Bioresource Technology 99 (2008) 8441–8444

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Bioresource Technology
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Methylene blue and iodine adsorption onto an activated desert plant

B. Bestani a,*, N. Benderdouche a, B. Benstaali b, M. Belhakem a, A. Addou a
a
Departement de chimie, Faculté des sciences et sciences de l’Ingénieur, Université de Mostaganem, BP188, Algeria
b
Department of Chemical Engineering, Faculty of Engineering, University of Bahrain, P.O. Box 32038, Bahrain

a r t i c l e i n f o a b s t r a c t

Article history: Although frequently less toxic than many colorless effluents, colored effluents are generally considered
Received 30 April 2004 by the public as an indicator of pollution. The present investigation aimed at identifying the effectiveness
Received in revised form 14 February 2008 of a local desert plant characteristic of Southwest Algeria and known as Salsola vermiculata, which was
Accepted 21 February 2008
pyrolyzed and treated chemically with a 50% zinc chloride solution, to remove methylene blue and
Available online 14 April 2008
iodine. The natural plant adsorption capacities were respectively 23 mg/g and 272 mg/g for methylene
blue and iodine. Corresponding results for the pyrolyzed plant uptakes were 53 mg/g and 951 mg/g,
while those for the pyrolyzed plant, chemically treated and activated at 650 °C, were 130 mg/g and
Keywords:
Adsorption
1178 mg/g, respectively. In comparison, the standard Merck activated carbon capacities were 200 mg/g
Salsola vermiculata for methylene blue and 950 mg/g for iodine. Consequently, this low-cost local plant may also prove useful
Methylene blue for the removal of large organic molecules as well as potential inorganic contaminants.
Iodine number Ó 2008 Elsevier Ltd. All rights reserved.
Zinc chloride activation

1. Introduction surface area of activated carbon (Vitidsant et al., 1999). Methylene

blue adsorption capacity values were 277 mg/g and 158 mg/g for
Commercial activated carbon is a remarkably high adsorbent rice husk (obtained from a local rice mill, ground in a domestic Su-
material with a large number of applications in the remediation meet mixer to obtain geometrical mean size of 424.2 lm, washed
of contaminated groundwater and industrial wastes such as col- with tap water then distilled water and dried in an electric oven
ored effluents. Conventional methods for water purification are at 80 °C), and hair (obtained from a local barber’s shop, washed
rather costly and sometimes not readily adapted to effluent treat- in distilled water, air-dried and cut manually to maintain a length
ment. The need to use other adsorbents as an alternative to the of 1–3 mm) (McKay et al., 1999), and 200 mg/g for Guava Seeds
standard activated carbons are due to its rising production cost (carbonized at 700 °C under a slow flowing of argon gas for one
compared to more advantageous and cheap natural products. A hour and soaked in 50% zinc chloride for 48 h) (Rahman and Saad,
variety of raw materials such as sawdust, tea leaves, tree barks, 2003). Among methods used for color removal from industrial
wool fiber, and fungal biomass, hardwood, bagasse and bark effluents, removal via adsorption onto an adsorbent appears to
among others have been used as precursors for activated carbon have considerable potential.
production for the removal of contaminants from water (Garg In the present study, attention was focused on the natural Sal-
et al., 2003; Yan and Viraraghavan, 2000; Marshall and Cham- sola vermiculata desert plant found in southwest Algeria. Prelimin-
pagne, 1995; Poots et al., 1976; Asfour et al., 1985; McKay et al., ary studies performed on untreated pulverized plant leaves
1987) due to their low cost and abundance. Most dyestuffs are de- revealed interesting adsorptive properties of methylene blue and
signed to be resistant to environmental conditions such as solar iodine from aqueous solutions, which led us to activate the pulver-
light, pH effects and microbial attack. It is desirable to remove col- ized leaves with zinc chloride to increase the adsorption potential
oring causing contaminants from effluents before their discharge of this low-cost material.
in nature. Dye removal by adsorption onto biosorbents and agricul-
tural residues has been the subject of intense interest. 2. Methods
Methylene blue removal has been studied by natural raw mate-
rials not only because of its toxicity but its color as well. Its adsorp- 2.1. Adsorbent preparation
tion gives a good indication of the existence of mesopores on
The desert species S. vermiculata (SV) leaves were dried in sun-
* Corresponding author. light for 30 days at an average daylight temperature of 32 °C before
E-mail address: [email protected] (B. Bestani). testing in the laboratory. They were then ground to a powder using

0960-8524/$ - see front matter Ó 2008 Elsevier Ltd. All rights reserved.
doi:10.1016/j.biortech.2008.02.053
8442 B. Bestani et al. / Bioresource Technology 99 (2008) 8441–8444

a jar mill to pass through a 0.071 mm (212 mesh) sieve. The acti- changing adsorbent concentration from 0.05 to 0.4 g/25 mL (1–
vated carbon production process consisted of two successive 16 g/L) while keeping the initial concentration at 150 mg/L at a
phases: carbonization followed by chemical activation with ZnCl2. pH of 6.94. For the all the concentration range studied (100–
Carbonization of 45 g of pulverized leaves was conducted in a 1000 mg/L), the mixture was magnetically stirred at 250 rpm for
tubular furnace at 600 °C under nitrogen gas flow for one hour. 90 min as determined from kinetic tests. Absorbance measure-
The precursor or char obtained (21 g) afterwards (SVPR for S. verm- ments were performed on methylene blue solutions at 660 nm
iculata pyrolyzate) was chemically treated by soaking in a 50% con- using a UV–VIS 120-01 Shimadzu spectrophotometer to determine
centrated ZnCl2 solution for 60 hours to ensure equilibrium and the equilibrium concentration. Solutions were diluted as required
then activated in a 181-3B muffle furnace at 650 °C for two hours so that their absorbance remained within the linear calibration
under nitrogen. The resulting activated carbon (SVAC) was washed range.
once with a HCl (0.1 N) solution and rinsed repeatedly with hot
distilled water to remove chloride and zinc compounds. This oper- 2.4. Iodine number determination
ation was stopped when no reaction was observed after adding
0.002 g of potassium ferro cyanide K4[Fe(CN)6], 3H2O to the rinsing The capacity of adsorbents for removing color can be evaluated
water indicating that no zinc was present. After overnight drying at through iodine adsorption from aqueous solutions using test con-
110 °C, the activated carbon obtained (SVAC), the inactivated or ditions referred to as iodine number determination. This indicates
untreated plant (UNSV), the pyrolyzed plant (SVPR) and the com- their relative activation level and the surface area available for
mercial activated carbon from Merck (MAC) were all tested for io- micropores. Usually adsorbents with a high iodine number have
dine and methylene blue adsorption. a high surface area and are suitable for adsorbing small compounds
(Noszko et al, 1984). The samples studied (UNSV, SVPR, SVAC,
2.2. Solutions preparation MAC) were characterized by measuring their iodine number (mg/
g) using the 0.1 N standardized iodine solution. Sample volumes
All reagents used were of analytical grade from Merck, (Ger- of 100 mL of the iodine solution were treated with 0.4, 0.6, and
many). A 102 M stock solution was prepared from methylene blue 0.8 g of the different samples. After equilibrium, the remaining io-
dye of chemical formula C16H18ClN3S with a molecular weight of dine in the supernatants was titrated with 0.1 N sodium thiosulfate
319.87 g/mol. Subsequent solutions were all prepared by diluting solutions. The iodine number expressed in (mg/g) was reported as
the stock solution. Iodine standard solutions (0.1 N) were prepared the amount of iodine adsorbed per gram of adsorbent at a residual
from sublimed iodine dissolved in potassium iodide and titrated iodine concentration of 0.02 N.
with (0.1 N) sodium thiosulfate which was standardized with
chemically pure potassium iodate.
3. Results and discussion
2.3. Methylene blue adsorption
3.1. Effect of contact time
Methylene blue adsorption studies are widely used for the eval-
uation of adsorbents because this dye can be viewed as a model for Preliminary tests were conducted to assess the contact time
visible pollution and is an indicator of mesoporosity. Adsorption necessary for each adsorption system to come to equilibrium
test of methylene blue on prepared activated carbon was studied and, for experimental purposes, each system was given a contact
using a batch process by mixing 0.1 g of adsorbent in stoppered time in excess of this period. To determine the equilibrium,
conical flasks with 25 mL of methylene blue solutions of concen- 25 mL of diluted solution containing 104 M of methylene blue
tration ranging from 100 to 1000 mg/L. The adsorbent loading of was separately mixed with 0.1 g of the untreated plant (UNSV),
0.1 g (4 g/L) was initially chosen on the basis that it was the lowest the pyrolyzed plant (SVPR), the chemically activated plant (SVAC)
dosage giving a high methylene blue removal percent as shown in and Merck activated carbon (MAC) at room temperature. The
Fig. 1. No noticeable improvement was observed for higher adsor- resulting supernatants were analyzed at 20-min time intervals un-
bent loadings. The adsorbent dosage was determined at 24 °C by til equilibrium was attained. The equilibrium times for the adsorp-
tion of methylene blue onto the different adsorbents were found to
be 65 min, 58 min, 48 min and 50 min, respectively. Hence, rela-
tively rapid equilibrium time was attained using all four adsor-
bents. As a consequence, subsequent adsorption experiments
140 Merck Activated Carbon
Chem. Activated Plant were all performed for 90 min, a period which was assumed to
Methylene blue removal (%)

120 Pyrolized plant be largely ample for performing all the experiments.
Untreated Plant
100 3.2. Effect of pH

80 Initial pH of the methylene blue solution was varied from 3 to 8,

by adding either 0.1 N NaOH or 0.1 N HCl solutions, to assess the
60 effect of pH on the dye adsorption onto the chemically activated
plant (SVAC). The experiments were also performed at 150 mg/L
40 initial dye concentration with 4g/L adsorbent dose for a 90-min
equilibrium time at 24 °C. At low pH values (Fig. 2), a decrease in
20 the dye uptake was observed whereas in the range 6–8, the uptake
efficiency was only slightly affected by pH. The decrease in the dye
0 uptake at lower pH values may be due to the protons competition
0 4 8 12 16 20 24 28
with the dye molecules for the available adsorption sites (Vadive-
Adsorbent dose (g/L)
lan and Kumar, 2005). As the pH is increased, the surface charge
Fig. 1. Percent methylene blue removal as a function of carbon dose for the adso- density on the SVAC changes and for an equilibrium pH value lar-
rbents studied (initial dye concentration: 150 mg/L. Adsorbent dose: 4 g/L). ger than pHZPC of 6.4, the adsorbent becomes negatively charged
 B. Bestani et al. / Bioresource Technology 99 (2008) 8441–8444 8443

65 250 Untreated plant

Pyrolyzed plant
Methylene blue removal (%)

60
Chem. activated plant
Merck activated carbon
200

Methylene blue uptake (mg/g)

55

150
50

45
100

40
2 3 4 5 6 7 8 9
Initial solution pH
50
Fig. 2. pH effect on methylene blue adsorption onto SVAC (initial dye concentra-
tion: 150 mg/L. Adsorbent dose: 4 g/L).

0
resulting in an enhanced attraction between the positively charged 0 50 100 150 200 250 300
dye molecule and the SVAC surface. Since this adsorption efficiency Ceq (mg/L)
was not affected greatly by pH variation, all the methylene blue
adsorption experiments were performed at the natural solution Fig. 3. Adsorption isotherms of methylene blue onto the adsorbents studied.
pH.
Table 1
3.3. Adsorption isotherms Langmuir constants for methylene blue, and iodine number values for Salsola
vermiculata plant and Merck activated carbon
The equilibrium adsorption isotherms are of fundamental
System Methylene blue Iodine number
importance in the design of adsorption systems. In a batch system, (mg/g)
equilibrium is established between the liquid phase (free solution) K (1/mg) b (mg/g)

and the solid phase (adsorbent-attached solute) concentrations. It Untreated plant (UNSV) 0.141 23 272
can be described by adsorption isotherms determined at a fixed Pyrolized plant (PRSV) 0.252 53 951
Chemically activated plant (SVAC) 0.77 130 1178
temperature. In general, Langmuir and Freundlich isotherms de- Commercial activated carbon (MAC) 0.135 200 950
scribe in a satisfactory way adsorption equilibriums. The relevant
model used in this study describing the adsorption process is the
Langmuir isotherm expressed in its linearized form by: and 140 mg/g (Manocha et al., 2002), respectively. The maximum
C eq 1 1 adsorption capacity attained here for the Merck activated carbon
¼ þ C eq
X=m Kb b was 200 mg/g, which is indicative of its large mesoporosity. Values
of the iodine number (mg/g), which reflect the adsorption capacity
where X/m (mg/g) is the adsorption density, Ceq (mg/L) is the con-
of activated carbon in micropores, ranged from 272 mg/g to
centration of adsorbate in solution at equilibrium, b (mg/g) is the
1178 mg/g for the untreated (UNSV) and chemically activated plant
adsorption capacity corresponding to complete monolayer cover-
(SVAC), respectively. Slightly lower values of 950 mg/g were ob-
age, and K (L/mg) is the Langmuir constant related to the energy
tained for the steam and phosphoric acid activated plant (Bestani
of adsorption. The linear behavior of Ceq/(X/m) versus Ceq yields
et al., 2003). For instance, Manocha et al., 2002 found a value of
the Langmuir constants b and K. The adsorption isotherms of meth-
1000 mg/g for babbool wood.
ylene blue studied on the samples prepared (UNSV, SVPR and SVAC)
compared to Merck powdered activated carbon are presented in
3.4. Development of surface area versus treatment
Fig. 3. It can be observed that the highest values for the adsorbed
concentrations were obtained for the Merck activated carbon and
The determination of specific surface area of solids using meth-
the chemically activated plant, while the lowest values were those
ylene blue adsorption has been widely applied to activated carbons
for the natural untreated plant. Therefore, a significant enhance-
and also to clays (Kaewprasit et al., 1998; Chen et al., 1999). Since
ment was attained through the activation process as was previously
the adsorption process of methylene blue was well described by
shown for the adsorption of acetic acid by phosphoric acid treat-
the Langmuir models, the adsorption capacity (for complete mono-
ment (Benderdouche et al., 2003). Table 1 lists the Langmuir con-
layer coverage) can be used to evaluate the available area for mes-
stants obtained from the equations of the fitted straight lines with
opores provided the area occupied by an adsorbed methylene blue
high correlation coefficients, R2 = 0.99. The highest values obtained
molecule is known. The latter is assumed to be 130 Å2 as it is fre-
from adsorption capacity (b) measurements for the activated sam-
quently cited in the literature (Santamarina et al., 2002). The fol-
ple (SVAC) are clear evidence that chemical activation process im-
lowing formula was used to compute this specific surface area (Sg):
proves the sorptive ability of the desert plant significantly, from
22 mg/g for the untreated plant up to 130 mg/g for the chemically NA
Sg ¼ b rMB ðm2 =gÞ
activated plant representing an enhancement in the adsorption M MB
capacity by a factor of 6. Comparatively, the adsorption capacity where b is the adsorption capacity obtained from previous curves,
for methylene blue onto biosorbents (hair and pyrolyzed babbool NA is Avogadro’s number, MMB is the molecular weight of methylene
wood at 900 °C) was found to be 158 mg/g (McKay et al., 1999) blue and rMB is the area occupied by an adsorbed methylene blue
8444 B. Bestani et al. / Bioresource Technology 99 (2008) 8441–8444

Table 2 make this desert plant a successful biosorbent in the treatment

Development of surface area of the Salsola biosorbent versus treatment compared to of colored effluent waters.
Merck activated carbon

Adsorbent Smesopores (m2/g) Smicropores (m2/g) References

Untreated Salsola plant (UNSV) 52 272
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Chemically activated plant (SVAC) 318 1178 on adsorption of basic dyes on hardwood. Journal of Chemical Technology and
Biotechnology 35A, 21–27.
Commercial activated carbon (MAC) 489 950
Benderdouche, N., Bestani, B., Benstaali, B., Derriche, Z., 2003. Enhancement of the
Smesopores and Smicropores are surface areas available for mesopores and micropores, adsorptive properties of a desert Salsola vermiculata species. Adsorption Science
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Bestani, B., Benderdouche, N., Benstaali B., 2003. Adsorptive properties of a desert
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