Journal of Environmental Chemical Engineering 2 (2014) 12611274

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Journal of Environmental Chemical Engineering

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Sorption of hexavalent chromium from aqueous solution using

marine green algae Halimeda gracilis: Optimization, equilibrium,
kinetic, thermodynamic and desorption studies
R. Jayakumar* , M. Rajasimman, C. Karthikeyan
Environmental Engineering Laboratory, Department of Chemical Engineering, Annamalai University, Annamalai Nagar 608002, Tamilnadu, India

a r t i c l e

i n f o

Article history:
Received 13 November 2013
Accepted 12 May 2014
Keywords:
Adsorption
Chromium(VI)
RSM
Thermodynamics
Kinetics
Green algae

a b s t r a c t
In this work, effect of operating variables on Cr(VI) uptake capacity of marine green algae Halimeda gracilis was
studied. Response surface methodology (RSM) was applied to optimize the operating variables. A maximum
percentage removal of Cr(VI) by H. gracilis occurs when, pH 4.9, sorbent dosage 2.2 g/L, agitation speed
136 rpm and contact time 47 min. The sorbent was characterized by using Fourier transform infrared
spectroscopy (FTIR) and scanning electron microscope (SEM) analysis. Experimental data were analyzed in
terms of pseudo rst order, pseudo second order intra particle diffusion, power function and Elovich kinetic
models. The results showed that the sorption process of Cr(VI) ions followed pseudo second order and power
function kinetics. The sorption data of Cr(VI) ions are tted to Langmuir, Freundlich, DubininRadushkevich
Temkin, Sips and Toth isotherms. Sorption of Cr(VI) onto H. gracilis biomass followed the Langmuir isotherm
model (R2 = 0.997) with the maximum sorption capacity of 55.55 mg/g. The calculated thermodynamic
parameters such as G , H and S showed that the sorption of Cr(VI) ions onto H. gracilis biomass was
feasible, spontaneous and endothermic. Desorption study shows that the sorbent could be regenerated using
0.2 M HCl solution, with up to 80% recovery.

c 2014 Elsevier Ltd. All rights reserved.

Introduction
Cr(VI) is one of the pollutants introduced into natural waters from
a variety of industrial wastewaters. Chromium is a highly toxic metal,
considered as a precedence pollutant because of its mutagenic and
carcinogenic properties [1]. Cr(VI) is both carcinogenic and mutagenic [2], and it may cause damages to the kidney, lungs and ulcerations to the skin [3]. According to the World Health Organization
(WHO) drinking water guidelines, the maximum allowable limit for
total chromium is 0.05 mg/L [4]. Sources of chromium pollution are
electroplating, leather tanning, textile dyeing, and metal nishing
industries. In metal cleaning, plating and metal processing industries, chromium concentration can approach 20,00075,000, 15,000
52,000 and 100,000270,000 mg/L, respectively [5]. Chromium exists
in several oxidation states (2 to + 6), the most stable and common
forms are the hexavalent Cr(VI) and trivalent Cr(III). The chemistry
of Cr(VI) is greatly dependent upon the pH and concentration of
the solution and it normally exists in the anionic form, as Cr2 O7 2
(dichromate), HCrO4 (hydrogen chromate) or CrO4 2 (chromate)
forms depending on pH and concentration. At pH value below 1, the
predominant species is H2 CrO4 (chromic acid). In acidic media around

* Corresponding author.
E-mail address: harrishjk@rediffmail.com (R. Jayakumar).

c 2014 Elsevier Ltd. All rights reserved.

2213-3437/$ - see front matter 
http://dx.doi.org/10.1016/j.jece.2014.05.007

2, Cr(VI) exists mostly in the form of dichromate (Cr2 O7 2 ) ions. At pH

between 2 and 6, Cr2 O7 2 and HCrO4 ions exist in equilibrium and
under alkaline conditions (pH > 8) it exists predominantly as chromate anion [6]. Several international environmental agencies have
introduced strict policy with regard to metal expulsion, especially
from industrial activities. According to USEPA, the permissible limit
for the discharge of Cr(VI) into surface water is 0.5 mg/L, while total Cr
including Cr(III), Cr(VI) and its other forms is synchronized to below
2 mg/L [7]. Many conventional techniques, including chemical precipitation, membrane separation, ion exchange, reverse osmosis and
solvent extraction have been employed for the treatment of metal
bearing industrial efuents [810]. However, the disadvantages of
these methods such as secondary pollution, high chemical or energy
requirements, or high cost have recently shifted a large number of
studies to develop more efcient removal processes for heavy metal
control.
Sorption is an emerging and innovative technology using different
biomass to remove pollutants from wastewater, especially those that
are not easily biodegradable such as heavy metals [1114]. Among
the biological materials, algae have been found to be potentially more
suitable sorbents because of their cheap availability both in fresh and
saltwater, relatively high surface area and high binding afnity [15].
Research in the eld of sorption has mostly anxious itself with green
algae [1618]. Green algae are mainly cellulose, and a high percentage
of the cell wall containing proteins bonded to polysaccharides to form

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R. Jayakumar et al. / Journal of Environmental Chemical Engineering 2 (2014) 12611274

Materials and methods

Nomenclature
RSM
FTIR
SEM
USEPA
WHO
CCD
AAS
EDS
Xi
Xo
G
H
S
K
qe

response surface methodology

Fourier transform infrared spectroscopy
scanning electron microscope
United States of Environmental Protection Agency
World Health Organization
central composite design
atomic absorption spectrophotometer
energy dispersive spectrum
uncoded value of the ith test variable
uncoded value of the ith test variable at center point
Gibbs free energy change
enthalpy change
entropy change
equilibrium constant
amount of adsorbed chromium per unit mass of
adsorbent (mg/g)
qt
amount of adsorbed chromium per unit mass of
adsorbent at time t (mg/g)
Co
initial concentration of chromium metal ion (mg/L)
Ce
equilibrium chromium metal ion concentration
(mg/L)
Ct
concentration of metal ion at time t (mg/L)
V
volume of solution treated (L)
M
amount of biomass (g m)
qm
maximum sorption capacity of the sorbent (mg/g)
b
Langmuir sorption constant (L/mg)
Kf
Freundlich constant relating the sorption capacity
1/n
empirical parameter relating the sorption intensity

activity coefcient related to sorption mean energy

(mol2 /kJ2 )
Polanyi potential
R
gas constant (8.314 103 kJ/mol K)
T
temperature (kelvin)
E
mean free energy of sorption per molecule of sorbate
B
heat of sorption
t
time (min)
KT
equilibrium binding constant (L/mg)
as , Ks , s Sips parameter
bT , nT
Toth parameter
K1
rate constant for the pseudo rst order equation
(min1 )
K2
rate constant for the pseudo second order equation
(g/mg min)
Kid
intra particle diffusion rate constant (mg/g min0.5 )
K, v
power function constant

initial adsorption rate (mg/g min)

desorption constant (g/mg)

KR
separation factor (dimensionless)
Ka
isotherm constant

Chemicals and equipment

All chemicals used were of analytical reagent grade. Deionized
double distilled water was used throughout the experimental studies.
Analytical grade HCl, NaOH and buffer solutions (E. Merk) were used
to adjust the solution pH. Elico (L1-129) make pH meter was used
for pH measurements. The metal concentrations in the samples were
determined using atomic absorption spectrophotometer (AAS) (Elico
SL-176).
Biomass preparation
The marine green algae H. gracilis were collected from the Mandapam coast, Ramanadhapuram district, Tamilnadu, India. They were
washed several times using deionized water to remove extraneous
materials and salts. The washing process was continued till the wash
water contained no dirt. The washed algae were completely dried in
sunlight for 10 days. The dried samples were cut into small pieces
and powdered using domestic mixer. The structure of the marine
algae was modied by adding 0.1 M HCl. The content was stirred at
200 rpm for 8.0 h at room temperature. The acid treated algal biomass
was then centrifuged and washed with the physiological saline solution and dried in an oven at 333.15 K. The dried sorbent was ground
on an agate stone pestle mortar and sieved. In this work, the powdered raw and acid treated algae of 100 mesh particle size were used
as sorbents for sorption process.
Preparation of metal ion solution
Metal ion solution was prepared from analytical grade K2 Cr2 O7
supplied by (Merck Ltd.) India. Stock solution of 1000 mg/L of Cr(VI)
was prepared from K2 Cr2 O7 using deionized water. The working solutions were prepared from the stock solutions by diluting it to appropriate volumes.
Electroplating wastewater was collected from a small scale industry located at Chennai, Tamilnadu, India. The wastewater was characterized according to APHA methods [19] and it was given in Table 1.

Batch adsorption experiment

All the batch experiments were carried out according to the CCD.
The sorbentsorbate mixtures were taken in a 250 mL conical ask
and agitated in an incubator shaker (LARK). The samples were centrifuged in the research centrifuge (REMI) at 10,000 rpm and the
supernatant was used for analysis of metal concentrations by using
AAS. Experimental analysis was repeated three times and the results
were statistically analyzed. The amount of adsorbed chromium per
unit mass of adsorbent (qe , mg/g) was obtained using the following
expression:

qe =
glycoproteins. These compounds contain several functional groups
(amino, carboxyl, sulphate, hydroxyl) which could play a vital role in
the sorption process.
In this work, marine macro green algae H. gracilis was used as a
sorbent for removing Cr (VI) from aqueous solution. The inuence of
various operating variables on the sorption of Cr(VI) onto Halimeda
gracilis was studied using a central composite design (CCD) method.
The experimental data are analyzed by thermodynamic, kinetic and
equilibrium isotherm. FTIR spectroscopy and SEM were used to characterize the sorbent.

(C o C e) V
m

(1)

The amount of adsorbed chromium per unit mass of adsorbent at time

t (qt , mg/g) was obtained by using following expression:
qt =

(C o C t ) V
m

(2)

where V is the volume of solution treated in liter, Co is the initial

concentration of chromium metal ion in mg/L, Ce is the equilibrium
Chromium metal ion concentration in mg/L, Ct (mg/L) is the concentration of adsorbents at time t, and m is the biomass in gram.

R. Jayakumar et al. / Journal of Environmental Chemical Engineering 2 (2014) 12611274

1263

Table 1
Characteristics of the electroplating wastewater.
Parameters

Characteristics

Color
pH
Total dissolved solids
BOD
COD
Sulphate
Phosphate
Cr(VI)
Copper
Zinc
Iron
Nickel

Dark brown
1.80
19,820 mg/L
346 mg/L
912 mg/L
374 mg/L
0.31 mg/L
112 mg/L
0.56 mg/L
153 mg/L
5.21 mg/L
28 mg/L

Experimental design by RSM

RSM is a statistical tool designed to nd the optimal response
within specic ranges of pre-established factors, through a secondorder equation. In industrial applications, RSM designs involve a small
number of factors, because the required number of experimental runs
increases dramatically with the number of factors [20]. CCD was chosen to study the effects of pH, sorbent dosage (g/L), agitation speed
(rpm) and contact time (min) on Cr(VI) sorption. In order to describe
the effects of these variables on percentage removal of chromium,
batch experiments were conducted. The coded values of the process
parameters were determined by the following equation.
Xi =

(Xi X0)
X

(3)

where Xi coded value of the ith variable, Xi uncoded value of the ith test
variable and Xo uncoded value of the ith test variable at center point.
The range and levels of individual variables were given in Table 2. The
experimental design was given in Table 3. The regression analysis
was performed to estimate the response function as a second order
polynomial.
A second-order polynomial equation is:
Y = 0 +

k


i X i +

i=1

k

i=1

ii X i2 +

k=1


k


ij X i X j

(4)

i =1, i < j j=2

where Y is the predicted response bi , bj , bij are coefcients estimated

from regression, they represent the linear, quadratic and cross products of x1 , x2 , x3 on response.
A statistical program package Design expert 7.1.5 was used for regression analysis of the data obtained and to estimate the coefcient
of the regression equation. The equation was validated by the statistical test called ANOVA analysis. After sorption, the contents of the
beakers were centrifuged at 10,000 rpm for 3 min. and the sorbent
was successfully separated from aqueous solution. The supernatants
were analyzed for residual Cr(VI) concentration using AAS. All the
experiments were performed in triplicate and average value was reported.

(Thermo Scientic Nicolet iS5 FTIR, USA) was used for the IR spectral
studies (4000400 cm1 ) of sorbent. For IR spectral studies, 10 mg of
sample was mixed and ground with 100 mg of KBr and made into
pellet to investigate the functional groups present in the H. gracilis
and to look into possible Cr(VI) binding sites.
Desorption/reuse procedure
The recycling of sorbent is a most important aspect from the economical point. Hence sorptiondesorption experiments were carried
out up to ten cycles using 10 mL of 0.2 M HCl. A single cycle sequence consists of sorption followed by desorption. In order to use
the biomass for the next stage of cycle, the biomass was washed with
excess of 0.2M HCl solution and distilled water, sequentially.
Desorption efciency =

Amount of metal ions desorbed

100
Amount of metal ions adsorbed

(5)

Results and discussion

Characteristics of sorbent
The physical and chemical properties of the green algae Helimeda
gracilis were determined by the standard methods. The elemental
analysis depicted the composition of sorbents as C, 20.3%; N, 5.02%;
S, 1.63%. The apparent density of the sorbent was determined to be
1.1 g/cm3 . EDX analysis of sorbent before and after Cr(VI) sorption
conrmed this observation. The humidity and the zeta potential were
calculated to be 1.26% and 0.051 V for the sorbent. The cell wall
of green algae contains cellulose, hydroxyproline, glucosides, xylans
(polysaccharides made from units of xylose) and mannan (polymer of
sugar mannose). The major functional groups that took part in adsorption were OH, C O, CO, CH and COOH. The functional group
SO3 2 was additionally involved in adsorption with H. gracilis. The
FTIR results obtained give an idea about the presence of functional
groups on the algal cell surfaces and also the mechanism of adsorption, which is dependent on functional groups especially hydroxyl,
carboxyl, and carbonyl groups.

SEM and EDS analysis

Effect of sorbent size
The micrographs were recorded using JEOL scanning electron
microscope model, JSM 5610 L V, with an accelerating voltage of
20 kV, at high vacuum (HV) mode and secondary electron image (SEI),
an energy dispersive spectrum analyzer (EDS) of oxford instrument
is attached with the SEM for elemental analysis.
FTIR measurements
FTIR spectra for both fresh and Cr(VI) treated H. gracilis were obtained by KBr pellets methods operated on FTIR spectrophotometer

Before optimization, the effect of sorbent size (36, 60, 100 and
150 mesh) on Cr(VI) sorption by Helimeda gracilis were carried out.
The sorbent was transferred to 250 mL Erlenmeyer ask containing
100 mL of Cr(VI) solutions and agitated at 120 rpm for a desired
contact time. Then the sorbents were separated and the Cr(VI) concentration in the supernatant was analyzed by AAS. From Fig. 1, it
was inferred that the Cr(VI) removal efciency increases as the mesh
size increases from 36 to 150 mesh. This is because; smaller particles
provide larger surface area and results in higher removal efciency.

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R. Jayakumar et al. / Journal of Environmental Chemical Engineering 2 (2014) 12611274

Table 2
Experimental range and levels of independent process variables.
Independent variable

pH
Sorbent dosage
(g/L)
Agitation speed
(rpm)
Contact time (min)

Coded levels
Code

+1

+2

A
B

3
1

4
1.5

5
2

6
2.5

7
3

40

80

120

160

200

20

30

40

50

60

Table 3
CCD based experimental design and its response for chromium removal.

Run order

(A) pH

(B) Sorbent dosage

(g/L)

(C) Agitation speed

(rpm)

(D) Contact time

(min)

Percentage Cr(VI) removal

Experimental

Predicted

1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31

1 (6)
1 (4)
0 (5)
0 (5)
0 (5)
0 (5)
1 (6)
2 (7)
0 (5)
0 (5)
0 (5)
0 (5)
1 (4)
1 (4)
0 (5)
1 (6)
0 (5)
1 (4)
0 (5)
1 (4)
1 (4)
1 (6)
1 (6)
0 (5)
1 (4)
1 (4)
1 (6)
1 (6)
2 (3)
0 (5)
1 (6)

1 (1.5)
1 (2.5)
0 (2)
2 (1)
0 (2)
0 (2)
1 (1.5)
0 (2)
0 (2)
0 (2)
0 (2)
0 (2)
1 (1.5)
1 (2.5)
0 (2)
1 (1.5)
0 (2)
1 (2.5)
0 (2)
1 (2.5)
1 (1.5)
1 (2.5)
1 (2.5)
2 (3)
1 (1.5)
1 (1.5)
1 (2.5)
1 (1.5)
0 (2)
0 (2)
1 (2.5)

1 (80)
1 (160)
0 (120)
0 (120)
0 (120)
2 (200)
1 (160)
0 (120)
0 (120)
0 (120)
0 (120)
0 (120)
1 (80)
1 (160)
2 (40)
1 (80)
0 (120)
1 (80)
0 (120)
1 (80)
1 (80)
1 (80)
1 (160)
0 (120)
1 (160)
1 (160)
1 (80)
1 (160)
0 (120)
0 (120)
1 (160)

1 (30)
1 (30)
0 (40)
0 (40)
0 (40)
0 (40)
1 (50)
0 (40)
0 (40)
0 (40)
2 (20)
0 (40)
1 (50)
1 (50)
0 (40)
1 (50)
2 (60)
1 (30)
0 (40)
1 (50)
1 (30)
1 (50)
1 (50)
0 (40)
1 (50)
1 (30)
1 (30)
1 (30)
0 (40)
0 (40)
1 (30)

34.41
62.11
79.22
25.76
79.22
77.8
44.5
25.75
79.22
79.22
42.56
79.22
43.07
66.43
63.2
47.43
79.22
64.87
79.22
61.9
49.13
71.5
72.5
80.9
58.22
60.6
41.99
41.12
65.36
79.22
52.81

27.435
68.791
79.220
32.483
79.220
74.578
48.785
31.926
79.220
79.220
47.883
79.220
47.548
74.953
62.380
43.244
69.855
62.133
79.220
70.418
49.911
72.876
74.214
70.135
56.286
60.771
46.419
35.097
55.141
79.220
49.880

Fitting models
Sorption of Cr(VI) was carried out according to the CCD and the
results obtained were given in Table 3. The results of theoretically predicted response were given in Table 3. The mathematical expression
of relationship to the response with variables is:
Y = 79.2200 5.80375 A + 9.41292 B + 3.04958C + 5.49292 D
8.92156 A2 6.97781 B 2 2.68531C 2 5.08781 D 2
+1.69063 AB 0.799375 AC + 4.54312 AD 1.05063 BC
+2.66188 B D 0.530625C D
Fig. 1. Effect of sorbent size on sorption of Cr(VI) on Helimeda gracilis. Initial Cr(VI)
conc. = 50 mg/L, sorbent dosage = 1 g/L, contact time = 60 min, and pH = 5.

The maximum removal efciency was attained for a mesh size of 150.
But for regeneration process, the smaller size particles will not with
stand the extreme conditions [21]. Hence 100 mesh particle size was
selected for further studies.

(6)

where Y is the percentage removal of Cr(VI) and A, B, C and D are the

coded values of pH, sorbent dosage(g/L), agitation speed (rpm) and
contact time (min) respectively.
The ANOVA results for Cr(VI) sorption onto green alga were given
in Table 4. F value of 11.51 implies that the model was signicant.
The sher F-test with a very low probability value (Pmodel > 0.0001)
reveals a very high signicance for the regression model. The goodness of t of the model was checked by coefcient of determination

R. Jayakumar et al. / Journal of Environmental Chemical Engineering 2 (2014) 12611274

Fig. 2. Interactive effect of pH and sorbent dosage on Cr(VI) removal by Halimeda

gracilis.

(R2 ). For a good statistical model, R2 value should be close to 1.0. The
R2 was found to be 0.9097, which implies that more than 90.97% of
experimental data was compatible with the data predicted by the
model. A low CV value (11.66), indicate that the deviations between
experimental and predicted values were low. Adeq precision measures the signal to noise ratio. A ratio greater than 4 is desirable. In
this work, the ratio is found to be 10.487, which indicates an adequate
signal. Values of P less than 0.05 indicates the signicance of model
terms. In this case, A, B, C, D, A2 , B2 , D2 and AD were signicant model
terms for the sorption of Cr(VI). This implies that the linear and square
effects of pH, sorbent dosage and contact time were more signicant
factors. The linear effect of agitation speed was more signicant factor
and the interactive effect of pH and contact time was also signicant.

Effect of variables on Cr(VI) removal

The sorption efciency depends on several parameters, like pH,
structural properties of both sorbate and sorbent, sorbent dosage,
contact time, agitation speed, initial concentration of metal ions, etc.
[20].
Effect of pH on sorption
The effect of pH on the sorption of chromium onto raw H. gracilis algae biomass were studied by changing the pH from 3.0 to 7.0.
The result obtained was shown in Fig. 2. It was observed from the
plot that the sorption was favored by acidic pH range of 3.05.0 and
maximum adsorption by the algae biomass was observed at pH 4.9.
Further increase in pH decreased the adsorption of chromium by the
algae. Maximum metal adsorption at pH 4.9 seems to be due to a
net positive charge on algae surface at low pH. Similar results were
reported by Srinivasa Popuri et al. [22] and Izabela Michalak et al.
[23]. Chromium, which may exist as HCrO4 , Cr2 O7 , etc. in solution at
optimum sorption pH has a tendency to bind the protonated active
sites of the sorbent [24]. But as pH of the solution increases, algae cell
wall becomes more and more negatively charged due to functional
groups, which repulse the negatively charged chromate ions thereby
affecting Cr(VI) sorption on the algae surface.
Effect of sorbent dose
The effect of sorbent dose on the removal of Cr(VI) was shown in
Fig. 3. The amount of sorbent signicantly inuenced the extent of
Cr(VI) sorption, i.e., the sorption of metal ions increases with increase
in biomass dosage and almost constant at dose higher than 2.2 g/L.

1265

Fig. 3. Interactive effect of agitation speed and contact time on Cr(VI) removal by
Halimeda gracilis.

This trend could be explained as a consequence of partial aggregation

of biomass at higher biomass concentration, which results in the decrease in effective surface area for the sorption [25]. Therefore, the
optimum algae biomass dose selected was 2.2 g/L for the rest of the
experimental studies.
Effect of agitation speed
The effect of agitation speeds on adsorption for Cr(VI) was studied
in the range of 40200 rpm. The results were presented in Fig. 3. From
the results, the maximum sorption of Cr(VI) occurred at 136 rpm for
H. gracilis sorbent. At low agitation speed, the sorbent do not spread
in the sample but accumulated. This may cover the active sites of the
lower layer adsorbent and only the upper layer adsorbent active sites
adsorb the metal ion. Therefore agitation rate should be sufcient
to assure that all the surface binding sites were readily available for
metal uptake. But at higher agitation speed, the percentage removal
decrease. This may be attributed to an increase desorption tendency
of adsorbate molecules [26].
Effect of contact time
Fig. 3 shows the interactive effect of agitation speed and contact
time on the sorption of Cr(VI) on to the green algae. It has been observed that the Cr(VI) removal efciency was high at the beginning
stages and then decreases slowly till it reaches the saturation level
(47 min). The initial phase may involve physical adsorption or ion
exchange at cell surface and the subsequent slower phase may involve other mechanisms such as complexation, micro-precipitation
or saturation of binding sites [27].
The perturbation plot (Fig. 4) shows the comparative effects of
the variables on the sorption of Cr(VI). A steep curvature in sorbent
dosage, B curve, shows that the sorption is very sensitive to sorbent
dosage. The comparatively semi-at C curve show less sensitivity of
the sorption to alter with respect to a change in agitation speed. It is
clear from the perturbation plot that the most signicant factor on
the response is sorbent dosage followed by pH and contact time.
Second order polynomial models obtained in this study was utilized to determine the optimum conditions. The optimum conditions were: initial pH 4.9, sorbent dosage 2.2 g/L, agitation
speed 136 rpm and contact time 47 min.
Effect of temperature and thermodynamic study
It is well known that, temperature inuences the sorption process
rate. An increase in temperature from 293.15 to 308.15K increases the
specic uptake to 43.5 mg/g of Cr(VI) by H. gracilis. Further increasing

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R. Jayakumar et al. / Journal of Environmental Chemical Engineering 2 (2014) 12611274

Table 4
ANOVA for chromium removal using Halimeda gracilis.
Source

Sum of squares

df

Mean square

F-value

P-value

Model
A
B
C
D
AB
AC
AD
BC
BD
CD
A2
B2
C2
D2
Residual
Lack of t
Pure error
Cor total

8121.96
808.40
2126.47
223.20
724.13
45.73
10.22
330.24
17.66
113.37
4.51
2276.06
1392.32
206.20
740.22
806.35
806.35
0.000
8928.31

14
1
1
1
1
1
1
1
1
1
1
1
1
1
1
16
10
6
30

580.14
808.40
2126.47
223.20
724.13
45.73
10.22
330.24
17.66
113.37
4.51
2276.06
1392.32
206.20
740.22
50.40
80.63
0.000

11.51
16.04
42.19
4.43
14.37
0.91
0.20
6.55
0.35
2.25
0.089
45.16
27.63
4.09
14.69

<0.0001
0.0010

<0.0001
0.0515
0.0016
0.3550
0.6585
0.0210
0.5621
0.1531
0.7688
<0.0001
<0.0001
0.0601
0.0015

Std. dev. 7.10; R-squared 0.9097; mean 60.89; adj. R-squared 0.8307; C.V. % 11.66
pred R-squared 0.7798; PRESS 4644.56; adeq precision 10.487.

Fig. 5. Plot of G versus T for the estimation of thermodynamic parameters for sorption of Cr(VI) by Halimeda gracilis.

Fig. 4. Perturbution plot on Cr(VI) removal by Halimeda gracilis.

the temperature from 308.15 to 313.15 K decreases the specic uptake

from 43.5 to 42.84 mg/g of Cr(VI). This is probably caused by a change
in the texture of the sorbent and a loss in the sorption capacity due
to material deterioration [28].
Thermodynamic parameters were calculated to conrm the adsorption nature of the investigation. The thermodynamic constants,
free energy change (G ), enthalpy change (H ) and entropy change
(S ) were calculated to evaluate the thermodynamic feasibility of
the process and to conrm the nature of the adsorption process. The
Gibbs adsorption process, free energy, as well as, the enthalpy process were calculated from experimental results using the following
equations:
G = RT ln K
G = H T S

(7)

Equilibrium isotherm study

(8)

In order to determine the mechanism of Cr(VI) sorption onto

H. gracilis, the batch experimental data was applied to the linear isotherms namely, Langmuir, Freundlich, DubininRadushkevich,
Temkin and three parameter isotherm namely Sips and Toth.

where R is the universal gas constant (8.314

kJ/mol K), T is the
temperature in Kelvin and K is the equilibrium constant, calculated as
the surface and solution metal distribution ratio (K = qe /Ce ) [29]. From
Fig. 5, the values of H and S were calculated from the intercept
and slope of a plot of G versus T according to Eq. (8) by linear
regression analysis. The calculated thermodynamic parameters were
listed in Table 5. Positive values of H suggest the endothermic
103

nature of the sorption and the negative values of G indicate the

spontaneous nature of the sorption process. However, the negative
value of G decreases with an increase in temperature, indicating
that the spontaneous nature of sorption is inversely proportional to
the temperature. Similar endothermic nature of the sorption process
has been reported for other sorbent systems [24,30]. The increase in
sorption with temperature may be attributed to either increase in the
number of active surface sites available for sorption on the adsorbent
or due to the decrease in the boundary layer thickness surrounding
the sorbent, so that the mass transfer resistance of sorbate in the
boundary layer decreased [31]. The positive values of S showed the
increasing the randomness at the solid/solution interface during the
sorption process.

Langmuir isotherm
Langmuir [32] proposed a theory to describe the sorption of gas
molecules onto metal surfaces. The linear form of Langmuir isotherm

R. Jayakumar et al. / Journal of Environmental Chemical Engineering 2 (2014) 12611274

1267

Table 5
Thermodynamic parameters for the sorption of Cr(VI) on to Halimeda gracilis.
Metal ion

Temp. (K)

G (kJ/mol)

S (kJ/mol k)

H (kJ/mol)

Cr(VI)
Cr(VI)
Cr(VI)
Cr(VI)
Cr(VI)

293.15
298.15
303.15
308.15
313.15

2.469
3.309
4.149
5.102
5.07

0.139
0.139
0.139
0.139
0.139

38.38
38.38
38.38
38.38
38.38

Fig. 6. Langmuir isotherm plots for the sorption of Cr(VI) onto H. gracilis at 308.15 K
temperature.

Fig. 7. Freundlich isotherm plots for the sorption of Cr(VI) onto Halimeda gracilis at
308.15 K temperature.

is given by,

innite surface coverage is predicted, indicating multilayer sorption

on the surface.

1
1
1
=
+
qe
qmbC e
qm

(9)

where qm is the monolayer sorption capacity of the sorbent (mg/g),

qe is the equilibrium metal ion concentration on the sorbent (mg/g),
Ce is the equilibrium metal ion concentration in the solution (mg/L),
and b is the Langmuir sorption constant (L/mg) related to the free
energy of sorption. Fig. 6 shows the Langmuir plots of Cr(VI) sorption
isotherms for H. gracilis at different initial metal concentration. The
constants qm and b are tabulated in Table 6. Table 7 represents the
comparison of sorption capacity (qm ; mg/g) of H. gracilis biomass for
Cr(VI) with various sorbents. Based on this table, it can be concluded
that the H. gracilis has very good potential for the removal of Cr(VI)
from aqueous solution. Afnity between sorbent and sorbate was
represented by the constant b. In general good sorbents have a high
qmax and a high R2 (0.997). H. gracilis have high saturation (qmax ) for
different initial metal concentration of Cr(VI).
Freundlich isotherm
The Freundlich [36] isotherm is an empirical equation used to describe heterogeneous systems. The linear form of Freundlich isotherm
is represented by the equation:
log qe = log K f +

1
log C e
n

(10)

where Kf is a constant relating the sorption capacity and 1/n is an empirical parameter relating the sorption intensity, which varies with
the heterogeneity of the material. From the graphs, Kf value was found
to be 19.67 and 1/n value was found as 0.206. Usually, 1/n values between 0 and 1 indicate good sorption. In this work, a value of 0.206
indicates that the sorption of Cr(VI) onto the H. gracilis was favorable.
Fig. 7 shows the Freundlich plots of Cr(VI) sorption isotherms for H.
gracilis at different initial metal concentration and the constants Kf
and 1/n were tabulated in Table 6. The values of Kf and 1/n were
calculated from the intercept and slope of the plot between log qe
versus log Ce . Kf , for all cases, the Langmuir equation ts the experimental data better than the Freundlich equation. This isotherm does
not predict any saturation of the adsorbent by the sorbate. Instead,

DubininRadushkevich isotherm
The linear form of the DR isotherm equation [37] is:
ln qe = ln qm  2

(11)

where qe is the amount of metal ions adsorbed on per unit weight

of biomass (mg/g), qm is the maximum sorption capacity (mg/g),
is the activity coefcient related to sorption mean energy (mol2 /kJ2 )
and is the Polanyi potential described as


1
(12)
 = RT ln 1 +
Ce
where R is the gas constant 8.314 103 kJ/mol K, T is the temperature in Kelvin and Ce is the equilibrium concentration of the Cr(VI)
in solution (mg/L). The mean free energy of sorption per molecule of
sorbate required to transfer 1 mol of ion from the innity in the solution to the surface of biomass and can be determined by the following
Eq. (13):
1
E = 
2

(13)

The DubininRadushkevich constants and qm were calculated

in from the slope and the intercept of the plot of ln qe versus 2
as shown in Fig. 8 and the results are given in Table 6. The energy
value obtained (Table 6) have E < 8 kJ/mol, which indicate that all
metal cation adsorptions were physical processes, since a chemical
adsorption process has an E > 8 kJ/mol [38,39]. The sorption capacity
was lower than the Langmuir model, which may be attributed to
different assumptions taken into consideration. From R2 values, it
was concluded that the sorption of Cr(VI) onto H. gracilis followed the
Langmuir model.
Temkin isotherm
The Temkin isotherm [40] has been used in the following form:
qe =

RT
RT
ln K T +
ln C e
b
b

(14)

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R. Jayakumar et al. / Journal of Environmental Chemical Engineering 2 (2014) 12611274

Table 6
Langmuir, Freundlich, DubininRadushkevich, Temkin, Sips and Toth constants for the sorption of Cr(VI) on to Halimeda gracilis.
Sl. no.

Isotherm model

Parameters

Cr(VI) sorption at temperature 308.15 K

1.

Langmuir

2.

Freundlich

3.

DubininRedushkevich

qmax
B
R2
Kf
1/n
R2
qmax

R2
qmax
nT
bT
R2

55.55 mg/g
0.162
0.997
19.67
0.206
0.927
49.25
4.259
0.342
0.975
7.881
6.22
0.937
0.2335
13.09
0.8616
0.578
55.69
1.145
0.228
0.577

4.

Temkin

5.

Sips

E
R2
B
KT
R2
as
Ks

6.

Toth

Table 7
Comparison of adsorption capacity of different sorbents for Cr(VI) removal.
Metal ion

Biosorbent

Sorption capacity

Reference

Cr(III)

Spirulina (sp.)
Spirogyra spp.
Sphaeroplea
Oedogonium hatei
Padina boergesenli
Ulva lactuca
Chlorella valgaris
Scenedesmus obliquus
Sargassum sp.
Padina (brown algae)
Sargassum (brown algae)
Sargassum sp.
Sargassum sp.
Sargassum siliquosum
Cysteria indica
Turbaneria ornate
Halimeda gracilis

34.6 (mg/g)
30.21 (mg/g)
29.8 (mg/g)
31 (mg/g)
49 (mg/g)
10.61 (mg/g)
0.5341.52 (mmol/g)
1.131 (mmol/g)
1.301.3257 (mmol/g)
54.6 (mg/g)
31.79 (mg/g)
68.94 (mg/g)
65 (mg/g)
66.4 (mg/g)
20.927.9 (mmol/g)
65%
55.55

[22]
[33]
[21]
[26]
[34]
[35]
[53]
[53]
[53]
[54]
[54]
[55]
[56]
[57]
[58]
[59]
Present study

Cr(VI)

Fig. 8. DubininRadushkevich isotherm plots for the sorption of Cr(VI) onto Halimeda
gracilis at 308.15 K temperature.

qe = B ln K T + B ln C e

Fig. 9. Temkin isotherm plots for the sorption of Cr(VI) onto Halimeda gracilis at
308.15 K temperature.

(15)

where constant B = RT/b, which is related to the heat of sorption, R

is the universal gas constant (kJ/mol K), T is the temperature (K), b
is the variation of sorption energy (J/mol) and KT is the equilibrium
binding constant (L/mg) corresponding to the maximum binding energy. From the plot, qe versus ln Ce (Fig. 9) the isotherm were found

and given in Table 6. The correlation factors show that the Langmuir
model approximation to the experimental results was better than the
Temkin model. Consequently, among the four isotherm models used,
the Langmuir model offers the best correlation factors.

R. Jayakumar et al. / Journal of Environmental Chemical Engineering 2 (2014) 12611274

1269

Fig. 11. Toth isotherm plots for the sorption of Cr(VI) onto Halimeda gracilis at 308.15 K
temperature.

Fig. 10. Sips isotherm plots for the sorption of Cr(VI) onto Halimeda gracilis at 308.15 K
temperature.

Sips isotherm
To circumvent the problem of continuing increase in the adsorbed
amount with a rising concentration as observed for Freundlich model;
an expression was proposed by Sips in 1948 which has a similar form
to the Freundlich isotherm, differs only on the nite limit of adsorbed
amount at sufciently high concentration.
qe =

K s C e s

(16)

1 + as C es

The parameter s is regarded as the parameter characterizing the

systems heterogeneity. Moreover, the heterogeneity could system
from the sorbent or the heavy metal, or a combination of both. As
a rule, all of the Sips parameters as , Ks and s were governed by
operating conditions such as pH, temperature, etc. The model shown
in Fig. 10 and the results are given in Table 6. In the adsorption of Cr(VI)
on H. gracilis, the parameter s stays close to unity [41]. However
the correlation coefcient was very low, the Langmuir isotherm is
considered more appropriate.
Toth isotherm
Another empirical equation that is popularly used and satises the
two end limits is the Toth equation. This isotherm was derived from
the potential theory. Toth equation has been proved as a valuable
tool in describing sorption for heterogeneous systems. It assumes an
asymmetrical quasi-Gaussian energy distribution with its left-hand
side form widened, i.e., most sites have sorption energy less than the
mean value [42].
qe = qmax

bT C e
n

1/ nT

(1 + (bT C e) T )

(17)

Fig. 12. Pseudo rst order plots for the sorption of Cr(VI) onto Halimeda gracilis.

equilibrium parameter KR (Table 8), which is dened by the following

relationship:
KR =

1
1 + K aC 0

(18)

where KR is a dimensionless separation factor, Co is initial metal concentration (mg/L) and Ka is isotherm constant (L/mg). From the KR
values in Table 9, it was found that, all isotherms were favorable.
High value of KR , shows that the Langmuir isotherm ts better than
all other isotherm.
Sorption kinetics
Equilibrium analysis is fundamental in order to evaluate the afnity or capacity of a sorbent. However, it is important to assess how
sorption rates vary with aqueous free metal concentrations, and how
rates are affected by sorption capacity or by the sorbent character
in terms of kinetics. Three kinetic models, pseudo rst order, pseudo
second order and intra particle diffusion, power function and Elovich
model were applied in order to interpret the experimental results.

Toth equation posses the correct Henry law type limit besides a parameter to describe the heterogeneities of the system. The model
shown in Fig. 11 and the results are given in Table 6.
However, this equation is still unable to predict the isotherm in
a particular heterogeneous system as illustrated in the sorption of
Cr(VI) into Helimeda gracilis.

Pseudo rst order model

Lagergren [45] suggested a pseudo rst order equation for the
sorption of a liquid/solid system based on the solid capacity. The
linear form of the pseudo rst-order rate equation is given as follows:

Separation factor to nd the feasibility and type of isotherm

The effect of isotherm shape can be used to predict whether an
adsorption system is favorable or unfavorable [43]. According to
Hall et al. [44], the essential features of the Langmuir isotherm can be
expressed in terms of a dimensionless constant separation factor or

where qt and qe (mg/g) were the amounts of the Cr(VI) ions sorbed
at equilibrium (mg/g) and t (min), respectively and K1 is the rate
constant of the equation (min1 ). The sorption rate constants (K1 ) is
determined and shown in Fig. 12 and the values were reported in
Table 10.

log (qe qt ) = log qe

K1
t
2.303

(19)

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R. Jayakumar et al. / Journal of Environmental Chemical Engineering 2 (2014) 12611274

Table 8
Seperation factor (KR ) values.
Values of KR

Type of isotherm

KR > 1
KR = 1
0 < KR < 1
KR = 0

Unfavorable
Linear
Favorable
Irreversible

Table 9
Separation factor and their condition to nd the feasibility and type of isotherm.
Type of isotherm

KR

Condition

Langmuir
Freundlich
DubininRedushkevich
Temkin
Sips
Toth

0.058
0.00050
0.0023
0.0016
0.0007
0.0086

Favorable
Favorable
Favorable
Favorable
Favorable
Favorable

Table 10
Kinetic parameters obtained from various kinetic models for Cr(VI) on to Halimeda gracilis.
Sl. no.

Kinetic model

1.

Pseudo rst order

2.

Pseudo second order

3.

Intra particle diffusion

4.

Power function

5.

Elovich

Parameters

Cr(VI) sorption at temperature 308.15 K

K1 (min )
R2
K2 ((g/mg)min)
R2
Kid ((mg/g)min0.5 )
R2
K
V
R2

R2

0.073
0.972
0.00081
0.999
6.579
0.978
7.175
0.4782
0.999
8.8657
0.0833
0.978

Intra particle diffusion model

Webers intra particle diffusion model [47] is dened by the following equation:
qt = K id t0.5 + C

(21)

is the intraparticle diffusion rate constant (mg/(g min0.5 ))

Pseudo second order model

The pseudo second order model predicts the sorption behavior
over the whole time adsorption [46].

where Kid
and C is the intercept. It was observed that all the plots have an initial
curved portion, followed by a linear portion and a plateau region. The
initial curve of the plot was due to the diffusion of metal ion through
the solution to the external surface of H. gracilis. The linear portion of
curves describes the gradual sorption stage, where intraparticle diffusion of metal ion on H. gracilis takes place and nal plateau region
indicates equilibrium uptake. Based on the results it may be concluded that intraparticle diffusion is not only the rate determining
factor. The rate constants of intra particle diffusion were calculated
from Fig. 14. The values for all the kinetic models were calculated
and summarized in Table 10. Pseudo second order model has higher
correlation coefcient values indicating that the sorption of Cr(VI) on
the sorbent follows pseudo second order kinetic model. Higher values
of R2 show a better tness of the sorption data [37,38].

t
1
1
=
+ t
qt
qe
K 2 qe2

Power function model

The power function can be expressed as

Fig. 13. Pseudo second order plots for the sorption of Cr(VI) onto Halimeda gracilis.

(20)

where K2 (g/mg min) is the rate constant of the second-order equation, qt (mg/g) is the amount of sorption time t (min) and qe is the
amount of sorption equilibrium (mg/g). In Fig. 13, sorption rate constants (K2 ) can be determined experimentally by plotting of t/qt versus t. The rate constants and R2 values were given in Table 10. However, the correlation coefcients, R2 , showed that the pseudo second
order model ts better with the experimental data than the pseudorst order model [39].

q = K tv

(22)

where q is amount of sorbate per unit mass of sorbent at time t, K and

v are constants and v is positive and <1. Eq. (22) is empirical, except
for the case where v = 0.5, when it is similar to the parabolic diffusion
equation. Eq. (22) and various modied forms have been used by a
number of researchers to describe the kinetics of reactions on natural
materials [48]. The constants of power function were calculated from
Fig. 15. The values for all the kinetic models were calculated and

R. Jayakumar et al. / Journal of Environmental Chemical Engineering 2 (2014) 12611274

1271

Fig. 14. Intra particle diffusion model plots for the sorption of Cr(VI) onto Halimeda
gracilis.

Fig. 16. Elovich model plots for the sorption of Cr(VI) onto Halimeda gracilis.

Fig. 15. Power function model plots for the sorption of Cr(VI) onto Halimeda gracilis.

summarized in Table 10. The model has higher correlation coefcient

values indicating that the sorption of Cr(VI) on the sorbent follows
the power function kinetic model.
Elovich model
The Elovich equation (23) [49] incorporates as the initial adsorption rate (mg/g min) and (g/mg) as the desorption constant. This
relates the extent of the surface coverage and activation energy for
chemisorptions.
dq
q
= et
dt

(23)

Eq. (23) can be simplied to Eq. (24) by considering  t and

by applying the boundary conditions qt = 0 at t = 0 and qt = qt at t = t
qt =

ln ( ) +

ln (t)

(24)

where qt is the amount of gas chemisorbed at time t. From the results

(Table 10) it was found that the Cr(VI) adsorption on green algae ts
the Elovich model [39]. A plot of qt versus ln(t) (Fig. 16) should give
a linear relationship with a slope of (1/ ) and an intercept of (1/ )
ln( ).

Fig. 17. Desorption efciency with different concentration of HCl (biomass concentration: 2.2 g/L; contact time: 45 min; temperature: 308.15 K).

initially, and then become almost stable. The maximum percentage

recovery of Cr(VI) was 98.02% with 0.2 M HCl solution.
The regenerated sorbent was reused for up to ten sorption
desorption cycles and the results were illustrated in Fig. 18. A maximum efciency of 95.02% recovery of Cr(VI) were obtained with 0.2
M HCl in the rst cycle and is therefore suitable for regeneration of
sorbent. There was a gradual decrease in Cr(VI) sorption with an increase in the number of cycles. After a sequence of ten cycles, the
Cr(VI) uptake capacity of the sorbent was reduced from 92.01% to
73.61%. The lost in the sorption capacity of the biomass for metal
ions was found to be 8%. This might be due to the ignorable amount
of biomass lost during the sorptiondesorption process. These results
indicate that the H. gracilis could be used repeatedly in Cr(VI) sorption
studies without any detectable loss in the total sorption capacity.

Desorption and regeneration studies

In sorption process, to decrease the processing cost and to open the
possibility of recovering the metal extracted from the liquid phase,
it is desirable to regenerate the sorbent material. In order to investigate desorption of metal ion from metal loaded H. gracilis, the metal
loaded sorbent was treated with HCl [5052]. Desorption studies were
performed with different HCl concentrations and the results were
shown in Fig. 17. From the results of this study, with the increasing
of hydrochloric acid concentration, the desorption rate also increased

SEM with EDS

SEM images were used for the surface analysis of H. gracilis as
shown in Fig. 19. These gures demonstrate the brous supercial
structure of the algal biomass surface where the metal cations could
be adsorbed. The EDS images for the seaweed before and after adsorption were presented in Fig. 20 and show the metal cations adsorbed
on the algae surface.

1272

R. Jayakumar et al. / Journal of Environmental Chemical Engineering 2 (2014) 12611274

Fig. 18. Biosorptiondesorption efciency with cycle number (biomass concentration:

2.2 g/L; contact time: 45 min; temperature: 308.15 K).

Fig. 20. EDS images for Cr(VI) on Halimeda gracilis: (A) before adsorption and (B) after
adsorption.

Fig. 21. FTIR Images for Cr(VI) on Halimeda gracilis: (A) before adsorption and (B) after
adsorption.

part in adsorption were OH, C O, CO, CH and COOH [60,61].

The functional group SO3 2 was additionally involved in adsorption
with H. gracilis.
Sorption of Cr(VI) from electroplating wastewater

Fig. 19. SEM images for Cr(VI) on Halimeda gracilis: (A) before adsorption and (B) after
adsorption.

FTIR Study
The infrared (IR) spectrum obtained from FTIR of the H. gracilis
was shown in Fig. 21. It displays a number of absorption peaks, indicating the complex nature of the examined biomass. The results
revealed sorbent heterogeneity, evidenced by different characteristic peaks. The infrared absorption wavelengths of each peak and the
corresponding functional groups were presented in Table 11 for H.
gracilis. As seen in Table 11, the major functional groups that took

The results obtained from the sorption of electroplating industry

using raw and acid treated H. gracilis was shown in Fig. 22. From the
gure it was inferred that a maximum of 85.21% and 83.69% Cr removal was achieved by the acid treated and raw algae, respectively
for electroplating wastewater. From the gure it was also found that,
the Cr removal was found to be higher for aqueous solution, than the
electroplating wastewater. The decrease in Cr removal in electroplating wastewater may be due to the presence of other metal ions like Cu,
Zn, Fe and Ni in wastewater as indicated in Table 1, which occupies
the sorption sites. In the aqueous sample of potassium dichromate
only Cr(VI) metal ions were present, so the binding sites on adsorbent
surface were occupied by the single metal ions, where as in a complex industrial wastewater where more than one metal ion species
are present. Hence Cr removal is higher in aqueous solution [62,63].
Conclusion
In this study, the feasibility of sorption of chromium(VI) onto a
green algae, H. gracilis, which is abundant and cheaply available, was
studied. RSM is utilized to optimize the operating conditions and

R. Jayakumar et al. / Journal of Environmental Chemical Engineering 2 (2014) 12611274

1273

Table 11
FTIR spectral characteristics of Halimeda gracilis before and after sorption of Cr(VI).
Wavelength range
(cm1 )

35003000
29002800
25002300
17401680
15001400
12801240
1150950
650480

Halimeda gracilis

Assignment

Before loading of Cr(VI)

After loading of Cr(VI)

Differences

3423.88
2961.91
2852.33
2545.53
2493.48
1786.82
1490.00
1261.87
1030.66
713.04

3421.57
2922.94
2855.07
2522.98
2323.64
1786.76
1489.59
1260.77
1022.45
713.08

2.31
38.97
+ 2.74
22.55
169.84
0.06
0.41
1.1
8.21
0.04

[7]

[8]

[9]

[10]

[11]
Fig. 22. Removal percentage of Cr (VI) from Aqueous and Electroplating wastewater
using raw and acid treated algae.

maximize the chromium(VI) removal. Analysis of variance showed a

high coefcient of determination value (R2 = 0.9097), thus ensuring
a satisfactory adjustment of the second order regression model with
the experimental data. The initial pH signicantly inuenced metal
uptake. Sorption kinetics follows a pseudo-second-order and power
function model. Experimental data were analyzed using Langmuir,
Freundlich, DubininRadushkevich, Temkin, Sips and Toth isotherm
models and it was found that the Langmuir model presented a better
t. SEMEDS conrmed the presence of Cr(VI) ions on the biomass
surface. Temperature affects the sorption process and the thermodynamic parameters show the spontaneous character of the sorption
reaction. The ndings of the present study indicates that H. gracilis
can be successfully used for separation of Cr(VI) from aqueous and
industrial waste water solutions.
Conict of interest

[12]

[13]

[14]

[15]

[16]

[17]

[18]

None.

[19]

References

[20]

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[2] IARC. Monographs on the Evaluation of Carcinogenic Risks to Humans: Overall
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[3] M. Cieslak-Golonka, Toxic and mutagenic effects of chromium(VI). A review,
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[4] WHO. Guidelines for Drinking-Water Quality Recommendations. (2004).
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[21]

[22]

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[24]

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