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Adsorption Properties of Coriander Seed Powder

(Coriandrum sativum): Extraction and Pre-concentration of
Pb(II), Cu(II) and Zn(II) Ions from Aque....

Article  in  Adsorption Science and Technology · December 2011

DOI: 10.1260/0263-6174.30.2.127

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 Adsorption Properties of Coriander Seed
Powder (Coriandrum sativum):
Extraction and Pre-concentration of Pb(II),
Cu(II) and Zn(II) Ions from Aqueous Solution

Rifaqat Ali Khan Rao and M. Kashifuddin

Reprinted from

Adsorption Science & Technology

2012 Volume 30 Number 2

Multi-Science Publishing Co. Ltd.

5 Wates Way, Brentwood, Essex CM15 9TB, United Kingdom
 127

Adsorption Properties of Coriander Seed Powder (Coriandrum sativum):

Extraction and Pre-concentration of Pb(II), Cu(II) and Zn(II) Ions from
Aqueous Solution
Rifaqat Ali Khan Rao* and M. Kashifuddin Environmental Research Laboratory, Department of Applied
Chemistry, Faculty of Engineering and Technology, Aligarh Muslim University, Aligarh 202002, UP, India.

(Received 31 August 2011; revised form accepted 8 December 2011)

ABSTRACT: Coriander seed powder has been shown to exhibit a remarkable

adsorption potential towards Pb(II), Cu(II) and Zn(II) ions from aqueous
solution, with the adsorption capacities following the order Pb(II) > Cu(II) >
Zn(II). The influences of pH, initial metal ion concentration, adsorbent dosage
and contact time on the process were investigated. The adsorption data at
different temperatures were well fitted by the Langmuir, Freundlich, Temkin
and Dubinin–Radushkevich (D–R) model isotherms. The kinetic data obeyed
the pseudo-second-order kinetic model. The thermodynamic parameters
showed that the adsorption of Pb(II) ions was endothermic and spontaneous.
Competitive adsorption in the Pb(II)–Cu(II) and Pb(II)–Zn(II) systems was
also studied. The breakthrough capacities of Pb(II), Cu(II) and Zn(II) ions in
single metal ion systems were higher than in multi-metal ion systems. The
analytical application of the adsorption process was demonstrated by the
removal of Pb(II) ions from the wastewater derive from the manufacture of
lead acid batteries. Excellent results were obtained when desorption of the
studied metal ion from very dilute solution was effected by column methods.
Hence, these methods were further utilized for the extraction and
pre-concentration of Pb(II), Cu(II) and Zn(II) ions from very dilute synthetic
mixtures of these metal ions prepared in doubly distilled water as well as in
tap water to enable their subsequent determination by atomic absorption
spectrometry.

INTRODUCTION

The increasing pollution of the environment highlights the adverse effect of heavy metal ions
(Ajmal et al. 2003). The main sources behind the increasing Pb(II) ion pollution are lead
storage batteries, energy and fuel production, metal surface treatment, and mining and metal-
related industries such as tanning, electric appliances manufacturing, etc. Heavy metal ions
such as Pb(II), Zn(II) and Cu(II) are commonly found in contaminated water (Babel and
Kurniwan 2003; Volesky 1990; Alkorta et al. 2004). According to the US Environmental
Protection Agency (EPA), the permissible limits for Pb(II), Zn(II) and Cu(II) ions in drinking
water are 0.015, 1.3 and 5.00 mg/
, respectively. It is extremely important to remove these
toxic metal ions from wastewater before its disposal into rivers, lakes or on land. Adsorption
technology has a high efficiency in detoxifying effluents (Kenduzler and Turker 2005),

*
Author to whom all correspondence should be addressed. E-mail: rakrao1@rediffmail.com (Rakrao).
128 R.A.K. Rao and M. Kashifuddin/Adsorption Science & Technology Vol. 30 No. 2 2012

exhibiting numerous advantages such as rapidity, versatility, effectiveness, regeneration for

multiple uses and high selectivity towards different metal ions (Soylak and Dogan 1996).
A pre-concentration step is sometimes necessary to allow the determination of heavy metal
ions present at ultra-trace levels by atomic absorption spectrophotometery (AAS), the use of
such pre-concentration prior to metal ion analysis being usually required due to the low levels
of metal ions in aquatic samples (Lee and Choi 2001). This step can be accomplished
successfully by using solid-phase extraction (SPE) techniques (Suleiman et al. 2008).
Successful studies of natural adsorbents such as wheat bran (Farajzadeh and Monji 2004), spent
grain (Low et al. 2000), tree fern (Ho and Wang 2004), walnut, hazelnut and almond shell
(Pehlivan and Altun 2008), Foeniculum vulgari (Rao et al. 2010), sunflower stalks (Sun and
Shi 1998), bael leaves (Chakravarty et al. 2010), red chilli (Sanjeev and Amarjit 2006), spices
(Hifsa et al. 2009), rice husk (Sharma et al. 2009), gular fruits (Rao and Rehman 2010),
coriander (Karunasagar et al. 2005), Azadirachta indica leaf powder (Bhattacharyya et al.
2010), Limonia acidissima (wood apple) shell (Sartape et al. 2010), coconut coir (Khan et al.
2010), etc. have already been reported.
Coriandrum sativum (commonly known as coriander) is commercially grown in India,
Morocco, Poland, Romania, Mexico, U.S.A., Russia, etc. India is the largest producer of coriander
in the world (CSIR 2001). Coriander is a tropical crop and is successfully grown under a wide
range of conditions. The months of October to February are the best period for cultivation (CSIR
2001). The coriander plant is a herb and has all the qualities necessary for food product. Its fruit
possesses a sweet and aromatic odour, while its seeds act as stimulants, antipyretics and
anthelmintics. Its fruit is useful in cases of vomiting, indigestion, flatulence, intestinal disorders,
bleeding piles, rheumatism and eye infections (CSIR 2001). Coriander oil is an essential oil
produced from the fruits upon distillation. The fragrant odour and pleasant aromatic taste is due
to the presence of essential oils whose content range from 0.1% to 0.3% in the seeds (CSIR 2001).
The major constituents of Indian coriander fruit oil are linalool (49.2%), p-cymene (14.7%),
camphor (9.6%) and α-pinene (5.4%).
The non-toxic nature of this plant has prompted us to explore the adsorption behaviour of
Coriandrum sativum (coriander) seed powder towards Pb(II), Cu(II) and Zn(II) ions. The ability
of coriander seeds to remove Pb(II) ions from aqueous solution and lead acid battery
manufacturing wastewater was also demonstrated. Complete desorption of Pb(II), Cu(II) and
Zn(II) ions allowed the possibility of extracting and pre-concentrating these metal ions from
distilled water and natural water (tap water) at trace levels prior to their determination.

2. MATERIALS AND METHODS

2.1. Preparation of the adsorbent

Coriander seeds were dried, crushed, sieved and washed in doubly distilled water (DDW) to
remove any dust, dirt, etc. Particles of 150–300 µm size were collected and kept in sealed bottles
prior to study.

2.2. Adsorbate solutions

Stock solutions of Pb(II), Cu(II) and Zn(II) ions (1000 mg/
) were prepared by dissolving the
desired quantity of their nitrate salts (A.R. grade) in DDW.
Adsorption Properties of Coriander Seed Powder (Coriandrum sativum) 129

2.3. Adsorption studies

Adsorption studies were carried out in batch mode. Thus, 0.5 g adsorbent was placed in a conical
flask to which 50 m
of an aqueous solution of the chosen metal ion at a desired concentration
was added and the mixture shaken in a temperature-controlled shaker incubator for 24 h. The
mixture was then filtered through a Whatman No. 41 filter paper and the final concentration of the
metal ion present in the filtrate was determined by atomic absorption spectrometry (AAS).

2.3.1. Effect of pH

The effect of pH on the adsorption of Pb(II), Cu(II) and Zn(II) ions was studied by taking 100 m

of a given metal ion solution (50 mg/
concentration) in a beaker and adjusting the pH of the
solution to the desired level by adding dilute solutions of 0.1 M HCl and 0.1 M NaOH as
appropriate. The concentration of metal ions in the resulting solution was determined (initial
concentration) and 50 m
of this solution was then taken in a conical flask and treated with 0.5 g
adsorbent. After equilibrium had been achieved, the final concentration of metal ions in the solution
was determined. The final or equilibrium pH (pHf) was also recorded with the aid of a pH meter.

2.3.2. Effects of contact time and initial metal ion concentration

The effect of contact time on the adsorption of Pb(II) ions was determined by analyzing the residual
Pb(II) ions in the aqueous solution after contact times ranging from 5 min to 300 min. Experiments
were again performed using the batch process at room temperature, with 0.5 g adsorbent being
added to 50 m
of each of a series of solutions with initial Pb(II) ion concentrations within the range
50–100 mg/
contained in a series of conical flasks. Samples were withdrawn from the conical
flasks after specified time intervals and analyzed for their residual metal ion content.

2.3.3. Effects of adsorbent dosage and temperature

A series of 250 m
conical flasks each containing 50 m
of Pb(II) ion solution of 50 mg/
initial
concentration were treated at 30 °C with varying amounts of adsorbent (0.1–1.0 g). The flasks
were shaken in a shaker incubator and, after equilibrium had been attained, the solutions were
filtered. The concentration of Pb(II) ions in the filtrate was then determined by AAS. The same
procedure was repeated employing temperatures of 40 °C and 50 °C.

2.3.4. Effect of electrolyte addition

The effects of various electrolytes such as NaCl, NaNO3, CaCl2 and MgCl2 on the adsorption of
Pb(II), Cu(II) and Zn(II) was investigated. In these experiments, 50 m
of a 50 mg/
solution of the
target metal ion prepared in each of the above electrolytes was treated with 0.5 g adsorbent. The
amount of metal ions adsorbed in the presence of the electrolyte was then determined as described
earlier.

2.3.5. Effect of Cu(II) and Zn(II) ions on the adsorption of Pb(II) ions

In order to investigate the possibility of interference due to the presence of Cu(II) and Zn(II) ions
on the adsorption of Pb(II) ions, binary mixtures were prepared containing varying Cu(II) ion
130 R.A.K. Rao and M. Kashifuddin/Adsorption Science & Technology Vol. 30 No. 2 2012

concentrations within the range 20–100 mg/
at a fixed initial concentration of Pb(II) ions of
50 mg/
. Then 50 m
of each mixture was treated with 0.5 g adsorbent (pH 4) and, after
equilibrium had been attained, the concentrations of Cu(II) and Pb(II) ions were determined by
AAS. The same procedure was performed employing the Zn(II)–Pb(II) system.

2.4. Point of zero charge

The point of zero charge of the adsorbent (pHpzc) was determined by the solid addition method.
Thus, 50 m
DDW was placed in a series of conical flasks and the pH value of each roughly
adjusted to values within the range 2–10 through the addition of either 0.1 M HCl or 0.1 M NaOH
solution. The initial pH (pHi) of these solutions was accurately noted. Then 0.5 g adsorbent was
added to each flask and allowed to equilibrate for 24 h with intermittent manual shaking. The final
pH (pHf) of the supernatant liquid was then noted. The difference between the initial pHi and pHf
values were plotted against pHi, the point of intersection of the resulting curve with the abscissa
(at which pHi − pHf = 0) gave the pHpzc value. The same procedure was repeated using 0.001
M, 0.01 M and 0.1 M KNO3 solutions.

2.5. Breakthrough capacity

To determine the breakthrough capacity of the adsorbent, 0.5 g of the latter was placed in a glass
column and supported on a glass wool plug. Then 500 m
of a Pb(II) ion solution of 50 mg/

initial concentration (C0) was passed through the column at a flow rate of 1 m
/min. The effluent
was collected in 50 m
fractions and the amount of Pb(II) ions in each fraction (C) determined
by AAS. A breakthrough capacity curve was obtained by plotting C/C0 versus the volume of the
effluent. The same procedure was adopted for Cu(II) and Zn(II) ions. The breakthrough
capacities of Pb(II), Cu(II) and Zn(II) ions were also determined in multi-metal ion systems in
which 500 m
of a solution containing a mixture of Pb(II), Cu(II) and Zn(II) ions (50 mg/
initial
concentration for each ion) was passed through the column under conditions identical to those
described above. The breakthrough capacities of the column to the metal ions in the mixtures
were determined in a manner similar to that above.

2.6. Desorption studies

To study the desorption behaviour in a single metal ion system, the exhausted column obtained
after the determination of the breakthrough capacity was washed several times with DDW to
remove any excess of Pb(II) ions from the column. Following this procedure, a 0.1 M HCl
solution was passed through the column containing adsorbed Pb(II) ions. The flow rate was
maintained at 1 m
/min and the desorbed Pb(II) ions were collected as 10 m
fractions. Desorption
of Cu(II) and Zn(II) ions was also performed in the similar way and the same procedure was used
for multi-metal ion systems.

2.7. Removal of Pb(II) ions from lead acid battery manufacturing wastewater

A wastewater sample was collected from the lead acid battery manufacturing industry and 1
of
the same was filtered. The initial pH of the collected water was found to be 1.5 and consequently
its pH was adjusted to a value of 5.2 prior to further study. After such adjustment, the sample was
passed through a column containing 0.5 g adsorbent at a flow rate of 1 m
/min. The column was
Adsorption Properties of Coriander Seed Powder (Coriandrum sativum) 131

washed several times with DDW and then 50 m
of a 0.1 M HCl solution was passed through the
column at a flow rate of 1 m
/min. The amount of desorbed Pb(II) ions present in the effluent was
then determined by AAS.

2.8. Pre-concentration of heavy metal ions from DDW and tap water

The pre-concentration of Pb(II), Cu(II) and Zn(II) ions was performed as follows. Thus, 500 m

of a solution containing Pb(II), Cu(II) and Zn(II) ions (2.5 mg/
initial concentration each) was
prepared in DDW as well as separately in tap water. The corresponding samples were then passed
through separate columns each packed with 0.5 g adsorbent. In each case, the flow rate was
maintained at 5 m
/min. The adsorbed metal ions were then desorbed employing a 0.1 M HCl
solution. The resulting effluent was collected in 10 m
fractions and analyzed by AAS.

3. RESULTS AND DISCUSSION

3.1. Adsorption characteristics of the adsorbent

The percentage adsorption of Pb(II), Cu(II), Zn(II), Ni(II), Cd(II) and Cr(VI) ions onto coriander seed
powder is shown in Figure 1. It will be seen from the figure that the adsorption efficiency followed
the order: Pb(II) > Cu(II) > Zn(II) > Ni(II) > Cd(II) > Cr(VI). Since the percentage adsorption of
Pb(II), Cu(II) and Zn(II) ions was found to be a maximum these metal ions were investigated in detail.

100

90

80

70
% Adsorrption

60

50

40

30

20

10

0
Cu(II) Ni(II) Cd(II) Pb(II) Cr(VI) Zn(II)
Metal ions

Figure 1. Percentage adsorption of heavy metal ions from aqueous solution onto coriander seed powder.

3.2. FT-IR spectroscopic analysis

The surface functional groups or binding sites were identified by FT-IR analysis of the native
[Figure 2(a) overleaf] and the Pb(II) ion-adsorbed adsorbent [Figure 2(b) overleaf] with a view to
understanding the surface-binding mechanism. The designations of the significant bands present in
the corresponding spectra are listed in Table 1 (Kalsi 2004). The bands at 1648, 1713 and 3361 cm−1
132 R.A.K. Rao and M. Kashifuddin/Adsorption Science & Technology Vol. 30 No. 2 2012

a
% Transmission

4000 3000 2000

Wavenumber (cm−1)

Figure 2. FT-IR spectra of coriander seed powder: (a) before Pb(II) ion adsorption and (b) after Pb(II) ion adsorption.

TABLE 1. FT-IR Spectroscopic Band Assignment of Surface Functional Groups on Coriander Seeds
Coriander seeds (native) Coriander seeds after Assignment
(cm−1) adsorption of Pb(II) ions (cm−1)

1155.33 1151.99 out-of-plane bending or wagging CH2

1457.48 1461.81 in-plane bending or scissoring [δs(CH2)]
1648.86 1644.53 C=C stretching
1713.72 1743.83 C=O stretching
2854.28 2856.03 symmetrical CH2 stretching
2925.56 2923.55 asymmetrical CH2 stretching
3361.94 3336.66 intermolecular hydrogen bonding

indicate the presence of C=C, C=O groups and intermolecular hydrogen bonding, respectively. The
data in Table 1 show that the bands due to C=O groups and hydrogen bonding were shifted to
1743 cm−1 and 3336 cm−1, respectively, after Pb(II) ion adsorption, indicating that the Pb(II) ions
had interacted with these particular groups present on the surface of the adsorbent.

3.3. Effect of time and concentration

The mechanism of the metal ion uptake generally depends on the initial concentration of the metal
ions in contact with the adsorbent. At low initial concentrations, all the specific sites responsible
for adsorption are not filled; however, with increasing metal ion concentration, filling of these
sites progressively occurs until all available sites are filled (Lehman and Harter 1984). The effect
of the initial concentration of Pb(II) ions on the extent of adsorption (Figure 3 overleaf) shows that
the adsorption of Pb(II) ions was concentration-dependent. The equilibrium time also increased
with increasing initial concentration. Thus, the equilibrium time increased from 20 min to 120 min
when the initial concentration was increased from 50 mg/
to 70 mg/
. Thereafter, the equilibrium
time became independent of the initial Pb(II) ion concentration. The adsorption capacities of
coriander seed powder towards Pb(II) ions at 50, 60, 70 and 100 mg/
initial Pb(II) ion
concentrations were found to be 4.3, 4.9, 5.6 and 8.3 mg/g, respectively. This might be due to the
increased driving force with increased Pb(II) ion concentration.
Adsorption Properties of Coriander Seed Powder (Coriandrum sativum) 133

Adsorption capacity (mg/g) 6

3
50 mg/ᐍ
2
60 mg/ᐍ
70 mg/ᐍ
1
100 mg/ᐍ

0
0 100 200 300 400
Time (min)

Figure 3. Effect of the initial concentration of Pb(II) ions on their adsorption from aqueous solution onto coriander
seed powder.

3.4. Effect of pH on the adsorption of Pb(II), Cu(II) and Zn(II) ions

The adsorption of Pb(II) ions was strongly influenced by varying the initial pH (pHi) of the
solution [Figure 4(a) overleaf], with the percentage adsorption increasing as the value of pHi
increased. However, increasing the value of pHi to above 6 resulted in a decrease in the percentage
adsorption of Pb(II) ions. In general, adsorption is also influenced by the equilibrium pH or final
pH (pHf) of the solution. The mechanism of adsorption with respect to pH can be explained on the
basis of the initial pH (pHi), final or equilibrium pH (pHf), surface charge of the adsorbent and the
speciation of the metal ions in the solution.
It will be seen from Figure 4(a) that the adsorption of Pb(II) ions was 62% at pH 2. Furthermore,
when pHi was adjusted to 2, pHf remained almost constant (pHf = 2.3), indicating that the
adsorption sites were protonated because of the presence of excess H+ ions. However, when pHi
was adjusted to 3, the value of pHf increased to 4.5 whilst, at the same time, the adsorption of Pb(II)
ions increased to 98.8%, possibly as a result of the adsorption of Pb2+ ions together with H+ ions.
At pHi = 4, the value of pHf increased to 6, but the adsorption of Pb(II) ions remained constant at
98.8%. When the value of pHi was further adjusted to 6, the value of pHf remained unaltered (pHf =
6.3) and the percentage adsorption remained constant (98.8%), indicating that over the pH range 4–6
the maximum amount of Pb(II) ions had been adsorbed in the Pb2+ form (since Pb2+ ions are the
dominant species within this pH range) together with some H+ ions, thereby causing an increase in
pHf. However, at pHi = 8, pHf was reduced to 7.7 and the adsorption of Pb(II) ions also decreased
to 89%. The decrease in pHf and the percentage adsorption indicated the formation of Pb(OH)+
species. At pHi = 10, the value of pHf was further reduced to 7.3 due to the formation of Pb(OH)2
which is the dominant species at this pH value (Yongjie et al. 2009), while the percentage
adsorption was also reduced to 32%. This latter observation may be due to the precipitation of
Pb(II) ions from the solution as Pb(OH)2 species. The pHpzc value of the adsorbent was found to be
4.8 (see Figure 5 below), indicating that the surface was positively charged below pH 4.8, neutral
134 R.A.K. Rao and M. Kashifuddin/Adsorption Science & Technology Vol. 30 No. 2 2012

(a) Pb(II) ions (b) Cu(II) ions

100 9 100 9
90 8 90 8
80 7 80 7
70 70
% Adsorption

% Adsorption
6 6
60 60
5 5
50 pHf 50 pHf
4 4
40 40
30 3 30 3
20 2 20 2
10 1 10 1
0 0 0 0
2 3 4 6 8 10 2 3 4 6 8 10
pHi pHi

(c) Zn(II) ions

100 9
90 8
80 7
70
% Adsorption

6
60
5
50 pHf
4
40
30 3
20 2
10 1
0 0
2 3 4 6 8 10
pHi

Figure 4. Effect of pH on the adsorption from aqueous solution of Pb(II) ions, (b) Cu(II) ions and (c) Zn(II) ions onto
coriander seed powder.

5 Doubly distilled water (DDW)

0.1 M KNO3
4 0.01 M KNO3
0.001 M KNO3

3
pHi − pHf

0
0 1 2 3 4 5 6 7 8 9 10 11
−1
pHi

Figure 5. Point of zero charge.

Adsorption Properties of Coriander Seed Powder (Coriandrum sativum) 135

at 4.8 and negatively charged at pH values greater than 4.8. The maximum adsorption of Pb(II) ions
as Pb2+ species over the pH range 4–6 supports this suggestion.
The adsorption of Cu(II) ions was smallest at pH 2 [Figure 4(b)] and increased to 80% at pH 4
due to deprotonation of the adsorption sites. Over the range 4 < pH < 5, Cu(II) ions were adsorbed
both as Cu2+ and Cu(OH)+ species, since both species exist over this pH range (Yongjie et al. 2009).
When the value of pHi was increased to 6, the adsorption of Cu(II) ions increased very slowly to
reach a value of 86%; at the same time, the value of pHf decreased to 5.3, indicating the formation
of greater quantities of Cu(OH)+ and Cu(OH)2 species. However, above pH 6, the adsorption of
Cu(II) ions decreased to 84% [Figure 4(b)] and the value of pHf also decreased, indicating that
Cu(II) ions precipitated as Cu(OH)2 since this is the major species in the system at pH > 6.
The adsorption of Zn(II) ions at various pHi values may be explained in a similar manner. The
percentage adsorption of Zn(II) ions was least (20%) at pH 2 [Figure 4(c)] and then increased with
increasing pHi value. Maximum adsorption (78–82%) occurred in the pH range 4–6, but above
pH 6 the percentage adsorption decreased due to the precipitation of Zn(II) ions as Zn(OH)2
(Yongjie et al. 2009). The decrease in the value of pHf over the 6 < pH < 10 also supported this
statement. Hence, it may be concluded that the maximum amounts of Pb(II), Cu(II) and Zn(II)
ions were adsorbed as Pb2+, Cu2+ and Zn2+ species up to a pH value of 4. However, above pH 4,
these metal ions were adsorbed in the form of other species.

3.5. Adsorption isotherms

In order to optimize the design of an adsorption system for the removal of Pb(II), Cu(II) and Zn(II)
ions from aqueous solution, it is important to explain the relationship between the weight of metal
ion adsorbed per unit weight of adsorbent at equilibrium (qe) and the residual concentration of metal
ions in solution at equilibrium (Ce). The Langmuir, Freundlich, Temkin and Dubinin–Radushkevich
(D–R) models were used to fit the experimental data for the adsorption of Pb(II) ions at 30 °C, 40
°C and 50 °C, while these models were applied to fit the adsorption data for the adsorption of Pb(II),
Cu(II) and Zn(II) ions at 30 °C. The corresponding results are reported overleaf in Table 2. The
fitting procedure was performed by using R-software version 2.10.1 (14-12-2009). In order to
evaluate the fitness of the data, the values of the correlation coefficient (R2), error and χ2 test analysis
between the experimental and calculated data were evaluated for each model.
According to the Langmuir model, adsorption occurs as a monolayer onto a homogeneous
adsorbent surface, with a constant heat of adsorption for all sites and without any interaction
between the adsorbed molecules (Kalavathy and Miranda 2010). The linear form of the Langmuir
model may be written as:
1 1 1
= + (1)
qe q m bCe qm

where Ce is the equilibrium concentration of metal ions in the solution (mg/
), qe is the amount of
metal ion adsorbed per unit weight of adsorbent (mg/g), qm is the amount of metal ion required to
form a monolayer (mg/g), i.e. the maximum monolayer adsorption capacity, and b is a constant
related to the energy of adsorption (
/mg). The values of b and qm can be calculated from the slope
and intercept of the linear plots of 1/qe versus 1/Ce at different temperatures. However, the data
obtained from the application of this model indicated that it did not fit the data at 30 °C well,
although a better fit was obtained for the data at 40 °C and 50 °C, as indicated by the high
correlation coefficient (R2), χ2 and RSE values (see Table 2 overleaf).
136 R.A.K. Rao and M. Kashifuddin/Adsorption Science & Technology Vol. 30 No. 2 2012

TABLE 2. Adsorption Isotherm Parameters for Pb(II) and Zn(II) Ions at Different Temperatures
Isotherms Parameters Pb(II) ions at 40 °C Zn(II) ions at 30 °C

Langmuir b (
/mg) 0.0051 0.5410

qm (mg/g) 47.7000 3.3310
R2 0.9776 0.9741
χ2 0.0347 0.0041
RSE 0.0125 0.0102
p-value < 0.05 < 0.05
Freundlich KF 1.8390 1.8270
n 1.0510 5.7490
R2 0.9907 0.9637
χ2 0.0259 0.0058
RSE 0.0207 0.0140
p-value < 0.05 < 0.05
Temkin A 1.2073 34.7300
B 0.6085 5.3659
R2 0.9797 0.9687
χ2 0.0601 0.0044
RSE 0.3184 0.0808
p-value < 0.05 < 0.05
D–R qm (mg/g) 0.00467 0.00008
KD–R 6.210 × 10−9 1.565 × 10−9
E (kJ/mol) 8.9730 17.8600
R2 0.9925 0.9716
χ2 0.0206 0.0049
RSE 0.0427 0.0286
p-value < 0.05 < 0.05

The Freundlich model is an empirical equation based on adsorption onto a heterogeneous

surface. The linear form of the Freundlich model can be written as:

log qe = log KF + 1
n log Ce (2)

where KF and n are the Freundlich constants related to multilayer adsorption and adsorption
intensity, respectively. A plot of log qe versus log Ce should generate a straight line with the values
of 1/n and KF being calculated from the slope and intercept, respectively. The data obtained from
this model indicated that the values of KF and n increased as the temperature increased from 30
°C to 50 °C, although the model was best obeyed at 40 °C because of the corresponding highest
R2 (0.99) and smallest χ2 values (Table 2).
The Temkin isotherm assumes that the decrease in the heat of adsorption is linear rather than
logarithmic, as implied by the Freundlich isotherm (Nemr 2009). The linear form of the Temkin
equation can be written as:

RT RT
qe =   ln A +   ln Ce (3)
 b   b 
Adsorption Properties of Coriander Seed Powder (Coriandrum sativum) 137

where (RT/b) = B, R is the universal gas constant, T is the absolute temperature and b is a constant.
The quantities A (g/
) and B are Temkin constants related to the adsorption potential and the heat
of adsorption, respectively. The values of A and B can be calculated from the slope and intercept
of the plot of qe versus ln Ce. The data obtained from the Temkin model (see Table 2) indicated
that this model was best fitted at 40 °C (R2 = 0.9797).
The Dubinin–Radushkevich (D–R) isotherm does not assume a homogeneous surface or a
constant sorption potential (Gonzalez et al. 2006). The linear form of this equation is represented as:

ln qe = ln qm − βε2 (4)

where ε is the Polanyi potential, qm is the monolayer capacity (mol/g), Ce is the equilibrium
concentration (mol/
) and β is a constant related to the adsorption energy. The Polanyi potential
(ε) and the mean free energy of adsorption (E, kJ/mol) can be calculated from the equations
 1
ε = RT ln 1 +  (5)
 Ce 
and
1
E = (6)
(−2β)

Low values of RSE, high correlation coefficients (R2) and least χ2 test values would indicate
the appropriateness of a given adsorption model. The data listed in Table 2 indicate that all the
above models gave a good fit to the experimental data obtained at 40 °C, with the p-values for all
the models being less than 0.05. The data also indicate that the most favourable results were
obtained for the adsorption of Zn(II) ions at 30 °C.

3.6. Thermodynamic studies

The effect of temperature on the adsorption of Pb(II) ions was studied over the temperature range
30–50 °C. Thermodynamic parameters such as the Gibbs’ free energy change (∆G0), the standard
enthalpy change (∆H0) and the standard entropy change (∆S0) were estimated using the following
relationships (Namasivayam and Ranganathan 1995):
C AC
Kc = (7)
Ce

where Kc is the adsorption equilibrium constant, and CAC and Ce are the equilibrium
concentrations of Pb(II) ions on the adsorbent and in solution, respectively,
∆G0 = − RT ln Kc (8)

where ∆G0 is the Gibbs’ free energy change, T is the temperature (K) and R is the gas constant, and
∆H0 ∆S0
ln Kc = − + (9)
RT R
where ∆H0 is the standard enthalpy change and ∆S0 is the standard entropy change. The quantities
Kc, R and T have their usual meanings. The values of ∆H0 and ∆S0 were calculated from the slope
and intercept of the plot of log Kc versus 1/T.
138 R.A.K. Rao and M. Kashifuddin/Adsorption Science & Technology Vol. 30 No. 2 2012

The values obtained for the various thermodynamic parameters are listed in Table 3. The values
of the Gibbs’ free energy change, ∆G0, were negative, thereby confirming that the adsorption of
Pb(II) ions was spontaneous and thermodynamically favourable. Since ∆G0 became more
negative with increasing temperature, this indicated that a higher driving force applied at higher
temperatures resulting in a higher adsorption capacity. The value of ∆H0 was positive showing that
the adsorption process was endothermic in nature. The small but positive value of ∆S0 over the
temperature range 30–50 °C suggested an increasing randomness at the solid/solution interface
during adsorption (Namasivayam and Ranganathan 1995). This may be attributed to the
adsorption of Pb(II) ions displacing some water molecules from the surface of the adsorbent with
a resultant increase in randomness in the system.

TABLE 3. Thermodynamic Parameters for the Adsorption of Pb(II) Ions onto Coriander Seed Powder
Temp. (°C) Kc –∆G0 (kJ/mol) ∆H0 (kJ/mol) ∆S0 [kJ/(mol K)] R2

30
40
50
9.00
10.11
11.19
5.50
6.00
6.43 } 5.60
} 0.036
} 0.9842

3.7. Adsorption kinetics

The rate constants for the adsorption process were calculated using the pseudo-first-order and
pseudo-second-order kinetic models. The pseudo-first-order rate expression (Lagergren 1898)
may be written as:
k1
log( q e − q t ) = − t + log q e (10)
2.303

where qe is the amount of Pb(II) ions adsorbed per unit weight of adsorbent at equilibrium (mg/g),
qt is the amount of Pb(II) ions adsorbed per unit weight of adsorbent at any given time t and k1 is
the rate constant for the pseudo-first-order model. The plot of log(qe – qt) versus t (not shown) was
linear, thereby confirming the applicability of the pseudo-first-order rate equation. The values of
k1 and qe (calc.) were calculated from the slope and intercept of this plot for various initial Pb(II)
ion concentrations.
The pseudo-second-order kinetic rate equation may be written as (Ho and McKay 2000):
t 1 t
= + (11)
qt k 2 q 2e qe

where k2 [g/(mg min)] is the rate constant for the pseudo-second-order kinetic model. The initial
2
rate of adsorption, h, is equal to k 2 q e . The fact that the plot of t/qt versus t was linear (see
Figure 6 overleaf) indicates the applicability of the pseudo-second-order model. The values of k2
and qe (calc.) were calculated from the intercept and slope of the linear plots of t/qt versus t at
various initial Pb(II) ion concentrations. Table 4 overleaf lists the kinetic parameters determined
from the application of the pseudo-first-order and pseudo-second-order models. It was found that
the values of qe calculated from the pseudo-first-order kinetic model, qe (calc.), differed
appreciably from the experimental values, qe (exp.), showing that the system did not follow
pseudo-first-order kinetics. With the pseudo-second-order kinetic model, the values of qe (calc.)
Adsorption Properties of Coriander Seed Powder (Coriandrum sativum) 139

80
50 mg/ᐍ
70 60 mg/ᐍ
70 mg/ᐍ
60 100 mg/ᐍ

50

t/qt 40

30

20

10

0
0 100 200 300 400
Time (min)

Figure 6. Pseudo-second-order kinetic plots for the adsorption of Pb(II) ions onto coriander seed powder.

TABLE 4. Kinetic Parameters for the Adsorption of Pb(II) Ions onto Coriander Seed Powder
Conc. qe (exp.) Pseudo-first-order kinetics Pseudo-second-order kinetics
(mg/
) (mg/g) k1 (min–1) qe (calc.) R2 k2 [g/(mg min)] qe (calc.) h [mg/(g min)] R2
(mg/g) (mg/g)

50 4.3 0.019 3.140 0.9999 101.64 4.6 0.21 0.9967

60 4.9 0.156 2.600 0.9198 4.00 4.9 6.05 1.0000
70 5.6 0.007 1.240 0.9476 49.50 5.7 0.67 0.9983
100 8.3 0.015 3.140 0.9830 90.14 8.6 0.83 0.9990

were very close to the qe (exp.) values at the various initial Pb(II) ion concentrations, in contrast
to the situation with the pseudo-first-order model. The values of the correlation coefficient (R2)
for the pseudo-first-order model were also lower than those for the pseudo-second-order model,
thereby demonstrating that the pseudo-second-order model was better obeyed by the system.

3.8. Adsorption of Pb(II) ions in the presence of Cu(II) and Zn(II) ions

The adsorption of Pb(II) ions in the presence of Cu(II) and Zn(II) ions was studied by varying the
concentrations of Cu(II) and Zn(II) ions separately over the concentration range 20–100 mg/
at
a fixed concentration of Pb(II) ions (50 mg/
). It was found that the adsorption of Pb(II) ions was
unaffected by the presence of Cu(II) and Zn(II) ions, indicating that Pb(II) ions were adsorbed
independently. However, the adsorption capacities towards Cu(II) and Zn(II) ions in the presence
of Pb(II) ions increased from 1.2 mg/g to 5.6 mg/g and from 1.7 mg/g to 5.4 mg/g, respectively,
as the initial concentrations of these ions were increased, which again supports the view that
Pb(II), Cu(II) and Zn(II) ions were all adsorbed independently.

3.9. Adsorption of Pb(II), Cu(II) and Zn(II) ions in the presence of various electrolytes

The data reported overleaf in Table 5 demonstrate the effect of various electrolytes on the
adsorption of Pb(II), Cu(II) and Zn(II) ions. Other than CaCl2, these electrolytes had no effect on
 140

TABLE 5. Influence of Electrolytes on the Adsorption of Pb(II), Cu(II) and Zn(II) Ions onto Coriander Seed Powder
Added electrolyte Pb(II) ions Cu(II) ions Zn(II) ions
(0.1 M) % Adsorption qe (mg/g) pHi pHf % Adsorption qe (mg/g) pHi pHf % Adsorption qe (mg/g) pHi pHf

NaCl 92.0 4.6 5.51 5.63 64 3.2 5.51 4.98 100 5.0 5.51 5.80
NaNO3 94.0 4.7 5.54 5.51 62 3.1 5.54 5.00 100 5.0 5.54 5.91
Na2SO4 92.0 4.6 6.25 5.50 54 2.7 6.25 5.14 100 5.0 6.25 5.74
MgCl2 92.0 4.6 5.30 5.10 58 2.9 5.30 4.62 100 5.0 5.30 5.43
CaCl2 70.0 3.5 5.40 4.85 54 2.7 5.40 4.44 100 5.0 5.40 5.63
H2O 95.2 4.7 4.20 6.10 84 4.2 4.00 5.07 79 3.9 4.00 5.27
R.A.K. Rao and M. Kashifuddin/Adsorption Science & Technology Vol. 30 No. 2 2012
Adsorption Properties of Coriander Seed Powder (Coriandrum sativum) 141

the adsorption of Pb(II) ions. The adsorption of Pb(II) ions was reduced to some extent in the
presence of CaCl2, possibly due to the fact that Ca2+ ions were also adsorbed simultaneously via
ion exchange, as indicated by the decrease in the final pH (pHf) of the solution related to the
release of H+ ions from the adsorbent. On the other hand, the adsorption of Cu(II) ions was
affected by the presence of Na2SO4, MgCl2 and CaCl2. A decrease in pH in the presence of these
salts indicated that the ions derived from them were also adsorbed together with Cu(II) ions. The
adsorption of Zn(II) ions was least affected by these electrolytes with the value of pHf remaining
unaltered at equilibrium, thereby indicating the possible specific adsorption of Zn(II) ions onto
coriander seed powder.

3.10. Breakthrough capacities of Pb(II), Cu(II) and Zn(II) ions

The breakthrough curve, which makes optimum use of the concentration gradient between the
solute adsorbed by the adsorbent and that remaining in the solution, provides an indication of
the most effective column process. Thus, the column should remain operational until metal
ions start appearing in the effluent, when for all practical purposes the working life of the
column is over. This point is called the breakthrough point. This is important in process
design because it directly affects the feasibility and economics of the process (Gupta et al.
2001).
The breakthrough curves in single metal ion systems (Figure 7) shows that 200 m
of Pb(II)
ions, 50 m
of Cu(II) ions and 50 m
of Zn(II) ions could be passed through the column without
these metal ions being detected in the effluent. The breakthrough capacities of Pb(II), Cu(II) and
Zn(II) ions were found to be 20 mg/g, 5 mg/g and 5 mg/g, respectively. Figure 8 overleaf shows
the breakthrough curves for a multi-metal ion system containing Pb(II), Cu(II) and Zn(II) ions.
The breakthrough capacities of Pb(II), Cu(II) and Zn(II) ions were reduced from their values for
single metal ion systems to 5, 3 and 1 mg/g, respectively, when a mixture of these metal ions (50
mg/
each) was passed through the column. The decrease in breakthrough capacity might be due
to increased loading and to the limited adsorption capacity of the adsorbent.

1.2

1.0

0.8

C/C0 0.6

0.4
Pb(II)
Cu(II)
0.2
Zn(II)

0
0 100 200 300 400 500 600
Effluent volume (mᐍ)

Figure 7. Breakthrough capacities for single metal ion systems.

142 R.A.K. Rao and M. Kashifuddin/Adsorption Science & Technology Vol. 30 No. 2 2012

1.2

1.0

0.8

C/C0 0.6

0.4

Pb(II)
0.2
Cu(II)
Zn(II)
0
0 50 100 150 200 250 300
Effluent volume (mᐍ)

Figure 8. Breakthrough capacities for multi-metal ion systems.

3.11. Desorption of Pb(II), Cu(II) and Zn(II) ions by column processes

In order to explore the functional and realistic usefulness of the adsorbent, the desorption of Pb(II),
Cu(II) and Zn(II) ions was undertaken by column processes examining the following systems.

3.11.1. Desorption and recovery from a single metal ion system

Excellent results were obtained when desorption studies of Pb(II), Cu(II) and Zn(II) ions were
carried out in a single metal ion system. Thus, in a breakthrough capacity experiment, it was found
that a total 11.6 mg of Pb(II) ions could be adsorbed before the column was exhausted and 11.2
mg (96.5%) was desorbed by a 0.1 M HCl solution employing 10 m
eluent fractions [Figure 9(a)
overleaf]. Similarly 3.4 mg of Cu(II) ions was adsorbed and 3.38 mg (99.4%) was recovered
[Figure 9(b) overleaf] within 30 m
eluent fractions. Finally, Figure 9(c) indicates that 2.54 mg of
Zn(II) ions was adsorbed and 2.59 mg (100%) was recovered within 30 m
eluent fractions.

3.11.2. Desorption and recovery from a multi-metal ion system

The desorption of Pb(II), Cu(II) and Zn(II) ions was also studied in a multi-metal ion system when
100% desorption of Pb(II) and Cu(II) ions was achieved. In a breakthrough capacity experiment for
a multi-metal ion system, the maximum amount of Pb(II) ions adsorbed was 5.15 mg while the amount
desorbed was 5.18 mg. The adsorption of Cu(II) ions was 3.2 mg while 3.0 mg was desorbed, while
4.11 mg of Zn(II) ions was adsorbed and 3.6 mg was recovered. All these metal ions were recovered
within 10 m
fractions employing 0.1 M HCl solution. Hence, this method can be utilized for the pre-
concentration and subsequent determination of these metal ions from a very dilute solution.

3.11.3. Analysis, removal and recovery of Pb(II) ions from battery manufacturing wastewater

The adsorbent was utilized for the removal and recovery of Pb(II) ions from battery
manufacturing wastewater by a column operation. Thus, wastewater collected from one of the
lead acid battery manufacturing industries in Aligarh (India) was analyzed (see Table 6). The
Adsorption Properties of Coriander Seed Powder (Coriandrum sativum) 143

(a) (b)

Cu(II) ions adsorbed/desorbed (mg)

Pb(II) ions adsorbed/desorbed (mg)

12 3.5
adsorption adsorption
10 desorption 3.0 desorption

2.5
8
2.0
6
1.5
4
1.0
2 0.5

0 0
0 100 200 300 400 500 600 0 50 100 150 200 250 300
Effluent volume (mᐍ) Effluent volume (mᐍ)

(c)
Zn(II) ions adsorbed/desorbed (mg)

2.5
adsorption
desorption
2.0

1.5

1.0

0.5

0
0 50 100 150 200 250 300 350
Effluent volume (mᐍ)

Figure 9. Adsorption/desorption of (a) Pb(II) ions, (b) Cu(II) ions and (c) Zn(II) ions from doubly distilled water to/from
coriander seed powder.

TABLE 6. Analysis of Battery Manufacturing Wastewater

Parameter Value

TDS 2780.00 mg/

Conductivity 10.13 mS
Pb(II) ion conc. 4.9 mg/

pH 1.5
Na+ ion conc. 35.00 mg/

K+ ion conc. 70.00 mg/

Ca2+ ion conc. 24.00 mg/

Temperature 24.9 °C

amount of Pb(II) ions adsorbed was 0.49 mg (100%) while 0.48 mg (97.95%) was recovered
employing 0.1 M HCl as the eluent (see Table 7 overleaf).

3.12. Pre-concentration of Pb(II), Cu(II) and Zn(II) ions

The solid-phase extraction method was applied for the determination of Pb(II), Cu(II) and Zn(II)
ions (2.25 mg/
each) in synthetic samples prepared in DDW as well as in tap water. Due to the
144 R.A.K. Rao and M. Kashifuddin/Adsorption Science & Technology Vol. 30 No. 2 2012

TABLE 7. Removal and Recovery of Pb(II) Ions from Battery

Manufacturing Wastewatera
Parameter Value

Volume of wastewater 100 m

Amt. of Pb(II) ions before adsorption 0.49 mg
Amt. of Pb(II) ions after adsorption 0 mg
Removal 100%
Amt. of Pb(II) ions desorbed 0.48 mg
Recovery 97.95%
a
Amt. of adsorbent employed = 0.5 g.

low concentration of trace metals in real samples, these analytes should be extracted in smaller
volumes. Table 8 summarizes the results of the pre-concentration step using 0.1 M HCl as a
desorbing reagent. It may be concluded that complete recovery (100%) of these metal ions was
possible from a 10 m
fraction of the effluent.

TABLE 8. Pre-concentration of Pb(II), Cu(II) and Zn(II) Ions in Doubly Distilled Water and Tap Water
Employing the Solid-phase Extraction Methoda
Metal ion Amount loaded Doubly distilled water (DDW) Tap water
(mg) Desorbed (mg) % Recovery Desorbed (mg) % Recovery

Pb(II) 1.125 1.2 100 1.2 100

Cu(II) 1.125 1.2 100 1.2 100
Zn(II) 1.125 1.2 100 1.2 100
a
Liquid volume = 500 m
.

3.13. Comparative value of the adsorption capacity of coriander seed powder

The adsorption of Pb(II) ions onto various adsorbents has already been reported by several
authors. On comparing the data obtained in the present study, it was shown that the adsorption
capacity (maximum monolayer capacity) of coriander seed powder was either higher or
comparable to the values reported for these adsorbents (see data in Table 9).

TABLE 9. Comparison of Maximum Adsorption Capacities of Various Natural Adsorbents

Adsorbent Maximum adsorption capacity, Reference
qm (mg/g)

Natural Jordanian 66.24 Al-Degs et al. (2006)

Tree fern 39.80 Ho et al. (2002)
Black grain husk 49.97 Saeed et al. (2005)
Jute 17.18 Shukla and Pai (2005)
Mango peel 96.32 Iqbal et al. (2009)
Maple sawdust 3.19 Yu et al. (2000)
Hazelnut shell 16.23 Bulut and Tez (2007)
Grape stalk waste 49.9 Martinez et al. (2006)
Coriander seed powder 347.70 Present study
Adsorption Properties of Coriander Seed Powder (Coriandrum sativum) 145

4. CONCLUSIONS

Coriander seed powder showed an excellent potential for the removal of Pb(II), Cu(II) and Zn(II) ions
from aqueous solution. The adsorption process was pH-dependent with the maximum adsorption
of these ions occurring in the pH range 4–6. The experimental data obtained at 40 °C were fitted
by the Langmuir, Freundlich, Temkin and D–R isotherms, with the p-value obtained for each fit
indicating their corresponding significance. Thermodynamic parameters indicated that the
adsorption of Pb(II) ions was endothermic and spontaneous. Kinetic data showed the applicability
of the pseudo-second-order model. The presence of high concentrations of Cu(II) and Zn(II) ions
and other electrolytes had a negligible effect on the adsorption of Pb(II) ions. Consequently, the
maximum amount of Pb(II) ions could be removed from aqueous solution even in the presence of
these ions. Desorption studies showed 96–100% recovery of Pb(II), Cu(II) and Zn(II) ions from
both single and multi-metal ion systems. In addition, 100% recovery of Pb(II) ions from the
wastewater generated by the lead acid battery manufacturing industry was achieved employing
small volumes of the effluent. Pre-concentration of Pb(II), Cu(II) and Zn(II) ions in doubly distilled
water as well as tap water showed 100% recovery of these ions. Hence, it may be concluded that
this technology can be utilized for the removal, recovery and pre-concentration of Pb(II), Cu(II)
and Zn(II) ions from very dilute solutions.

ACKNOWLEDGEMENT

The authors wish to thank the Chairman of the Department of Applied Chemistry at Aligarh
Muslim University for providing research facilities.

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