorbents (SAC or NAC) was constant during equilibrium adsorption tests (0.8 g/L), the decrease of removal effi- ciency with increased AMX concentration was related to limited availability of adsorption sites for increased amounts of AMX mol- ecules [32] . The increased adsorption capacity as a function of AMX concentration under the conditions of these tests can is also dem- onstrated by the constant state of the concentration of the adsor- bent; therefore, increasing the concentration of AMX led to an increased mass transfer of AMX molecules to a given mass of adsorbent, thus increasing the adsorption capacity. These findings are in accordance with those of other research. For instance, Wang et al. [33] reported a similar trend of changing adsorption rate and capacity as a function of initial adsorbate concentration, although tests were done with a different adsorbent (walnut hull) and ads- robate (Cr(VI)). Overall, it has been demonstrated that NAC had a

(a) (b)
(a)
(b)

Fig. 8. The adsorption percentage and capacity of various concentrations of amoxicillin (50–500 mg/L) onto (a) SAC and (b) NAC under equilibrium condition (see Table 1 for the experimental conditions).

greater removal rate and capacity than SAC for removal of AMX from aqueous solutions, confirming that the activation method used was an effective and promising method in modification of activated carbon and thus improvement of the favorability the resultant adsorbent for the removal of antibiotics from contami- nated streams. The equilibrium adsorption results were further analyzed with isotherm models of Langmuir, Freundlich, and Dub- inin-Radushkevich as given in following equations [34] :

Langmuir:

C e

¼

1

þ C e

q

q

e

bq max

max

ð

8Þ

where the q max (mg/g) is the maximum adsorption capacity. The b parameter is the Langmuir constant (L/mg). Values of q max and b are determined from the linear regression plot of C e versus C e .

q

e

126

G. Moussavi et al. / Chemical Engineering Journal 217 (2013) 119–128

Freundlich:

ln q e ¼ ln K F þ 1

n ln C e

ð 9Þ

where K F and n are constants from the Freundlich equation. The constant K F represents the capacity of the adsorbent for the adsor- bate, and 1/n is the reciprocal of reaction order. A linear regression plot of ln q e versus ln C e gives the K F and n values.

Dubinin-Radushkevich (D-R):

ln q e ¼ ln q m K DR e 2

ð 10Þ

where K DR is the D-R constant (mol 2 /kJ 2 ) and e represents the Pola- nyi potential (J/mol), which is determined by:

e

¼ RT ln½ 1 þ 1=C e

ð11Þ

K DR is related to the mean of adsorption free energy E (kJ/mol) by the following equation:

E ¼

1

p

ffiffiffiffiffiffiffiffiffiffiffi

2K DR

ð12Þ

Information on the isotherm analysis is given in Table 5 . Based on data given in Table 5 , the R 2 values of the Langmuir isotherm were greater than those of the other isotherms. This means that adsorption of AMX molecules onto SAC and NAC particles is better described by the Langmuir model, which implies that AMX molec- ular adsorption occurs as a monolayer adsorb on homogenously distributed adsorption sites on the surfaces of the selected adsor- bents. As seen in Table 5 , the value of R L (a dimensionless param- eter derived from the Langmuir equation) falls between 0 and 1, indicating that AMX adsorption onto the prepared adsorbent was favorable. The maximum monolayer adsorption capacity of AMX onto SAC and NAC based on Langmuir model was around 262 and 437 mg/g, respectively. The greater AMX adsorption capacity of NAC than SAC (at similar experimental conditions) can further be explained by considering the BET constant, term C , summarized in Table 2 as well as the best fitted isotherm (Langmuir isotherm) to data of the experiment. The BET constant, term C , is attributed to the adsorption energy in the first adsorbed layer. Accordingly, the va- lue of C indicates the magnitude of interactions between adsorbate and adsorbent; the greater the C value the greater the interactions between adsorbate and adsorbent and thus the higher the adsorp-

tion rate and capacity. As above indicated, the adsorption of AMX molecules onto SAC and NAC adsorbs mainly as a monolayer on homogenously distributed adsorption sites on the surfaces of selected adsorbents. The values of C constant for SAC and NAC are 692 and 1089, respectively, demonstrating that AMX had a significantly greater interaction with the surface of NAC that that of SAC resulting in adsorption of a greater number of AMX molecules onto NAC than onto SAC. The greater interaction between AMX and the NAC than the SAC can be related to the higher density of charge and surface functional groups in NAC compared to that in SAC ( Fig. 4 ). It means the greater available sites on the surface of NAC than on the SAC for interaction with the AMX molecules. This finding indicates that the activated carbon prepared in this study had a maximum adsorption capacity considerably greater (67%) than SAC, presenting NAC as a promising candidate for appli- cation as an adsorbent to control environmental pollution. There is limited scientific research on adsorption of AMX from water. The efficacy of a few adsorbents have been investigated, examples as follows; chitosan beads [35] ; bentonite and activated carbon [23] ; and almond shell ash [20] . These studies investigated adsorp- tion of AMX antibiotic from contaminated water; the maximum AMX adsorption capacity reported for a commercial activated car- bon was with the value of around 222 mg/g [23] . Putra et al. [23] reported that both Langmuir and Freundlich models could equally well-fit the results of tests of adsorption of AMX onto a commercial activated carbon with the maximum adsorption capacity of around 222 mg/g at an optimum acidic pH of 4.98. Accordingly, the devel- oped adsorbent in the present work achieved an adsorption capac- ity significantly greater than adsorbents previously tested, and thus presents an effective adsorbent for elimination of antibiotics from contaminated streams. Accordingly, the high adsorption capacity, profound availability and ease of accessibility of the base material in nature, as well as simplicity of preparation, presents NAC as a promising, efficient and economically viable adsorbent for eliminating antibiotics from contaminated streams.

3.3.4. Thermodynamic of adsorption and its modeling To investigate the thermodynamics of AMX adsorption onto SAC and NAC, the adsorption of AMX was investigated at various solution temperatures between 10 and 50 C under the conditions specified in Table 1 (run 5). The results in terms of AMX removal percentage as a function of solution temperature are shown in Fig. 9 . As seen in Fig. 9 , the AMX adsorption percentages onto SAC increased from 67.4% to 81.5% with the increase of

Table 5 The isotherm information of amoxicillin adsorption onto NAC and SAC.

Isotherm

 

Adsorbent

 

NAC a

SAC b

Langmuir

 

R

2

0.994

0.998

q

max

438.6

261.8

b

0.128

0.166

R L ¼

 

1

0.02

0.01

ð

1 þ

bC 0 Þ

Freundlich

R 2

 

0.959

0.96

K F

76.25

89.48

n

2.7

4.95

Dubinin-Radushkevich

 

R 2

 

0.831

0.819

K DR

0.0016

0.0001

E

17.7

70.7

a NH 4 Cl-induced activated carbon.

b Standard activated carbon.

Cl-induced activated carbon. b Standard activated carbon. Fig. 9. The effect of solution temperature (10–50 C)

Fig. 9. The effect of solution temperature (10–50 C) on adsorption of amoxicillin onto PAC and NAC (see Table 1 for the experimental conditions).

G. Moussavi et al. / Chemical Engineering Journal 217 (2013) 119–128

127

temperature from 10 to 25 C (equilibrium temperature). Further increase of temperature to 50 C resulted in decrease of AMX removal by SAC to 61.5%. For AMX adsorption onto NAC, AMX re- moval improved from 76.8% to 92% when the temperature of the solution increased from 10 to 35 C (equilibrium temperature). However, a further increase of temperature to 50 C led to a declin- ing AMX removal percentage to 78.1%. The improvement of AMX adsorption with increased temperature is attributed to enhance- ment of the interaction rate between AMX molecules and the adsorption sites with increased temperature [36] . Moreover, the increase of AMX adsorption percentages as a function of tempera- ture reveals that AMX adsorption onto SAC and NAC is an endo- thermic process under the selected conditions of this experiment [37] . Hence, the increase of temperature up to the optimum level accelerated AMX mass transfer through the boundary liquid layer thereby a higher amount of AMX molecules were transferred onto the surface of SAC/NAC particles and thus greater removal percent- ages were achieved. Meanwhile, the decrease of AMX with in- creased temperature related to desorption of AMX adsorbed and its release into the solution [38] , suggesting that MAX adsorption is an exothermic process at an elevated temperature. Another important point is made in Fig. 9 ; the equilibrium temperature for AMX adsorption onto NAC (35 C) is significantly greater than that of SAC (25 C). This is an important feature for NAC from the point of view of application; NAC can be efficiently applied for a wider range of water temperatures compared to SAC. The thermodynamics of AMX adsorption on the prepared adsor- bents were analyzed using the following equations [10] :

DG ¼

RT ln K

ln K ¼ DH RT

þ DS

R

DG ¼ DH T DS

ð13Þ

ð14Þ

ð15Þ

The obtained thermodynamics information is given in Table 6 .

Based on the information presented in Table 6 , values of D G for the temperatures tested for AMX adsorption were calculated to be between 2.25 and 4.08 kJ/mol for SAC and between 4.97

adsorp-

and 8.60 kJ/mol for NAC. Also, the D H and D S for AMX

tion onto SAC and NAC adsorption 31.5 kJ/mol and 119.3 J/k mol, and 37.1 kJ/mol and 148.5 J/k mol. Overall, the negative values of

Table 6 The thermodynamic information of amoxicillin adsorption onto SAC and NAC.

Adsorbent Temperature

K

d

D G

R 2

D H

D S (J/K mol)

 

(K)

(mL/g)

(kJ/mol)

(kJ/mol)

SAC a

283

2.61

2.25

0.994 31.5

119.3

288

3.45

2.97

293

4.13

3.45

298

5.19

4.08

298

5.19

4.08

0.987

32

93.3

303

4.70

3.90

308

3.59

3.27

313

2.86

2.73

323

2.00

1.86

NAC b

283

8.28

4.97

0.992 37.1

148.5

288

11.01

5.74

293

14.17

6.46

298

17.66

7.11

303

25.28

8.14

308

28.75

8.60

308

28.75

8.60

0.991 63.52

178.58

313

17.50

7.45

323

8.92

5.88

 

a Standard activated carbon.

b NH 4 Cl-induced activated carbon.

D G and the positive value of D H reveal that adsorption of AMX onto SAC (at temperatures up to 25 C) and NAC (at temperatures up to 35 C) are a spontaneous and endothermic favorable process [29,39]. In addition, the greater positive value of D S for NAC than SAC indicates the higher affinity of NAC toward AMX molecules and increasing randomness at the interface of NAC–AMX solution during the interaction of AMX molecules with the active adsorp- tion sites on NAC [18] compared with SAC. Moreover, the values of distribution coefficient ( K d = q t / C t ; mL/g) at different tested tem- peratures for AMX adsorption onto SAC/NAC are given in Table 6 . As seen in Table 6 , values of K d for adsorption onto both SAC and NAC increased with increasing temperature, confirming that AMX adsorption onto both SAC and NAC is an endothermic process.

4. Conclusion

In this study, an activated carbon was prepared from agricul- tural waste using innovated NH 4 Cl-induced activation method (NAC) and its adsorption potential was compared with standard activated carbon (SAC) supplied by Merck Co. in adsorption of AMX. NAC was a mesoporous particle with a higher volume of pores, greater surface area of functional groups, and greater inter- action with AMX compared with SAC. These features resulted in a much greater AMX adsorption rate and capacity than were achieved by SAC under similar conditions. Accordingly, NAC is hereby presented as a mesoporous adsorbent with high pore vol- ume and specific surface area from a low/no cost agricultural bio- mass that is promising for application in the control of water pollution and presents a very valuable economic with benefits to the environment.

Acknowledgement

The authors are grateful to the Tarbiat Modares University for providing financial and technical support.

References

[1] J.L. Martinez, Environmental pollution by antibiotics and by antibiotic resistance determinants, Environ. Pollut. 157 (2009) 2893–2902. [2] V. Homem, L. Santos, Degradation and removal methods of antibiotics from

aqueous matrices: a review, J. Environ. Manage. 92 (2011) 2304–2347. [3] S.-H. Lin, R.-S. Juang, Adsorption of phenol and its derivatives from water using synthetic resins and low-cost natural adsorbents: a review, J. Environ. Manage.

90 (2009) 1336–1349.

[4] R. Han, D. Ding, Y. Xu, W. Zou, Y. Wang, Y. Li, L. Zou, Use of rice husk for the adsorption of congo red from aqueous solution in column mode, Bioresource Technol. 99 (2008) 2938–2946. [5] Z. Aksu, Ö. Tunç, Application of biosorption for penicillin G removal:

comparison with activated carbon, Process Biochem. 40 (2005) 831–847. [6] A. Demirbas, Agricultural based activated carbons for the removal of dyes from aqueous solutions: a review, J. Hazard. Mater. 167 (2009) 1–9. [7] K.Y. Foo, B.H. Hameed, Coconut husk derived activated carbon via microwave induced activation: effects of activation agents, preparation parameters and adsorption performance, Chem. Eng. J. 184 (2011) 57–65. [8] J. Rivera-Utrilla, G. Prados-Joya, M. Sánchez-Polo, M.A. Ferro-García, I. Bautista- Toledo, Removal of nitroimidazole antibiotics from aqueous solution by adsorption/bioadsorption on activated carbon, J. Hazard. Mater. 170 (2009)

298–305.

[9] D. Dimitrakopoulou, I. Rethemiotaki, Z. Frontistis, N.P. Xekoukoulotakis, D. Venieri, D. Mantzavinos, Degradation, mineralization and antibiotic inactivation of amoxicillin by UV-A/TiO 2 photocatalysis, J. Environ. Manage.

98 (2012) 168–174.

[10] Y. Zhao, B. Zhang, X. Zhang, J. Wang, J. Liu, R. Chen, Preparation of highly ordered cubic NaA zeolite from halloysite mineral for adsorption of ammonium ions, J. Hazard. Mater. 178 (2010) 658–664. [11] I. Puziy, O. Poddubnaya, A. Martínez-Alonso, F. Suárez- García, J. Tascón, Synthetic carbons activated with phosphoric acid III. Carbons prepared in air, Carbon 41 (2003) 1181–1191. [12] T. Yang, A. Lua, Characteristics of activated carbons prepared from pistachio- nut shells by physical activation, J. Colloid Interface Sci. 267 (2003) 408–417. [13] D. Cuhadaroglu, O.A. Uygun, Production and characterization of activated carbon from a bituminous coal by chemical activation, Afr. J. Biotechnol. 7 (2008) 3703–3710.

128

G. Moussavi et al. / Chemical Engineering Journal 217 (2013) 119–128

[14] O.A. Ioannidou, A.A. Zabaniotou, G.G. Stavropoulos, Md.A. Islam, T.A. Albanis, Preparation of activated carbons from agricultural residues for pesticide adsorption, Chemosphere 80 (2010) 1328–1336. [15] V. Gómez-Serrano, M. Acedo-Ramos, C. Valenzuela-Calahorro, A.J. López- Peinado, Regeneration of activated carbon after contact with sulfuric acid solution, J. Chem. Technol. Biotechnol. 75 (2000) 835–839. [16] W. Tongpoothorn, M. Sriuttha, P. Homchan, S. Chanthai, C. Ruangviriyachai, Preparation of activated carbon derived from Jatropha curcas fruit shell by simple thermo-chemical activation and characterization of their physico- chemical properties, Chem. Eng. Res. Des. 89 (2011) 335–340. [17] R. Fu, L. Liu, W. Huang, P. Sun, Studies on the structure of activated carbon fibers activated by phosphoric acid, J. Appl. Polym. Sci. 87 (2003) 2253–2261. [18] K.Y. Foo, B.H. Hameed, Adsorption characteristics of industrial solid waste derived activated carbon prepared by microwave heating for methylene blue, Fuel Process. Technol. 99 (2012) 103–109. [19] G.N. Rolinson, Laboratory evaluation of AMX, J. Infect. Dis. 129 (1974) 143. [20] V. Homem, A. Alves, L. Santos, Amoxicillin removal from aqueous matrices by sorption with almond shell ashes, Int. J. Environ. Anal. Chem. 90 (2010) 1063–1084. [21] G. Moussavi, M. Mahmoudi, Removal of azo and anthraquinone reactive dyes from industrial wastewaters using MgO nanoparticles, J. Hazard. Mater. 168 (2009) 806–812. [22] E. Çalıs kan, S. Göktür, Adsorption characteristics of sulfamethoxazole and metronidazole on activated carbon, Sep. Sci. Technol. 45 (2010) 244–255. [23] E.K. Putra, R. Pranowo, J. Sunarso, N. Indraswati, S. Ismadji, Performance of activated carbon and bentonite for adsorption of amoxicillin from wastewater:

mechanisms, isotherms and kinetics, Water Res. 43 (2009) 2419–2430. [24] S. Basha, D. Keane, A. Morrissey, K. Nolan, M. Oelgemöller, J. Tobin, Studies on the adsorption and kinetics of photodegradation of pharmaceutical compound, indomethacin using novel photocatalytic adsorbents (IPCAs), Ind. Eng. Chem. Res. 49 (2010) 11302–11309. [25] Y. Liu, New insights into pseudo-second-order kinetic equation for adsorption, Colloid Surf. A. 320 (2008) 275–278. [26] J.M. Salman, V.O. Njoku, B.H. Hameed, Bentazon and carbofuran adsorption onto date seed activated carbon: kinetics and equilibrium, Chem. Eng. J. 173 (2011) 361–368. [27] F.W. Shaarani, B.H. Hameed, Ammonia-modified activated carbon for the adsorption of 2,4-dichlorophenol, Chem. Eng. J. 169 (2011) 180–185.

[28] D. Rameshraja, V.C. Srivastava, J.P. Kushwaha, I.D. Mall, Quinoline adsorption onto granular activated carbon and bagasse fly ash, Chem. Eng. J. 181–182 (2012) 343–351. [29] S. Nethaji, A. Sivasamy, Adsorptive removal of an acid dye by lignocellulosic waste biomass activated carbon: equilibrium and kinetic studies, Chemosphere 82 (2011) 1367–1372.

[30] W.J. Weber Jr., J.C. Morris, Kinetics of adsorption on carbon from solution, J. Sanit. Eng. Div. 89 (1963) 31–60. [31] G.E. Boyd, A.W. Adamson, L.S. Myers, The exchange adsorption of ions from aqueous solutions by organic zeolites. II. Kinetics, J. Am. Chem. Soc. 69 (1947)

2836–2848.

[32] G. Moussavi, R. Khosravi, Removal of cyanide from wastewater by adsorption onto pistachio hull wastes: parametric experiments, kinetics and equilibrium analysis, J. Hazard. Mater. 183 (2010) 724–730. [33] X.S. Wang, Z.Z. Li, S.R. Tao, Removal of chromium (VI) from aqueous solution using walnut hull, J. Environ. Manage. 90 (2009) 721–729. [34] B.H. Hameed, Evaluation of papaya seeds as a novel non-conventional low-cost adsorbent for removal of methylene blue, J. Hazard. Mater. 162 (2009) 939–

944.

[35] W.S. Adriano, V. Veredas, C.C. Santana, L.R.B. Gonçalves, Adsorption of amoxicillin on chitosan beads: kinetics, equilibrium and validation of finite bath models, Biochem. Eng. J. 27 (2005) (2005) 132–137. [36] G. Moussavi, S. Talebi, M. Farrokhi, R. Mojtabaee Sabouti, The investigation of mechanism, kinetic and isotherm of ammonia and humic acid co-adsorption onto natural zeolite, Chem. Eng. J. 171 (2011) 1159–1169. [37] H. Zheng, L. Han, H. Ma, Y. Zheng, H. Zhang, D. Liu, S. Liang, Adsorption characteristics of ammonium ion by zeolite 13X, J. Hazard. Mater. 158 (2008)

577–584.

[38] D. Karadag, Y. Koc, M. Turan, B. Armagan, Removal of ammonium ion from aqueous solution using natural Turkish clinoptilolite, J. Hazard. Mater. B136 (2006) 604–609. [39] F.M. Pachado, C.P. Bergmann, T.H.M. Fernandes, E.C. Lima, B. Royer, T. Calvete, S.B. Fagan, Adsorption of reactive red M-2BE dye from water solutions by multi-walled carbon nanotubes and activated carbon, J. Hazard. Mater. 192 (2011) 1122–1131.