Adsorption of Chromium From Wastewater By: Platanus Orientalis Leaves
Adsorption of Chromium From Wastewater By: Platanus Orientalis Leaves
Adsorption of Chromium From Wastewater By: Platanus Orientalis Leaves
191-196
*Corresponding author-Email: ahmahvi@yahoo.com
Tel: +98 21 8895 4914, Fax: +98 21 8895 0188
191
ADSORPTION OF CHROMIUM FROM WASTEWATER BY
PLATANUS ORIENTALIS LEAVES
*1
A. H. Mahvi,
2
R. Nabizadeh,
2
F. Gholami,
2
A. Khairi
1
Department of Environmental Health Engineering, School of Public Health and Center for Environmental
Researche, Medical Sciences/University of Tehran, Tehran, Iran
2
Department of Environmental Health Engineering, School of Public Health and Institute of Public Health
Researches, Medical Sciences/University of Tehran, Tehran, Iran
Received 10 May 2007; revised 29 May 2007; accepted 28 J une 2007
ABSTRACT
The Cr (VI) adsorption characteristics of platanus orientalis leaves and their ash were examined as a
function of contact time, initial pH and metal ion concentration. Batch adsorption experiments were
performed. The effects of Ca
2+
, Mg
2+
, Na
+
and K
+
on adsorption werestudied. The effect of this adsorbent
on COD in wastewater showed that 2g/L of adsorbent caused increase of 110mg/L and 76mg/L COD in
deionized water in 120 minutes for platanus orientalis leaves and their ash , respectively. The maximum
removal took place in the pH range of 6-7, contact time of 60 minutes and initial concentration of
2mg/L. Studies showed that the Freundlich adsorption model better fitted with the results than Langmuir
with R
2
>0.85. The study showed platanus orientalis leaves ash was more favorable than living ones as
well as in removing chromiumfromthe aqueous solution.
Key words: Cadmium removal, Platanus orientalis leaves, ash, aqueous solution
INTRODUCTION
The presence of heavy metals in drinking water
can be toxic to consumers; these metals can
damage nerves, liver and bones and block
functional groups of vital enzymes (Ewan and
Pamphlet, 1996). In the recent years, increasing
awareness of water pollution and its far reaching
effects has prompted concerted efforts towards
pollution abatement .Among the different heavy
metals fromtoxic pollutant introduced into natural
waters (Donmez and Aksu, 2002).
There are two major sources of heavy metals
contamination, wastewater metal finishing
industries (hexavalent chromium) and tanneries
(trivalent chromium). Chromium occurs most
frequently as Cr(VI) or Cr(III) in aqueous solutions
(Dakikiy et al., 2002).
Both valences of chromiumare potentially harmful
but hexavalent chromiumhave a grater risk due to
its carcinogenic properties (Dakikiy et al., 2002).
Hexavalent chromium which is primarily present
in the form of chromate(CrO
4
2-
) and dichromate
(Cr
2
O
7
2-
), poses significantly higher levels of
toxicity than the other valences states(Sharma and
Forester, 1995).The toxicity of hexavalent
Chromium, even in small concentrations has been
well documented. Since the addition of Chromium
ions through industrial waste effluents into natural
bodies of water causes serious environmental
disruption, strict wastewater standards have been
setup in many countries. In J apan the standard on
wastewater quality states that the maximumlevel
permitted in wastewater are 2mg/dm
3
for total Cr
and 0.05 mg/dm
3
for Cr (VI) (Masakazu, 2003).
Techniques for removal of heavy metals from
industrial wastewater include precipitation, ion
exchange, adsorption, electrodialysis and filtration;
but these methods have limitations on selective
separation and high cost of investment and
operation of equipment (Dae et al., 2003).
Adsorption of heavy metal ions on to activated
carbon has been widely applied as a unit operation
in the treatment industrial wastewater. The use of
commercial activated carbon is not suitable for
developing countries because of its high cost.
Iran. J. Environ. Health. Sci. Eng., 2007, Vol. 4, No. 3, pp. 191-196
192
A. H. Mahvi, et al., ADSORPTION OF CHROMIUM FROM...
Therefore, there is a need to produce activated
carbon from cheaper and readily available
materials, which can be used economically on a
large scale. Activated carbons prepared fromrice
husk, ground nut husk, fertilizer waste slurry,
peanut hull, jute stick, moringa olefera seed husk,
coconut husk and sawdust (Manju and Anirudhun,
1997; Raji et al., 1997; Warhurst et al., 1997) have
been used for wastewater treatment and the
potential of their ultimate usage may be determined
by their adsorption capacity, regeneration
characteristics and physical properties of the
subsequent product. In recent years, adsorption
has emerged as a cost-effective and efficient
alternative for the removal of heavy metals from
low strength wastewaters.
Biosorption is the uptake of heavy metal ions and
radionuclides from aqueous environments by
biological materials such as: algae, bacteria , yeast,
fungi , plant leaves and root tissues which can be
used as biosorbents for detoxification and recovery
of toxic or valuable metals from industrial
discharges (Veglio and Beolchini, 1997). Certain
waste materials from industrial or agricultural
operations may be potential alternative biosorbents
(Baylor, et al., 1999). It has been reported that
wood wastes such as saw dust, barks and tree
leaves effectively adsorb cadmiumspecies from
aqueous systems (Kumar and Dara, 1982;
Aoyama, et al., 1999).
The binding mechanisms of heavy metals by
biosorption could be explained by the physical and
chemical interactions between cellwall ligands and
adsorbates by ion exchange, complexation,
coordination and microprecipitation. The diffusion
of the metal fromthe bulk solution to active sites
of biosorbents occurs predominantly by passive
transport mechanisms (Veglio and Beolchini, 1997)
and various functional groups such as carboxyl,
hydroxyl, amino and phosphate existing on the cell
wall of biosorbents can bind the heavy metals
(Avery and Tobin, 1993).
Tree leaves that are in agricultural operations are
generally little or no economic value. In Tehran,
plants and trees such as Plataneus Orientalis
have been widely planted as street and park trees.
Although the pruning of these trees produces waste
foliage in large quantities, they are discarded. Large
piles of the waste foliage pose problems in its
disposal.
This study was performed to investigate the
efficiency of Platanus orientalis leaves (POL)
and their ash on removing chromium fromdilute
aqueous solutions. The parameters that affect
biosorbtion such as initial chromiumconcentration,
contact time , pH and the presence of metals such
as (Ca
+2
,Mg
+2
,Na
+
and K
+
) were also investigated;
the effect of this biosorbent on increasing COD in
wastewater was studied.
MATERIALS AND METHODS
Platanus Orientalis leaves used were obtained
from various parks in Tehran. They were washed
with deionized water to clean and then laid down
to be flatted dried. Dry leaves were then ground
with mechanical grinder. After being ground
grinded, the leaf particles were sieved with 60-70
mesh sieves (0.20-0.3mm). Then, leaf was dried
at 100
o
C to reach the constant weight. Adsorbents
were stored in desiccators unitl use. The POL ash
was obtained from burning of POL in oven at
550
o
C for 30 minutes.
Adsorption of chromium(VI) in wastewater on
POL and their ash were examined by optimizing
various physicochemical parameters such as: pH,
contact time and concentration of Cr(VI).
The
effect of metals such as (Ca
2+
, Mg
2+
, Na
+
and K
+
)
were also studied.
Stock solution of chromium (1000 mg/L) was
prepared by dissolving titrazol chromium(VI) in
distilled water. The concentration range of
chromium prepared from stock solution varied
between 2 to 40 mg/L for both POL and their ash.
Before mixing the adsorbent, pH of each solution
was adjusted to the required value with diluted and
concentrated H
2
SO
4
and NaOH solution,
respectively. Ca
2+
, Mg
2+
, Na
+
and K
+
solutions were
prepared by their salts in concentration of 2 mol/L.
The experiments were carried out in batch for the
measurement of adsorption capacities. Each
chromiumsolution was placed in 1000 mL beaker
and known amount of adsorbents (l g) were added
to each beaker. The beakers were agitated on jar
test equipment at a 300 rpmconstant mixing rate
for 30-240 minutes to ensure equilibrium was
reached.
Iran. J. Environ. Health. Sci. Eng., 2007, Vol. 4, No. 3, pp. 191-196
193
Finally the fitness of the Freundlich and Langmuir
adsorption models to the equilibriumdata were
investigated for chromium-sorbent system. A
duplicate analysis for each sample to track
experimental error and show capability of
reproducing results was done.
The residual chromium was analyzed through
atomic spectrometry using an ALPH-4-flame
atomic absorption spectrophotometer at
wavelengths=357.9 nm and an acetylene air flame
according to standard methods for analyzing water
and wastewater (APHA, 2005).
q
e
was calculated according to the equation (1):
(1)
Where:
q
e
= adsorbent phase concentration after
equilibrium, mg adsorbate/g adsorbent
C
o
=initial concentration of adsorbate, mg/L
C
e
=final equilibrium concentration of adsorbate
after absorption has occurred, mg/L
V =volume of liquid in the reactor, L
m=mass of adsorbent, g
RESULTS
The effect of contact time
In this experiment, the adsorption of chromium
increased with increasing contact time and became
almost constant after 120 min for Platanus
orientalis leaves and their ash showed in Fig. 1.
These results also indicate that the sorption process
can be considered very fast because of the largest
amount of chromiumattached to sorbent within
the first 60 min of adsorption.
Effect of pH
Experiments concerning the effect of pH on the
sorption were carried out with the range of pH
that was not influenced by the metal precipitation,
as metal hydroxide in the range of 3-7. The suitable
pH ranges for chromiumwas performed for the
pH range variations of 3-9.
Fig. 2 shows that in most cases, the removal
increased steadily with pH. Adsorption of metal
cation on adsorbent depends upon the nature of
adsorbent surface and species distribution of the
m
V ) C C (
q
e
e
=
0.0
0.2
0.4
0.6
0.8
1.0
0 100 200 300 400
Time (min)
q
e
(
m
g
/
g
)
POL
POL (ash)
Fig. 1: Effect of contact time on the removal of chromium
(VI) by POL and their ash (adsorbent dosage =2g/L;
chromium concentration =2 mg/L)
0.0
0.1
0.2
0.3
0.4
0.5
0.6
0.7
0.8
2 3 4 5 6 7 8 9 10
pH
q
e
(
m
g
/
g
)
POL
POL (ash)
Fig. 2: Effect of pH on the removal of chromium (VI) by
POL and their ash (adsorbent dosage =2g/L; chromium
concentration =2 mg/L)
Effect of metal ion concentration
The effect of metal Ion concentration on the
adsorption capacity of Platanus orientalis leaves
and their ash were studied under optimum
conditions. (pH=7, temperature=24-25C).
Adsorption of chromium on POL and its ash
increased with increasing initial concentration of
Cr(VI) to reach to 20mg/L. These results may be
explained by an increase in the number of metal
ions competing for the available binding sites in
the adsorbent for complexation of Cr(VI) ion at
higher concentration levels. These results are
shown in Fig. 3.
metal cation. Surface distribution mainly depends
on the pH of the system (Namasivayam and
Ranganathan, 1995).
Iran. J. Environ. Health. Sci. Eng., 2007, Vol. 4, No. 3, pp. 191-196
194
A. H. Mahvi, et al., ADSORPTION OF CHROMIUM FROM...
Effect of metals on adsorption
The effect of light metals on adsorption were
studied in combination of two metal solutions and
has shown that these ions can disturb the
adsorption of heavy metals on any adsorbent. Ca
+2
and Mg
+2
had more effect than Na
+
and K
+
in
decreasing of q
e
for Cr(VI) adsorption. The effect
of these metals on adsorption is shown in Fig. 4.
Adsorption isotherms
Two models, (Langmuir and Freundlich) were
used to determine adsorption of chromiumon to
Platanus orientalis leaves and their ash.The
0
1
2
3
4
5
6
7
0 20 40 60
C (mg/L)
q
e
(
m
g
/
g
)
POL
POL (ash)
Fig. 3: Effect of chromium concentration on the removal
of chromium (VI) by POL and their ash (adsorbent
dosage=2g/L; pH
=7; T=24
C; 300rpm; 120min)
0.47
0.82
0.52
0.49
0.835
0.46
0.84
0.855
0.0
0.1
0.2
0.3
0.4
0.5
0.6
0.7
0.8
0.9
Ca Mg Na K
q
e
(
m
g
/
g
)
Fig. 4: The effect of other metals on chromium adsorption
capacity (Cr=2mg/L; 2mol/L of Ca
2+
, Mg
2+
, Na
+
, K
+
)
Freundlich isothermbetter fitted than the Langmuir
isotherm as was evident from the values of
regression coeffient with R
2
>0.9. Results are given
in Fig. 5 and Fig. 6.
Effect of adsorbents on COD
The effect of adsorbents on COD in aqueous
solutions were studied. These studies show that
2g/L adsorbent causes 110 mg/L and 76mg/L COD
increase in deionizd water after 120min for
Plat anus orientalis leaves and their ash,
respectively. This is favorable for biological
treatment in industrial wastewater treatment plant
after chemical treatment.
P OL
y =0.5777x - 0.0242
R2 =0.8894
pol (ash)
y =0.6276x +0.0811
R2 =0.9562
-0.4
-0.2
0.0
0.2
0.4
0.6
0.8
-0.5 0.0 0.5 1.0 1.5
Log Ce
L
o
g
q
e
POL
POL (ash)
Linear (POL)
Linear (POL (ash))
Fig. 5: Langmuir adsorption isotherm for chromium (VI) by POL and their ash
R
2
=0.9562
R
2
=0.8894
Iran. J. Environ. Health. Sci. Eng., 2007, Vol. 4, No. 3, pp. 191-196
195
DISCUSSION
Tree leaves can be used in the wastewater
treatment process for the removal of metal ions.
The percent of adsorption for chromium(VI) ion
decreased with the decrease in pH, because
protons compete with metal ion for sorption sites
on the adsorbent surface as well as the
concomitant decrease of negative charge of the
same surface (Namasivayamand Ranganathan,
1995).The optimumpH in this study was 7. It has
been reported that precipitation of chromiumstarts
at pH=7.5 (Namasivayam and Ranganathan,
1995; Ajmalet et al., 2003).
Removal efficiency of chromium(VI) was greater
than 85% and the adsorption of metal ion on tree
leaves reached equilibriumin 120 min, pH=6-7 and
initial concentration of 2mg/L. The Freundlich
isothermfitted better than the Langmuir isotherm
with R
2
>0.89 for POL and R
2
>0.96 for POL ash,
respectively. Similar results were reported by Alavi,
2005. Plat anus orientalis leaves used as
adsorbent in aqueous solutions may cause COD
increase.
ACKNOWLEDGEMENTS
The authors would like to thank the Deputy of
Research and School of Public Health, Tehran
University of Medical Sciences, for financial grant
for this research.
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POL (ash)
y =0.1198x +0.7984
R2 =0.7949
POL
y =0.1415x +1.1995
R2 =0.6461
0.0
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1.0
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0 5 10 15
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Linear (POL (ash))
Linear (POL)
Fig. 6: Freundlich adsorption isotherm for chromium (VI) by POL and their ash
R
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=0.7949
R
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=0.6461
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