Removal of lead (II) and copper (II) from aqueous solution using pomegranate peel as a new adsorbent

E.-S.Z. El-Ashtoukhy *, N.K. Amin A , O. Abdelwahab Chemical Engineering Department, Faculty of Engineering, Alexandria University, Alexandria, Egypt Tel. +0102550356; email: elsayed_elashtoukhy@hotmail.com Environmental Division, National Institute of Oceanography and Fisheries, Alexandria, Egypt Received 20 December 2006; accepted 3 January 2007 Abstract The effective removal of heavy metals from aqueous wastes is among the most important issues for many industrialized countries. Removal of lead (II) and copper (II) from aqueous solutions were studied using pomegranate peel (raw), activated carbon prepared from pomegranate peel (AC 1 ) and activated carbon prepared from chemically treated pomegranate peel (AC 2and AC 3 ). Batch adsorption experiments were performed as a function of pH, contact time, solute concentration and adsorbent dose. The optimum pH required for maximum adsorption were found to be 5.6 and 5.8, for lead and copper respectively. The experimental equilibrium adsorption data are tested for the Langmuir, Freundlich and Temkin equations. Results indicate the following order to fit the isotherms: Langmuir > Temkin > Freundlich in case of lead ions and Freundlich > Temkin > Langmuir in case of copper ions. Adsorption kinetics data were modeled using the pseudo-first and pseudo-second order, Elvoich equations and intra-particle diffusion models. The results indicate that the second-order model best describes adsorption kinetic data Keywords:Adsorption; Isotherms; Heavy metals; Lead; Copper; Pomegranate peel adsorbent 1. Introduction The presence of heavy metal ions from the transition series, viz, Cu, Fe, Ni, Pb, etc. in the environment is of major concern due to their toxicity to many life forms. Unlike organic pollutants, the majority of which are susceptible to biological degradation, metal ions do not degrade into harmless end products [1]. Heavy metals contamination exists in aqueous waste stream from many industries such asmetal plating, mining, tanneries, painting, car radiator manufacturing, as well as agricultural sources where fertilizers and fungicidal spray intensively used. The removal of heavy metal in an effective manner from water and wastewater is, thus, ecolog-ically very important. There are many reported and established technologies for the recovery of metals from wastewater, which include chemical precipitation [2],flotation [3], biosorption [46] electrolytic recovery, membrane separation [7], removal by adsorption onminerals [8,9] and activated carbon adsorption [10,11]. In spite of its prolific use, activated carbon remains an expen-sive material since the higher the quality of acti-vated carbon, the greater its

cost. Activated carbon also requires complexingagents to improve its removal performance for inorganic matters [12]. Therefore, this situation makes it no longer attrac-tive to be widely used in small-scale industries because of cost inefficiency. In recent years, the search for low-cost adsorbents that have metal-binding capacities has intensified. Agricultural by-products have been widely studied for metal removal from water. These include peat, wood, pine bark, banana pith, soybean and cotton seed hulls, peanut shells, hazelnut shell, rice husk, saw dust, wool, orange peal, compost and leaves [13]. Pomegranate fruits are widely consumed fresh and in processed forms as juice, jams and wine. Pomegranate peel, a by-product of the pomegran-ate juice industry is therefore an inexpensive. Pomegranate peel is rich in ellagitannins (ETs) such as punicalagin and its isomers, as well as lesser amounts of punicalin (4,6-gallagylglucose), gallagic acid, ellagic acid (EA) and EA-glycosides [14]. Pomegranate peel is a material composed of several constituents, including polyphenols, ellagic tannis and gallic and ellagic acids [15]. In the present work the sorption of lead and copper ions from aqueous solution by using activated carbon produced from pomegranate peel was investigated. The adsorption capacity of adsorbent was investi-gated using batch experiments. The influence of pH, contact time, metal ions and adsorbent con-centrations were investigated and the experimental data obtained were evaluated and fitted using adsor-bent equilibrium isotherms, and kinetic models. 2. Materials and methods 2.1. Materials Lead acetate (A.R) and copper sulfate were used for the preparation of stock Pb(II) and Cu(II) solutions in distilled water respectively. For pH adjustment throughout the experiment, hydro-chloric acid and/or sodium hydroxide solutions were used as necessary. Phosphoric acid (28% wt), zinc chloride and nitric acid (10% wt) were used for the chemical treatment of pomegranate peel. 2.2. Biosorbent preparation Pomegranate peel was usedas a biosorbent for the removal of heavy metals. Pomegranate peel was washed with distilled water, dried in an oven for two hours at 105C, ground in a ball mill and sieved to particle size range 0.30.6 mm. The material after sieving is divided into four parts: The first part was used as it is for biosorption of heavy metals, it was labeled by Raw. The second part was placed in a purpose-made stainless steel tube in absence of air and positioned at the center of a muffle furnace for one hour at 500C, then the activated carbon produced iscooled in a dissicator (AC 1 ). The third part was soaked for twenty four hours in a solution prepared from phosphoric acid and zinc chloride in a ratio of 1:1, then dried and carbonized as mentioned above (AC 2 ), finally the fourth part was soakedfor twenty four hours in nitric acid (10% wt),then dried and carbonized as mentioned above (AC 2 ). The yield from each prepared biosorbent was calculated from the following equation (1) where: Wo is the mass of material before carbon-ization, Wc is the mass of material after carbon-ization. The physicochemical characteristics of all adsorbents were measured using standard procedures. The data are illustrated in Table 1.

2.3. Adsorption experiments Batch adsorption experiments were carried out at room temperature by shaking a series of bottles containing the desired dose of adsorbent in a predetermined concentration of heavy metal solution. Samples were withdrawn at different time intervals. Supernatant was separated by fil-tration and analyzed for remaining heavy metalcontent. Experiments were carried out at initial pH values ranging from 1 to 9.4. The initial pH of the solution was adjusted to the desired value either by hydrochloride acid or sodium hydroxide solution. The percent removal of heavy metal from solution was calculated by the following equation: (2) where C0 is initial concentration of heavy metal, Ciis final concentration of heavy metal. Isotherm studies were recorded byvarying the initial con-centrations of heavy metal solutions from 10 to 50 mg/L and from 10 to 80 mg/L for lead and copper respectively. A known amount of different activated carbons is then added into solutions followed by agitating the mixture at 150 rpm till equilibrium. The adsorption capacity q e (mg/g) after equilibrium was calculated by mass balance relationship equation as follows (3) where Vis the volume of the solution (L) and W is the mass of adsorbate (g). 3. Results and discussions 3.1. Characteristics of adsorbing material A scanning electron microscope (SEM) was used to examine the surface of the four adsorbents and the SEM photographs (Fig. 1) shows pro-gressive changes in the surface of the particles. Table 1 shows the physical characteristics of thefour adsorbents used in the present study. 3.2. Effect of pH The pH of the solution has a significant impact on the uptake of heavy metals, since it determines the surface charge of the adsorbent, the degree of ionization and speciation of the adsorbate. In order to establish the effect of pH on the bio-sorption of lead (II) and copper (II) ions, the batch equilibrium studies at different pH values were carried out in the range of 1.59.4 and 18 for the two metals respectively (Fig. 2(a and b)). Fig. 2(a) shows that the maximum percent removal oflead (II) ions on the adsorbents was observed at pH 5.67.6 and significantly decreased by reducing the pH values and slightly decreased at higher pH values. The maximum percent removal of copper ions were observed at pH 68 as shown in Fig. 2(b), and significantly decreased at lower pH value. According to Low et al. [16], little sorption at lower pH could be ascribed to the hydrogen ions competing with metal ions for sorption sites. This means that at higher H + concentration, the biosorbent surface becomes more positively charged, thus, reducing the attraction between adsorbent and metal ions. In contrast as the pH increases, more negatively charged sur-face become available, thus, facilitating greater metal uptake [17]. At a higher pH, the lead and copper ions precipitated as their hydroxide which decreased the rate of adsorption and sub-sequently the percent removal of metal ions. Also, it was observed that at constant pH, the percent removal increased in the order of AC 3> AC2> AC1> Raw, and this means that the chemically