Environ Sci Pollut Res (2013) 20:22102219 DOI 10.

1007/s11356-012-1066-y

RESEARCH ARTICLE

Comparative and competitive adsorption of Cr(VI), As(III), and Ni(II) onto coconut charcoal
Yunhai Wu & Yajun Wen & Jianxin Zhou & Julin Cao & Yanping Jin & Yunying Wu

Received: 30 May 2012 / Accepted: 2 July 2012 / Published online: 13 July 2012 # Springer-Verlag 2012

Abstract This study evaluates the behavior of coconut charcoal (AC) to adsorb Cr(VI), As(III), and Ni(II) in mono- and multicomponent (binary and ternary) systems. Batch experiments were carried out for mono- and multicomponent systems with varying metal ion concentrations to investigate the competitive adsorption characteristics. The adsorption kinetics followed the mechanism of the pseudosecond-order equation in both single and binary systems, indicating chemical sorption as the rate-limiting step of adsorption mechanism. Equilibrium studies showed that the adsorption of Cr(VI), As(III), and Ni(II) followed the Langmuir model and maximum adsorption capacities were found to be 5.257, 0.042, and 1.748 mg/g, respectively. In multicomponent system, As(III) and Ni(II) adsorption competed intensely, while Cr(VI) adsorption was much less affected by competition than As(III) and Ni(II). With the presence of Cr(VI), the adsorption capacities of As(III) and Ni(II) on AC were higher than those in single system and the metal sorption followed the order of Ni(II)>As(III)>Cr (VI). The results from the sequential adsorptiondesorption cycles showed that AC adsorbent held good desorption and reusability.

Keywords Adsorption . Coconut charcoal . Equilibrium . Kinetics . Metal . Multicomponent . Single system Nomenclature b Langmuir adsorption constant (liters per milligram) C0 Initial concentration of solute in solution (milligrams per liter) Ce Equilibrium concentration of solute in bulk solution (milligrams per liter) E Mean free energy of adsorption (kilojoules per mole) k1 Equilibrium rate constant of pseudo-first-order sorption (per minute) k2 Equilibrium rate constant of pseudo-second-order sorption (grams per(milligrams per minute)) K Constant related to free energy (in square moles per square kilojoules) Kf Freundlich constant indicative of the relative sorption capacity of the sorbent (milligrams per gram) n Freundlich constant indicative of the intensity of sorption qe Amount of solute adsorbed per unit weight of adsorbent at equilibrium (milligrams per gram) qt Amount of solute adsorbed per unit weight of adsorbent at any time (milligrams per gram) Qm Monolayer maximum adsorption capacity of the sorbent (milligrams per gram) r2 Correlation coefficient R Gas constant (8.314 J/(moles per Kelvin)) RL Langmuir separation factor t Time (minute) T Absolute temperature (Kelvin) Greek letters Elovich constant indicative of the initial sorption rate (milligrams per (grams per minute)) Desorption constant of Elovich (grams per milligram) Polanyi potential

Responsible editor: Vinod Kumar Gupta Y. Wu Key Laboratory of Integrated Regulation and Resources Development of Shallow Lakes, Ministry of Education, Hohai University, Nanjing 210098, China Y. Wen : J. Zhou : J. Cao : Y. Jin College of Environment, Hohai University, Nanjing 210098, China Y. Wu (*) Department of Chemistry, Hanshan Normal University, Chaozhou, China e-mail: wenkevin@hhu.edu.cn

Environ Sci Pollut Res (2013) 20:22102219

2211

Introduction Heavy metals are highly toxic at low concentrations and can accumulate in living organisms, causing both short-term- and long-term adverse effects (Gen-Fuhrman et al. 2008). Toxic metals such as chromium, arsenic, and nickel among others are commonly detected in industrial effluents. Soluble hexavalent chromium (Cr(VI)) is extremely toxic and exhibits carcinogenic effects on biological systems due to strong oxidizing nature (Klimaviciute et al. 2010). Strong exposure of Cr(VI) causes cancer in digestive tract and lungs and may cause epigastric pain, nausea, vomiting, severe diarrhea, and hemorrhage (Jain et al. 2009). The permissible limit of Cr(VI) in potable water is 0.05 mg/L (Gupta and Babu 2009; Gupta et al. 2011a). Groundwater contamination by arsenic (As) has been recognized as a global problem since it is present to some extent in every continent (Salameh et al. 2010). Arsenic concentrations in drinking water >100 g/L can cause vascular disorders (Tuzen et al. 2009). In order to protect public health, the World Health Organization has decided to lower the maximum contaminant level of arsenic in drinking water to <10 g/L (Aryal et al. 2010). Nickel (Ni) ion intake over the permissible levels results in different types of disease such as skin dermatitis, pulmonary fibrosis, and renal edema (Akhtar et al. 2004). The US Environmental Protection Agency requires nickel in drinking water not to exceed 0.5 mg/L (Gupta et al. 2010a). These stringent standards will inevitably require many utilities to upgrade their present systems or consider new treatment options (Banerjee et al. 2008). In comparison with such conventional methods as precipitation, chemical oxidation or reduction, and membrane separation, adsorption is regarded as one of the most effective and attractive processes with several advantages associated with no chemical sludge and high removal efficiency to remove metal ions (Li et al. 2011; Ahmaruzzaman and Gupta 2011). Activated carbons, with their high surface area, microporous structure, and chemical nature of their surface, are potential adsorbents for the removal of different heavy metals from industrial wastewaters (Wang et al. 2011). Due to its heavy metal removal capabilities, recently, coconut charcoal (AC) has been developed into one of the promising options. The exchange/sorption properties of coconut shell are due to the presence of some functional groups, such as carboxylic, hydroxyl, and lactone, which have a high affinity for metal ions (Babel and Kurniawan 2004). Most of the work reported in literature involves singlecomponent adsorption of heavy metal ions. Industrial effluents, however, contain several metals necessitating simultaneous removal of two or more metals. Therefore, the study on the simultaneous adsorption of heavy metals from binary and ternary aqueous systems is very important. In this paper, we report a study on adsorption of Cr(VI), As(III), and Ni (II) in single, binary, and ternary systems using AC. The

main objective of the study was to determine the adsorption capacity of AC in single and multicomponent system and to establish the applicable isotherm model and to elucidate the sorption mechanism.

Materials and methods Materials The AC that bought from the company were washed with deionized water and boiled for 20 min, then dried at 393 K in oven for 24 h. The main physical characteristics of AC, BET surface area (8001,000 m2/g), pore volume (0.9 1.0 cm3/g), intensity (90 %), pHpzc (7), filling density (0.380.45 g/cm3), and particle size (0.050.08 cm) were given by the company. All the other reagents used in this work were of analytical grade. K2Cr2O7, NaAsO2, and NiSO46H2O were used as sources for Cr6+, As3+, and Ni2 + ions, respectively. Atomic absorption spectrometry standard solutions of 1,000 mg/L Cr(VI), As(III), and Ni(II) were used for adsorption experiments. Working standards were prepared from the dilution of stock solutions every day. All aqueous solutions were prepared by deionized water with conductivity <1 mho/cm at room temperature (Heidari et al. 2009). The pH measurements were made using an Orion pH meter. The pH of the solution was adjusted to required values using 0.1 M HCl or NaOH. Adsorption isotherm and kinetics Single, binary, and ternary adsorption of Cr(VI), As(III), and Ni(II) ions onto AC were performed in a batch mode at 303 K. Basically, 1.0 g of the adsorbent was added to 100 mL of solute concentration, at the desired pH, in

Fig. 1 Effect of pH on the adsorption of metal ions onto AC in the single-ion situation (initial concentration of Cr(VI), As(III), and Ni(II) 25, 0.5, and 5 mg/L; adsorbent dosage1.0 g; contact time360 min)

2212 Table 1 Parameters for Cr(VI), Ni(II), and As(III) adsorption by AC according to different equilibrium models Metal ions Isotherm parameters Temperature (C) 293 Cr(VI) Langmuir Qm (mg/g) b (L/mg) r2 Kf (mg/g) 1/n r2 Qm (mg/g) r2 Qm (mg/g) b (L/mg) r2 Kf (mg/g) 1/n r2 Qm (mg/g) r2 Qm (mg/g) b (L/mg) r2 Kf (mg/g) 1/n r2 Qm (mg/g) r2 3.889 0.258 0.994 1.328 0.318 0.987 3.105 0.913 0.034 0.069 0.999 0.035 0.051 0.990 0.034 0.999 1.155 0.242 0.998 0.244 0.626 0.999 0.619 0.968 298 3.973 0.291 0.991 1.442 0.305 0.972 3.218 0.928 0.038 0.057 0.995 0.038 0.066 0.984 0.038 0.997 1.218 0.264 0.997 0.273 0.620 0.991 0.670 0.987 303 5.007 0.227 0.993 1.428 0.380 0.961 3.752 0.940 0.042 0.035 0.996 0.044 0.107 0.969 0.042 0.994 1.227 0.215 0.997 0.297 0.606 0.997 0.691 0.968 308 5.257 0.258 0.994 1.556 0.384 0.993 3.911 0.891 0.032 0.096 0.993 0.032 0.036 0.981 0.032 0.994 1.748 0.192 0.999 0.294 0.709 0.997 0.776 0.971

Environ Sci Pollut Res (2013) 20:22102219

Freundlich

D-R As(III) Langmuir

Freundlich

filtered using Whatman no. 42 filter paper and the concentration of the residual aqueous phase was determined using an atomic adsorption spectrophotometer (Shimadzu AA 6300, Japan). The effect of pH on the sorption capacity of AC was evaluated by adjusting the pH in the range of 110 for Cr(IV) and As(III), 17 for Ni(II) with the concentration of 25, 0.5, and 5 mg/L, respectively. For isotherm experiments, the mass of adsorbent was varied from 0.3 to 1.0 g for each metal ion in single, binary, and ternary system. The experiments were carried out at four different temperatures, i.e., 293, 298, 303, and 308 K. Adsorption kinetic studies were carried out at pH 5.0, 25 mg/L Cr(VI), 0.5 mg/L As (III), and 5 mg/L Ni(II), respectively, and the samples were withdrawn at predetermined time intervals. The adsorption procedures were the same as those described earlier. The adsorption kinetics and isotherm experiments were conducted in duplicate and the average of two values was used in the calculations. The maximum difference between the two values was less than 3 % of the value. Desorption experiments The desorption studies of Cr(VI), As(III), and Ni(II) from AC was carried out by using 0.5 M NaOH, and 0.3 M HNO3. After determination of metal contents of the final solutions, the adsorbent was washed with excess of the distilled water in order to reuse for next experiment. Consecutive sorptiondesorption cycles were repeated six times to establish the reusability of the adsorbent.

D-R Ni(II) Langmuir

Freundlich

D-R

Results and discussion 250 mL Erlenmeyer flasks and was agitated at 130 rpm in a rotary shaker until the equilibrium time was reached. The contact time and conditions were selected on the basis of preliminary experiments, which demonstrated the equilibrium was established in 360 min. All equilibrium tests were conducted for 360 min. After this period, solutions were
Table 2 Kinetic parameters for Cr(VI), As(III), and Ni(II) adsorption by AC

Effect of pH for single-ion situation pH is one of the most important parameters controlling the metal ion adsorption process (Gupta et al. 2011b; Saleh and Gupta 2012). The relation between the initial pH of the

Metal ions

C0 (mg/L)

Pseudo-first-order k1 qe.cal 0.915 2.132 3.090 0.043 0.039 0.097 0.349 1.322 2.324 r2 0.937 0.856 0.933 0.996 0.997 0.970 0.909 0.894 0.932

Pseudo-second-order k2 0.035 0.019 0.014 0.039 0.027 0.058 0.065 0.022 0.006 qe.cal 1.014 2.322 3.351 0.066 0.064 0.128 0.397 1.473 2.759 r2 0.998 0.993 0.991 0.995 0.996 0.991 0.992 0.995 0.992

Elovich 0.211 2.195 4.220 0.001 0.001 0.002 0.047 0.388 0.130 6.439 3.575 2.571 76.92 97.09 33.78 15.18 4.684 1.842 r2 0.978 0.990 0.951 0.985 0.989 0.997 0.993 0.990 0.999

Cr(VI)

As(III)

Ni(II)

10 25 50 0.5 1.0 5.0 5 25 50

0.024 0.025 0.025 0.004 0.003 0.008 0.018 0.021 0.014

Environ Sci Pollut Res (2013) 20:22102219

2213

solution and the percentage removal of metal ions is shown in Fig. 1. Figure 1 shows that adsorption efficiency of Cr(VI) and Ni(II) is considerably affected by the pH. The extent of Cr (VI) removal increases as the solution pH decreases, but Ni (II) adsorption increases with the increase of pH. The pH of the solution has a little effect on the adsorption of As(III) on AC. As the pH of the solution increase from 1.0 to 10.0, the removal of Cr(VI) decrease from 99 to 42 %. The pH dependence of Cr(VI) adsorption can be related to the type and ionic state of functional groups present on the adsorbent and chromium speciation in solution. At high pH, the competition of the OH with the bichromate anion for the effective adsorption sites could lead to a reduction in the percentage adsorption of Cr(VI) (Kumar et al. 2012). The higher adsorption at acidic pH range is mainly due to ionizable surface charge of AC. Perusal of literature on Cr(VI) shows the dominant species at low pH is HCrO4 which leads to electrostatic attraction between positively charged adsorbent surface and negatively charged chromium species (Jain et al. 2011). The maximum Ni(II) removal occurred at pH 0 7.0 (79.3 %). At pH <9, the predominant specie is Ni 2+. Therefore, the low Ni2+ adsorption at low pH is attributed partly to the competition between H+ and Ni2+ on the surface sites (Yang et al. 2009). With the increase of pH, more ligands with negative charges exposed and attracted more positively charged nickel ions for binding which lead to more adsorption of Ni(II) at higher pH (Subbaiah et al. 2009). It was evident that maximum As(III) removal (51.8 %) is achieved at pH 0 5.0. The pH of the solution determines the concentration distribution of the ionic forms of the As(III). At pH range between 1 and 9, As(III) is present as neutral H3AsO3 and as AsO2 species at higher than 9 (Saleh et al. 2011). At the range of pH 0 14, van der Waals force between the solute and the AC surface is expected. As the pH increase toward 5, the anionic species H2AsO3 increase; thus, more arsenic uptake onto AC due to more specific binding. The adsorption of As(III) dropped may be due to the influence of charged repulsion forces while pH >5. Adsorption isotherm The analysis of adsorption data is important to develop an equation which accurately represents the results and which could be used for design purposes (Gupta et al. 2007a). The most commonly applied isotherms, in solid/liquid system, are the theoretical equilibrium isotherm: Langmuir, Freundlich, and DubininRadushkevich (D-R). In this paper, attempts have been made to analyze adsorption by these three models.
Fig. 2 a Time profiles of Cr(VI) adsorption by AC in mixture of Cr-As or Cr-Ni at different concentrations (initial concentration of Cr(VI), 25 mg/L; pH 0 5; adsorbent dosage, 1.0 g). b Time profiles of As(III) adsorption by AC in mixture of As-Cr or As-Ni at different concentrations (initial concentration of As(III), 0.5 mg/L; pH 0 5; adsorbent dosage, 1.0 g). c Time profiles of Ni(II) adsorption by AC in mixture of Ni-Cr or Ni-As at different concentrations (initial concentration of Ni (II), 5 mg/L; pH 0 5; adsorbent dosage, 1.0 g)

2214

Environ Sci Pollut Res (2013) 20:22102219

Langmuir's model of adsorption depends on the assumption that intermolecular forces decrease rapidly with distance and consequently predicts the existence of monolayer coverage of the adsorbate at the outer surface of the adsorbent (Gupta and Ali 2004; Gupta and Rastogi 2008a). A linearized form of the Langmuir equation is (Srivastava et al. 1997; Gupta et al. 1998, 2005, 2006a, b, c, 2007b, c, d; Gupta and Rastogi 2008b; Gupta et al. 2012; Gupta and Nayak 2012) 1 1 1 qe bQm C e Qm 1

The constant K gives the mean free energy E of sorption per molecule of the sorbate when it is transferred to the surface of the solid from infinity in the solution and can be calculated using the relationship (Dubey and Gupta 2005) 1 E p 2K 5

The Freundlich isotherm is an empirical equation based on an exponential distribution of sorption sites and energies (Gupta et al. 2010a). In mathematical form, it is represented as
1=n qe Kf Ce

The D-R approach assumes that there is a surface area where the adsorption energy is homogeneous (Kundu and Gupta 2006). The D-R isotherm is expressed by qe Qm expK "2 3

" RT ln1

1 Ce

The adsorption parameters for each metal ion obtained from the fitting of different isotherm models with the experimental data are listed in Table 1. For the three studied systems, the Langmuir isotherm correlated better (r2 >0.99) than the others with the experimental data from adsorption equilibrium of metal ion by AC, suggesting a monolayer adsorption. The maximum adsorption capacities (Qm, in milligrams per gram) using Langmuir isotherm equation were as follows: Cr(VI) (5.257)>Ni(II) (1.748)>As(III) (0.042). The Langmuir isotherm model shows that the b value of Cr(VI) ion is higher than those of Ni(II) and As (III) ions, indicating that the adsorption energy of Cr(VI) ion is higher than those of Ni(II) and As(III) ions. The Langmuir isotherm fits the experimental data better in contrast to Freundlich which may be due to the homogeneous distribution of active sites on the AC surface, since the Langmuir equation assumes that the surface is homogeneous and all sites have equal adsorption energies. The essential feature of the Langmuir isotherm can be expressed by means of RL, a dimensionless constant

Table 3 Kinetic parameters for Cr(VI), As(III), and Ni(II) in binary system onto AC

Binary systems

Metal ions

Concentration (mg/L)

Pseudo-first-order k1 qe.cal 2.032 2.015 1.930 0.049 0.043 0.035 2.090 2.060 2.031 0.381 0.394 0.423 0.346 0.356 0.378 0.025 0.021 0.017 r2 0.986 0.989 0.995 0.999 0.982 0.989 0.993 0.997 0.998 0.990 0.989 0.991 0.996 0.992 0.999 0.998 0.998 0.993

Pseudo-second-order k2 0.018 0.018 0.020 0.256 0.236 0.110 0.018 0.021 0.024 0.091 0.090 0.098 0.079 0.096 0.067 0.095 0.153 0.341 qe.cal 2.247 2.217 2.109 0.059 0.053 0.048 2.292 2.238 2.186 0.420 0.433 0.461 0.387 0.393 0.426 0.037 0.030 0.022 r2 0.997 0.998 0.999 0.997 0.991 0.993 0.999 0.999 0.999 0.998 0.998 0.999 0.999 0.999 0.999 0.998 0.999 0.998

Cr(VI)-As(III)

Cr(VI)

As(III)

Cr(VI)-Ni(II)

Cr(VI)

CAs 0 0.5 CAs 0 1.0 CAs 0 5.0 CCr 0 10 CCr 0 25 CCr 0 50 CNi 0 5.0 CNi 0 25 CNi 0 50 CCr 0 10 CCr 0 25 CCr 0 50 CAs 0 0.5 CAs 0 1.0 CAs 0 5.0 CNi 0 5.0 CNi 0 25 CNi 0 50

0.011 0.010 0.010 0.006 0.005 0.003 0.010 0.011 0.012 0.010 0.010 0.011 0.009 0.010 0.008 0.002 0.003 0.004

Ni(II)

Ni(II)-As(III)

Ni(II)

As(III)

Environ Sci Pollut Res (2013) 20:22102219

2215

referred to as separation factor or equilibrium parameter (Gupta et al. 2001; Tunali et al. 2006). RL 1 1 bC0 6

(Namasivayam and Sureshkumar 2008). The linear form of this equation is written as qt 1 1 lnab lnt b b 9

As the RL values lie between 0 and 1, the adsorption process is favorable. The maximum values RL for Cr(VI), As(III), and Ni(III) were found to be 0.150, 0.054, and 0.511, respectively, suggesting adsorption was favorable. The single-component Freundlich constant 1/n indicates the adsorption intensity. The lower the value of 1/n, the more nonlinear is the adsorption isotherm, and as 1/n becomes less than 0.1, the adsorption approaches a socalled rectangular or irreversible isotherm. The higher the value of the exponent 1/n, the higher will be the affinity and the heterogeneity of the adsorbent sites (Srivastava et al. 2008). It is found from Table 1 that the AC shows the greatest heterogeneity for Ni(II) followed by that for Cr(VI) and As(III) ions. Since 1/n <1, both metal ions are favorably adsorbed by AC at studied conditions. Kinetic studies for single-ion situation In order to evaluate the kinetics mechanism of Cr(VI), As(III), and Ni(II) that controls the adsorption process using AC as an adsorbent, three kinds of kinetic models: pseudo-first-order, pseudo-second-order, and Elovich kinetic models were considered to interpret the experimental data. A good correlation of the kinetic data explains the adsorption mechanism of the metal ions on the solid phase. The pseudo-first-order model is the first equation for the adsorption of liquid/solid system based on solid capacity. The pseudo-second-order model predicts the behavior over the whole time adsorption and is in agreement with adsorption mechanism being the rate-controlling step. The mathematical representations of pseudo-first- and second-order kinetic models are given in (Gupta and Rastogi 2009; Gupta et al. 2010b) logqe qt log qe k1 t 2:303 7

t 1 t 2 qt k 2 qe qe

The Elovich equation is commonly used to determine the kinetics of chemisorption of gasses onto heterogeneous solids, and in recent years, this equation has also been used to describe the sorption of pollutants from aqueous solutions

Fig. 3 Time profiles of metal sorption by AC in mixture of Cr(VI), As (III), and Ni(II) at different concentrations: a Cr(VI); b As(III); and c Ni(II) (pH 0 5; adsorbent dosage, 1.0 g)

2216

Environ Sci Pollut Res (2013) 20:22102219

The kinetic parameters for adsorption of Cr(VI), As(III), and Ni(II) ions by AC are given in Table 2. Based on the obtained correlation coefficients (r2 >0.99), the pseudosecond-order equation was the model that furthered the best fit for the experimental kinetic data for all metal ions. The qe,cal values calculated from the pseudo-secondorder kinetic model exhibit excellent agreement with the experimental qe values. Thus, the sorption process is pseudo-second-order, suggesting chemical sorption as the rate-limiting step of the adsorption mechanism (Wu et al. 2001; Yurdako et al. 2005; Zhou et al. 2009; Monier et al. 2010). The competitive adsorption of ions from binary system In general, three possible types of behavior are exhibited in multicomponent adsorbatesadsorbents: synergism (the effect of the mixture is greater than that the individual adsorbates in the mixture), antagonism (the effect of the mixture is less than that of each of the adsorbates in the mixture), and non-interaction (the mixture has no effect on the adsorption of each of the adsorbates in the mixture) (Mahamadi and Nharingo 2010). The competitive adsorption for Cr(VI)/As(III), Cr(VI)/Ni(II), and Ni(II)/As(III) binary solutes were obtained by fixing the initial concentration of interferential metal ions. Effect of the presence of As(III) or Ni(II) on Cr(VI) binding The effect of the presence of As(III) or Ni(II) on the removal of Cr(VI) is quantitatively demonstrated in Fig. 2a, which show that there is no pronounced inhibitory effect on the adsorption of Cr(VI) in the presence of an increasing concentration As(III) or Ni(II). As(III) exerted a greater inhibitory effect on Cr(VI) removal than Ni(II). For example, at C0,Cr 0 25 mg/L and when 0.5 or 5.0 mg/L As(III) was added into the system, the adsorption capacity toward Cr(VI) was decreased to 2.14 and 1.95 mg/g, respectively. When 5.0 and 50 mg/L Ni(II) were added, the adsorption capacity of Cr(VI) decreased to 2.18 and 2.10 mg/g, respectively. The maximum uptake of Cr(VI) in single-metal system was 2.25 mg/g.

Effect of the presence of Cr(VI) or Ni(II) on As(III) binding The effect of the presence of Cr(VI) or Ni(II) on As(III) adsorption is shown in Fig. 2b; Cr(VI) exerted a greater impact on As(III) than Ni(III) did. The uptake of As(III) was higher than that in the single system and it decreased with increasing concentration of Cr(VI). Cr(VI) exerted a significant synergism effect on As(III) removal. The maximum capacity of As(III) in single system was 0.028 mg/g, while the value increased to 0.043 mg/g in the presence of 25 mg/ L of Cr(VI). The uptake of As(III) decreased with increasing concentration of Ni(II). Ni(II) exerted a antagonism effect on As(III) removal. The most likely reason for the antagonistic effect is the competition for adsorption sites on the adsorbent surfaces and/or the screening effect by the competing metal ions (Sheng et al. 2007). Effect of the presence of Cr(VI) or As(III) on Ni(II) binding Ni(II) uptake was reduced in the presence of Cr(VI) or As (III) (Fig. 2c), the maximum uptake obtained at initial concentration of Ni(II) 5 mg/L, pH 0 5 was found to be 0.364 mg/g in the single-ion situation, while the uptake obtained in the binary metal solutions at the same initial concentration of Ni(II) and adsorption conditions was found to be 0.398, 0.414, and 0.436 mg/g when concentration of Cr(VI) was 10, 25, and 50 mg/L, respectively. The uptake of Ni(II) increased with increasing concentration of Cr(VI). As(III) in the binary solution did not affect Ni(II) adsorption on AC as much as Cr(VI). The maximum Ni(II) uptake obtained at the same conditions was found to be 0.358, 0.370, and 0.382 mg/g when concentration of As(III) was 0.5, 1.0, and 5.0 mg/L, respectively. The kinetic studies of Cr(VI), As(III), and Ni(II) in binary system are also studied using two kinetic models as in single system. The adsorption rate constants are listed in Table 3. The correlation coefficients ( r 2 ) obtained for the pseudo-second-order kinetic model were greater than 0.99 for all metals. It can be concluded that the adsorption process from binary systems follows the pseudo-second-order kinetics.

Fig. 4 Schematic illustration for the displacement mechanism between the three metals when competing for the same adsorption site

Environ Sci Pollut Res (2013) 20:22102219 Table 4 Kinetic parameters for Cr(VI), As(III), and Ni(II) in ternary systems onto AC

2217

Metal ions

Concentration (mg/L)

Pseudo-first-order k1 qe.cal 2.151 2.132 2.101 0.028 0.027 0.032 0.410 0.435 0.441 r2 0.908 0.798 0.849 0.816 0.844 0.709 0.953 0.742 0.733

Pseudo-second-order k2 0.016 0.016 0.016 0.103 0.099 0.126 0.091 0.070 0.061 qe.cal 2.091 2.056 2.024 0.025 0.022 0.030 0.394 0.424 0.432 r2 0.984 0.989 0.979 0.977 0.980 0.988 0.973 0.993 0.994

Cr(VI) 25 mg/L

As(III) 0.5 mg/L

Ni(II) 5 mg/L

CAs 0 0.5 CNi 0 5.0 CAs 0 5.0 CNi 0 5.0 CAs 0 0.5 CNi 0 50 CCr 0 25 CNi 0 5.0 CCr 0 25 CNi 0 50 CCr 0 50 CNi 0 5.0 CCr 0 25 CAs 0 0.5 CCr 0 25 CAs 0 5.0 CCr 0 50 CAs 0 0.5

0.014 0.013 0.014 0.011 0.012 0.010 0.014 0.014 0.012

The competitive adsorption of ions from ternary system The tri-metal adsorption of Cr(VI), As(III), and Ni(II) by AC was investigated to establish the effect of the presence of two metal ions on the adsorption of each one of them. The equilibrium uptake of any ion by AC in the presence of varied concentrations of other ions as function of metal concentration and contact time was compared with those in the single-ion situation (Fig. 3). As shown in Fig. 3a, the maximum uptake obtained at initial concentration of Cr(VI) was found to be 2.25 mg/g in the single-ion situation, while the minimum uptake obtained in the ternary metal solutions at the same initial concentration of Cr(VI) and adsorption conditions was found to be 2.05 mg/g. The presence of As (III) and Ni(II) in the solution did not significantly influence the capacity of Cr(VI) adsorption on AC. Figure 3b shows that As(III) adsorption in ternary component system was better than in single system. The maximum uptake of As(III) was found to be 0.029 mg/g in As (III) (0.5 mg/L)Cr(VI) (25 mg/L)Ni(II) (5 mg/L) component system. It was lower than in As(III) (0.5 mg/L)Cr(VI) (25 mg/L) component system (0.043 mg/g) but higher than in As(III) (0.5 mg/L) Ni(II) (5 mg/L) component system (0.020 mg/g). Ni(II) adsorption in ternary component system was also better than in single-component system (Fig. 3c). The maximum uptake of Ni(II) was found to be 0.411 mg/g in Ni(II) (5 mg/L)Cr(VI) (25 mg/L)As(III) (0.5 mg/L) component system. It was lower than in Ni(II) (5 mg/L)Cr(VI) (25 mg/L) component system (0.414 mg/g) but higher than in Ni(II) (5 mg/L)As(III) (0.5 mg/L) component system (0.358 mg/g). Multicomponent systems have additional features versus those of single components. According to the description above, the combined effect of the binary and ternary mixture seems to be antagonistic. The factors that affect the sorption preference of an adsorbent for different kinds of adsorbates may be related to the characteristics of the binding sites (e.g.

functional groups, structure, surface properties, etc.), the properties of the adsorbates (e.g. concentration, ionic size, ionic weight, ionic charge, molecular structure, ionic nature or standard redox potential, etc.), and the solution chemical characteristics (e.g. pH, ionic strength, etc.). The affinity of metal ions to AC in this study is due to the normal reduction potential of the three ions (Eo Cr2 =Cr 0:59V > Eo As3 =As 0:24V > E o Ni2 =Ni 0:25V ) (Mohan et al. 2006; Liu et al. 2008). When the three metals compete for the same adsorption site, the metal ion with lower normal reduction potential could replace the higher one, i.e., Ni2+ could displace As3+ and As3+ could displace Cr6+ (Fig. 4). The kinetic parameters of Cr(VI), As(III), and Ni(II) in ternary system are listed in Table 4. We applied the dynamic data of competitive sorption into pseudo-first-order and pseudo-second-order sorption equations. All sorptions relevant to Cr(VI), As(III), and Ni(II) sorption showed a good correlation with pseudo-second-order in ternary system. Thus, a pseudo-second-order model can be used to predict and

Fig. 5 Reusability of AC with repeated sorptiondesorption cycle

2218

Environ Sci Pollut Res (2013) 20:22102219

control the amounts of metals removed when AC is employed to treat the mixture solutions of Cr(VI), As(III), and Ni(II). Desorption and reusability In order to make the adsorption process more economical and feasible, desorption efficiency and regeneration potential of AC was studied. It was observed that the highest desorption values for As(III) (99.1 %) and Cr(VI) (73.2 %) were obtained using 0.5 M NaOH solution. For the desorption of Ni(II), the best performance was obtained using 0.3 M HNO3 solution with desorption value of 93.4 %. To test the reusability of AC, adsorptiondesorption cycles were repeated six times using the same adsorbents. Figure 5 shows that the adsorption capacities of Cr(VI), As(III), and Ni(II) slightly decreased with the increase in adsorptiondesorption cycle; at the end of the sixth cycle, more than 64, 90, and 84 % of the initial adsorption capacities were obtained for Cr(VI), As(III), and Ni(II), respectively. The regeneration ability of AC decreased the operation cost and indicated the industrial applicability.

References
Ahmaruzzaman M, Gupta VK (2011) Rice husk and its ash as low-cost adsorbents in water and wastewater treatment. Ind Eng Chem Res 50:1358913613 Akhtar N, Iqbal J, Iqbal M (2004) Removal and recovery of nickel(II) from aqueous solution by loofa sponge-immobilized biomass of Chlorella sorokiniana: characterization studies. J Hazard Mater 108:8594 Aryal M, Ziagova M, Liakopoulou-Kyriakides M (2010) Study on arsenic biosorption using Fe(III)-treated biomass of Staphylococcus xylosus. Chem Eng J 162:178185 Babel S, Kurniawan TA (2004) Cr(VI) removal from synthetic wastewater using coconut shell charcoal and commercial activated carbon modified with oxidizing agents and/or chitosan. Chemosphere 54:951967 Banerjee K, Amy GL, Prevost M, Nour S, Jekel M, Gallagher PM, Blumenschein CD (2008) Kinetic and thermodynamic aspects of adsorption of arsenic onto granular ferric hydroxide (GFH). Water Res 42:33713378 Dubey SS, Gupta RK (2005) Removal behavior of Babool bark (Acacia nilotica) for submicro concentrations of Hg2+ from aqueous solutions: a radiotracer study. Sep Purif Technol 41:2128 Gen-Fuhrman H, Wu P, Zhou Y, Ledin A (2008) Removal of As, Cd, Cr, Cu, Ni and Zn from polluted water using an iron based sorbent. Desalination 226:357370 Gupta VK, Ali I (2004) Removal of lead and chromium from wastewater using bagasse fly asha sugar industry waste. J Colloid Interface Sci 271:321328 Gupta S, Babu BV (2009) Modeling, simulation, and experimental validation for continuous Cr(VI) removal from aqueous solutions using sawdust as an adsorbent. Bioresour Technol 100:5633 5640 Gupta VK, Nayak A (2012) Cadmium removal and recovery from aqueous solutions by novel adsorbents prepared from orange peel and Fe2O3 nanoparticles. Chem Eng J 180:8190 Gupta VK, Rastogi A (2008a) Biosorption of lead(II) from aqueous solutions by non-living algal biomass Oedogonium sp. and Nostoc sp. a comparative study. Colloids Surf B 64:170178 Gupta VK, Rastogi A (2008b) Equilibrium and kinetic modeling of cadmium (II) biosorption by nonliving algal biomass Oedogonium sp. from aqueous phase. J Hazard Mater 153:759 766 Gupta VK, Rastogi A (2009) Biosorption of hexavalent chromium by raw and acid-treated green alga Oedogonium hatei from aqueous solutions. J Hazard Mater 163:396402 Gupta VK, Mohan D, Sharma S (1998) Removal of lead from wastewater using bagasse fly asha sugar industry waste material. Separ Sci Technol 33:13311343 Gupta VK, Gupta M, Sharma S (2001) Process development for the removal of lead and chromium from aqueous solutions using red mudan aluminium industry waste. Water Res 35:1125 1134 Gupta VK, Saini VK, Jain N (2005) Adsorption of As(III) from aqueous solutions by iron oxide-coated sand. J Colloid Interface Sci 288:5560 Gupta VK, Mittal A, Gajbe V, Mittal J (2006a) Removal and recovery of the hazardous azo dye acid orange 7 through adsorption over waste materials: bottom ash and de-oiled soya. Ind Eng Chem Res 45:14461453 Gupta VK, Mittal A, Jain R, Mathur M, Sikarwar S (2006b) Adsorption of Safranin-T from wastewater using waste materialsactivated carbon and activated rice husks. J Colloid Interface Sci 303:8086

Conclusions In this study, we investigated the ability of AC binding heavy metal ions in single and multicomponent solutions. The following specific conclusions were obtained: 1. The pH of the solution significantly influenced the adsorption capacity of AC toward Cr(VI), As(III), and Ni(II). Low pH was favorable for Cr(VI) adsorption; the adsorption of Ni(II) strongly increased at higher pH; As(III) adsorption was optimum in the pH 0 5 in single system. 2. Equilibrium data were well described by the Langmuir isotherm, suggesting the homogeneous nature of the adsorptions of Cr(VI), As(III), and Ni(II) on AC. 3. Pseudo-second-order kinetic model was in good agreement with the experimental data for all metal ion systems at the different concentrations studied, indicating chemisorption is the rate-limiting step. 4. In multicomponent system, As(III) and Ni(II) adsorption competed intensely, while Cr(VI) adsorption was much less affected by competition than As(III) and Ni (II). The adsorption capacities of As(III) and Ni(II) on AC with the presence of Cr(VI) are higher than those in single system. AC removed ternary metal ions with the selectivity order of Ni(II)>As(III)>Cr(VI). 5. Desorption of the metal ions was carried out using 0.5 M NaOH and 0.3 M HNO3, and the repeated adsorptiondesorption study showed that the adsorbent AC can be effectively used as an adsorbent for the removal of heavy metal ions.

Environ Sci Pollut Res (2013) 20:22102219 Gupta VK, Mittal A, Kurup L, Mittal J (2006c) Adsorption of a hazardous dye, erythrosine, over hen feathers. J Colloid Interface Sci 304:5257 Gupta VK, Ali I, Saini VK (2007a) Defluoridation of wastewaters using waste carbon slurry. Water Res 41:33073316 Gupta VK, Jain R, Mittal A, Mathur M, Sikarwar S (2007b) Photochemical degradation of the hazardous dye Safranin-T using TiO2 catalyst. J Colloid Interface Sci 309:464469 Gupta VK, Jain R, Varshney S (2007c) Electrochemical removal of the hazardous dye Reactofix Red 3 BFN from industrial effluents. J Colloid Interface Sci 312:292296 Gupta VK, Jain R, Varshney S (2007d) Removal of Reactofix golden yellow 3 RFN from aqueous solution using wheat huskan agricultural waste. J Hazard Mater 142:443448 Gupta VK, Rastogi A, Nayak A (2010a) Biosorption of nickel onto treated alga (Oedogonium hatei): application of isotherm and kinetic models. J Colloid Interface Sci 342:533539 Gupta VK, Rastogi A, Nayak A (2010b) Adsorption studies on the removal of hexavalent chromium from aqueous solution using a low cost fertilizer industry waste material. J Colloid Interface Sci 342:135141 Gupta VK, Agarwal S, Saleh TA (2011a) Chromium removal by combining the magnetic properties of iron oxide with adsorption properties of carbon nanotubes. Water Res 45:22072212 Gupta VK, Agarwal S, Saleh TA (2011b) Synthesis and characterization of alumina-coated carbon nanotubes and their application for lead removal. J Hazard Mater 185:1723 Gupta VK, Ali I, Saleh TA, Siddiqui MN, Agarwal S (2012) Chromium removal from water by activated carbon developed from waste rubber tires. Environ Sci Pollut Res. doi:10.1007/ s11356-012-0950-9 Heidari A, Younesi H, Mehraban Z (2009) Removal of Ni(II), Cd(II), and Pb(II) from a ternary aqueous solution by amino functionalized mesoporous and nano mesoporous silica. Chem Eng J 153:7079 Jain M, Garg VK, Kadirvelu K (2009) Chromium(VI) removal from aqueous system using Helianthus annuus (sunflower) stem waste. J Hazard Mater 162:365372 Jain M, Garg VK, Kadirvelu K (2011) Investigation of Cr(VI) adsorption onto chemically treated Helianthus annuus: optimization using response surface methodology. Bioresour Technol 102:600605 Klimaviciute R, Bendoraitiene J, Rutkaite R, Zemaitaitis A (2010) Adsorption of hexavalent chromium on cationic cross-linked starches of different botanic origins. J Hazard Mater 181:624632 Kumar ASK, Kalidhasan S, Rajesh V, Rajesh N (2012) Application of celluloseclay composite biosorbent toward the effective adsorption and removal of chromium from industrial wastewater. Ind Eng Chem Res 51:5869 Kundu S, Gupta AK (2006) Arsenicadsorption onto iron oxide-coated cement (IOCC): regression analysis of equilibrium data with several isotherm models and their optimization. Chem Eng J 122:93106 Li LJ, Liu FQ, Jing XS, Ling PP, Li AM (2011) Displacement mechanism of binary competitive adsorption for aqueous divalent metal ions onto a novel IDA-chelating resin: isotherm and kinetic modeling. Water Res 45:11771188 Liu ZR, Zhou LM, Wei P, Zeng K, Wen CX, Lan HH (2008) Competitive adsorption of heavy metal ions on peat. J China Univ Mining & Technol 18:255260

2219 Mahamadi C, Nharingo T (2010) Competitive adsorption of Pb, Cd, and Zn ions onto Eichhornia crassipes in binary and ternary systems. Bioresour Technol 101:859864 Mohan D, Pittman CU Jr, Steele PH (2006) Single, binary and multicomponent adsorption of copper and cadmium from aqueous solutions on Kraft lignina biosorbent. J Colloid Interface Sci 297:489504 Monier M, Ayad DM, Wei Y, Sarhan (2010) Adsorption of Cu(II), Co (II), and Ni(II) ions by modified magnetic chitosan chelating resin. J Hazard Mater 177:962970 Namasivayam C, Sureshkumar MV (2008) Removal of chromium(VI) from water and wastewater using surfactant modified coconut coir pith as a biosorbent. Bioresour Technol 99:22182225 Salameh Y, Al-Lagtah N, Ahmad MNM, Allen SJ, Walker GM (2010) Kinetic and thermodynamic investigations on arsenic adsorption onto dolomitic sorbents. Chem Eng J 160:440446 Saleh TA, Gupta VK (2012) Column with CNT/magnesium oxide composite for lead(II) removal from water. Environ Sci Pollut Res 19:12241228 Saleh TA, Agarwal S, Gupta VK (2011) Synthesis of MWCNT/MnO2 and their application for simultaneous oxidation of arsenite and sorption of arsenate. Appl Catal B: Environ 106:4653 Sheng PX, Ting YP, Chen JP (2007) Biosorption of heavy metal ions (Pb, Cu, and Cd) from aqueous solutions by the marine alge Sargassum sp. in single- and multiple-metal systems. Ind Eng Chem Res 46:24382444 Srivastava SK, Gupat VK, Mohan D (1997) Removal of lead and chromium by activated slaga blast furnace waste. J Environ Eng 123:461468 Srivastava VC, Mall ID, Mishra IM (2008) Antagonistic competitive equilibrium modeling for the adsorption of ternary metal ion mixtures from aqueous solution onto bagasse fly ash. Ind Eng Chem Res 47:31293137 Subbaiah MV, Vijaya Y, Kumar NS, Reddy AS, Krishnaiah A (2009) Biosorption of nickel from aqueous solutions by Acacia leucocephala bark: kinetics and equilibrium studies. Colloids Surf B Biointerfaces 74:260265 Tunali S, Akar T, zcan AS, Kiran I, zcan A (2006) Equilibrium and kinetics of biosorption of lead(II) from aqueous solutions by Cephalosporium aphidicola. Sep Purif Technol 47:105112 Tuzen M, Sar A, Mendil D, Uluozlu OD, Soylak M, Dogan M (2009) Characterization of biosorption process of As(III) on green algae Ulothrix cylindricum. J Hazard Mater 165:566572 Wang XJ, Liang X, Wang Y, Wang X, Liu M, Yin DQ, Xia SQ, Zhao JF, Zhang YL (2011) Adsorption of copper(II) onto activated carbons from sewage sludge by microwave-induced phosphoric acid and zinc chloride activation. Desalination 278:231237 Wu FC, Tseng RL, Juang RS (2001) Kinetic modeling of liquid-phase adsorption of reactive dyes and metal ions on chitosan. Water Res 35:613618 Yang S, Li J, Shao D, Hu J, Wang X (2009) Adsorption of Ni(II) on oxidized multi-walled carbon nanotubes: effect of contact time, pH, foreign ions and PAA. J Hazard Mater 166:109116 Yurdako M, Seki Y, Karahan S, Yurdako K (2005) Kinetic and thermodynamic studies of boron removal by Siral 5, Siral 40, and Siral 80. J Colloid Interface Sci 286:440446 Zhou LM, Wang YP, Liu ZR, Huang QW (2009) Characteristics of equilibrium, kinetics studies for adsorption of Hg(II), Cu(II), and Ni(II) ions by thiourea-modified magnetic chitosan microspheres. J Hazard Mater 161:9951002