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Mohammad Reza Hadjmohammadi, Mina Salary and Pourya Biparva, 2011.

Removal of Cr (VI) from Aqueous


Solution Using Pine Needles Powder as a Biosorbent.



1

Journal of Applied Sciences in Environmental Sanitation, 6 (1): 1-13.










Research Paper

REMOVAL OF Cr (VI) FROM AQUEOUS SOLUTION USING PINE NEEDLES
POWDER AS A BIOSORBENT

MOHAMMAD REZA HADJMOHAMMADI, MINA SALARY and POURYA BIPARVA*


Department of Chemistry, University of Mazandaran, Babolsar, Iran
*Corresponding Author: Phone:+98-112-5342380; Fax: +98-112-5342350; E-Mail: P.biparva@umz.ac.ir

Received: 5
th
September 2010; Revised: 18
th
November 2010; Accepted: 18
th
November 2010

Abstract: The removal of Cr (VI) from aqueous solution was performed using pine
needles powder as a biosorbent by batch adsorption technique. The operating variables
studied were adsorbent dose, particle size, agitation speed, pH of solution, contact time
and initial Cr (VI) concentration. Adsorption process was found to be highly pH
dependent. The optimum pH range for adsorption of Cr (VI) was found to be between 2
and 3. Adsorption isotherms were modeled with the Langmuir, Freundlich, Dubinin
Radushkevich and Tempkin isotherms. Langmuir equation is found to best represent the
equilibrium data for Cr (VI) - pine needles powder system than other isotherms (R
2
=
0.9946). The maximum monolayer adsorption capacity was found to be 40.0 mg g
-1
at
298K.

Keywords: Adsorption, batch technique, isotherms, sorbent


INTRODUCTION

Advances in water and wastewater treatment technology need spur for the development of
technologies that may be more effective and less costly. Nowadays, the contamination of water
by toxic heavy metals through the discharge of industrial wastewater is a world wide
environmental problem. The term heavy metal refers to the metallic elements having density
greater than or equal to 6.0 gcm
-3
[1]. The most familiar metals are cadmium (8.65 gcm
-3
),
chromium (7.19 gcm
-3
), cobalt (8.90 gcm
-3
), copper (8.95gcm
-3
), lead (11.34 gcm
-3
), mercury
(13.53 gcm
-3
), nickel (8.91 gcm
-3
) and zinc (7.14 gcm
-3
). Among these toxic metals chromium
has major impact on environment and it has both beneficial and detrimental properties. In
aqueous phase chromium mostly exists in two oxidation states such as trivalent chromium ( i.e.,
Cr
3+
, Cr(OH)
2+
or Cr(OH)2
+
, etc.) and hexavalent chromium ( i.e., HCrO4
-
, CrO4
2-
or Cr2 O7
2-
,



ISSN 0126-2807


V o l u m e 6 , N u m b e r 1 : 1 - 1 3 , M a r c h , 2 0 1 1
T2011 Depart ment of Envi ronment al Engi neer i ng
S e p u l u h No p e mb e r I n s t i t u t e o f T e c h n o l o g y , S u r a b a y a
& Indonesian Society of Sanitary and Environmental Engineers, Jakarta
Op e n A c c e s s h t t p : / / ww w. t r i s a n i t a . o r g / j a s e s



This work is licensed under the Creative Commons Attribution 3.0 Unported License, which permits
unrestricted use, distribution, and reproduction in any medium, provided the original work is properly cited.

Mohammad Reza Hadjmohammadi, Mina Salary and Pourya Biparva, 2011. Removal of Cr (VI) from Aqueous
Solution Using Pine Needles Powder as a Biosorbent.



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Journal of Applied Sciences in Environmental Sanitation, 6 (1): 1-13.

etc.). Most of the hexavalent compounds are toxic, carcinogenic and mutagenic and even it can
cause lung cancer also[2,3]. Cr (III) is essential for human nutrition (especially in glucose
metabolism) and it is relatively innocuous and immobile. Cr (VI) ions mostly exists as H2CrO4
form at high acidic medium (pH =1.0). At pH 2-6 there is equilibrium between Cr2O7
2-
and HCrO4
-

species, if the Cr (VI) concentration is less than 0.02 M, HCrO4
-
is predominant form, when Cr
(VI) concentration is greater than 0.02 M the dichromate ion (Cr2O7
2-
) is the predominant species
and under alkaline condition ( pH>8 ) it exists as chromate CrO4
2-
anion[4]. Chromium and its
compounds are widely used in electroplating, leather tanning, cement, dyeing, metal processing,
wood preservatives, paint and pigments, textile and steel fabrication industries. These industries
produce large quantities of toxic metal wastewater effluents. But the maximum exit Cr (VI)
concentration based on USEPA guidelines for potable water is 0.05 mg/l and the United Nations
Food and Agricultural Organization recommended maximum level for irrigation waters is 0.1 mg/l
[5]. In general, a wide range of processes have been reported to eliminate the Cr(VI) from water
and wastewater such as chemical precipitation, electrochemical reduction, sulphide precipitation,
cementation, ion-exchange, reverse osmosis, elecrodialysis, solvent extraction and evaporation,
etc.[6]. The application of such methods is however cost intensive and is unaffordable for large-
scale treatment of wastewater. Hence, more economical means such as adsorption for the
removal of toxic metals have been sought for. Therefore, there is a need to search an effective
low cost adsorbent for economical wastewater treatment.

A variety of natural plant biomass like
green algae, rice brand, sugar industrial waste, tamarind hull, tea waste, Azadirachta indica
(neem) leaf powder, pomegranate peel, olive bagasse and hazelnut shell, etc. are used in the
previous investigations. Literature survey reveals that the plant biomass is capable of reducing Cr
(VI) to Cr (III) due to the active participation of its several anionic functional groups like hydroxyl,
carbonyl, carboxyl, sulfydryl and phosphoryl groups [611].
In the present work, we describe the use of pine needles powder (PNP) as an effective and
inexpensive material for the removal of hexavalent chromium from aqueous solution. The effects
of adsorbent dose, pH, contact time and initial metal ion concentration on the adsorption capacity
were investigated. The equilibrium of adsorption was modelled by using the Langmuir,
Freundlich, DubininRadushkevich and Tempkin isotherms.

MATERIALS AND METHODS

Preparation of adsorbent
Pine needles were collected from local forest fields in the north of Iran as solid waste. The
collected materials were then washed with distilled water for several times to remove water-
soluble impurities and surface adhered particles. The washed materials were dried in a hot air
oven at 80 C for 48 h. Dry pine needles were ground in ball mill and the resulting crumbs were
sieved to different particle sizes: 125-180, 180-250, 250-355 and 355-500 m. Finally, the
products obtained were stored in glass bottle for further use. No other chemical or physical
treatments were used prior to adsorption experiments.

Preparation of Cr (VI) solutions
A stock solution of Cr (VI) (1000 mg/l) was prepared by dissolving appropriate quantity of AR
grade K2Cr2O7 in 1000 ml of Elix water from Millipore purification unit. The stock solution was
further diluted with deionised water to desired concentration for obtaining the test solutions. The
initial metal ion concentrations ranged from 50 to 400 mg/l were prepared.


Mohammad Reza Hadjmohammadi, Mina Salary and Pourya Biparva, 2011. Removal of Cr (VI) from Aqueous
Solution Using Pine Needles Powder as a Biosorbent.



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Journal of Applied Sciences in Environmental Sanitation, 6 (1): 1-13.

Batch experiments
Adsorption experiments were carried out in batch mode at ambient temperature. In order to
investigate the nature of Cr (VI)PNP interaction, initially the effect of pH on percentage removal
was carried out and then further experiments on the effect of contact time, initial concentration
and adsorption dose were conducted by using optimized pH. Only one parameter was changed at
a time while others were maintained constant. In the first set of experiment, percentage
adsorption was studied at various pH of (18) at PNP of 0.5 g/50 ml, initial Cr (VI) of 50 mg/l and
the predetermined time (45 min) in a rotary shaker at a speed of 170 rpm.
Next second set of experiments were conducted with various contact time, various initial Cr
(VI) concentration (from 50 to 400 mg/l) at constant adsorbent (0.5 g/50 ml) dose and at
optimized pH 3.0. In the third set of experiment PNP dose was varied (0.11.0 g/50 ml) while
other parameters such as initial Cr (VI) concentration (50 mg/l), optimum time (45 min) and
optimum solution pH kept constant. After completion of every set of experiments the supernatant
was separated by filtration using Whatman filter paper no. 42 and only 10 ml of each sample was
stored for residual chromium analysis. The pH of each solution was adjusted using required
quantity of 1N HCl (or) 1N NaOH before mixing the adsorbent. Three replicates per sample were
done and the average results are taken for calculation.

Metal analysis
Final residual metal (Cr (III) and Cr (VI)) concentration after adsorption was directly
measured by flame atomic absorption spectrometer (Perkin-Elmer Model 2380) with an air
acetylene flame. To estimate the percentage removal of chromium from aqueous solution the
following equation was used:

100 ) ( of Removal

=
initial
final initial
C
C C
VI Cr (1)

Metal uptake (qe) at equilibrium time was calculated from the following equation:

w
v C C
q
e
e
1000
) (
0

= (2)

where qe (mg/g) is the amount of chromium adsorbed, Co and Ce are the initial and equilibrium
metal ion concentration (mg/l), v is the volume of aqueous solution (ml) and w is the adsorbent
weight (g).

RESULTS AND DISCUSSION

Effect of adsorbent dose
To study the effect of adsorbent dose(g) on the uptake of Cr
(VI), experiments were done with 50 ml of 50 mg/l ion solutions, while the amount of adsorbent
added was varied from (0.1 1.0 g ). Results in Figure 1 showed that the percentage removal of

Mohammad Reza Hadjmohammadi, Mina Salary and Pourya Biparva, 2011. Removal of Cr (VI) from Aqueous
Solution Using Pine Needles Powder as a Biosorbent.



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Journal of Applied Sciences in Environmental Sanitation, 6 (1): 1-13.

Cr (VI) from aqueous solution increased with the adsorbent dose and reached a platue at 0.5g of
sorbent. The increase in ion removal was due to the increase in the available sorption surface
sites.

Fig. 1: Effect of adsorbent dose on removal of Cr (VI) by PNP (conditions: ion concentration=50 mg/l;
contact time=45 minute; particle size=250-355m; agitation speed=170 rpm; pH= 3; temperature=25C).

Effect of pH
Figure 2 shows the effect of pH on percentage removal of chromium. It was observed that
the adsorption of Cr (VI) decreased with increase in initial pH from 2.0 to 7.0. The maximum
removal was occurred at initial pH 3.0 for PNP. At lower pH the surface area of the adsorbent
was more protonated and competitive negative ions adsorption occurred between positive
surface and free chromate ion. Adsorption of Cr (VI) at pH 3.0 shows the bind of the negatively
charged chromium species (HCrO4

) occurred through electrostatic attraction to the positively


charged (due to more H
+
ions) surface functional groups of the adsorbent. But in highly acidic
medium (pH 2) H2CrO4 (neutral form) is the predominant species of Cr (VI) as reported by
Agrawal et al. [4].Hence, at pH 2.0 percentage adsorption decreased due to the involvement of
less number of HCrO4

anions on the positive surface. At higher pH due to more OH

ions
adsorbent surface carrying net negative charges, which tend to repulse the metal anions
(CrO4
2
)[12]. Therefore, maximum removal of Cr (VI) from aqueous solution was achieved at pH
3.0 and all the further studies were carried out by maintaining the solution at pH 3.0.

Fig. 2: Effect of pH on the adsorption of Cr (VI) by PNP (conditions: adsorbent dose= 0.50g; ion
concentration=50 mg/l; contact time=45 minute; particle size=250-355m; agitation speed=170 rpm;
temperature=25C ).

Mohammad Reza Hadjmohammadi, Mina Salary and Pourya Biparva, 2011. Removal of Cr (VI) from Aqueous
Solution Using Pine Needles Powder as a Biosorbent.



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Journal of Applied Sciences in Environmental Sanitation, 6 (1): 1-13.

Effect of agitation speed
Effect of agitation speed on removal of Cr (VI) ion by PNP was studied using 50 ml of 50
mg/l ion concentration with shaking rate of 50 - 200 rpm (Figure 3). It is shown that the ion up-
take was found to increase with an increase in agitation rate from 50 to 150 rpm and then
remained constant for higher agitation rate. It is due to the fact that the increase of agitation rate,
improves the diffusion of ions towards the surface of the adsorbents and shaking rate of 170 rpm
is used to assure the surface binding for ions up-take.


Fig. 3: Effect of agitation speed on removal of Cr (VI) by PNP (conditions: adsorbent dose=0.50g; ion
concentration=50 mg/l; contact time=45 minute; particle size=250-355m; pH =3; temperature=25C).

Effect of particle size
The batch adsorption experiments were carried out using four different particle sizes (125-
180, 180-250, 250-355, 355-500 m) of the adsorbent using 50 ml of 50 mg/l ion concentration.
The results shown in Figure 4 indicated that the size of the adsorbent doesn't play an important
role in the adsorption process.


Fig. 4: Effect of particle size on removal of Cr (VI) by PNP (conditions: adsorbent dose=0.50g; ion
concentration=50 mg/l; contact time=45 minute: agitation speed=170 rpm; pH =3; temperature=25C).

Mohammad Reza Hadjmohammadi, Mina Salary and Pourya Biparva, 2011. Removal of Cr (VI) from Aqueous
Solution Using Pine Needles Powder as a Biosorbent.



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Journal of Applied Sciences in Environmental Sanitation, 6 (1): 1-13.

Effect of contact time
The experimental runs measuring the effect of contact time (5-120 minute) on the batch
adsorption of Cr (VI) and at initial pH value 3 and initial Cr (VI) concentration of 50 mg/l indicated
that increase in contact time from 5 to 45 minute enhanced the percent removal of Cr (VI)
significantly. The initial rapid adsorption gives away a very slow approach to equilibrium. The
nature of adsorbent and its available sorption sites affected the time needed to reach the
equilibrium. For pine needles powder this time was 45 minute. Figure is not shown.

Effect of initial ion concentration
The adsorption data of Cr (VI) at different initial concentrations ranging from 50-400 mg/l
obtained at optimum values of pH, agitation speed, particle size and adsorbent dose. However,
the experimental data were measured at 120 minutes to make sure that full equilibrium was
attained. It is well known that by increasing the concentration of metal ions, the adsorbed amount
increases (Figure 5).


Fig. 5: Effect of various initial dye concentrations for Cr (VI) adsorption onto PNP (conditions: adsorbent
dose=0.50g; agitation speed=170 rpm; particle size=125-180 m; pH =3; temperature=25C ).

Adsorption equilibrium study
To optimize the design of an adsorption system for the adsorption of adsorbates, it is
important to establish the most appropriate correlation for the equilibrium curves. Various
isotherm equations have been used to describe the equilibrium nature of adsorption. Some of
these equations are Freundlich, Langmuir, Dubinin - Radushkevich and Tempkin equations.

Langmuir and Freundlich isotherms
The Langmuir equation is given in the following equation [13]:


e L
e L
e
C K
C K q
q
+
=
1
max
(3)

Mohammad Reza Hadjmohammadi, Mina Salary and Pourya Biparva, 2011. Removal of Cr (VI) from Aqueous
Solution Using Pine Needles Powder as a Biosorbent.



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Journal of Applied Sciences in Environmental Sanitation, 6 (1): 1-13.

where qe is the solid phase adsorbate concentration in equilibrium (mg/g), qmax the maximum
adsorption capacity corresponding to complete monolayer coverage on the surface (mg/g), Ce the
concentration of adsorbate at equilibrium (mg/l) and KL is the Langmuir constant (l/mg).
Equation (3) can be rearranged to a linear form:

max max
1
q
C
K q q
C
e
L e
e
+ = (4)

The plot of Ce/qe versus Ce gives a straight line of slope 1/qmax and intercept 1/qmax KL (Figure
6a). The Langmuir constants are reported in Table 1. The isotherm was found to be linear over
the entire concentration range studied with a good squared correlation coefficient showing that
data correctly fit the Langmuir relation. The monolayer saturation capacity, qmax, was found to be
40.0 mg/g. This value was comparable to the sorption capacities of some other adsorbent
materials (Table 2). The fact that Langmuir isotherm fits the experimental data very well confirms
the monolayer coverage of ion onto particles and also the homogenous distribution of active sites
on the material, since the Langmuir equation assumes that the surface is homogenous. The
essential features of the Langmuir isotherm can be expressed in terms of a dimensionless
constant called separation factor (RL, also called equilibrium parameter) which is defined by the
following equation [14] :

0
1
1
C K
R
L
L
+
= (5)

where C0 is the initial concentration (mg/l) and KL is the Langmuir constant related to the energy
of adsorption (l/mg). The value of RL indicates the shape of the isotherms to be either unfavorable
(RL > 1), linear (RL = 1), favorable (0 < RL < 1) or irreversible (RL = 0) [15]. The calculated RL
values at different initial Cr (VI) concentration are reported in Figure 7. Also higher RL values at
lower ion concentrations showed that adsorption was more favorable at lower concentration.
The Freundlich equation is an empirical equation employed to describe heterogeneous
systems, in which it is characterized by the heterogeneity factor 1/n and is as the following [16]:

n
e F e
C K q
/ 1
= (6)

where qe is the solid phase adsorbate concentration in equilibrium (mg/g), Ce the equilibrium
liquid phase concentration (mg/l), KF the Freundlich constant (mg/g)(l/mg)
1/n
and 1/n is the
heterogeneity factor. A linear form of the Freundlich expression can be obtained by taking
logarithms of Equation (6):

e F e
C
n
K q ln
1
ln ln + = (7)

Therefore, a plot of ln qe versus ln Ce enables the constant KF and exponent 1/n to be
determined (Figure 6b). The Freundlich isotherm describes reversible adsorption and is not
restricted to the formation of the monolayer. Examination of the linear Freundlich isotherm plot
for Cr (VI) suggested that the Langmuir model yielded a much better fit than the Freundlich


Mohammad Reza Hadjmohammadi, Mina Salary and Pourya Biparva, 2011. Removal of Cr (VI) from Aqueous
Solution Using Pine Needles Powder as a Biosorbent.



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Journal of Applied Sciences in Environmental Sanitation, 6 (1): 1-13.

model. Freundlich constants, KF, nF, and R
2
are also presented in Table 1. The value of R
2
was
much lower than the Langmuir isotherm value. The value of Freundlich exponent in the range 1
10, indicates the favorable adsorption. However, based on the R
2
value, the linear form of the
Langmuir isotherm appears to produce a reasonable model.


Fig. 6: Adsorption isotherms for the adsorption of Cr (VI) by PNP at 25C: (a) Langmuir isotherm, (b)
Freundlich isotherm (conditions: adsorbent dose=0.50g; contact time=120 minutes; agitation speed=170
rpm; particle size=125-180 m; pH =3 ).


Mohammad Reza Hadjmohammadi, Mina Salary and Pourya Biparva, 2011. Removal of Cr (VI) from Aqueous
Solution Using Pine Needles Powder as a Biosorbent.



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Journal of Applied Sciences in Environmental Sanitation, 6 (1): 1-13.


Fig. 7: Separation factor RL for adsorption of Cr (VI) by PNP at 25C.

Table 1: Isotherms parameters for adsorption of chromium onto PNP.


Table 2: Reported maximum adsorption capacities (qmax in mg/g) in the literature for chromium
obtained on low-cost adsorbents.
Adsorbent q max (mg/g) Reference
Almond 10.62 [20]
Coconut husk fibres 29.00 [21]
Eucalyptus bark 45.00 [22]
Red mud 75.00 [23]
Coal 6.78 [20]
Sago waste activated carbon 5.78 [24]
Saw dust 20.70 [25]
Neem bark 19.60 [25]
Fly ash 23.86 [25]
pine needles 40.00 Present work
Langmuir constants
qmax (mg/g) KL ( l/mg) RL R
2

40.00 2.63 0.0075- 0.0009 0.9946
Freundlich constants
KF (mg/g)(l/mg)
1/n
nF R
2

21.22 3.74 0.9843
Dubinin -Radushkevich constants
qs (mg/g) E (kj/mol) R
2

31.180 6.360 0.8690
Tempkin constants
KT (l/mg) B1 R
2

311.060 4.640 0.9327

Mohammad Reza Hadjmohammadi, Mina Salary and Pourya Biparva, 2011. Removal of Cr (VI) from Aqueous
Solution Using Pine Needles Powder as a Biosorbent.



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Journal of Applied Sciences in Environmental Sanitation, 6 (1): 1-13.

Dubinin and Radushkevich isotherm

Another equation used in the analysis of isotherms was proposed by Dubinin and Radushkevich
[17].

) exp(
2
B q q
s e
= (8)
where qs is D-R constant and can be correlated:
)
1
1 ln(
e
C
RT + = (9)
The constant B gives the mean free energy E of sorption per molecule of sorbate when it is
transferred to the surface of the solid from infinity in the solution and can be computed using the
following relationship [18]:
B
E
2
1
= (10)

Calculated Dubinin-Radushkevich constants for the adsorption of Cr (VI) on PNP are reported in
Table 1, the D-R isotherm is plotted against the experimental data points, as shown in Figure 8a.
From this figure, it is clear that the sorption energy value is lowest for adsorption of Cr (VI) on
PNP. The value of correlation coefficient is much lower than the other three isotherms values. In
all cases, the D-R equation represents the poorer fit of experimental data than the other isotherm
equation.

Tempkin isotherm
Tempkin isotherm contains a factor that explicitly takes into account adsorbing species-
adsorbate interactions. This isotherm assumes that: (i) the heat of adsorption of all the molecules
in the layer decreases linearly with coverage due to adsorbate-adsorbate interactions, and (ii)
adsorption is characterized by a uniform distribution of binding energies, up to some maximum
binding energy [19]. Tempkin isotherm is represented by following equation:

) ln(
e T e
C K
b
RT
q = (11)
Equation (11) can be expressed in its linear form as:
e T e
C B K B q ln ln
1 1
+ = (12)
Where
b
RT
B =
1
(13)
The adsorption data can be analysed according to equation (12). A plot of qe versus ln Ce
enables the determination of the isotherm constants KT and B1. KT is the equilibrium binding
constant (l/mol) corresponding to the maximum binding energy and constant B1 is related to the
heat of adsorption. This isotherm is plotted in Figure 8b for Cr (VI) adsorption on PNP and values
of the parameters are given in Table 1. Analysis of R
2
values from Table 1 shows that langmuir
equation is found to best represent the equilibrium data for Cr (VI)-PNP system. Figure 9 depicts
the comparison of experimental and predicted amount of chromium adsorbed on PNP for all the
isotherm models studied.


Mohammad Reza Hadjmohammadi, Mina Salary and Pourya Biparva, 2011. Removal of Cr (VI) from Aqueous
Solution Using Pine Needles Powder as a Biosorbent.



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Journal of Applied Sciences in Environmental Sanitation, 6 (1): 1-13.





Fig. 8: Adsorption isotherms for the adsorption of Cr (VI) by PNP at 25C: Dubinin -Radushkevich
isotherm (b) Tempkin isotherm (conditions: adsorbent dose=0.50g; contact time=120 minutes; agitation
speed=170 rpm; particle size=125-180 m; pH =3 ).

Mohammad Reza Hadjmohammadi, Mina Salary and Pourya Biparva, 2011. Removal of Cr (VI) from Aqueous
Solution Using Pine Needles Powder as a Biosorbent.



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Journal of Applied Sciences in Environmental Sanitation, 6 (1): 1-13.


Fig. 9: Equilibrium isotherms for chromium adsorption on PNP.


CONCLUSIONS

The present work shows that pine needles , is an efficient sorbent for the removal of Cr (VI)
from aqueous solution and it will be an alternative to more costly adsorbents such as activated
carbon. Experimental data indicated that the adsorption capacity was dependent of operating
variables such as adsorbent dose, particle size, agitation speed, pH, contact time and initial ion
concentration. The sorption data of PNP were well fitted with the Langmuir isotherm model.
Based on the Langmuir isotherm analysis, the monolayer adsorption capacity was determined to
be 40.0 mg/g. The dimensionless separation factor RL revealed the favourability of PNP on Cr
(VI) adsorption.

Acknowledgments: The authors would also like to acknowledge financial support from the Postgraduate
Studies of the University of Mazandaran.

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Mohammad Reza Hadjmohammadi, Mina Salary and Pourya Biparva, 2011. Removal of Cr (VI) from Aqueous
Solution Using Pine Needles Powder as a Biosorbent.



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Journal of Applied Sciences in Environmental Sanitation, 6 (1): 1-13.

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Mohammad Reza Hadjmohammadi, Mina Salary and Pourya Biparva, 2011. Removal of Cr (VI) from Aqueous
Solution Using Pine Needles Powder as a Biosorbent.



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