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Procedia Environmental Sciences 18 (2013) 794 799

2013 International Symposium on Environmental Science and Technology (2013 ISEST)

Untreated Chinese ephedra residue as biosorbents for the removal of Pb2+ ions from aqueous solutions
Ningchuan Feng*, Fengyuan Zhang
School of Basic Medical Science, Ningxia Medical University, Yinchuan 750004, China

Abstract

The objective of this work was to propose an alternative use for ephedra residue (ER) as untreated biosorbents for the removal of Pb2+ ions from aqueous solutions. Biosorption studies were conducted as a function of the solution pH, contact time and initial metal ion concentration. The biosorption kinetics was determined by fitting second-order kinetic models to the experimental data, being described by the pseudo-second-order model (R2 > 0.99). Both Langmuir and Freundlich sorption models fit the experimental sorption equilibrium data, with Langmuir providing the best fit (R2 > 0.97). According to the Langmuir equation, the maximum uptake capacity for Pb 2+ ions was 1.0 mmol/g at 298K. A comparison of the maximum sorption capacity of several untreated biomaterial-based residues showed that the ER is a suitable candidate for use as biosorbents in the removal of Pb2+ ions from aqueous solutions.
The Authors. Authors. Published Publishedby byElsevier ElsevierB.V. B.V. 2013 The Selection and peer-review under responsibility of Beijing Institute of Technology. and/or peer-review under responsibility of Beijing Institute of Technology.
Keywords: Ephedria residue; Pb2+ ions; Biosorption; Isotherms; Kinetics

1. Introduction It is well recognized that the presence of heavy metals in the environment can be detrimental to a variety of living species, including man. Many methods, such as chemical precipitation, ion exchange, membrane processes and adsorption onto activated carbon etc., have been used to remove lead from various aqueous solutions [1]. However, the application of such processes is often restricted because of technical or economic constraints [2]. Recently, attentions have been focused on the development of low cost adsorbent for the application concerning treatment of wastewater [3,4]. Chinese ephedra residue, being a low-cost and easily available adsorbent, could be an alternative for more costly wastewater

* Corresponding author. +86-951-6980-120; fax: +86-951-6980-110. E-mail address: ncfeng@sina.com.

1878-0296 2013 The Authors. Published by Elsevier B.V. Selection and peer-review under responsibility of Beijing Institute of Technology. doi:10.1016/j.proenv.2013.04.107

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treatment processes. Ephedra sinica Stapf is a traditional Chinese medicine plant of the family Ephedraccae; its main active constituents are alkaloids, primarily ephedrine and pseudoephedrine. Beside the production of ephedrine and pseudoephedrine, a large amount of solid waste ephedra residue is also an output from Chinese traditional medicine industry. Currently, they are disposed through combustion or land filling, which produces secondary pollution easily. The use of the ephedra residue as biosorbents material presents strong potential due to its high content of cellulose, hemicellulose and lignin. As a low cost, ephedra residue is an attractive and inexpensive option for the biosorption removal of dissolved metals. The present work was thus undertaken to evaluate the application potential of cellulose-rich ephedra residue (ER) as a new, inexpensive and environment-friendly biosorbent material for treating wastewaters containing toxic metals. We understand that to date no study on the use of ephedra residue as a metal sorbent to treat wastewaters has been reported. Metal ions such as Pb 2+, being most toxic to human and aquatic life, and commonly released in the environment via wastewaters of many industrial processes, were selected as sorbates for this investigation. 2. Materials and methods 2.1. Chemicals Aqueous solutions of Pb2+ ions for the batch experiments were prepared by dissolving analytical grade nitrate (Pb(NO3)2) salts in 0.05 mol/L hydrochloric acid solution and in a solution of 0.05 mol/L N-2hydroxyethylpiperazine-N-2-ethanesulphonic acid (HEPES), a buffer reagent, followed by mixing these two solutions at an ordinary volume ratio to adjust pH, while dilute sodium hydroxide solution was used to prepare higher pH solutions. Before mixing with ephedria residue biosorbents, initial pH of each solution was adjusted to an appropriate value by adding 0.1mol/L HCl or/and NaOH solutions. All the reagents were analytical grade. A pHs-3C model acidity meter (made in China) was used to measure pH values of all solutions. Double distilled water was used to prepare all solutions. 2.2. Biosorbent preparation Ephedra residue (ER) was kindly provided by Tangmin pharmaceutical company, an ephedrine producer at Ningxia Hui Autonomous Regions, China. Ephedra residue were washed several times with distilled water to remove dirt, and dried at 80 C for 24 h in a convection oven. The dried residue was milled with a muller, and then sieved by 80-mesh sieve. The particles under 80-mesh were used in further experiments without any pretreatment. 2.3. Biosorption tests Batch adsorption experiments were conducted by mixing biosorbent with 25mL of Pb 2+ ions solutions of desired concentrations in 100mL sealed conical flask using a shaking thermostat machine at a speed of 200 rpm at 25. The effect of solutions pH on the equilibrium adsorption of Pb 2+ was investigated by mixing 0.100g of ER with 25mL of Pb2+ ions solutions of 2mmol/L between pH 1.7 and 6.0. In kinetic experiments, 2mmol/L Pb2+ ions solutions were used. The adsorption time was varied from 0 to 480min. In isotherm experiments, 0.100g of biosorbent was added in 25mL of Pb2+ ions solutions at various concentrations (1-12 mmol/L). After the pre-set contact time was reached, the samples were withdrawn and then solutions were filtered through filter paper. The concentration of Pb2+ was titrated with standard

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EDTA solution, 0.1% xylenol orange was chosen as indicator and 30% hexamethylene tetramine was used as buffer solution. The amount of biosorptions (q) was calculated by the following equations:
q (C0 Ce )V m
C0 Ce 100 C0

(1)

The biosorption efficiency, A%, of the metal ion was calculated from: (2) where C0 and Ce are the initial and equilibrium Pb2+ ions concentrations, respectively (mmol/L). V is the volume of the solutions (L) and m is the amount of adsorbent used (g). All the adsorption experiments were conducted in duplicate, and the mean values were calculated. 3. Results and discussion 3.1. Effect of pH on Pb2+ions biosorption The pH of a suspension is one of the most important parameters that affect the adsorption process [5,6]. The effect of initial pH on Pb2+ ions biosorption capacity of ER is shown in Fig. 1. Due to hydrogen ion competition at low solution pH values, the Pb2+ uptake was small. There is an increase in metal ions uptake as the pH value increases from 1.7 to 6.0. The solution pH affects the surface charge of the adsorbent, the degree of ionization, and the speciation of the surface functional groups. The increase in metal removal as the pH increases can be explained on the basis of a decrease in competition between proton and metal cations (Pb2+) for the same functional groups and by the decrease in positive surface charge of the ER, which results in a lower electrostatic repulsion between the surface and the metal ion [7]. 3.2. Biosorption kinetics The ER biosorption data, at 25 and pH 5.3, showed that a contact time of 6h assured attainment of equilibrium for lead ions. The results obtained for the metal sorption tests are presented in Fig. 2. It can be readily observed that sorption occurred at faster rates in the first 0.5 h and the amount of adsorbed metal ion was 70% and then biosorption rate rises step by step with reaction time prolonging; and biosorption rates are up to 95.6% when reaction time is 6 h. The kinetics of Pb2+ ions biosorption on ER was analyzed using pseudo-second order [8] Eq. (3):
A%

1 t t 2 qt k2 qe qe

(3)

where k2 is the rate constant of second-order adsorption (g/mmol min). The second-order rate constant k2 and qe values were calculated from the slope and intercept of the plots t/q vs. The rate constants (k2), correlation coefficients of the plots together with the experimental and theoretical qe values are given in Table 1. It was found from these results that the correlation coefficients are very high and the calculated qe values agree well with experimental qe values. This suggests that the second-order kinetic model based on the assumption that the rate limiting step may be chemical sorption involving valency forces through

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sharing or exchange of electrons between Pb2+ ions and the biosorbent, provides the best correlation data for the metal ions.
100

100

80

80

Adsorption(%)

60

Adsorption(%)
1 2 3 4 5 6

60

40

40

20

20

0 0 100 200 300 400 500

Initial pH

t(min)

Fig. 1. The effect of pH on biosorption of Pb2+ ions.

Fig. 2. Biosorption kinetics of Pb2+ ions.

Table 1. Kinetic parameters of t pseudo-second order model for Pb2+ ions biosorption on ER. qe( exp.) (mmol/g) 0.478 Second-order kinetic model k2(g/mmol min) qe (cal.) (mmol/g)0.139 0.496 R2 0.999

3.3. Biosorption isotherms Biosorption isotherms describe the relationship between the mass of the adsorbed component per biosorbent mass and the concentration of this component in the solution [4]. Determination of equilibrium parameters provides important information that allows for future design of adsorption systems. Two wellknown adsorption isotherms, Langmuir and Freundlich isotherms were chosen to fit the experimental data regarding the sorption of metal ions on the surface of the biomass. The Langmuir isotherm assumes monolayer coverage of adsorbate over a homogeneous adsorbent surface, and the adsorption of each molecule onto the surface has equal adsorption activation energy. The Langmuir isotherms can be expressed as:
Ce Ce 1 qe q maxb q max

(4)

where qmax is monolayer capacity of the adsorbent (mmol/g), and b is the adsorption constant (L/mmol). The plot of Ce/qe versus Ce should be a straight line with slope 1/qmax and intercept 1/ qmax b when the adsorption follows the Langmuir equation. The Freundlich isotherm supposes a heterogeneous surface with a nonuniform distribution of heat of adsorption over the surface and a multilayer adsorption can be expressed. The Freundlich equation can be expressed as:

1 ln qe ln K F ln Ce n

(5)

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where KF and n are Freundlich constants; n gives an indication of how favorable the adsorption process is; and KF is the adsorption capacity of the adsorbent. It is generally considered that the adsorption process is favorable if the values of n are in the range 2-10, 1-2 moderately difficult, and less than 1 poor adsorption characteristics [9,10]. If the eq. (5) applies, a plot of lnqe versus lnCe will give a straight line of slope 1/n and intercept KF. Fig. 3 presents the experimental biosorption isotherm of Pb 2+ ions on ER at 298K. It could be seen that qe increased initially with an increase in Ce until equilibrium was reached, after which qe remained constant with further increase in Ce. The Langmuir and Freundlich adsorption constants evaluated from the isotherms with the correlation coefficients were listed in Table 2. As it can be seen that the Langmuir isotherm gave better fits than the Freundlich isotherm, which illustrated that the biosorption on the surface of ER was a monolayer adsorption. According to the Langmuir equation, the maximum uptake capacities at 298 K for Pb2+ ions were 1.00 mmol/g. The studied materials are favorable adsorbents for Pb2+ (n2).
Table 2. Langmuir and Freundlich constants for Pb2+ ions biosorption on ER. Langmuir model T(K) 298 qmax (mmol/g) 1.00 b (L/mmol) 1.77 R
2

Freundlich model Kf 0.579 n 3.39 R2 0.982

0.985

Many workers have experimented other waste biomass as low cost adsorbents for metal ion removal. Langmuir constants, qmax, values obtained for adsorption of Pb2+ onto various other biomass types reported in the literature are listed in Table 3. Results show that ER is a better adsorbent compared to some of the biomass used.
Table 3. Comparison of the maximum adsorptive capacity for Pb2+ ions on different adsorbents. Adsorbents Sugar beet pulp Lichen (C. furcata) Tea waste Wheat bran Tobacco dust Orange peel Ephedria residue (ER) qmax(mg/g) 73.8 12.3 65.0 63.9 39.6 113 207 References 7 11 12 13 14 15 This study
1.0 0.9 0.8

qe(mmol/g)

0.7 0.6 0.5 0.4 0.3 0.2 0 1 2 3 4 5 6 7

Ce(mmol/L)

Fig. 3. Biosorption isotherms of Pb2+ ions on ER.

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4. Conclusions ER was found to be an effective biosorbent for the removal of Pb 2+ ions from an aqueous solution. The study showed that pH of the solution play an important role in the Pb2+ ions biosorption. The adsorptive capacity of Pb2+ increases with the increase in pH from 1.7 to 6.0. Equilibrium was attained after 6 h of contact time. Biosorption kinetics was best described by a pseudo-second-order model. Biosorption isotherms were better described by Langmuir model in comparison to Freundlich. ER maximum biosorption capacity (evaluated based on Langmuir fit) was higher than other untreated residues such as s sugar beet pulp, rice husk, tea waste, mango and orange peel, tobacco dust and so on. It can be also concluded that the ER is an effective and alternative biomass for the removal of Pb2+ ions from wastewaters in terms of high biosorption capacity, natural and abundant availability and low cost. Acknowledgements This work was supported by the National Natural Science Foundation of China (No. 21266026) and the Ningxia Natural Science Foundation of China (NZ1083). References
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