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 Cu
2+
, Co
2+
, Ni
2+
, Zn
2+
, and Pb
2+
in the concentration range of
525 mg/L using low-cost banana and orange peel wastes was examined at 30
o
C. Under comparable
conditions, the amount of adsorption decreased in the order Pb
2+
> Ni
2+
> Zn
2+
> Cu
2+
> Co
2+
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 Pb
2+
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
Cu
2+
, Zn
2+
, Co
2+
, Ni
2+
, and Pb
2+
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 CuSO
4
,
CoSO
4
, NiSO
4
, ZnSO
4
, and Pb(NO
3
)
2
. The sieved peels were treated separately with
0.4 mol L
1
NaOH, 0.4 mol L
1
HNO
3
, 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
HNO
3
for 24 h. They were filtered and rinsed with distilled water
until the filtrate was near neutral.
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 (q
e
) and their remaining concentrations
in the solutions (C
e
). The adsorption ability decreases in the order Pb
2+
> Ni
2+
> Zn
2+
>
Cu
2+
> Co
2+
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/q
e
= (1/q
e
) + (1/K
L
q
mon
)(1/C
e
), (1)
where K
L
is the Langmuir constant and q
mon
the amount adsorbed corresponding to com-
plete coverage. A plot of (1/q
e
) vs. (1/C
e
) gives K
L
and q
mon
from the slope and intercept.
The Langmuir parameters obtained are listed in Table 1. The adsorption capacities are
7.97 (Pb
2+
), 6.88 (Ni
2+
), 5.80 (Zn
2+
), 4.75 (Cu
2+
), and 2.55 mg/g (Co
2+
) at an equili-
brium pH of around 5.45.8 using banana peel; and are 7.75 (Pb
2+
), 6.01 (Ni
2+
), 5.25
(Zn
2+
), 3.65 (Cu
2+
), and 1.82 mg/g (Co
2+
) 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 q
e
= ln K
F
+ (1/n)ln C
e
. (2)
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A plot of ln q
e
vs. ln C
e
will give n and K
F
, 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 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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0 4 8 12 16 20 24 28
Heavy metal concentration (mg/L)
0
2
4
6
8
10
12
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(
m
g
/
g
)
0 4 8 12 16 20 24 28
Concentration of heavy metal (mg/L)
0
2
3
5
6
8
9
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(
m
g
/
g
)

Figure 1 Effect of metal concentration on metal
removal by banana peel. (L) Pb pH 5.89;
(N N) Ni pH 6.89; (N) Zn pH 6.54; (G) Cu pH
5.92;(N) Co pH 6.66
Figure 2 Effect of metal concentration on metal
removal by orange peel. (L) Pb pH 5.89;
(N) Zn pH 6.54; (N N) Ni pH 6.89; (G) Cu pH
5.92 (N) Co pH 6.66
1.5 3.0 4.5 6.0 7.5 9.0
pH
0
2
4
6
8
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h
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a
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s
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b
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(
m
g
/
g
)
Zn
Ni
Cu
Co
1.5 3.0 4.5 6.0 7.5 9.0
pH
0
2
4
6
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(
m
g
/
g
)
Zn
Ni
Cu
Co
Figure 3 Effect of pH on metal removal by banana
peel (N) Zn; (N 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 N) Zn; (N) Ni; (G) Cu; and (N) Co.
Initial metal concentration 15 mg/L
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(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)
0 5 10 15 20
Energy (keV)
0
200
400
600
800
1000
Counts
C
Ca
O
Si
S
S
Ca
Ca
0 5 10 15 20
Energy (keV)
0
200
400
600
800
1000
Counts
C
Ca
O
Ca
Ca
(a) (b)
0 5 10 15 20
Energy (keV)
0
500
1000
1500
2000
Counts
C
Ca
O
Cu
Zn
Cu
Zn
Si
Ca
Ca
Cu
Zn
Cu
Zn
0 5 10 15 20
Energy (keV)
0
500
1000
1500
2000
Counts
C
Ca
O
Cu
Zn
Cu
Zn
Ca
Ca
Cu
Zn
Cu
Zn
(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
q
mon
(mg/g) K
L
(L/mg) R q
mon
(mg/g) K
L
(L/mg) r
Cu
2+
4.75 8.54 0.9841 3.65 12.2 0.9561
Co
2+
2.55 9.04 0.9868 1.82 13.1 0.9575
Ni
2+
6.88 7.55 0.9509 6.01 10.2 0.9436
Zn
2+
5.80 7.28 0.9678 5.25 9.53 0.9509
Pb
2+
7.97 6.60 0.9697 7.75 9.70 0.9626
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 Co
2+
by banana and orange peel is possibly due to saturation of the sorp-
tion site by Zn
2+
, Cu
2+
, Ni
2+
, and Pb
2+
. It is evident that Pb
2+
has the greatest adsorption
affinity. The low affinity of Ni
2+
and Cu
2+
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.
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Table 2 Parameters obtained for the Freundlich isotherm
Metal Banana peel Orange peel
K
F
(mg/g)(mg/L)
n
1/n R K
F
(mg/g)(mg/L)
n
1/n r
Cu
2+
0.93 1.22 0.9989 0.59 1.10 0.9908
Co
2+
0.41 1.09 0.9996 0.41 1.06 0.9945
Ni
2+
1.77 1.44 0.9939 0.97 1.20 0.9854
Zn
2+
1.38 1.34 0.9982 1.43 1.33 0.9822
Pb
2+
2.87 1.77 0.9994 1.79 1.42 0.9875
2 4 6 8
pH
-60
-45
-30
-15
0
Zn
Co
Cu
Ni
Z
e
t
a

p
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t
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t
i
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(
m
V
)
2 4 6 8
pH
-75
-60
-45
-30
-15
0
Zn
Co
Cu
Ni
Z
e
t
a

p
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t
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i
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(
m
V
)
Figure 7 Zeta potential measurements for metal
removal by banana peel. Original: (); after adsorp-
tion: (G) Cu; (N) Co; (N) Ni; (N N) Zn (Initial concen-
tration of 15 mg/L)
Figure 8 Zeta potential measurements for metal
removal by orange peel. Original: (); after adsorp-
tion: (G) Cu; (N) Co; (N) Ni; (N N) Zn (Initial concen-
tration of 15 mg/L)
Table 3 Metal adsorption capacities (in mg/g) for various adsorbents
Type of adsorbent Cu
2+
Co
2+
Ni
2+
Zn
2+
Pb
2+
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
Conclusions
This work examined the adsorption of metals (Cu
2+
, Zn
2+
, Co
2+
, Ni
2+
, Pb
2+
) from synthetic
solutions using the acid-, alkali-, and water-treated banana and orange peels. The adsorp-
tion capacity was found to be 7.97 (Pb
2+
), 6.88 (Ni
2+
), 5.80 (Zn
2+
), 4.75 (Cu
2+
), and
2.55 mg/g (Co
2+
) using banana peel; and was 7.75 (Pb
2+
), 6.01 (Ni
2+
), 5.25 (Zn
2+
), 3.65
(Cu
2+
), and 1.82 mg/g (Co
2+
) using orange peel. Favorable adsorption was achieved at high
pH, with its maximum level of Pb
2+
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.
References
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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
Cu
2+
2.25 0.82 0.85 0.62 0.61 1.85 2.00 1.85 1.62
Co
2+
1.25 0.45 0.85 0.75 0.72 1.00 1.15 1.00 1.10
Ni
2+
2.14 1.24 1.25 1.10 1.05 2.85 3.00 2.95 2.85
Zn
2+
2.75 0.98 1.00 0.85 0.65 2.55 2.65 2.55 2.45
Pb
2+
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
Cu
2+
1.85 0.52 0.65 0.62 0.52 1.25 1.68 1.55 1.45
Co
2+
1.14 0.63 0.65 0.64 0.63 1.01 1.02 1.00 1.00
Ni
2+
2.14 0.85 1.15 0.98 0.92 2.05 2.08 1.95 1.85
Zn
2+
2.75 0.64 1.25 1.00 1.02 2.45 2.55 2.25 2.10
Pb
2+
3.20 0.85 2.25 2.00 2.10 2.65 2.98 2.65 2.55