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Journal of Environmental Management 87 (2008) 3745 www.elsevier.com/locate/jenvman

Removal of copper (II) from aqueous solution by adsorption onto low-cost adsorbents
Haluk Aydna,, Yasemin Buluta, C - ig dem Yerlikayab
a

Department of Chemistry, Faculty of Science and Arts, University of Dicle, 21280 Diyarbakr, Turkey b Graduate School of Sciences, University of Dicle, 21280 Diyarbakr, Turkey Received 13 October 2005; received in revised form 5 October 2006; accepted 2 January 2007 Available online 8 March 2007

Abstract The use of low-cost adsorbents was investigated as a replacement for current costly methods of removing metals from aqueous solution. Removal of copper (II) from aqueous solution by different adsorbents such as shells of lentil (LS), wheat (WS), and rice (RS) was investigated. The equilibrium adsorption level was determined as a function of the solution pH, temperature, contact time, initial adsorbate concentration and adsorbent doses. Adsorption isotherms of Cu (II) on adsorbents were determined and correlated with common isotherm equations such as Langmuir and Freundlich models. The maximum adsorption capacities for Cu (II) on LS, WS and RS adsorbents at 293, 313 and 333 K temperature were found to be 8.977, 9.510, and 9.588; 7.391, 16.077, and 17.422; 1.854, 2.314, and 2.954 mg g1, respectively. The thermodynamic parameters such as free energy (DG0), enthalpy (DH0) and entropy changes (DS0) for the adsorption of Cu (II) were computed to predict the nature of adsorption process. The kinetics and the factors controlling the adsorption process were also studied. Locally available adsorbents were found to be low-cost and promising for the removal of Cu (II) from aqueous solution. r 2007 Elsevier Ltd. All rights reserved.
Keywords: Adsorption; Adsorption modeling; Low-cost adsorbents; Heavy metals; Adsorption of copper (II)

1. Introduction The contamination of water by toxic heavy metals through the discharge of industrial wastewater is a worldwide environmental problem (Ajmal et al., 2003). Their presence in streams and lakes has been responsible for several health problems with animals, plants and human beings. Numerous metals such as Sb, Cr, Cd, Cu, Pb, Hg, etc. have toxic effects on human and environment (TatyCostodes et al., 2003). Since copper is a widely used material, there are many actual or potential sources of copper pollution. Copper may be found as a contaminant in food, expecially shellsh, liver, mushrooms, nuts, and chocolate. Briey, any processing or container involving copper material may contaminate the products such as food, water or drink. Copper is essential to human life and
Corresponding author. Tel.: +90 412 2488550x3164; fax: +90 412 2488039. E-mail address: halukaydin@dicle.edu.tr (H. Aydn).

health but, like all heavy metals, is potentially toxic as well. For example, continued inhalation of copper-containing spray is linked with an increase in lung cancer among exposed workers (Yu et al., 2000). The permissible limit of Cu is 2.5 mg L1 in water (Prasad and Freitas, 2000). Various technologies exist for the removal of such metals. They include ltration, chemical precipitation, ion exchange, adsorption using activated carbon, electrodeposition and membrane process. All these methods are generally expensive (Low et al., 2000). Recently, Bailey et al. (Bailey et al., 1999) reviewed a wide variety of low-cost adsorbents for the removal of heavy metals. A low-cost adsorbent is dened as one which is abundant in nature, or is a by-product or waste material from another industry. The review concluded that these low-cost processes involved the use of activated carbon and ion-changers. The cost of these biomaterials is negligible compared with the cost of activated carbon or ion-exchange resins that are in the range of approximately $2.0$4.0/kg (Ferro-Garcia et al., 1988). The removal of heavy metals from industrial

0301-4797/$ - see front matter r 2007 Elsevier Ltd. All rights reserved. doi:10.1016/j.jenvman.2007.01.005

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38 H. Aydn et al. / Journal of Environmental Management 87 (2008) 3745

wastewater is considered an important application of adsorption processes using suitable adsorbent. At present, there is growing interest in using low-cost, commercially available materials for the adsorption of heavy metals. A wide variety of materials such as rice husk (Ajmal et al., 2003), modied cellulosic materials (Okieimen et al., 1985), y ash (Panday et al., 1985), wheat brean (Bulut and Baysal, 2006), modied bark (Gloaguen and Morvan, 1997), sawdust (Ajmal et al., 1998), pine bark (Al-Asheh and Duvnjak, 1998), animal bones (Al-Asheh et al., 1999), holly oak (Prasad and Freitas, 2000), modied sawdust of walnut (Bulut and Tez, 2003) and tea-industry waste (C - ay et al., 2004) are being used as low-cost alternatives to expensive adsorbents. The aim of this paper is to assess the ability of low-cost adsorbents such as shells of lentil (Lens culinaris Medik), wheat (Triticum durum Desf) and rice (oryza sativa L.) to adsorb Cu (II) from aqueous solution. The effect of the solution pH, temperature, contact time, initial adsorbate concentration and adsorbent doses on the removal of Cu (II) was studied. The thermodynamic parameters for the adsorption Cu (II) have also been computed and discussed. The kinetics and the factors controlling the adsorption process were also studied.

2.2. Chemicals All chemicals [Cu(NO3)2 3H2O, HCl, NaOH, NaHCO3 and Na2CO3)] were purchased from Merck. All the compounds used to prepare reagent solutions were of analytic reagent grade. The 1000 mg L1of stock solution of Cu (II) was prepared by dissolving Cu(NO3)2 3H2O in double-distilled water. 2.3. Apparatus Absorbance values were measured with a Unicam Model 929 atomic absorption spectrometer (AAS). A pH-meter (Jenway 3010) and shaker (Nuve ST 400) were used for pH adjustment and shaking, respectively. Elemental analysis was carried out with an EA 1108 Fisons instruments. The surface area was determined by a single-point N2 gas adsorption method by using a model micromeritics Flow Sorb II. 2300. 2.4. Procedure The effect of initial concentration on the adsorption by adsorbents from aqueous solution was investigated for a kinetic study, whose initial concentration was known. In addition, 2.0 g samples of adsorbent were mixed with 100 mL samples of Cu (II), and then mixtures were shaken (agitation speed 150 rpm). Suspension was centrifuged in centrifuge test tubes for 5 min at 2000 rpm. Absorbance was measured with AAS. Moreover, the effects of temperature, adsorbent doses, contact time and pH on the adsorption of Cu (II) by adsorbents from solution aqueous were similarly investigated. The effect of pH on the adsorption phenomenon was studied by adding either 0.1 N HCl or NaOH in Cu (II) solution. Then, an isotherm study for Cu (II) was investigated. First, 1.0 g samples of adsorbent were mixed with 100 mL samples of solutions of different initial concentration (25500 mg L1) prepared from stock solutions of Cu (II) and shaken for their equilibrium contact times at different temperatures (293, 303, and 333 K) and 150 rpm. The equilibrium concentration of Cu (II) was determined by AAS. The experiments were repeated twice for each point. 3. Results and discussion 3.1. C, H analysis Elemental analysis was carried out with an EA 1108 Fisons instruments. A sample of adsorbents was put in an oven at 1273 K under oxygen in order to obtain a quick and complete combustion. H2O and CO2 were released and conducted in a copper oven at 923 K, then passed through a 2 m column with helium vector gas, and analyzed by a catharameter detector. The results of analysis are shown in Table 1.

2. Materials and methods 2.1. Adsorbents Shells of lentil (LS), wheat (WS) and rice (RS) used as adsorbent were supplied from the South-eastern Anatolia of Turkey. The chemical and physical characteristics of the adsorbents are presented in Table 1. For the experimental studies, only the adsorbents were washed several times with double distilled water to remove surface impurities. The process was followed by air drying at 383 K for 24 h. The adsorbents were sieved through 0.6 mm sieve and used as such without any pretreatment.
Table 1 Physical and chemical properties of adsorbents used in the experiments Chemical characteristic Percent LS Moisture content Water soluble components (inorganic matter) Insoluble components (organic matter) Ash content Total loss of ignition C content H content pH Physical characteristics Surface area (BET) (m2 g1) Bulk density (g cm3) Particle size (mm) 6.58 18.12 78.85 9.18 89.28 33.53 4.67 5.03 0.19 0.49 0.60 WS 6.40 22.33 75.14 2.58 88.45 44.59 6.56 6.05 0.67 0.36 0.60 RS 5.46 6.46 89.41 22.80 72.55 51.37 6.93 5.98 0.83 0.38 0.60

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H. Aydn et al. / Journal of Environmental Management 87 (2008) 3745 39

3.2. Other chemicalphysical characteristics Characteristics of the adsorbents such as bulk density, moisture content, ash content, solubility in water (inorganic and organic matter), total loss of ignition were determined. The ash content was determined by burning it in a furnace at 1173 K (Ricordel et al., 2001). The results are summarized in Table 1. 3.3. pH of adsorbent surface The sample of 1.0 g of dry adsorbent powder was added to 30 mL of water and the suspension was stirred overnight to reach equilibrium. Then, the pH of slurry was measured. The results are shown in Table 1. 3.4. Functional groups dosage Knowing the chemical structure of the used adsorbent is important to understand the adsorption processes. The adsorption capacity of adsorbent is strongly inuenced by the chemical structure of their surface (Ricordel et al., 2001). The oxygenated surface groups were determined according to the method by Bohem. First, 1.0 g of adsorbent was placed in 50 mL of each of the following 0.05 N solutions: sodium hydroxide, sodium carbonate, sodium bicarbonate, and hydrochloric acid. Vials were sealed and shaken for 24 h and then 5 mL of each ltrate was pipetted; the excess of the base or acid was titrated with HCl or NaOH, as required. The numbers of acidic sites of various types were calculated on the assumption that NaOH neutralizes carboxylic, phenolic, and lactonic; Na2CO3 neutralizes carboxylic and lactonic groups; and NaHCO3 neutralizes only carboxylic groups (Adib et al., 1999). The number of surface basic sites was calculated from the amount of hydrochloric acid which reacted with the adsorbents; the results of Bohem titration (numbers of acidic and basic groups) are summarized in Table 2. 3.5. Contact time The contact time experiments were carried out at 293 K temperature. The dependence of adsorption of Cu (II) with time is presented in Fig. 1. The adsorption increased with increasing contact time, and the equilibrium was attained after shaking for 3 h. Therefore, in each experiment, the

shaking time was set to 3 h. The reason for LS that not constant after 3 h is due to the experimental mistake. 3.6. Effect of pH The pH of the aqueous solution is an important controlling parameter in the adsorption process (TatyCostodes et al., 2003). Therefore, the effect of hydrogen ion concentration was examined from solutions at pH ranging from 2 to 9. Fig. 2 summarizes the uptake of Cu (II) shells of LS, WS and RS used as adsorbent at various pH values. At lower pH values, the H3O+ ions compete with the metal ions for the exchange sites in the adsorbent. There is an increase in metal ions uptake as the pH value increases from 2 to 6. The peak percentage adsorption of Cu (II) was attained at pH 6.0. After that, the sharp decrease adsorption of Cu (II) is due to the Cu(II) begins to precipitate as Cu(OH)2. One of the reasons for the metal ions adsorption behavior of the bio-adsorbent (LS, WS, and RS) is that the adsorbents surface contains a large number of active
8 LS 6 qt (mgg-1) WS RS 4

0 0 100 200 t (min)

Fig. 1. Effect of contact time on the adsorption of Cu (II).

300

400

80 WS 60 Ceq (mgL-1) LS RS 40

Table 2 Results of Boehm titration (mmol g1) Sample LS WS RS Carboxylic 0.434 0.146 0.166 Lactonic 0.051 0.020 0.076 Phenolic 0.586 0.842 1.212 Basic 0.00 0.00 0.00 Acidic 1.071 1.008 1.454

20

0 0 2 4 6 pH 8 10 12

Fig. 2. Effect of pH on the adsorption of Cu (II).

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40 H. Aydn et al. / Journal of Environmental Management 87 (2008) 3745

sites. The metal uptake depends on these active sites as well as on the nature of the metal ions in solution. The afnities of the surface sites of LS, WS and RS depend on the nature of ions. This may be further explained in relation to a competition effect between the H3O+ and Cu (II) ions. At low pH values, the concentration of metal ions, hence the former ions occupy the binding sites on the LS, WH and RS, leaving metal ions free in solution. When the pH increases, the concentration H3O+ ions decreases, and the sites on the adsorbent surface mainly turn into dissociated forms (Fig. 3a) and can exchange H3O+ ions with metallic ions in solution (Fig. 3b) (Taty-Costodes et al., 2003). In other respects, the property of the adsorbents to uptake metal ions can also be explained by the carbonyl groups (CO) or the hydroxyl groups (OH) of polyphenols. The oxygen of each carbonyl and hydroxyl group is considered a strong Lewis base because of the presence of its vacant double electrons. Thanks to this doublets, the oxygen base makes a complex of coordination with the

chemical entities low in electrons (metal ions, for example) (Fig. 4) (Prasad and Freitas, 2000)

3.7. Effect of adsorbent dosage Adsorbent dosage is an important parameter because it determines the capacity of an adsorbent for a given initial concentration of the adsorbate. The effect of adsorbent dosage (adsorbent prepared in different batches) was studied on Cu(II) removal, keeping all other experimental conditions constant (Table 3). The results show that, as the adsorbent concentration increases, percentage adsorption generally increases, but the amount adsorbed per unit mass of the adsorbent decreases considerably. The decrease in unit adsorption with increase in the dose of adsorbent is basically due to adsorption sites remaining unsaturated during the adsorption reaction (Raji and Anirudhan, 1997).

a
R1 HO O OH OH R1 OH R1 OH 2H2O(1) -2H2O(2) HO O OH OH R1 O O
+ + 2H3O (aq)

b
R1 HO O OH OH R1

OH R1 OH + M2+(aq) 2H2O (1) -2H2O (2) OH R1 HO O OH

O M2+ O
+ + 2H3O (aq)

Fig. 3. Mechanism of biosorption: (a) represents the rst stage of ion-exchange (deprotonation), while (b) shows attachment (adsorption) of the metal cations onto the deprotonated active sites on the sawdust surface (Taty-Costodes et al., 2003). Symbol M is a metal ion of charge 2+.

H 2O O H O M O O H H O

O M O O H

H 2O

Fig. 4. Formation of metal complexes with the functional groups on the adsorbent surface.

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H. Aydn et al. / Journal of Environmental Management 87 (2008) 3745 Table 3 Effect of adsorbent dosage on the adsorption of Cu (II) with the different initial concentrations (T 293 K, contact time 3 h) Adsorbent Adsorbent dosage (g) Co 100 mg L1 qeq (mg g1) 0.5 1.0 2.0 4.0 8.0 0.5 1.0 2.0 4.0 8.0 0.5 1.0 2.0 4.0 8.0 9.56 6.72 3.92 2.14 1.09 6.45 2.71 1.19 0.61 0.39 0.46 0.74 1.09 0.89 0.44 %A 47.79 67.20 78.48 85.76 87.36 21.23 22.05 23.74 24.35 31.10 2.32 7.39 21.81 35.40 35.23 Co 200 mg L1 qeq (mg g1) 9.40 8.44 5.18 2.68 1.37 6.50 5.64 4.97 2.29 1.17 0.72 0.28 0.93 0.91 0.72 %A 23.50 42.20 51.78 53.60 54.62 16.25 28.20 49.65 45.8 46.70 1.80 1.40 9.30 18.25 28.65 Co 500 mg L1 qeq (mg g1) 15.62 14.54 14.56 10.38 5.57 11.00 9.14 4.74 4.29 3.21 1.78 3.60 2.33 1.45 0.93 %A 15.62 29.08 58.22 83.07 89.13 11.00 18.28 18.94 34.28 51.28 1.78 7.20 9.30 11.62 14.92 41

LS

WS

RS

3.8. Effect of initial Cu(II) concentration The equilibrium sorption capacity of the biomass for Cu(II) ion increased with a rise in initial ion concentration, as also shown in Table 3. Ion removal is higly concentration dependent. This increase in loading capacity of the bioadsorbent with relation to metal ions concentration is probably due to a high driving force for mass transfer. In fact, the more concentrated the solution is, the better the adsorption. At 293 K, when the initial metal ions concentration was increased from 100 to 500 mg L1, the loading capacity of dried adsorbent increased from 6.72 to 14.54 mg of Cu(II) per gram of LS, 2.71 to 9.14 mg of Cu(II) per gram of WS and 0.74 to 3.60 mg of Cu(II) per gram of RS (Table 3). 3.9. Adsorption kinetics It is well known that the rate of the sorption process is modied by several parameters such as the structural properties of the adsorbent (i.e. porosity, specic area, particle size, etc.), the properties of the metallic ions (ionic radius, number of coordination, and speciation), metallic ions concentration, chelates formation between metallic ions, and the adsorbent, etc. This is why, intraparticular diffusion was also studied in the present work. Temperature and stirring speed were constant for all experiments. In order to determine the adsorption kinetics of Cu(II) ions, the rst-order and second-order kinetics models were checked. The rst-order rate expression of Lagergren based on solid capacity is generally expressed as follows (TatyCostodes et al., 2003). logqeq qt log qeq kpf t=2:303,
1

0.8 LS 0.4 log (qeq-qt) WS RS 0

-0.4

-0.8 0 30 60 t (min)
Fig. 5. Pseudo rst-order sorption kinetics of Cu (II) on LS, WS and RS.

90

120

150

plot of log(qeqqt) versus time (Fig. 5) suggest the applicability of the Lagergren equation for the present system (Bulut and Tez, 2003). The values of kpf were determined from the slope of the plots and are given in Table 4. Recently, Ho and Mc Kay (Mc Kay and Ho, 1999) have reported that most of the sorption systems followed a second-order kinetic model which can be expressed as t=qt 1=kps q2 eq t=qeq , (2)

(1)

where qeq is the amount adsorbed (mg g ) at equilibrium, qt the amount adsorbed (mg g1) at time t and kpf the adsorption rate constant (min1). The straight line of the

where kps is the adsorption rate constant (g mg1 min1). The plot of t/qt versus time (Fig. 6) is similar as shown in (Weber and Morris). The values of kps were determined by the slope of the plot and are given in Table 4. The rate constant for intraparticle diffusion (kid) is given as (Dog an et al., 2004): qt kid t1=2 , (3)

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42 H. Aydn et al. / Journal of Environmental Management 87 (2008) 3745 Table 4 Adsorption kinetic parameters of Cu (II) on LS, WS and RS (T 293 K, adsorbent 20 g L1, Co 100 mg L1) Adsorbent First-order kinetic model kpf (min1) LS WS RS 0.016 0.018 0.011 qeq (mg g1) 4.449 1.707 1.747 R2 0.993 0.834 0.917 Second-order kinetic model kps (g mg1 min1) 4.33 103 18.44 103 3.189 103 qeq (mg g1) 7.962 3.925 3.88 R2 0.997 0.999 0.933 Intraparticle diffusion kid (mg g1 min1/2) 0.343 0.149 0.187 R2 0.995 0.937 0.938

120 LS WS t / qt (minmg-1g) 80 qt (mgg-1) RS

8 LS 6 WS RS 4

40

0 0 100 200 t (min) 300 400 0 5 10 t1/2 (min1/2)

Fig. 7. Intraparticle diffusion plots of Cu (II) on LS, WS and RS.

15

20

Fig. 6. Pseudo second-order sorption kinetics of Cu (II) on LS, WS and RS.

where qt is the amount adsorbed (mg g1) at time t (min). The plots of qt versus t1/2 for different adsorbents are shown in Fig. 7. All plots have a similar general trend and initial curved part, followed by a linear one and then a plateau. The initial curved part may be attributed to the bulk diffusion; the linear one to the intraparticle diffusion and the plateau to the equilibrium. This indicates that the transport of Cu(II) ions from solution through the particle solution interface into the pores of the particles as well as the adsorption on the available surface of adsorbents are both responsible for the uptake of Cu(II) ions (Yu et al., 2000). kid (mg g1 min1/2) is characteristic for the rate of adsorption in the region, where intraparticle diffusion is rate-controlling. The extrapolation of the linear curve parts of the plots back to the axis provides the intercepts, which are proportional to the extent of the boundary layer thickness, i.e. the larger the intercept, the greater the boundary layer effect (Khraisheh et al., 2004). The deviation of the curves from the origin also indicates that intraparticle transport is not the only rate limiting step (Yu et al., 2000). The values of rate constants (kid) of LS, WS and RS were 0.343, 0.149, and 0.187 mg g1 min1/2, respectively (Table 4). 3.10. Adsorption model The equilibrium adsorption of Cu (II) was studied as a function of concerntration (the initial Cu(II) concentration

is in the range of 25500 mg L1). The amount of Cu (II) adsorbed (qeq) has been plotted against the equilibrium conceration (Ceq) for the adsorbents and is shown in Fig. 8 for Cu (II). Several isotherm models are available. In this study the Langmuir and Freundlich adsorption isotherms were employed (Magdy and Daifullah, 1998). The Langmuir isotherm can be represented by following equation: qeq Qm bC eq =1 bC eq ,
1

(4)

where qeq (mg g ) is the amount of Cu (II) adsorbed per unit mass of adsorbent particles at equilibrium and Ceq (mg L1) is the equilibrium liquid phase concentration of Cu (II), b is the equilibrium constant (L mg1) and Qm is the amount of adsorbate required to form a monolayer (mg g1). The linearized equation of Langmuir is represented as follows: C eq =qeq 1=bQm C eq =Qm . (5)

Hence, a plot Ceq/qeq versus Ceq should be a straight line with a slope 1/Qm and intercept as 1/Qmb. Their values are summarized in Table 5. The Freundlich model was also used to model the observed phenomena as given by the following equation:
=n qeq K f C 1 eq ,

(6)

where qeq is the amount of Cu (II) adsorbed per unit mass of the adsorbent and n, Kf are constants. Eq. (6) may be

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H. Aydn et al. / Journal of Environmental Management 87 (2008) 3745 43

12

4 LS

RS

qeq (m gg-1)

qeq (m gg-1) 293 K 313 K 333 K

293 K 0 400 0 200

313 K 400

333 K 600

0 0 100 200 300 Ceq (mgL-1) 12 WS

Ceq (mgL-1)

qeq (m gg-1)

293 K 0

313 K

333 K 400

200 Ceq (mgL-1)

Fig. 8. Isotherms of Cu (II) adsorption from solution at different temperatures.

Table 5 Freundlich and Langmuir isotherm constants for adsorption of Cu (II) onto LS, WS and RS Adsorbent T (K) Freundlich costants K n R2 Langmuir constants Qm (mg g1) b (L mg1) 293 313 333 293 313 333 293 313 333 0.648 1.202 1.138 0.019 0.034 0.022 0.108 0.148 0.130 2.769 2.578 2.867 10.909 9.594 13.428 2.787 2.816 3.188 0.993 0.964 0.901 0.912 0.955 0.945 0.996 0.929 0.938 8.977 9.510 9.588 7.391 16.077 17.422 1.854 2.314 2.954 0.019 0.022 0.041 0.002 0.004 0.005 0.011 0.016 0.018 (L mol1) 1207 1398 2605 127 254 318 699 1017 1143 0.980 0.981 0.999 0.925 0.791 0.883 0.991 0.982 0.987 R2

LS

WS

RS

linearized via a logarithmic plot as follows: log qeq log K f 1=n log C eq . (7)

The parameters Kf and n were calculated and the results are presented in Table 5. Adsorption isotherms of Cu (II) on LS, WS and RS are shown in Fig. 8. The Langmuir isotherms for RS and LS

are obeyed better than the Freundlich isotherms at 313 and 333 K, which is evident from the value of regression coefcients (R2). The adsorption isotherm of WS is obeyed by the Freundlich isotherm at 313 and 333. The adsorption of Cu (II) increased with increase in temperature (Table 5). Langmuir model is an indication of surface homogeneity of the adsorbent.

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44 H. Aydn et al. / Journal of Environmental Management 87 (2008) 3745 Table 6 Previously reported adsorption capacities of various low-cost adsorbents for Cu (II) Low-cost adsorbents Adsorption capacity (mg g1) 27.55 55.56 1.54 1.79 12.07 1.62 8.64 9.59 17.42 2.95 Reference

Diatomite Modied diatomite Fly ash Sawdust Peat Low-rank Turkish coals Tea-industry waste LS (Shells of lentil) WS (Shells of wheat) RS (Shells of rice)

Gaballah et al., 1997 Gaballah et al., 1997 Panday et al., 1985 Yu et al., 2000 Babel and Kurniawan, 2003 Karabulut et al., 2000 C - ay et al., 2004 In this study In this study In this study

Thus, a plot of ln b versus 1/T should be a straight line. DH0 and DS0 values were obtained from the slope and intercept of this plot, respectively. DG0, DH0 and DS0 were obtained from the Eqs. (8) and (9) and are given in Table 7. Negative values of DG0 indicate the feasibility of the process and spontaneous nature of the adsorption with a high preference of Cu (II) for all adsorbents. Positive value of DH0 indicates the endothermic nature of the process, while positive value of DS0 reects the afnity of the adsorbents for the Cu (II) ions and suggests some structual changes in adsorbate and adsorbent (Panday et al., 1985). 4. Conclusion The following conclusions can be drawn based on investigation of Cu (II) removal by LS, WS and RS. First, LS, WS and RS appears to be a promising adsorbent for removal of Cu (II) from aqueous solution. At these adsorption levels, a process using LS, WS, and RS for the removal and recovery of a heavy metal is potentially more economical than current process technology. Secondly, adsorption of Cu (II) is dependent on its initial concentrations, the amount of adsorbent, time of contact, temperature and pH of the metal solution, maximum removal of Cu (II) on LS, WS, and RS are at pH about 6.0. The removal of Cu (II) increased with increase in temperature. Thirdly, isothermal data of Cu (II) adsorption on adsorbents can be modeled by both Freundlich and Langmuir isotherm. The capacity of adsorbents for adsorption of Cu (II) can be calculated by using these models. The maximum adsorption capacities for Cu (II) on LS, WS, and RS adsorbents at 293, 313, and 333 K temperature were found to be 8.977, 9.510, and 9.588; 7.391, 16.077, and 17.422; 1.854, 2.314, and 2.954 mg g1, respectively. The maximum adsorption capacities for other metals may be very different. As it can be seen from these values, removal efciency of the adsorbents increases and follows the order WS4LS4RS. The results show that adsorbents which have a very low economical value may be used effectively for removal of Cu (II) ions from aqueous systems for environmental cleaning purpose. Acknowledgments We extend our thanks to the Dicle University, Research and Project Coordination for their support to our Project PAK-FF-02-105). (No: DU References
Adib, F., Bagreev, A., Bandosz, TJ., 1999. Effect of pH and surface chemistry on the mechanism of H2S removal by activated carbons. Journal of Colloid and Interface Science 216, 360369.

Table 7 Values of thermodynamic parameters for the adsorption of Cu (II) on LS, WS and RS Adsorbent T (K) DG0 (kJ mol1) 17.286 18.848 21.775 11.800 14.401 15.953 15.956 18.021 19.493 DH0 (kJ mol1) DS0 (Jmol1 K1)

LS

WS

RS

293 313 333 293 313 333 293 313 333

15.373

111

18.791

105

10.054

89

As seen in Table 5 and Fig. 8, the maximum adsorption capacities for Cu (II) on LS, WS and RS adsorbents at 293, 313 and 333 K temperature were found to be 8.977, 9.510 and 9.588; 7.391, 16.077 and 17.422; 1.854, 2.314 and 2.954 mg g1, respectively. By comparison of the results obtained from this study to the previously reported work (Table 6) on adsorption capacities of various low-cost adsorbent in aqueous solution for Cu (II) ions, it can be stated that our ndings are well. The free energy of adsorption (DG0) can be related with the equilibrium constant K (L mol1), corresponding to the reciprocal of the Langmuir constant, b, by the following equation (Silva et al., 2004): DG 0 RT ln b, (8)

where R is the gas universal constant (8.314 J mol1 K1) and T is the absolute temperature. Also, enthalpy (DH0) and entropy (DS0) changes can be estimated by the following equations, respectively. ln b DS0 =R H 0 =RT (9)

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