Removal of Lead II Ions From Waste Water PDF

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Original Article

Removal of Lead (II) Ions from Waste Water


by Using Lebanese Cymbopogon citratus
(Lemon Grass) Stem as Adsorbent
Mona Sobh1,2, Mhamad-Aly Moussawi1,Wassim Rammal4, Akram Hijazi*1, Hassan
Rammal1, Mohamad Reda2, Joumana Toufaily2,3 and Tayssir Hamieh3
1
Doctoral School of Science and Technology, Research Platform for Environmental Science
(PRASE), Lebanese University, Lebanon
2
Laboratory of Materials, Catalysis, Environment and Analytical Methods (MCEMA), Lebanese
University, Lebanon
3
School of Mechanical and Materials Engineering, Washington State University, Washington State,
United State of America
4
Radiocom Laboratory, Lebanese University, IUT-Saida, P.O Box 813, Lebanon

ABSTRACT

The objective of this study was to investigate the possibility of using


Lebanese Cymbopogon citratus stems as an alternative adsorbent for
the removal of Pb (II) ions from aqueous solutions. The effect of
different parameters such as the initial metal ion concentration, pH,
Address for adsorbent dose, contact time and temperature were studied.
Correspondence Maximum adsorption capacity (93%) of lead (II) ion was obtained at
pH 4 and 25˚C after 1 hour for150 mg/L initial concentration. FT-IR
Doctoral School of analysis pointed out the involvement of amine and carboxyl group in
Science and the adsorption process. The adsorption isotherm was better described
Technology, Research by Freundlich rather than Langmuir model. Based on these results, it
Platform for can be concluded that the stem of Cymbopogon citratus is effective
Environmental Science as an alternative adsorbent for the removal of toxic Pb (II) from
(PRASE), Lebanese waste water.
University, Lebanon.
E-mail: hijazi_akram Keywords: Cymbopogon citratus, Adsorption, Langmuir and
@hotmail.com Freundlich isotherm models.

INTRODUCTION
Water pollution caused by heavy Heavy metals generated by industrial
metals has caught increasing public attention activities (battery manufacturing, mining
and many techniques have been used for activities, printed circuit board
their removal from wastewater such as: manufacturing) are disposed to water
chemical precipitation, electro dialysis, ion streams without proper treatment. They are
exchange, adsorption and others. non-biodegradable and therefore persist for
long periods in aquatic as well as terrestrial

American Journal of Phytomedicine and Clinical Therapeutics www.ajpct.org


Hijazi et al_________________________________________________ ISSN 2321 – 2748

environments. They may be transported also MATERIALS AND METHODS


through soils to reach groundwater or may
be taken up by plants, including agricultural Adsorbent
crops.1 The Cymbopogon citratus (Lemon
Lead is among these heavy metals Grass) stems were collected from a local
used in such industries. It is of high toxicity Lebanese plantation. The stems were
and accumulates in the body after ingestion. thoroughly rinsed with water, died at room
Chronic lead poisoning may cause temperature for 10 days, and then grounded
gastrointestinal disorders, constipation, into a fine powder using a grinding mill.
fatigue, muscular atrophy and CNS
syndrome that may result in coma and death. Adsorbate
2 The stock solution of 1000 mg/L of
Many studies have been conducted Pb (II) was prepared by dissolving Pb (NO3)2
to find low-cost adsorbents as a replacement in 1L de-ionized water. All the required
for costly current methods. An adsorbent is solutions were prepared by diluting the stock
considered of low-cost if it is naturally solution with de-ionized water. Analysis of
abundant, requires little processing or is a standards and simulated samples was done
byproduct of waste material from waste using an AA-140 Atomic Absorption
industry according to Bailey et al3. Due to Spectrometer.
their low economic value, plant wastes are
considered to be cheap adsorbents. Plants as: Experimental procedure
grape stalk wastes4, papaya wood5, teak leaf The procedure mentioned by Al-Afy
powder6, rice husk ash and neem bark7 were et al9 were followed, where several batches
used as adsorbents and they have shown were prepared to study the effect of initial Pb
promising results. (II) concentration, pH, contact time, adsorbent
In the present work, the capacity of dose and temperature on the adsorption of the
Lebanese Cymbopogon citratus (Lemon Pb (II) ions from its solution. All the
Grass) stems to remove Pb (II) ions from adsorption experiments were carried out at
wastewater has been studied in different room temperature except where the effect of
experimental conditions such as initial metal temperature was being investigated. The
ion concentration, contact time, adsorbent initial pH was adjusted with HNO3 (1M) or
dose, temperature and pH. NaOH (1M).
Cymbopogon citratus staff is
popularly known as citronella grass or Effect of metal ion concentration
lemon grass. This species belongs to the 0.5g of the adsorbent was stirred with
Gramineae family, which comprises 50 ml of different concentrations of Pb (II)
approximately 500 genus and 8,000 herb solution. The mixture was continuously
species. Lemon grass is a tufted perennial agitated at 400 rpm, 25±2˚C and pH 4 for 1
grass growing to a height of 1 meter with hour. The obtained suspension was filtered in
numerous stiff leafy stems arising from short 2 steps: first by Buchner filtration then with a
rhizomatous roots. It has an economic 0.45μm filter. After that, the final
lifespan for about 5 years.8 concentration of Pb (II) in the filtrate was
determined using AAS.

Effect of pH
By fixing the four other parameters (1
hour, 25±2˚C, 0.5 g of adsorbent and 150

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mg/L), the effect of pH on the adsorption was Where,


investigated in the pH range 2-10 in. The pH Co: initial concentration (mg/L)
was adjusted using a few drops of HNO3 (1M) Cf: final concentration (mg/L)
or NaOH (1M). Remaining Pb (II) ions were The adsorption capacity qm was
then measured using AAS. calculated according to the following
equation:
Effect of contact time
The effect of the contact time was also
performed with 50mL of 150 mg/L Pb (II) Where,
solution at a pH 4. 0.5g of adsorbent at qm: Adsorption capacity (mg/g)
25±2˚C was added to an aqueous solution V: volume of the reaction mixture (L)
with respect to the following times: 30, 60, m: mass of adsorbent used (g)
120, 180, 210 min and mixed with a magnetic C0: initial concentration (mg/L)
stirrer at 400 rpm. After that, the samples Cf: final concentration (mg/L)
were filtered and the filtrate was then
analyzed by AAS in order to determine the RESULTS AND DISCUSSION
adsorption capacity.
FT-IR analysis
Effect of temperature The FT-IR spectrum of Cymbopogon
The same procedure was followed to citratus was used to investigate the functional
find the effect of temperature on the groups present on the surface that may be
adsorption process. By fixing all other responsible for the removal of heavy metal
parameters, only temperature has been varied. species. The spectrum of the adsorbent was
(0˚C, 25˚C, 45˚C, and 60˚C). measured within the range of 4000-400 cm-1
using JASCO FT/IR-6300 spectrometer. FT-
Effect of the adsorbent dose IR spectra before and after the adsorption
Adsorption dose experiments were were compared. Cymbopogon citratus stems
also performed following the same procedure show a number of absorption peaks that
as described earlier at pH 4, 150 mg/L Pb (II), reflect its complex nature. Three peaks
25±2˚C, 400 rpm for 1 hour with the between 3300 and 3500 cm-1 are due to the
following adsorbent doses: 0.2, 0.5, 0.8, 1.4, presence of N-H stretching vibration. A peak
1.8 and 2.2 g, the samples were filtered and at 2930 cm-1 corresponds to sp3 C-H
the filtrate was analyzed by AAS. stretching vibration. The absorption peak at
When Cymbopogon citrates stem 1750 cm-1 could be assigned to the carboxyl
powder was tested for its ability to adsorb Pb group, 1100 cm-1 to C-O stretch.
(II) from aqueous solution, initial pH 4 was After adsorption, a broad peak at 3420
-1
used for most experiments. The effects of the cm corresponds to the overlapping of N-H
following experimental parameters (pH, peak, also, a broad peak at 1750 cm-1. This
initial concentration, contact time, phenomenon may be attributed to the water
temperature and the adsorbent dose) on molecule directly interacting with amide.
adsorption were studied. The percentage of After Pb (II) binding, a change of
the uptake or adsorption of Pb (II) was peak position occurs indicating the change in
calculated using the following equation: the environment of these groups. The shift in
the wavelength corresponds to the change in
the energy of functional groups that indicates
the existence of a Pb binding process done on
the surface. 10

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Effect of concentration Effect of temperature


To study the effect of the initial The adsorption of Pb (II) from its
concentration of Pb (II) on the adsorption solutions at different temperatures was
capacity, several samples with different investigated. Samples were subjected to
concentrations varying from 25 to 800 mg/L temperatures which ranged from 0 to 60˚C.
was taken while fixing the other parameters. The adsorption capacity increased to a
Figure 2 shows that there is a rapid increase in maximum which was reached at 45˚C and
the adsorption of Pb (II) up to 700 mg/L, thereafter it decreased gradually.
which is due to the interaction between the The temperature has important effects
metal ion and the active site of the adsorbent. on the adsorption process. Thermodynamic
Then, adsorption became constant due to the parameters like heat of adsorption and energy
saturation of the active sites. of activation play an important role in
predicting the adsorption behavior and both
Effect of pH are strongly dependent on temperature.
The pH is another parameter that Changing the temperature will change the
controls the adsorption of Pb (II).11 Figure 3 equilibrium capacity of the adsorbent for
shows that best adsorption occurs in the acid particular adsorbate.15
range. pH of solution affects the surface of the
adsorbent and yet the degree of ionization of Effect of adsorbent dose
the adsorbate. At (less than 3) low pH, the Adsorption is also affected by the
amount of protons H+ is important that dose of the adsorbent responsible for the
prevents the formation of a bond between Pb uptake of the metal. The percentage removal
(II) and the active site. At moderate pH (3 to of Pb (II) increases with increasing the mass
6), the number of H+ becomes less important, of the adsorbent from 93.82% at 0.5 g to 98%
and thus many of Pb (II) ions will be at 1.8 g. A further increase in the adsorbent
adsorbed on the active sites.12 At high pH, the mass to 2.2 g does not increase the removal of
Pb (II) ions precipitate under the form of Pb the metal ion due to the overcrowding of the
(OH)2, Pb (OH)3-, Pb2 (OH)3+, Pb3 (OH)42+ solution with the adsorbent particles.
and Pb4 (OH)44+ which prevents adsorption of
Pb (II) onto active site.13 Bio-sorption isotherms
The adsorption is generally described
Effect of contact time by isothermal, that are functions relating the
There is a general increase in the % amount of adsorbate on the adsorbent, with
adsorption of Pb (II) with time. However, the the pressure (if gas) or the concentration (if
adsorption slowed down after 2 hours. This liquid). Langmuir and Freundlich models are
could possibly be the time required for the used to describe the adsorption process.
equilibrium to be established. Generally
equilibrium is established on the surface of Freundlich isotherm
adsorbent after some time or it can be Freundlich isotherm model is the
instantaneous. This probably resulted from well-known earliest relationship which
saturation of absorbent surfaces with heavy describes the adsorption process. It can be
metals followed by adsorption and desorption applied to non-ideal sorption on
processes that occur after saturation. 14 The heterogeneous surfaces as well as multilayer
equilibrium uptake of Pb (II) was about 95.77 sorption9; its linear form is expressed by:
% that occur after 2 hours.

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Where, But the qm (theoretical)> qm (experimental).


qe: equilibrium adsorption capacity (mg/g) Langmuir isotherm is not favorable
Ce: equilibrium concentration (mg/L) for the adsorption of Pb (II) on Cymbopogon
KF: Freundlich constant related to adsorption citratus surface.
capacity (L/mg). The n value in Freundlich equation
n: constant related to the adsorption intensity was found to be 0.76 for the Cymbopogon
(g/L). citratus. Since n is smaller than 1, this
The value of n indicates the degree of indicates the Chemical bio-sorption of Pb (II)
non-linearity between solution concentration onto Cymbopogon citratus.
and adsorption as follows:
Linear adsorption if n=1 CONCLUSION
Chemical adsorption if n< 1
Physical adsorption if n>1 This study investigated the adsorption
of Pb (II) ions from aqueous solution onto
Langmuir isotherm Cymbopogon citratus stem that was found to
It is based on the assumption that:16 be dependent on different parameters as initial
 Uniform surface metal ion concentration, pH, adsorbent dose,
 Monolayer coverage of the adsorbate on temperature and contact time. To provide the
the outer surface. best correlation for bio-sorption of Pb (II)
ions onto Cymbopogon citratus, Freundlich
 No lateral interaction between the sorbed
and Langmuir isotherms were demonstrated.
molecules.
From this study, it was observed that stems of
The linear form of the Langmuir
Cymbopogon citratus can be used as an
adsorption isotherm can be written as follows:
alternative low cost, eco-friendly and
effective adsorbent for treatment of waste
water containing Pb (II).
Ce: equilibrium concentration (mg/L).
qm: saturation capacity of the theoretical ACKNOWLEDGEMENT
maximum monolayer adsorption or (mg/g).
KL: Langmuir constant related to energy of The Lebanese university is gratefully
sorption (L/g). acknowledged for financial support.
The initial quality of the Langmuir
isotherm can be measured by calculating RL, REFERENCES
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Table 1. Equilibrium constants for Pb (II) adsorption


Langmuir qm (mg.g-1) KL (L.mg-1) R2
1000 0.0005 0.992
Freundlich n KF (L.mg-1) R2
0.76 0.385 0.998

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Figure 1. FT-IR of Cymbopogon citratus before and after adsorption

Figure 2. Effect of initial concentration of Pb (II)

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Figure 3. Effect of the pH of solution

Figure 4. Effect of contact time

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Figure 5. Effect of temperature

Figure 6. Effect of adsorbent dose

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Figure 7. Langmuir isotherm

Figure 8. Freundlich isotherm

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Figure 9. Lemon grass

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