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Adsorption of Heavy Metals From Water Using Banana and

Orange Peels

Article  in  Water Science & Technology · January 2003

DOI: 10.2166/wst.2003.0049 · Source: PubMed

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Adsorption of heavy metals from water using banana and

Water Science and Technology Vol 47 No 1 pp 185–190 © IWA Publishing 2002

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
5–25 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 confirmed 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

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 differ-
ent 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 plat-
ing industries, nickel batteries, pigments, and as stabilizers of alloys (Low and Lee, 1991).
The conventional methods for metal removal from water include reduction, precipita-
tion, 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 185
 oven at 100°C 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 L–1 NaOH, 0.4 mol L–1 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 L–1 HNO3 for 24 h. They were filtered and rinsed with distilled water
until the filtrate was near neutral.
G. Annadurai et al.

Batch studies
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 atom-
ic 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 L–1) for 24 h. The adsorbent was
washed several times with distilled water in order to remove excess acid. It was again treat-
ed 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 previ-
ously 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 com-
plete 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 equili-
brium pH of around 5.4–5.8 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 4.8–5.0 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)
186
 12

Amount of heavy metal adsorbed (mg/g)

Amount of heavy metal adsorbed (mg/g)
9

10
8

8
6

6
5

4 3

G. Annadurai et al.
2 2

0 0
0 4 8 12 16 20 24 28 0 4 8 12 16 20 24 28

Heavy metal concentration (mg/L) Concentration of heavy metal (mg/L)

Figure 1 Effect of metal concentration on metal Figure 2 Effect of metal concentration on metal
removal by banana peel. (▲) Pb – pH 5.89; removal by orange peel. (▲) Pb – pH 5.89;
◆ ) Ni – pH 6.89; (◆) Zn – pH 6.54; (●) Cu – pH
(◆ ◆ ) Ni – pH 6.89; (●) Cu – pH
(◆) Zn – pH 6.54; (◆
5.92;(◆◆ ) Co – pH 6.66 ◆ ) Co – pH 6.66
5.92 (◆
8 6
Amount of heavy metal adsorbed (mg/g)

Amount of heavy metal adsorbed (mg/g)

Zn Zn
Ni

6
Ni
4
Cu
Cu

Co 2
2
Co

0 0
1.5 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 Figure 4 Effect of pH on removal of metals by

◆ ) Ni; (●) Cu; and (◆
peel (◆) Zn; (◆ ◆ ) Co. Initial metal orange peel. (◆ ◆ ) Zn; (◆) Ni; (●) Cu; and (◆
◆ ) Co.
concentration 15 mg/L 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 adsorp-
tion 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 6–8 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 187
G. Annadurai et al.

(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 Counts
1000 C
1000 C

800 800

600 600

O
400 O 400

200 S 200
S Ca Ca
Ca Si Ca Ca
0 Ca
0
0 5 10 15 20 0 5 10 15 20
Energy (keV) Energy (keV)

(a) (b)
Counts Counts
C C
O
2000 2000

1500 O 1500

1000 1000
Si
Zn
Zn
Cu
Cu 500
500 Zn Ca Cu
Zn Ca Cu
Cu Zn
Cu Ca Zn Ca
Ca Cu Zn
Ca Cu Zn
0 0
0 5 10 15 20 0 5 10 15 20
Energy (keV) 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 Banana peel Orange peel

qmon (mg/g) KL (L/mg) R qmon (mg/g) KL (L/mg) r

Cu2+ 4.75 8.54 0.9841 3.65 12.2 0.9561

Co2+ 2.55 9.04 0.9868 1.82 13.1 0.9575
Ni2+ 6.88 7.55 0.9509 6.01 10.2 0.9436
Zn2+ 5.80 7.28 0.9678 5.25 9.53 0.9509
188 Pb2+ 7.97 6.60 0.9697 7.75 9.70 0.9626
Table 2 Parameters obtained for the Freundlich isotherm

Metal Banana peel Orange peel

KF (mg/g)(mg/L)n 1/n R KF (mg/g)(mg/L)n 1/n r

Cu2+ 0.93 1.22 0.9989 0.59 1.10 0.9908

Co2+ 0.41 1.09 0.9996 0.41 1.06 0.9945
Ni2+ 1.77 1.44 0.9939 0.97 1.20 0.9854
Zn2+ 1.38 1.34 0.9982 1.43 1.33 0.9822

G. Annadurai et al.
Pb2+ 2.87 1.77 0.9994 1.79 1.42 0.9875

0
0

-15
-15
Zeta potential (mV)

Zeta potential (mV)

-30
-30 Zn
Zn Co
Co Cu
Cu -45 Ni
Ni

-45
-60

-60 -75
2 4 6 8 2 4 6 8
pH
pH

Figure 7 Zeta potential measurements for metal Figure 8 Zeta potential measurements for metal
removal by banana peel. Original: (✙); after adsorp- removal by orange peel. Original: (✙); after adsorp-
◆ ) Co; (◆) Ni; (◆
tion: (●) Cu; (◆ ◆ ) Zn (Initial concen- ◆ ) Co; (◆) Ni; (◆
tion: (●) Cu; (◆ ◆ ) Zn (Initial concen-
tration of 15 mg/L) tration 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 sorp-
tion 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 report-
ed (Low and Lee, 1994, 1995).

Adsorbent regeneration
Tables 4 and 5 list the desorption tests of metals on the peels by batch operation after regen-
eration cycle by 0.04, 0.05, 0.06, and 0.07 mol L–1 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 2.14 1.44 3.14 2.75 4.00

Alkali-treated banana peel 2.00 1.40 3.08 2.25 3.65
Water-treated banana peel 1.80 1.20 2.85 2.15 3.25
Acid-treated orange peel 1.85 1.25 2.14 2.75 3.20
Alkali-treated orange peel 1.55 1.15 2.05 2.65 2.85
Water-treated orange peel 1.35 1.00 1.65 1.85 2.25
189
 Table 4 Amount of metal desorbed on banana peel treated with HCl

Metal Loaded Cycle one (mg/L) Cycle two (mg/L)

(mg/g) 0.04 M 0.05 M 0.06 M 0.07 M 0.04 M 0.05 M 0.06 M 0.07 M

Cu2+ 2.25 0.82 0.85 0.62 0.61 1.85 2.00 1.85 1.62
Co2+ 1.25 0.45 0.85 0.75 0.72 1.00 1.15 1.00 1.10
Ni2+ 2.14 1.24 1.25 1.10 1.05 2.85 3.00 2.95 2.85
Zn2+ 2.75 0.98 1.00 0.85 0.65 2.55 2.65 2.55 2.45
Pb2+
G. Annadurai et al.

4.00 2.15 2.25 2.10 2.00 3.55 3.85 3.65 3.64

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

Metal Loaded Cycle one (mg/L) Cycle two (mg/L)

(mg/g) 0.04 M 0.05 M 0.06 M 0.07 M 0.04 M 0.05 M 0.06 M 0.07 M

Cu2+ 1.85 0.52 0.65 0.62 0.52 1.25 1.68 1.55 1.45
Co2+ 1.14 0.63 0.65 0.64 0.63 1.01 1.02 1.00 1.00
Ni2+ 2.14 0.85 1.15 0.98 0.92 2.05 2.08 1.95 1.85
Zn2+ 2.75 0.64 1.25 1.00 1.02 2.45 2.55 2.25 2.10
Pb2+ 3.20 0.85 2.25 2.00 2.10 2.65 2.98 2.65 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 adsorp-
tion 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. NSC89-
2211-E-002-008 is gratefully appreciated.

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