Adsorption of heavy metals from water using banana and orange peels

G. Annadurai*, R.S. Juang** and D.J. Lee*

* Department of Chemical Engineering, National Taiwan University, Taipei 106, Chinese Taiwan ** Department of Chemical Engineering, Yuan Ze University, Chung-Li 320, Chinese Taiwan Abstract Liquid-phase adsorption removal of Cu2+, Co2+, Ni2+, Zn2+, and Pb2+ in the concentration range of 525 mg/L using low-cost banana and orange peel wastes was examined at 30 oC. Under comparable conditions, the amount of adsorption decreased in the order Pb2+ > Ni2+ > Zn2+ > Cu2+ > Co2+ for both adsorbents. The adsorption isotherms could be better described by the Freundlich equation. The amount of adsorption increased with increasing pH and reached a plateau at pH > 7, which was conrmed by the variations of zeta potentials. The application potential of such cellulose-based wastes for metal removal (up to 7.97 mg Pb2+ per gram of banana peel at pH 5.5) at trace levels appeared to be promising. Keywords Adsorption removal; fruit peels; heavy metals; zeta potentials

Water Science and Technology Vol 47 No 1 pp 185190 IWA Publishing 2002

Introduction

Industrial and agricultural wastes pollute water with heavy metals, which reach tissues through the food chain (Laxen, 1983; Florence, 1982). The toxicity of heavy metals to aquatic organisms has been a subject of interest to biologist for many years. Among different types of pollution the industrial wastes constitute the major sources of metal pollution. Toxic metals such as Cd, Zn, Cr, Pb, and Cu find their ways to the industries as metal plating industries, nickel batteries, pigments, and as stabilizers of alloys (Low and Lee, 1991). The conventional methods for metal removal from water include reduction, precipitation, ion exchange, electrochemical reduction, and reverse osmosis. Most of them involve high capital costs with recurring expenses, which are not suitable for small-scale industries. Studies on treatment of metal-bearing effluents have revealed adsorption to be effective among the physicochemical processes. Adsorption with activated carbon is widely applied for removal of heavy metals at trace levels (Huang and Blankenship, 1984). Despite the versatibility of carbon adsorbents in water treatment, it remains costly. In recent years the use of low-cost materials as alternatives to carbon has been encouraged (Kumar and Dara, 1981; Pollards et al., 1992). Other biological materials including polymerized corncob (Henderson et al., 1977), moss (Low and Lee, 1987), hulls and bran (Marshall et al., 1993), and water-hyacinth roots (Low et al., 1994) were also reported to be suitable for metal removal. This paper reports the potential of banana and orange peels as adsorbents for removal of Cu2+, Zn2+, Co2+, Ni2+, and Pb2+ from water. The residues of banana and orange peels can be processed and converted to be adsorbents because they have large surface areas, high swelling capacities, excellent mechanical strengths, and are convenient to use and have great potential to adsorb harmful contaminants such as heavy metals.
Experimental
Materials

Banana and orange peels were cut into small pieces, dried, crushed, and washed thoroughly with double distilled water to remove the adhering dirt. They were finally dried in an air

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oven at 100C for 24 h. After drying, the adsorbents were sieved. The particle sizes were 1 to 5 mm. Synthetic solutions were prepared from analytical-reagent grade CuSO4, CoSO4, NiSO4, ZnSO4, and Pb(NO3)2. The sieved peels were treated separately with 0.4 mol L1 NaOH, 0.4 mol L1 HNO3, and distilled water. A typical process of acid and alkali treatment was described as follows. Banana or orange peels (15 g) were soaked in 200 mL of 0.4 mol L1 HNO3 for 24 h. They were filtered and rinsed with distilled water until the filtrate was near neutral.
Batch studies

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A batch adsorption run was made to determine the adsorption capacity of metal. Tests were performed by agitating 0.1 g of adsorbent with 100-mL metal solution at 180 rpm for 24 h. On centrifugation at 10,000 rpm for 20 min, the residual metal was determined by an atomic absorption spectrophotometer (Varian Model 202FS). The amount of metals adsorbed was calculated by mass balance. Each experiment was carried out in duplicate. Reproducibility was within 3%.
Zeta potential and microscopic observations

Zeta potential of the solution was measured by the Zetasizer 3000HS system (Malvern Instruments Ltd., UK). For the SEM imaging, the moistures in the specimens were dried to their critical points, glued into aluminum plates and spattered with 15 nm gold for scanning electron microscopy analysis (Model JSM-5600, JEOL Japan) operated at 15 kV.
Regeneration studies

An amount of adsorbent (0.1 g) was treated with 100 mL of heavy metal solution (5 mg/L) in a conical flash and after equilibrium times it was filtered. The adsorbent was then treated with 100 mL of HCl solution (0.04, 0.05, 0.06, 0.07 mol L1) for 24 h. The adsorbent was washed several times with distilled water in order to remove excess acid. It was again treated with 100 mL of metal solution and the above procedure was repeated.
Results and discussion
Metal adsorption

Figures 1 and 2 show adsorption isotherms i.e. the relations between the amount of metal adsorbed per unite mass of banana and orange peel (qe) and their remaining concentrations in the solutions (Ce). The adsorption ability decreases in the order Pb2+ > Ni2+ > Zn2+ > Cu2+ > Co2+ under comparable conditions. Such trends are similar to those obtained previously for metal adsorption by orange peel (Ajmal et al., 2000), banana pith (Low et al., 1995), and peanut hull carbon (Periyasamy and Namasivayam, 1996). The most widely used two-parameter equation is the Langmuir equation, represented as: 1/qe = (1/qe) + (1/KLqmon)(1/Ce), (1)

where KL is the Langmuir constant and qmon the amount adsorbed corresponding to complete coverage. A plot of (1/qe) vs. (1/Ce) gives KL and qmon from the slope and intercept. The Langmuir parameters obtained are listed in Table 1. The adsorption capacities are 7.97 (Pb2+), 6.88 (Ni2+), 5.80 (Zn2+), 4.75 (Cu2+), and 2.55 mg/g (Co2+) at an equilibrium pH of around 5.45.8 using banana peel; and are 7.75 (Pb2+), 6.01 (Ni2+), 5.25 (Zn2+), 3.65 (Cu2+), and 1.82 mg/g (Co2+) at an equilibrium pH of about 4.85.0 using orange peel. The Freundlich equation is an empirical one used to describe the isotherm data: ln qe = ln KF + (1/n)ln Ce. (2)

Amount of heavy metal adsorbed (mg/g)

Amount of heavy metal adsorbed (mg/g)

12

9 8 6 5 3

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2 0

0 0 4 8 12 16 20 24 28

12

16

20

24

28

Heavy metal concentration (mg/L)

Concentration of heavy metal (mg/L)

Figure 1 Effect of metal concentration on metal removal by banana peel. (L) Pb pH 5.89; (N ) Ni pH 6.89; (N) Zn pH 6.54; (G) Cu pH 5.92;(N ) Co pH 6.66
8

Figure 2 Effect of metal concentration on metal removal by orange peel. (L) Pb pH 5.89; (N) Zn pH 6.54; (N ) Ni pH 6.89; (G) Cu pH 5.92 (N ) Co pH 6.66
6

Amount of heavy metal adsorbed (mg/g)

Amount of heavy metal adsorbed (mg/g)

Zn

Zn Ni

Ni Cu

Cu

4
Co

2
Co

0 1.5

0
3.0 4.5 6.0 7.5 9 .0

1.5

3.0

4.5

6.0

7.5

9 .0

pH

pH

Figure 3 Effect of pH on metal removal by banana peel (N) Zn; (N ) Ni; (G) Cu; and (N ) Co. Initial metal concentration 15 mg/L

Figure 4 Effect of pH on removal of metals by orange peel. (N ) Zn; (N) Ni; (G) Cu; and (N ) Co. Initial metal concentration 15 mg/L

A plot of ln qe vs. ln Ce will give n and KF, which are listed in Table 2. This equation, which is suitable for a highly heterogeneous surface, often gives a good representation of adsorption data over a restricted range of concentration (Huang and Blankenship, 1984).
Effect of pH

The amount of metal adsorption increases with pH (Figures 3 and 4), which is typical of metal adsorption by banana and orange peels. Metal adsorption depends on the nature of the adsorbent surface and species solution. At lower pH, H+ competes with metals for the exchange sites in the system thereby partially releasing the latter. The heavy metals are completely released under circumstances of extreme acidic conditions. The amount of adsorption is a minimum at pH 2 and increases as pH increases. The maximum adsorption occurs at pH 68 for banana and orange peels. But adsorption decreases when pH increases further. The minimum adsorption at low pH (< 2) may be due to the higher concentration and high mobility of H+. The H+ ions are preferentially adsorbed over metal ions. Solution pH would affect both aqueous chemistry and surface binding-sites of the banana and orange peels. The amount of adsorption increases with increasing pH up to the point (> 8) where the metals precipitate.
SEM and zeta potentials

Figure 5 shows the SEM images of the banana and orange peels. The original peels have a highly porous structure. Peels have a surface partially covered by heavy metals for the used peels. Figures 6a and 6b show the EDS spectra for the original peels, and 6c and 6d for the used particles equilibrated with 5 mg/L of both Cu and Zn. The EDS peaks demonstrate

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Counts 1000 800 600 400 200 0 Ca 0 Si O S S C Ca Ca 5 10

(a)

(b)

(c)

(d)

Figure 5 SEM images. (a) original banana peel (b) original orange peel (c) banana peel after adsorption (Initial condition: 5 mg/L of Cu and Zn) (d) orange peel after adsorption (5 mg/L of Cu and Zn)
Counts 1000 800 600 400 200 0 Ca 0 O

Ca Ca 5 10 15 20 Energy (keV)

15

20 Energy (keV)

(a)
Counts C 2000 1500 1000 Zn Cu 500 Zn Cu Ca 0 0
2000 1500 1000 500 0 Zn Cu Zn Cu Ca 0 Counts C O

(b)

Si Cu Zn Cu Zn 5 10 15 20 Energy (keV)

Ca Ca

Ca Ca 5

Cu Zn Cu Zn 10 15 20 Energy (keV)

(c)

(d)

Figure 6 EDS Spectra. (a) original banana peel (b) original orange peel (c) banana peel after adsorption (Initial condition: 5 mg/L of Cu and Zn) (d) orange peel after adsorption (5 mg/L of Cu and Zn)

Table 1 Parameters obtained for the Langmuir isotherm

Metal qmon (mg/g) Banana peel KL (L/mg) R qmon (mg/g) Orange peel KL (L/mg) r

Cu2+ Co2+ Ni2+ Zn2+ Pb2+

4.75 2.55 6.88 5.80 7.97

8.54 9.04 7.55 7.28 6.60

0.9841 0.9868 0.9509 0.9678 0.9697

3.65 1.82 6.01 5.25 7.75

12.2 13.1 10.2 9.53 9.70

0.9561 0.9575 0.9436 0.9509 0.9626

Table 2 Parameters obtained for the Freundlich isotherm

Metal KF (mg/g)(mg/L)n Banana peel 1/n R KF (mg/g)(mg/L)n Orange peel 1/n r

Cu2+ Co2+ Ni2+ Zn2+ Pb2+

0

0.93 0.41 1.77 1.38 2.87

1.22 1.09 1.44 1.34 1.77

0.9989 0.9996 0.9939 0.9982 0.9994

0

0.59 0.41 0.97 1.43 1.79

1.10 1.06 1.20 1.33 1.42

0.9908 0.9945 0.9854 0.9822 0.9875

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-15

-15

Zeta potential (mV)

Zeta potential (mV)

-30

-30

Zn Co Cu Ni

Co
-45

Zn Cu Ni

-45

-60

-60 2 4 6 8

-75 2 4 6 8

pH

pH

Figure 7 Zeta potential measurements for metal removal by banana peel. Original: (); after adsorption: (G) Cu; (N ) Co; (N) Ni; (N ) Zn (Initial concentration of 15 mg/L)

Figure 8 Zeta potential measurements for metal removal by orange peel. Original: (); after adsorption: (G) Cu; (N ) Co; (N) Ni; (N ) Zn (Initial concentration of 15 mg/L)

the existence of both Cu and Zn metals on the peel surface. Figures 7 and 8 show the zeta potentials of the banana and orange peel. The original peels exhibit a negative zeta potential and the used particles possess a less negative potential. All these results reveal that the waste peels had adsorbed the metal ions.
Treated adsorbents

Table 3 shows the amount of metal adsorption of the acid-, alkali-, and water-treated peels. The low uptake of Co2+ by banana and orange peel is possibly due to saturation of the sorption site by Zn2+, Cu2+, Ni2+, and Pb2+. It is evident that Pb2+ has the greatest adsorption affinity. The low affinity of Ni2+ and Cu2+ in other biological systems has also been reported (Low and Lee, 1994, 1995).
Adsorbent regeneration

Tables 4 and 5 list the desorption tests of metals on the peels by batch operation after regeneration cycle by 0.04, 0.05, 0.06, and 0.07 mol L1 HCl. The adsorption remains high (2.25 mg/g) up to the one regeneration cycle and then goes to 3.85 mg/g in the second cycle. The adsorbent can be used successfully for two regenerations for removal and recovery of heavy metals.
Table 3 Metal adsorption capacities (in mg/g) for various adsorbents
Type of adsorbent Cu2+ Co2+ Ni2+ Zn2+ Pb2+

Acid-treated banana peel Alkali-treated banana peel Water-treated banana peel Acid-treated orange peel Alkali-treated orange peel Water-treated orange peel

2.14 2.00 1.80 1.85 1.55 1.35

1.44 1.40 1.20 1.25 1.15 1.00

3.14 3.08 2.85 2.14 2.05 1.65

2.75 2.25 2.15 2.75 2.65 1.85

4.00 3.65 3.25 3.20 2.85 2.25

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Table 4 Amount of metal desorbed on banana peel treated with HCl

Metal Loaded (mg/g) 0.04 M Cycle one (mg/L) 0.05 M 0.06 M 0.07 M 0.04 M Cycle two (mg/L) 0.05 M 0.06 M 0.07 M

Cu2+ Co2+ Ni2+ Zn2+ Pb2+

2.25 1.25 2.14 2.75 4.00

0.82 0.45 1.24 0.98 2.15

0.85 0.85 1.25 1.00 2.25

0.62 0.75 1.10 0.85 2.10

0.61 0.72 1.05 0.65 2.00

1.85 1.00 2.85 2.55 3.55

2.00 1.15 3.00 2.65 3.85

1.85 1.00 2.95 2.55 3.65

1.62 1.10 2.85 2.45 3.64

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Table 5 Amount of metal desorbed on orange peel treated with HCl

Metal Loaded (mg/g) 0.04 M Cycle one (mg/L) 0.05 M 0.06 M 0.07 M 0.04 M Cycle two (mg/L) 0.05 M 0.06 M 0.07 M

Cu2+ Co2+ Ni2+ Zn2+ Pb2+

1.85 1.14 2.14 2.75 3.20

0.52 0.63 0.85 0.64 0.85

0.65 0.65 1.15 1.25 2.25

0.62 0.64 0.98 1.00 2.00

0.52 0.63 0.92 1.02 2.10

1.25 1.01 2.05 2.45 2.65

1.68 1.02 2.08 2.55 2.98

1.55 1.00 1.95 2.25 2.65

1.45 1.00 1.85 2.10 2.55

Conclusions

This work examined the adsorption of metals (Cu2+, Zn2+, Co2+, Ni2+, Pb2+) from synthetic solutions using the acid-, alkali-, and water-treated banana and orange peels. The adsorption capacity was found to be 7.97 (Pb2+), 6.88 (Ni2+), 5.80 (Zn2+), 4.75 (Cu2+), and 2.55 mg/g (Co2+) using banana peel; and was 7.75 (Pb2+), 6.01 (Ni2+), 5.25 (Zn2+), 3.65 (Cu2+), and 1.82 mg/g (Co2+) using orange peel. Favorable adsorption was achieved at high pH, with its maximum level of Pb2+ reaching about 7.97 (banana) and 7.75 mg/g (orange). The banana and orange peels appeared to be useful in the removal of trace metals from synthetic solutions.
Acknowledgement

Support for this work by the National Science Council, ROC, under Grant No. NSC892211-E-002-008 is gratefully appreciated.
References
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