12 - Chapter 3 PDF

Chapter – III Literature Review
LITERATURE REVIEW
The major pollution for the present society is Environmental pollution.
The review of the literature indicates various methods for removal of heavy metals
from aqueous solutions using different biosorbents. The author has obtained
literature from various sources and the literature obtained on various methods for
removal of chromium and lead is summarized below along with response surface
methodology.
3.1 CHROMIUM (Cr):
Agarwal et al [27] have studied on biosorption of aqueous chromium (VI) by
Tamarindus indica seeds. In this study the effectiveness of low cost agro-based
materials namely, Tamarindus indica seed (TS), crushed coconut shell (CS),
almond shell (AS), ground nut shell (GS) and walnut shell (WS) were evaluated
for Cr (VI) removal. Batch test indicated that hexavalent chromium sorption
capacity (qe) followed the sequence qe (TS) > qe (WS) > qe (AS) > qe (GS) > qe
(CS). Due to high sorptive capacity, tamarind seed was selected for detailed
sorption studies. Sorption kinetic data followed first order reversible kinetic fit
model for all the sorbents. The equilibrium conditions were achieved within 150
min under the mixing conditions employed. Sorption equilibria exhibited better
fit to Freundlich isotherms (R > 0.92) than Langmuir isotherm (R < 0.87).
Hexavalent chromium sorption by TS decreased with increase in pH, and slightly
reduced with increase in ionic strength. Cr (VI) removal by TS seems to be
mainly by chemisorption.
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Ahmet Sarı et al [28] have studied on biosorption of total chromium from
aqueous solution by red algae (Ceramium virgatum): Equilibrium, kinetic and
thermodynamic studies. This study focused on the biosorption of total chromium
onto red algae (Ceramium virgatum) biomass from aqueous solution.
Experimental parameters affecting biosorption process such as pH, contact time,
biomass dosage and temperature were studied. The effect of biomass dosage on
the biosorption of total chromium was studied using different biomass dosage in
the range, 0.4–40 g/L and optimum is attrained at 10 g/L. The effect of pH on the
removal efficiency of total chromium onto C. virgatum was studied by changing
pH values in the range of 1–8 and the results were presented and the maximum
value attained at pH 1.5. The biosorption capacity of C. virgatum biomass for
total chromium was found to be 26.5 mg/g at and 10 g/L biomass dosage, pH 1.5,
90 min equilibrium time and 20 ◦C. From the D–R isotherm model, the mean free
energy was calculated as 9.7 kJ/mol, indicating that the biosorption of total
chromium was taken place by chemisorptions.
Annadural et al [29] examined the liquid-phase adsorption removal of Cu2+,
C02+, Ni2+, Zn2+, and Pb2+ in the concentration range of 5-25 mg/L using low-cost
banana and orange peel wastes at 30 °C. Under comparable conditions, the
amount of ldsorption decreased in the order Pb2+ > Ni2+ > Zn2+ > Cu2+ > C02+ for
both adsorbents. The adsorption isotherms were better described by the
Freundlich equation. The amount of adsorption increased with increasing pH and
reached a plateau at pH > 7, which was confirmed by the variations of zeta
potentials. The application potential of such cellulose-based wastes for metal
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removal (up to 7.97 mg Pb2+ per gram of banana peel at pH 5.5) at trace levels
appeared to be promising.
Aoyama [30] investigated the effect of initial metal concentration, contact time
and solution temperature on the removal of Cr (VI) from solution by waste
London plane leaves, generated by the pruning of street trees, in batch mode
conditions. The removal of Cr (VI) was highly concentration dependent and was
shown to be mainly governed by physico-chemical adsorption under the weak
acidic conditions. The equilibrium data fitted well in the Langmuir isotherm
model. The Langmuir constants were calculated at different temperatures and
both the adsorption capacity and adsorption intensity increqsed with rising
temperature. The endothermic nature of the Cr (VI) adsorption was confirmed by
the thermodynamic parameters. The study showed that the waste leaves could be
used as an effective adsorbent for removal of Cr (VI) from wastewater.
Aoyama and Tsuda [31] investigated the ability of larch (Larix leptolepis Gold)
bark to remove Cr (VI) from dilute aqueous solutions. The research parameters
included the solution pH, contact time, temperature and initial concentration of Cr
(VI) in solution. Of the parameters studied, the solution pH was found to be the
most crucial. The Cr (VI) removal decreased steadily throughout the pH range
studied (pH 2-6), while the Cr adsorption peaked at pH 3. Because the chemical
reduction of Cr (VI) to trivalent state occurred to lesser extent even in strong
acidic media, the Cr (VI) removal was mainly governed by physico-chemical
adsorption. The positive value of the heat adsorption (HO) indicated that the
endothermic nature of the Cr (VI) adsorption. The relatively slow rate and
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irreversible nature of the adsorption as well as the order of the magnitude of the
heat adsorption value suggested that the adsorption was of a chemical type. The
adsorption data obtained from equilibrium experiments were well fitted to both
Langmuir find Freundlich isotherms.
Atac Uzel et al [32] have studied on metal biosorption capacity of the organic
solvent tolerant Pseudomonas fluorescens TEM08. The effects of pH, contact
time and metal ion concentration on the biosorption of Cr (VI) and Ni (II) were
studied. The time intervals of metal sorption were 2, 5, 15, 30, 60, 90 and 120
min. The effects of the initial concentrations of Cr (VI) and Ni (II) ions were
studied at pH 2.0 and 5.0. All pH adjustment were made using reagent grade HCl
and NaOH. The samples were centrifuged at 10,000 g for 20 min at room
temperature. According to the Q values, the biosorption capacity of the type I
(40.8 mg/g) and type II (40.7 mg/g) cells was nearly same for Cr (VI). However,
a 9.67% decrease was observed between type I (12.4 mg/g) and type II (11.2
mg/g) cells for Ni (II) biosorption.
Awan ct al [33] studied the removal of heavy metals i.e., Pb, Cr, Cu, and Zn from
their aqueous solutions using ordinary sand as an adsorbent. The experiments
were carried out at 20 °C. The amount of metal adsorbed to form monolayer on
sand (am), which was obtained from Langmuir isotherm, exhibited the preference
of metals for sand in the order Pb>Cr>Cu>Zn. The heavy metal-sand adsorption
phenomenon was illustrated on the basis of the interaction between surface
functional group of silicates (sand) and the metal ions. It was deduced that sand
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can be used as a low-cost adsorbent: or the removal of heavy metal from waster
(containing low concentrations of metals), especially in the developing countries.
Bala Kiran et al [34] have studied on biosorption of Cr (VI) by native isolate of
Lyngbya putealis (HH-15) in the presence of salts. The present study reports on
biosorption of Cr (VI) by native isolate of Lyngbya putealis HH-15 in batch
system under varying range of pH (2.0–10.0), initial metal ion concentration (10–
100 mg/L) and salt concentration (0–0.2 %). Maximum metal removal (94.8 %)
took place at pH 3.0 with initial Cr concentration of 50 mg/L, which got reduced
(90.1 %) in the presence of 0.2 % salts. Adsorption equilibrium and kinetic
behavior of Cr (VI) in solution was also examined. Both Langmuir and
Freundlich models fitted well to explain the adsorption data (R2 = 0.90 and 0.87,
respectively) at 0.2 % salt concentration. Pseudo-second order kinetic model also
fitted well to both the systems, viz. Cr (VI) and Cr (VI) salt.
Balibek et al [35] studied the Chromium (VI) biosorption by dried Rhizopus
arrhizus. In this study the biosorption of chromium (VI) from saline solutions on
dried Rhizopus arrhizus was studied as a function of pH, initial chromium (VI)
and salt (NaCl) concentrations in a batch system. In the absence of salt, when the
initial chromium (VI) concentration increased from 25 to 250 mg/L
approximately, the loading capacity increased from 23.2 to 108.9 mg/g due to the
increase in the number of ions competing for the available binding sites on the
biomass surface. The uptake of chromium (VI) reached a plateau at 250 mg/L
showing the saturation of binding sites at higher concentration levels. For the
optimum pH experiments were performed at different initial pH values (1.0–6.0)
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and at different initial NaCl concentrations (0–50 g /L). The maximum sorption
obtained at pH 2.0 Equilibrium uptakes of chromium (VI) increased with
increasing chromium (VI) concentration and decreased considerably by the
presence of increasing concentrations of salt. And as the concentration of salt
increased from 0 to 50 g/L, the amount of chromium (VI) adsorbed by dried
R.arrhizus and chromium (VI) removal yield diminished from 23.2 to 18.4 mg/g
and from 92.1 to 72.2 %.
Bayat [36] compared the removals of Cr (VI) and Cd (II) from an aqueous
solution using two different Turkish fly ashes Afsin-Elbistan and Seyitomer as
adsorbents. The influence of four parameters (contact time, solution pH, initial
metal concentration in solution and ash quality) on the removal at 20 ± 2 °C was
studied. Fly ashes were found to have a higher adsorption capacity for the
adsorption of Cd (II) as compared to Cr (VI) and both Cr (VI) and Cd (II) required
an equilibrium time of 2h. The adsorption of Cr (VI) was higher at pH 4.0 for
Afsin-Elbistan fly ash (25.46 %) and pH 3.0 for Seyitomer fly ash (30.91 %)
while Cd (II) was adsorbed to a greater extent (98.43 % for Afsin-Elbistan and
65.24 % for Afsin-Elbistan fly ash) at pH 7. The adsorption of Cd (II) increased
with an increase in the concentrations of these metals in solution while Cr (VI)
adsorption decreased by both fly ashes. The lime (crystalline CaO) content in fly
ash seemed to be a significant factor in influencing Cr (VI) and Cd (II) ions
removal. The linear forms of the Langmuir and Freundlich equations were
utilized for experiments with metal concentrations- of 55 ± 2 mg/I for Cr (VI) and
6 ± 0.2 mg/I for Cd (II) as functions of solution pH (3.0-8.0). The adsorption of
Cr (VI) on both fly ashes was not described by both the Langmuir and Freundlich
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isotherms while Cd (II) adsorption on both fly ashes satisfied only the Langmuir
isotherm model. The adsorption capacities of both fly ashes were nearly three
times less than that of activated carbon for the removal of Cr (VI) while Afsin-
Elbistan Oy ash with high-calcium content was as effective as activated carbon for
the removal of Cd (II). Therefore, there were possibilities for use the adsorption
of Cd (II) ions onto fly ash with high-calcium content in practical applications in
Turkey.
Blázquez et al [37] have studied on the effect of pH on the biosorption of Cr (III)
and Cr (VI) with olive stone. In this work, the biosorption of trivalent and
hexavalent chromium has been studied using olive stone, a low-cost natural
sorbent, analysing the pH effect in the biosorption process. Removal of Cr (III)
and Cr (VI) with olive stone is very sensitive to solution pH. The percentage of
Cr (III) removed reaches a maximum at range pH between 4 and 6, reaching
values close to 90 %. However, at pH 3 the retention of Cr (III) is less than 50 %.
The percentage of Cr (VI) removed is higher than 80 % when the pH is equal or
lower than 2, whereas as the pH increases this percentage drops to values than
15%. Also, the results obtained for the final concentration of total Cr, Cr (VI) and
Cr (III) indicate that a combined effect of biosorption and reduction is involved in
the Cr (VI) removal specially when the pH value is lower than 3.
Calero et al [38] have made a study of Cr (III) biosorption in a fixed-bed column.
The effects of flow rate and inlet concentration on Cr (III) biosorption by olive
stone were studied by varying the flow rate from 2 to 6 mL/min and inlet Cr (III)
concentration from 10 to 50 mg/L, while the bed height was held constant at
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8.9cm (10 g of olive stone). The olive stone sorption capacity, qe, increases as the
inlet Cr (III) concentration increases until a value close to 0.800 mg/g is reached,
then qe remains constant. Column data obtained at different conditionswere
described using the Adams–Bohart, Thomas, Yoon and Nelson, and Dose–
Response models. The breakthrough curve prediction by the Adams–Bohart and
Dose–Response models were found to be very satisfactory. In particular, the
Adams–Bohart model can be used to represent the initial region of breakthrough
curve, whereas the Dose–Response model is the one which best reproduces the
whole curve for all the inlet Cr (III) concentrations used.
Carlo Solisio et al [39] have studied on the effect of acid pre-treatment on the
biosorption of chromium (III) by sphaerotilus natans from industrial wastewater.
Batch experiments carried out at starting acid conditions (pH 3.0 ± 3.5) show that
the pH progressively increases but the removing activity starts only when
conditions closed to neutrality are reached. The equilibrium concentration is
achieved more rapidly (only 25 h) during the tests carried out at Cmo 113 ± 16
mg/L and at an intermediate initial biomass concentration (0.40 g/L), while a
longer time is necessary using both lower (0.27 g/L) and higher (0.85 g/L) initial
biomass levels.
Chergui et al [40] have studied on simultaneous biosorption of Cu2+, Zn2+ and
Cr6+ from aqueous solution by Streptomyces rimosus biomass. The Cu2+, Zn2+
and Cr6+ biosorption capacity of the Streptomyces rimosus biomass pretreated
with NaOH was studied in the batch mode. Five grams of native biomass were
maintained for 30 min in 500 ml NaOH (0.1 M) with a stirring speed of 250 rpm
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and at ambient temperature (around 25 °C). Under optimal experimental
conditions, a biosorption capacity of 30 mg/g Cu2+ biomass, 27.4 mg/g Zn2+
biomass and 26.7 mg/g Cr6+ biomass was obtained. The equilibrium data poorly
fitted the Langmuir and Freundlich model isotherms over the whole range of
initial Cu2+, Zn2+ and Cr6+ concentrations tested (0–300 mg/L).
Deepa Prabhu Mungasavalli et al [41] have studied on biosorption of chromium
from aqueous solutions by pretreated Aspergillus niger: Batch and column
studies. An initial factorial design of experiments showed that factors such as pH
of the solution, temperature and biomass mass were important. The kinetics of
biosorption of chromium was found to follow Ho pseudo-second order reaction.
Isotherm studies conducted at 5 ± 2, 15 ± 2, 22 ± 2 and 30 ± 2 ◦C provided
maximum biosorption capacities of 14.5, 15.2, 10.6, and 11.6 mg/g, respectively.
Reusability of biomass was examined by the desorption studies, in which NaOH
eluted 90 % chromium.
Donghee Park et al [42] have studied on XAS and XPS studies on chromium-
binding groups of biomaterial during Cr (VI) biosorption. In this study, abiotic Cr
(VI) reduction by the biomass was performed with various contact times, pHs and
initial Cr (VI) concentrations, and surface and bulk characteristics of the Cr-laden
biomass was then investigated using X-ray photoelectron spectroscopy (XPS) and
X-ray absorption spectroscopy (XAS). In conclusion, it was obvious that oxygen
containing groups, such as carboxyl and phenolic groups, play a major role in the
binding of the Cr (III) resulting from the abiotic reduction of Cr (VI) by the
biomass.
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Donghee Park et al [43] have worked on how to study Cr (VI) biosorption: Use
of fermentation waste for detoxifying Cr (VI) in aqueous solution. To determine
the effects of Cr (VI) removal of pH variation, pH values of 1–4 were used; of
initial Cr (VI) concentration variation, concentrations of 25, 50, 75 and 100 mg/L
were used; and of biomass concentration variation, biomass concentrations of 5,
10, 15 and 20 g/L were used. The flasks were agitated on a shaker at 200 rpm.
For the 25 mg/L of initial Cr (VI) concentration, Cr (VI) was completely removed
in 2 h, while the complete removal of 100 mg/L of Cr (VI) required 10 h of
contact time.
Donghee Park et al [44] have worked on studies of hexavalent chromium
biosorption by chemically-treated biomass of Ecklonia sp. The aims of the
present investigation were to enhance the Cr (VI) reducing capacity of the
biomass using various chemical treatments and to elucidate the mechanisms
governing Cr (VI) reduction. Among the various chemical treatments, acid-
treatment showed the best performance with regards the improvement of Cr (VI)
removal from the aqueous phase, while organic solvent-treatment significantly
improved the removal efficiency of total Cr in the equilibrium state. These
findings indicated that the amino and carboxyl groups take part in the Cr (VI)
removal from the aqueous phase.
Elangovan et al [45] have studied on biosorption of hexavalent and trivalent
chromium by palm flower (Borassus aethiopum). Batch kinetic and equilibrium
experiments were conducted to determine the adsorption kinetic rate constants and
maximum adsorption capacities. Both Cr (III) and Cr (VI) adsorption followed
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the second-order kinetics. For Cr (III), maximum adsorption capacity was 6.24
mg/g by raw adsorbent and 1.41 mg/g by acid treated adsorbent. In case of Cr
(VI), raw adsorbent exhibited a maximum adsorption capacity of 4.9 mg/g,
whereas the maximum adsorption capacity for acid treated adsorbent was 7.13
mg/g. There was a significant difference in the concentrations of Cr (VI) and total
chromium removed by palm flower. In case of Cr (VI) adsorption, first it was
reduced to Cr (III) with the help of tannin and phenolic compounds and
subsequently adsorbed by the biosorbent. Acid treatment significantly increased
Cr (VI) adsorption capacity of the biosorbent whereas, alkali treatment reduced
the adsorption capacities for Cr (VI). However, in case of Cr (III), acid treatment
significantly reduced the adsorption capacity whereas the adsorption capacity of
alkali treated biosorbent was slightly less than that of raw adsorbent. FT-IR
spectrum showed the changes in functional groups during acid treatment and
biosorption of Cr (VI) and Cr (III).
Elangovan et al [46] have studied on biosorption of chromium species by aquatic
Weeds. Batch kinetic and equilibrium experiments were conducted to determine
the adsorption kinetic rate constants and maximum adsorption capacities of
selected biosorbents. In most of the cases, adsorption followed a second-order
kinetics. For Cr (III), maximum adsorption capacity was exhibited by reed mat
(7.18 mg/g). In case of Cr (VI), mangrove leaves showed maximum
removal/reduction capacity (8.87 mg/g) followed by water lily (8.44 mg/g). There
was a significant difference in the concentrations of Cr (VI) and total chromium
removed by the biosorbents. In case of Cr (VI) removal, first it was reduced to Cr
(III) with the help of tannin, phenolic compounds and other functional groups on
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the biosorbent and subsequently adsorbed. Acid treatment significantly increased
Cr (VI) removal capacity of the biosorbents where as, alkali treatment reduced the
Cr (VI) removal capacities of the biosorbents. FTIR spectrum showed the
changes in functional groups during acid treatment and biosorption of Cr (VI) and
Cr (III).
Erol Pehlivan et al [47] have studied on biosorption of chromium (VI) ion from
aqueous solutions using walnut, hazelnut and almond shell. The potential to
remove Cr (VI) ion from aqueous solutions through biosorption was investigated
in batch experiments. Kinetic experiments revealed that the dilute chromium
solutions reached equilibrium within 100 min. The effect of pH on adsorption of
Cr (VI) was studied at room temperature by varying the pH of metal solution–
shell suspension from 2.0 to 9.0. The biosorptive capacity of the shells was
dependent on the pH of the chromium solution, with pH 3.5 being optimal.
Adsorption of Cr (VI) ion uptake is in all cases pH dependent showing a
maximum at equilibrium pH values between 2.0 and 3.5, depending on the
biomaterial,that correspond to equilibrium pH values of 3.5 for (WNS), 3.5 for
(HNS) and 3.2 for (AS). The adsorption data fit well with the Langmuir isotherm
model. The sorption process conformed to the Langmuir isotherm with maximum
Cr (VI) ion sorption capacities of 8.01, 8.28, and 3.40 mg/g for WNS, HNS and
AS, respectively. Percentage removal by WNS, HNS and AS was 85.32, 88.46
and 55.00 %, respectively at a concentration of 0.5 mM.
Ertugay et al [48] have studied on biosorption of Cr (VI) from aqueous solutions
by biomass of Agaricus bisporus. In this study, biosorption of Cr (VI) ion was
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investigated by using biomass of Agaricus bisporus (a species of mushroom) in a
temperature and shaking speed controlled shaker.the batch adsorption studies at
different pH values were carried out in the range of 1.0, 2.0, 3.0, 5.0 and 7.0. The
highest uptake yield of Cr (VI) at pH 1.0 was found to be 92.4 %. For biosorption
experiments, Cr (VI) solution having 25–125 mg/L was prepared and used.
Optimum biosorption conditions were found to be pH 1, C0 = 50 mg/L, m= 10
g/L, shaking speed = 150 rpm, T = 20 ◦C Cr (VI), respectively.
Etinkaya Donmez et al [49] have done a comparative study on eavy metal
biosorption characteristics of some algae. The experiments were conducted with
pH range 1-6 and varying concentrations from 25 to 250 mg/L. The flasks were
agitated on a shaker for 24 h. Samples were taken at pre-determined time
intervals (0, 5, 15, 30, 60, 120, 180, 240, 300, 960 and 1440 min) for the residual
metal ion concentrations in the solution. Optimum adsorption pH values of
copper (II), nickel (II) and chromium (VI) were determined as 5.0, 4.5 and
2.0.respectively, for all three algae. At the optimal conditions, metal ion uptake
increased with initial metal ion concentration up to 250 mg/L.
Fadali ct al [50] studied the removal of chromium from tannery effluents by
adsorption onto cement kiln dust. Tannery effluent was characterized not only by
heavy loads but also with toxic heavy metals especially chromium ions.
Chromium was considered as an important source of contamination due to large
volume of exhaust liquid discharged and solid sludge produced. Details on
adsorption studies were carried out using synthetic chromium salts (chromium
chloride) as adsorbate, and cement kiln dust (a waste from white cement industry)
as adsorbent. Equilibrium isotherms have been determined for the adsorption of
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chromium ions on cement kiln dust. Kinetic study provided that the adsorption
process is diffusion controlled. The experimental results have been fitted using
Freundlich. Langmuir isotherms. The maximum adsorption capacity of cement
kiln dust was found to be 33 mg/g. Industrial tannery effluent (22 mg/L
chromium and COD 952 mg/L) was also treated by cement dust. The treated
effluent (using 20 g cement dust per 1 L) contained only 0.6 mg/L chromium and
COD 200 mg/L.
Gholamreza Moussavi et al [51] have studied on biosorption of chromium (VI)
from industrial wastewater onto pistachio hull waste biomass. In the present
work, pistachio hull powder (PHP) was investigated for the removal of hexavalent
chromium (Cr (VI)) from wastewater. The effects of pH (2–8), PHP concentration
(0.5–8 g/L), Cr (VI) concentration (50–200 mg/L), temperature (5–50 ◦C) and
contact time (1–60 min) were studied on the removal of Cr (VI) from aqueous
solution. The results revealed that PHP adsorbs over 99% of chromium from
solutions containing 50–200 mg/L of Cr (VI) at a pH of 2 and an adsorbent
concentration of 5 g/L after 60 min of equilibration. The percent chromium
adsorbed from solution increased with an increase in temperature from 5 to 40 ◦C.
Kinetic and isotherm modeling studies demonstrated that the experimental data
best fit a pseudo-second order and Langmuir model, respectively. The maximum
Langmuir adsorption capacity was 116.3 mg/g. In the second part of the study,
the efficacy of PHP was examined by analyzing the removal of Cr (VI) from
industrial wastewater. Results revealed that 2 g/L of PHP decreased the Cr (VI)
concentration from 25 mg/L to less than 0.05 mg/L after 30 min of equilibration.
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Gokhale et al [52] have studied on kinetic and equilibrium modeling of
chromium (VI) biosorption on fresh and spent Spirulina platensis/Chlorella
vulgaris biomass. In the current study, pH was varied from 1.5 to 5.5. The
optimum pH was found to be 1.5. Algal cell concentration varied from 0.2 g/L to
2.4 g/L. The initial chromium (VI) ion concentration was kept fixed at 100 mg/L.
For both the species it was found that at an algal concentration of 2.4 g/L, almost
complete removal of chromium (VI) ions from the solution was achieved. Fresh
algal biomass of S. platensis gave maximum of 73.6 % biosorption of chromium
(VI) in 100 ppm solution at 1 g/L cell loading. The maximum biosorption by
spent biomass was increased to 86.2 %. Thus, this two step process not only
showed improved efficiency in biosorption (17% increase) but also gave valuable
byproduct, namely b-carotene.
Gokhale et al [53] have studied on modeling of chromium (VI) biosorption by
immobilized Spirulina platensis in packed column. This study describes
biosorption of chromium (VI) by immobilized Spirulina platensis, in calcium
alginate beads. Three aspects viz. optimization of bead parameters, equilibrium
conditions and packed column operation were studied and subsequently modeled.
In these experiments, 10 g of beads were contacted to 100 ml chromium (VI) ion
solution of concentration 100 mg /L. Samples were taken at 0, 1, 2, 3, 4, 5, 7.5,
10, 12.5, 15, 17.5, 20, 25, 30, 40, 50, 60, 75, 90, 105, 120 min and analyzed for
chromium (VI) ion concentration. Optimized beads were used for these
equilibrium studies. In these experiments, beads were contacted to chromium
(VI) ion solution in varying quantities (4, 8, and 12 g per 100 ml). Chromium
(VI) ion concentration in the solutionwas varied as 100, 150, 200 mg/L. The
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flaskswere rotated on a shaker at 180 rpm for 4 h and the samples were analyzed
for residual chromium (VI) ions in solution. Under optimized bead diameter (2.6
mm), calcium alginate concentration (2 %, w/v) and biomass loading (2.6 %, w/v)
maximum biosorption was achieved. 140 g/L loading of optimized beads resulted
in 99 % adsorption of chromium (VI) ions from an aqueous solution containing
100mg/L of chromium (VI).
Gupta et al [54] have studied on biosorption of hexavalent chromium by raw and
acid-treated green alga Oedogonium hatei from aqueous solutions. Batch
experiments were conducted to determine the biosorption properties of the
biomass. It is observed that the equilibrium chromium sorption was favored by
acidic pH range of 1–2.0 and maximum adsorption by the algal biomass was
observed at pH 2.0. The effect of temperature on the adsorption of Cr (VI) on the
biomass is investigated at three different temperatures (298, 308 and 318
K).optimum temperature is 318 K. To assess the effect of biosorbent dose,
different amounts (0.1–1.0 g/L) of biosorbent the optimum algal biomass dose
selected was 0.8 g/L. It has been observed that the metal adsorption rate is high at
the beginning for both the algal biomasses and then decreases slowly till
saturation levels were completely reached at equilibration point (110 min). Under
the optimal conditions, the biosorption capacities of the raw and acid-treated algae
were 31 and 35.2 mg Cr (VI) per gm of dry adsorbent, respectively.
Gupta et al [55] have studied on biosorption of chromium (VI) from aqueous
solutions by green algae spirogyra species. Batch experiments were conducted to
determine the adsorption properties of the biomass and it was observed that the
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adsorption capacity of the biomass strongly depends on equilibrium pH.
Equilibrium isotherms were also obtained and the percent adsorption of Cr (VI)
increases with increase in pH from pH 1.0 to 2.0 and thereafter decreases with
further increase in pH, the maximum removal of Cr (VI) was around 14.7 x 10 (3)
mg metal/kg of dry weight biomass at a pH of 2.0 in 120 min with 5 mg/L of
initial concentration.
Guven Ozdemir et al [56] have studied on biosorption of chromium (VI),
cadmium (II) and copper (II) by Pantoea sp. TEM18. In this work, among
microorganisms isolated from wastewater treatment of a petrochemical industry, a
gram-negative bacterium Pantoea sp. TEM18 exhibited the greatest copper
tolerance. It was able to survive in the medium containing copper at
concentrations as high as 180 mg/L. The biosorption properties of bacterial
biomass for cadmium and the effects of environmental factors (i.e. pH, metal
concentration contact time) on the chromium, cadmium and copper biosorption
were explored. Optimum adsorption pH values ranging from 1.0 to 8.0 of
chromium (VI), cadmium (II) and copper (II) were determined as 3.0, 6.0 and 5.0,
respectively. Experimental results also showed the influence of initial metal
concentration on the metal uptake for dried biomass.
Guven Ozdemir et al [57] have studied on heavy metal biosorption by biomass
of Ochrobactrum anthropi producing exopolysaccharide in activated sludge. In
these tests, initial pH values of 100 mg/L aqueous metal solutions were adjusted in
the range 1.0–8.0, Optimum adsorption pH values of chromium (VI), cadmium
(II) and copper (II) were 2.0, 8.0 and 3.0 respectively. Maximum equilibrium
uptakes of copper (II) ions were also determined as 26.0 mg/g at 91.6 mg/L of
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initial copper (II) ion concentrations. Experimental results also showed the
influence of initial metal concentration on the metal uptake for dried biomass.
Handan Ucun et al [58] have studied on biosorption of chromium (VI) from
aqueous solution by cone biomass of Pinus sylvestris. The study was done with
variation in the parameters of pH, initial metal ion concentration and agitation
speed. The biosorption of Cr (VI) was carried out at different initial Cr (VI) ion
concentrations ranging from 50 to 300 mg/L. The biosorption of Cr (VI) was
increased when pH of the solution was decreased from 7.0 to 1.0. The maximum
chromium biosorption occurred at 150 rpm agitation. An increase in
chromium/biomass ratio caused a decrease in the biosorption efficiency.
Hua Yin et al [59] have studied on improvement of chromium biosorption by
UV–HNO2 cooperative mutagenesis in Candida utilis. Batch sorption
experiments were performed at various aqueous phase pH values (1.0, 3.0, 5.0,
7.0, 9.0, 11.0 and 13.0) by keeping all other experimental conditions constant
(temperature, 30 ◦C; agitation, 120 rpm; biosorbent, 2.5 g; chromium
concentration, 20 mg/L). pH 1–5 and pH 1–3 were optimal ranges for CRC2811-
1 and CR-001, respectively. The experiments were carried out using Cr (VI)
solutions (pH 2.0) ranging from 5–200 mg/L at 30 ◦C. 3.2.4. Effect of absorbent
dosage on biosorption Different amounts of biomass ranging from 0–30 g/L were
added to the final concentration 20 mg/L Cr (VI) solutions at pH 2, after shaking
for 2 h. The removal efficiency of these mutants CRU132-26, CRC7-2,
CRC2811-1, CRC2811-2, CRC2814-8 and CRY182-1 for 20 mg/L Cr (VI)
solutions were 85.6 %, 95.2 %, 87.0 %, 82.5 %, 94.7 % and 82.7 %, respectively.
104
Hugo Figueiredo et al [60] have made a study on the ffect of the supporting
zeolite structure on Cr biosorption: Performance of a single-step reactor and of a
sequential batch reactor. This work presents a study on the applicability of a
zeolite-biomass system to the entrapment of metallic ions, starting from Cr (VI)
solutions up to 100 mg Cr/L, in batch processes. The effect of the zeolitic support
on the overall system performance was evaluated comparing two large pore
zeolitic structures which differ in chemical composition and ion-exchange
capacity. The systems were tested in single-step and in sequential processes. In
single-step studies, HY zeolite was found to be the most efficient support when
applied to low Cr concentrations (overall Cr removal of 93.4 %), whereas for the
higher initial Cr concentration, the higher ion-exchange capacity of NaY zeolite
was determinant to achieve the highest overall Cr removal of 77.6 %.The
evolution of Cr (VI) entrapment was strongly dependant on the zeolitic support
used in the system. In sequential batch processes, HY zeolite was found to be the
most efficient support with a 98.2 % overall Cr removal. The reduction of Cr (VI)
promoted by the biomass is more suited to the dynamics of the sequential process.
NaY zeolite behaved similarly to HMOR and NaMOR zeolites, as these systems
removed between 87.3 and 93.4 % of the initial Cr.
Huidong Li et al [61] have studied a novel technology for biosorption and
recovery of hexavalent chromium in wastewater by bio-functional magnetic
beads. The goal of this study was to develop an applied technique for the removal
and recovery of heavy metal in wastewater. The results indicated that the beads
were kept in good operating conditions under different pH values ranging from 1
to 12 at agitation speed 200 rpm for 96 h. At the same time, the performance of
105
these beads was not affected by temperature between 0 ◦C and 50 ◦C. The
parameters effecting Cr (VI) removal were obtained: the optimum pH 1.0 and
optimum temperature 28 ◦C. It was observed that the sorption capacity increased
with lowering pH and the maximum sorption capacity was found to be 6.73 mg/G
at initial concentration 40 mg/L and pH 1.0.
Jang et al [62] conducted a series of adsorption experiments in order to assess the
ability of three mulches to remove several of the heavy metal ions typically
encountered in urban runoff. Three types of mulch, cypress bark (C), hardwood
bark (H), and pine bark nugget (P), were selected as potential adsorbents to
capture heavy metals in urban runoff. The hardwood bark (H) mulch had the best
physicochemical properties for adsorption of heavy metal ions. In addition,
because of its fast removal rate and acceptably high capacity for all the heavy
metal ions, it was concluded that the H mulch is the best of the three adsorbents
for treatment of urban runoff containing trace amounts of heavy metals. In order
to investigate the sorption isotherm, two equilibrium models, the Freundlich and
Langmuir isotherms, were analyzed. The sorption of these metals on H mulch
conformed to the linear form of the Langmuir adsorption equation. At pH 5 and
6, the Langmuir constants (S(m)) for each metal were found to be 0.324 and 0.359
mmol/g (Cu); 0.306 and 0.350 mmol/g (Pb); and 0.185 and 0.187 mmol/g (Zn) at
25 °C.
Jinshao Ye et al [63] have studied on biosorption of chromium from aqueous
solution and electroplating wastewater using mixture of Candida lipolytica and
dewatered sewage sludge. In this study, the objective was to investigate Cr
106
removal from aqueous solutions, as well as Cr, Cu, Ni and Zn from electroplating
wastewaters by the mixture of Candida lipolytica and sewage sludge. The effect
of biosorbent dosage on the biosorption of 30 mg/ L Cr (VI) solution at initial pH
3.0 was studied using different dosage ranging from 0.1 to 5.0 g/L. 1.0 g/L of C.
lipolytica and 3.0 g/L of sewage sludge was selected for further experiments. The
biosorption studies were carried out with different initial pH values ranging from
1.0 to 12.0. The range of optimal pH for the mixture (1–5) was wider than C.
lipolytica (1–4) and sewage sludge (2–4), respectively. The effect of Cu and Zn in
combination was significant on the removal of total Cr and the bioreduction of
Cr (VI).
Jorge L. Brasil et al [64] have studied on statistical design of experiments as a
tool for optimizing the batch conditions to Cr (VI) biosorption on Araucaria
angustifolia wastes. Based on this, preliminary experiments about the
optimization of the biosorption of Cr (VI) on pinh˜ao wastes were carried out
using 5.00–100.0 mg/L Cr (VI), the acidity was adjusted at pH 2.0, biosorbent
concentration of 5 g/L, speed of agitation of 120 strikes/min and contact time of
5–360 min. It was observed that for solutions 5.00 mg/L of Cr (VI) after shaking
for 5 min, the removal of Cr (VI) from solution was 100.0 %. For a 100.0 mg/L of
Cr (VI) solution a similar behavior was observed; however, at 5 min the removal
of the element was 90.2 % and attained 100.0 % after 30 min of contact with the
biosorbent.
Kadirvelu et al [65] predicted the efficiency of activated carbons prepared from
various agricultural wastes for the removal of dyes and metal ions from aqueous
107
solutions. Activated carbons were prepared from agricultural solid wastes, silk
cotton hull, coconut tree sawdust, sago waste, maize cob and banana pith and used
to eliminate heavy metals and dyes from aqueous solution. Adsorption of all dyes
and metal ions required a very short time and gave quantitative removal.
Experimental results showed that all carbons were effective for the removal of
pollutants from water. Since all agricultural solid wastes used in this investigation
were freely, abundantly and locally available, the resulting carbons were expected
to be economically viable for wastewater treatment. Based on the above
information, it is found that the use of neem leaf powder as adsorbent is meager.
So in his present investigation equilibrium and kinetic studies are carried out for
removal of chromium using neem leaf powder as adsorbent.
Kondapalli Srividya et al [66] have studied on biosorption of hexavalent
chromium from aqueous solutions by Catla catla Scales. The percentage removal
of Cr (VI) increased from 35.06 to 60.89 when the dose was changed from 0.05 to
0.4 g as the doseage range is from 0-045 g. the effect of contact time for five
different initial concentrations of Cr (VI) (10–0 mg/L) with biosorbent dose (0.05
g) at natural pH of the solution. The figure shows that percentage removal of Cr
(VI) adsorption increases with time from 0 to 180 min ormore and then becomes
almost constant up to the end of the experiment. The highest metal uptake was
reported to be 27.18 mg/g obtained at pH 1.0 and the overall metal uptake of Cr
(VI) decreased to 2.44 mg/g as pH increased up to 6.
Lee ct al [67] studied the feasibility of using green sands as a low cost reactive
medium in permeable reactive barriers (PRBs). Waste green sands were industrial
108
byproducts of the gray iron foundry industry. These green sands were composed
of fine silica sand, clay binder, organic carbon, and residual iron particles.
Because of their potential sorptive and reactive properties, tests were performed to
determine the feasibility of using green sands as a low cost reactive medium in
permeable reactive barriers (PRBs). Serial batch kinetic tests and conventional
batch sorption tests were conducted to determine the removal characteristics for
zinc in aqueous solutions. Removal characteristics for zinc in the presence of
green sands are comparable to those of Peerless iron, a common reactive medium
used in PRBs. High removal capacities for zinc of green sands were attributed to
clay, organic carbon, and residual run particles, which were known sorptive media
for heavy metals. Furthermore, high pH values in the presence of clay and
residual iron particles enhanced sorption and precipitation of zinc.
Lei Yang et al [68] have studied on biosorption of hexavalent chromium onto raw
and chemically modified Sargassum sp. Hexavalent chromium biosorption by raw
algae is always accompanied with significantly high organic leaching. In this
study, hydrochloric acid, sodium hydroxide, calcium chloride, formaldehyde, and
glutaraldehyde were used for modification of raw Sargassum sp. Seaweed. At pH
ranging from 1 to 14, there are four soluble Cr (VI) species, which are CrO2+4,
Cr2O2+7, HCrO+4 and H2CrO4. From pH 1 to pH 6, the percentage of HCrO+4
changes from 86.1 % to 93.8 %. From pH 6 to pH 10 or even higher, the
percentage of H2CrO4 increases sharply from 2.3 % to 100 %. It is shown that pH
2.0 is the optimal pH for the Cr (VI) uptake for both biosorbents. At the optimal
pH of 2.0, the maximum biosorption capacities of MSW and RSW are 1.123 and
0.601 mmol g/L, respectively. The surface treatment improves the reduction
109
capacity of the biosorbents. The complete uptake of hexavalent chromium is
achieved in 20 h.
Levankumar Lakshmanraj et al [69] have studid on the biosorption of
hexavalent chromium from aqueous solutions by using boiled mucilaginous seeds
of Ocimum americanum. Batch experiments were conducted to study the
biosorption kinetics of chromium removal for the concentrations 10 mg/L, 20
mg/L and 40 mg/L of chromium (VI) solutions. The chromium reduction was
82% and 78 % for the pH values 1 and 1.5. However it decreased to 20 % with
increase in pH of chromium (VI) solution to 7. The optimum chromium reduction
takes place at the pH range 1–1.5. The continuous column study was also carried
out at the flow rate of 27 mL/h for the initial concentration 25 mg/L of chromium
(VI) feed solution using a packed bed column filled with boiled mucilaginous
seeds. The maximum reduction of chromium (VI) to chromium (III) in the packed
bed was 80 %. The percentage removal of reduced chromium from the aqueous
solution was 56.25 %. This valuewas maintained constant until 0.52 L of
chromium (VI) solutionwas pumped through the packed bed column.
Liping Deng et al [70] have studied on biosorption of Cr (VI) from aqueous
solutions by nonliving green algae Cladophora albida. The experiments were
conducted in 250 mL flasks containing 50 mL Cr (VI) solution and 0.1 g biomass
with varying pH from 0.5 to 12. Effect of initial Cr (VI) concentration from 20 to
154 mg/L was studied. The mixtures were shaken on a rotary shaker (agitation
rate, 200 rpm) for 24 h. the optimum pH was chosen at a range of 1.0–3.0 algal
dosage was varied from 0.2 to 10 g/ in 50 mL metal solution at 25 oC. The
110
optimum algal dosage 2 g/L was used in the experiment. The removal rate of Cr
(VI) was relatively rapid in the first 60 min, but then the rate decreased gradually.
Margarita Enid R. Carmona et al [71] have studied on biosorption of chromium
using factorial experimental design. The three factors considered were pH,
temperature, and metal concentration at two markedly different levels: Cr3+, pH
(2.0 and 6.0), T (29 and 55 oC), and metal concentration (10 and 1200 mg/L);
Cr6+, pH (1.0 and 3.0), T (29 and 55 oC), and metal concentration (10 and 1200
mg/L). Experiments were carried out in a batch type reactor system with 0.2 g of
biosorbent (Sargassum sp.), and 50mL of Cr3+ or Cr6+ solutions. The efficiency of
chromium removal during an exposition time of 6 h was then evaluated. The most
significant effect regarding Cr3+ uptake was ascribed to interaction between metal
concentration and pH. For Cr6+, the most significant effect was ascribed to metal
concentration.
Maria X. Loukidou et al [72] have studied on equilibrium and kinetic modeling
of chromium (VI) biosorption by Aeromonas caviae. Biosorption of hexavalent
chromium, from aqueous solutions, on Aeromonas caviae particles was
investigated in a well-stirred batch reactor. Equilibrium and kinetic experiments
were performed at various initial bulk concentrations, biomass loads, temperatures
and ionic background. a detailed analysis has been conducted testing several
chemical reaction kinetic models in order to identify a suitable kinetic equation,
assuming that biosorption is chemical sorption controlled.
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Martin-Dupont et al [73] investigated equilibria and mechanisms involved in the
adsorption process of metal ions (Cr3+, Cu2+, Ni2+, Pb2+ and Zn2+) from aqueous
solutions using coniferous barks as biosorbent substrate. Crude barks were used
in this study since previous experiments showed a decreasing uptake for
chemically treated barks in the considered granulometry. In the experimental
conditions, the maximum binding capacity of barks followed, the decreasing order
Cr3+ > Cu2+ > Pb2+ > Ni2+ > Zn2+ whereas their general binding affinity decreased
as: Pb2+ > Cr3+ > Ni2+ > Zn2+ > Cu2+. Adsorption isotherms at the optimal
physicochemical conditions were established and the adsorption phenomenon was
described by the non-competitive Langmuir adsorption model which fitted well
the experimental data. An evaluation of adsorption capability was carried out
using model parameters which were graphically determined. Models for removal
of cations have been discussed; they represent efficient tools for predicting the
behaviour of the biosorbents in metal ion adsorption systems.
Murphy et al [74] have studied on comparative study of chromium iosorption by
red, green and brown seaweed biomass. pH experiments in this study were
conducted in the pH range 1.5–6. Metal sorption was highly pH dependent with
maximum Cr (III) and Cr (VI) sorption occurring at pH 4.5 and pH 2,
respectively. Extended equilibrium times were required for Cr (VI) binding over
Cr (III) binding (180 and 120 min, respectively) thus indicating possible
disparities in binding mechanism between chromium oxidation states. However,
at high initial metal concentrations F. vesiculosus had the greatest removal
efficiency for Cr (III) and performed almost identically to P. lanosa in terms of Cr
(VI) removal. The Langmuir Isotherm mathematically described chromium
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binding to the seaweeds where F. vesiculosus had the largest qmax for Cr (III)
sorption (1.21 mmol/g) and P. lanosa had the largest Cr (VI) uptake (0.88
mmol/g). P. palmata had the highest affinity for both Cr (III) and Cr (VI) binding
with b values of 4.94 m/M and 8.64 m/M, respectively.
Murugan and Subramanian [75] investigated Cupressus Female Cone (CFC),
an inexpensive plant material, as an adsorbent for the removal of Cr (VI) from
synthetic solution as well as from industrial wastewater so as to help its safe
disposal. Batch sorption studies were conducted, involving various process
parameters such as pH, agitation time, initial Cr (VI) concentration, particle size
and adsorbent dosage. Maximum sorption occurred at the acidic pH range of 0.2-
0.5 but it decreased on increasing the pH. Increase in initial concentration of Cr
(VI) and adsorbent particle size was found to reduce the amount of sorption,
demonstrating the role of surface effects on sorption. When the temperature was
raised the amount of sorption increased, exhibiting an endothermic nature. The
sorption capacity was remarkably higher, amounting 119.4 mg/g (91 per cent) at
30 ◦C and at a pH 1 to 5; it further increased to 124.5 mg/g (99.6 per cent) at 50◦C.
Sorption process followed first order kinetics and the data fitted to the Langmuir
adsorption isotherm.
Nagesh and Krishnaiah [76] developed a method for removal of chromium from
water effluents by adsorption process on different carbon materials. In order to
understand the sorption behavior of chromium and also to evaluate the extent of
reduction from hexavalent chromium to trivalent chromium, a number of batch
experiments were conducted on each adsorbent-adsorbate system at various pH
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values (pH 1-6). The results illustrated that the reduction was maximum at pH 1
and adsorption was maximum when the values of pH between 2 and 3 depending
upon the adsorbent. The results were interpreted on the basis of interaction
between adsorbent and adsorbate.
Narsi R. Bishnoi et al [77] have studied on biosorption of Cr (III) from aqueous
solution using algal biomass Spirogyra spp. In the present investigation, a fresh
water green algae Spirogyra spp. was used as an inexpensive and efficient
biosorbent for Cr (III) removal from aqueous solution. The effects of various
physico-chemical parameters were studied, e.g. pH 3.0–6.0, initial metal ions
concentration 20–150 mg/L, algal dose 1.0–3.0 g/ L, and contact time 15–180
min, respectively. Biosorption of Cr (III) is highly pH dependent. Maximum
81.02 % adsorption of Cr (III) was observed with 0.2 M CaCl2 treated biomass at
pH 5.0. Removal of Cr (III) was more than 70 % in 45 min of contact time with
different treated and untreated algal biomass at concentration 30 mg/L. Maximum
metal uptake (Qmax) was observed as 30.21 mg/g with 0.2 M CaCl2 treated algal
biomass indicate good biosorbents than other treated and untreated biomass.
Neetu Tewari et al [78] have made a study on biosorption of Cr (VI) by Mucor
hiemalis. The effect of initial Cr (VI) concentration was studied in the range 10–
600 mg/L. Different amounts of sorbent were added to vary the sorbent to solute
ratio in the range of 20–100 g/g. The pH of the solution was varied from 1.0 to
8.0. The highest Cr (VI) uptake of 53.5 mg/g at an initial pH of 2.0. The
activation energy of the biosorption (Ea) was estimated as 4.0 kJ/mol using
Arrhenius equation.
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Ozgur Dogan Uluozlu et al [79] have studied on biosorption of Pb (II) and Cr
(III) from aqueous solution by lichen (Parmelina tiliaceae) biomass. Throughout
the study, the contact time was varied from 5 to 120 min, the pH from 2 to 8, the
initial metal concentration from 25 to 400 mg/L, and the biosorbent dosage from
0.8 to 20 g/L. The monolayer biosorption capacity of P. tiliaceae biomass for Pb
(II) and Cr (III) ions was found to be 75.8 mg/g and 52.1 mg/g, respectively.
From the D–R isotherm model, the mean free energy was calculated as 12.7kJ/mol
for Pb (II) biosorption and 10.5 kJ/mol for Cr (III) biosorption, indicating that the
biosorption of both metal ions was taken place by chemical ion-exchange.
Pérez Marín et al [80] have studed on biosorption of chromium (III) by orange
(Citrus cinensis) waste. Batch kinetic and isotherm studies were carried out on a
laboratory scale to evaluate the adsorption capacity of orange waste. The effects
of particle size, adsorbent dose and solution pH on Cr (III) removal were also
studied. The results showed that the higher the adsorbent dosage and the pH, the
higher the percentage of metal removal. Equilibrium assays displayed a
maximum sorption capacity ranging from 0.57 mmol/g to 1.44 mmol/g when the
pH increased from 3 to 5, according to the Sips model, which along with the
Redlich–Peterson equation, is very suitable for correlating equilibrium data.
Prakasham et al [81] have studied on biosorption of chromium VI by free and
immobilized Rhizopus arrhizus. Biosorption of chromium (VI) was studied by
using non-living free and immobilized biomass of Rhizopus arrhizus at pH 2. A
biphasic chromium adsorption pattern was observed in all experimental
115
conditions. Chromium removal rate was slightly more in free biomass conditions
over immobilized state. Stirred tank reactor studies indicated maximum
chromium biosorption at 100 rpm and at 1:10 biomass ± liquid ratio. Fluidized
bed reactor is more efficient in chromium removal over stirred tank reactor.
Immobilization of biomaterial has a little effect on chromium biosorption by this
R. arrhizus biomass.
Prasad and Freitas [82] investigated the potential of Quercus ilex phytomass
from stem, leaf and root as an adsorbent of chromium (Cr), nickel (Ni), copper
(Cu), cadmium (Cd) and lead (Pb) at ambient temperature. The metal uptake
capacity of the root for different metals was found to be in the order:
Ni>Cd>Pb>Cu>Cr; stem Ni>Pb>Cu>Cd>Cr; and leaf Ni>Cd>Cu>Pb>Cr. The
highest amount adsorbed was Ni (root>leaf>stem). Data from this paper
demonstrated that Ni was sequestered mostly in the roots, where concentrations
could be as high as 428.4 ng/g dry wt., when I-year-old seedlings were treated
with Ni (2000 mg/L) in pot culture experiments, compared to 7.6] mg/g dry wt.,
control (garden and greenhouse soil) topsoil where Ni was present in trace
amounts. This proved that the root biomass of Q. ilex has the capacity for
complexing Ni. Cr exhibited the least adsorption values for all the three types of
phytoma$S compared to other metals. The trend of adsorption of the phytomass
was similar for Ni and Cd, i.e. root>lcaf>stem. Desorption with 10 mM Na (4)
EDTA was effective (55-90 %) and hence, there exists the possibility of recycling
the phytomass. The biosorption results of recycled phytomass suggested that the
selected adsorbents were re-usable. The advantages and potential of the Q. ilex
116
phytomass as a biofilter of toxic trace metals. The scope and need for enhancing
the efficiency of the Q. lilex phytomass as an adsorbent of metals were presented.
Preetha et al [83] have studied on batch and continuous biosorption of chromium
(VI) by Rhizopus arrhizus. This was studied by evaluating the physicochemical
parameters of the solution such as initial chromium ion concentration in both
batch and packed bed reactor. Batch experiments demonstrate that the sorption
process corresponds to the second-order kinetic model and the kinetics of sorption
indicates the process to be diffusion controlled. The diffusivity of chromium in
Rhizopus-alginate gel beads was calculated using the shrinking core model, and
the diffusivity values were in the ranges of 0.049 × 10−5 to 0.521 × 10−5 cm2/s.
Quintelas et al [84] have studied on biosorption of Cr (VI) by three different
bacterial species supported on granular activated carbon. The results showed
metal uptake values of 5.82, 5.35 and 4.12 mg/g bios, respectively, for S.
equisimilis, B. coagulans and E. coli, for an initial metal concentration of 100
mg/L. In the same order and for the initial concentration of 50 mg/L, metal
uptake values were 2.33, 1.98 and 3.60 mg/g bios. Finally, for the initial metal
concentration of 10 mg/L, those values were, respectively, 0.66, 1.51 and 1.12
mg/g bios. Studies made with an industrial effluent, with the aim of testing these
biofilms in a real situation, showed values of Cr uptake of 0.083, 0.090 and 0.110
mg/g bios, respectively, for S. equisimilis, B. coagulans and E. coli, for an initial
concentration of 4.2 mg/L of total Cr. The quantification of polysaccharides,
playing a key role in the whole process, was made and it was concluded that the
117
production of polysaccharides is higher for B. coagulans followed by S.
equisimilis and E. coli (9.19, 7.24 and 4.77 mg/g bios.).
Quintelas et al [85] have studied on biosorption of Cr (VI) by a Bacillus
coagulans biofilm supported on granular activated carbon (GAC). The ability of a
biofilm of Bacillus coagulans supported on granular activated carbon (GAC) to
biosorb Cr (VI) was investigated in batch and column studies so it may be applied
to low metal concentration wastewater treatment. The quantification of
polysaccharides and polymeric net revealed a value of 9.19 mg/g biosorbent for
the polysaccharides and 75 mg/g biosorbent, for the polymeric net. The results
obtained with open systems showed uptake values of 1.50, 1.98 and 5.34
mg/gbiosorbent, respectively, for initial concentrations of 10, 50 and 100 mg/L of
Cr (VI). Column studies performed with an industrial effluent showed values of
Cr uptake of 0.090 mg/gbiosorbent, for an initial concentration of 4.2 mg/L. The
presence of functional groups on the cell wall surface of the biomass that may
interact with the metal ion, was confirmed by FTIR. The equilibrium studies in
batch systems were described by Freundlich, Langmuir, Reddlich–Peterson,
Dubinin–Radushkevich, Sips and Toth model isotherms. Best fit was obtained
with Toth model isotherm.
Rabbani et al [86] have studied on biosorption of chromium (III) by new
bacterial strain (NRC-BT-2). The effect of initial concentration of the metal
solution in the range of 10–250 ppm pH from 1-4 and contact time 5-150 min has
been studied, and the maximum removal occurs in 10 ppm, in pH 4 and 1 h of
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contact time (100 %). Sodium acid, high temperature and g-ray did not affect the
biosorption.
RadojkaRazmovski et al [87] have studied on biosorption of Cr (VI) and Cu (II)
by waste tea fungal biomass. Batch experiments were carried out with live and
dried biosorbent samples (both 0.5 g/L of dry matter) at 25 oC in Erlenmeyer
flasks on a rotary shaker at 200 rpm in the pH range 2.0–8.0 at various sorbent
dosage, ranging from 0.15 to 4.0 g/L of DM. the optimum pH values for Cr (VI)
and Cu (II) were 2.0 and 4.0, respectively. Itwas observed that the percentage of
metal ions removal increased with increase in biosorbent dosage.
Rajender Kumar et al [88] have stdied on biosorption of chromium (VI) from
aqueous solution and electroplating wastewater using fungal biomass. The
influence of pH of the solution, biosorbents dose, concentration of ions and
contact time on biosorption capacity of Cr (VI) ions was studied. The optimum
pH for biosorption of Cr (VI) ions was found to be 2.0. The removal of Cr (VI)
was 91.03% with A. niger at biosorbent dose 0.6 g/50 mL, whereas, 87.95 % and
86.61 % with A. sydoni and P. janthinellum at biosorbent dose 0.8 g/50mL but
uptake capacity (mg/g) of Cr (VI) ions decreased with increased biosorbent dose.
Initially percent removal of Cr VI) ions from solution was increased with increase
in concentration from 10 to 30 mg/L and maximum percent removal was observed
at concentration 30 mg/L after that percent removal decreased. Whereas, uptake
capacity was increased with increase in concentration of Cr (VI) ions from 10 to
60 mg/L. Uptake rate of Cr (VI) increased from 1.72 to 2.39 mg/g with A. niger,
1.22 to 1.76 mg/g with A. sydoni and 1.18 to 1.77 mg/g with P. janthinellum with
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increases time from 15 to 120 min. Removal of Cr (VI) from electroplating
wastewater was observed less than from synthetic solution.
Ringqvist ct al [89] determined metal adsorption and surface charge of well
characterized Sphagnum and Carex peat samples. The aim of this investigation
was to determine metal adsorption from complex wastewaters onto these peat
samples and compared it to the adsorption onto peat granules, clinoptilolite,
glauconite and a flue dust from steel production. A sulphide mine leachate, a
landfill leachate and a laundry wastewater were chosen and was given a variation
in pH, ionic strength, total organic carbon and concentrations of metals. Metal
adsorption was determined in batch and column experiments. The wastewater
composition was of great importance for metal removal efficiency, mainly due to
the difference in dominating metal species. In the sulphide mine leachate,
containing free metal ions, a high metal adsorption was observed onto both peat
and inorganic adsorbents. In the landfill leachate the metals formed carbonate and
organic complexes and a low metal removal was achieved. Contrary to the
leachates, the laundry wastewater contained suspended particles. The high
amount of metals removed, 80 % of the Cu and 30-60 % of the Zn concentration,
was probably withdrawn bound to the particle fraction. The highest removal of
metal ions was obtained in the sulphide mine leachate with Carex peat, removing
97-99 % of the Zn and 85-100 % of the Cu content. The Sphagnum peat sample
removed 37-77 % of the Zn and 80-100 % of the Cu content. The differences
found between Sphagnum and Carex peat were attributed to the original chemistry
of the plant material and the habitat conditions at. the time of peat formation.
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Generally, the combination of glauconite or clinoptilolite with the peat samples in
column experiments gave a minor improvement in metal removal.
Rio ct at [90] tested the fly ashes obtained from two fluidized bed power plants to
Pb2+ ,Cu2+,Cr3+, Ni2+, Zn2+ and Cr6+ from aqueous solutions. Experimental design
methodology was used to study the removal and the leaching as a function of (i)
the water pollutant content, (ii) the metal concentration in water, (iii) the pH of the
solution and (iv) the addition of lime to fly ashes. The results showed that the
percentage of adsorbed ions was greater when they were in contact with silica-
aluminous fly ashes than silico-aluminous fly ashes, except in the case of the ion
Ni2+. The removal of metallic ions increased with increasing pH. The authors
compared the adsorption capacity of fly ashes with activated carbon or low cost
adsorbents by carrying out similar tests and concluded that adsorption onto fly ash
was an interesting alternative.
Sandra Lameiras et al [91] have studied on biosorption of Cr (VI) using a
bacterial biofilm supported on granular activated carbon and on zeolite. In this
study Two mini-columns partially filled with granular activated carbon (GAC)
and/or a natural zeolite, covered by a bacterial biofilm of Arthrobacter viscosus,
were used in a continuous flow system to remove Cr (VI) from solutions with
initial concentration of 70 mg/L and a working pH ranging between 4.5 and 5.5.
Comparatively, the biosorption system supported on GAC reaches similar removal
values, 19 %, as the one supported on the zeolite, 18 %, but when these two beds
are used in combination better performances are reached, i.e. 42% removal. The
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maximum uptake values ranged from 0.57 mg/g Cr Support to 3.58 mgCr/g
support.
Saravananc et al [92] presented a comparative study of removal efficiency of
heavy metals [Chromium—Cr (VI), Copper—Cu (II), Manganese—Mn (II),
lron—Fe (Il), Nickel—Ni (Il), Lead—Pb (II) and Zinc—Zn (II)] from aqueous
solution by adsorption on non-conventional materials and on chemically activated
non-conventional materials. It was found that the adsorption potential varied as a
function of contact time, concentration, particle size, pH and flow rate. Of all the
low cost adsorbents used in the study, saw dust was found to possess greater
adsorption efficiency for all metals, than rice husk under identical experimental
conditions. Chemically activated saw dust could remove 98.28% of Cu (II); 100%
of Mn (II); 96.72 % of Fe (II); 96.72 % of Cd (II); 75 % of Cr (VI); 80 % of Ni
(Il); 95 % of Pb (II) and 93 % of Zn (II), from the corresponding metal solution
taken one at a time.
Schmuhl et al [93] studied the ability of chit os an as an adsorbent for Cu (II) and
Cr (VI) ions in aqueous solution. The experiments were done as batch processes.
Equilibrium studies were done on both cross-linked and non-cross-linked chitosan
for both metals. Cr (VI) adsorption behavior could be described using the
Langmuir isotherm over the whole concentration range of 10 to 1000 mg/L Cr.
The maximum adsorption capacity for both types of chitosan was found to be 78
mg/g for the non-cross-linked chitosan and 50 mg/g for the cross-linked chitosan
for the Cr (VI) removal. For the Cu (II) removal the Freundlich isotherm
described the experimental data over the whole concentration range of 10 to 1000
mg/L Cu (II). The maximum adsorption capacity for both types of chitosan can
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be estimated to be greater than 80 mg/g. Cr (VI) removal was the highest at pH 5
but pH did not have a large influence on Cu (II). From these results it is clear that
the adsorption of heavy metals is possible with chitosan, but that with this method,
end concentrations of below 1mg/L can hardly be obtained.
Semra Ilhon et al [94] investigated the selective biosorption of chromium, lead
and copper ions from industrial wastewaters by microorganisms. Microorganisms
were isolated from soil and in this research a bacterium that is identified as
staphylococcus saprophyticus was used. The effects of pH, temperature and
initial concentration of metal ions on the hiosorption capacity were investigated.
The optimum pH values for chromium, lead and copper biosorption were found to
be 2.0, 4.5 and 3.5 respectively. The maximum adsorption was observed for Cr6+,
Pb2+ and Cu2+ at the initial concentrations of 193.66 mg/L Cr6+; 100 mg/L Pb6+
and 105 mg/L Cu6+ and under these conditions the biosorption values were found
to be 88.66 mg/L Cr6+, 100 mg Pb6+ / L and 44.94 mg Cu6+ / L, respectively. The
results indicated that saprophytic us was suitable for biosorption of lead and
chromium from wastewaters.
Shaik Basha et al [95] have studied on biosorption of hexavalent chromium by
chemically modified seaweed, Cystoseira indica. The sorption of hexavalent
chromium by marine brown algae Cystoseira indica, which was chemically-
modified by cross-linking with epichlorohydrin (CB1, CB2), or oxidized by
potassium permanganate (CB3), or only washed by distilled water (RB) was
studied with variation in the parameters of contact time, pH, initial metal ion
concentration and solid/liquid ratio. The adsorption characteristics of Cr (VI) with
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various pH in the range of 1.0–5.0 are studied at initial concentration of 30 mg/L.
The highest uptake capacity of Cr (VI) is 22.7 and 24.2 mg/g for CB1 and CB2,
respectively, at pH 3.0. The biosorption of Cr (VI) was carried out at different
initial Cr (VI) ion concentrations ranging from 10 to 100 mg/L at pH 3.0. The
uptake of Cr (VI) by all the four sorbents gave a plateau at 30–100 mg/L showing
the saturation of binding sites at higher concentration levels. The maximum
amounts of Cr (VI) adsorbed are 22.7, 24.2, 20.1 and 17.8 mg/g, respectively for
CB1, CB2, CB3 and RB.
Shailendra Mishra et al [96] have studied on Novel chromium tolerant
microorganisms: Isolation, characterization and their biosorption capacity. A total
of 29 chromium tolerant isolates from solid waste and 39 isolates from liquid
effluent were obtained. At a maximum chromium concentration of 700 mg/L,
three organisms from solid waste and six from liquid effluent were isolated. It is
seen from the kinetics that chromium concentration is lowered to less than 3 % of
200 mg/L concentration in about 20 h. The initial rate of this biological removal
of chromium with most active organism isolated from solid waste (solid 1) and
liquid effluent (liquid 4) are 90.4 and 89.9 mg/L/h, respectively. The removal of
90 % of 200 mg/L of chromium in 5 h and more than 95 % in about 20 h has been
observed in the current study.
Shrivastava and Thakur [97] reported the bio absorption potential of
Acinetobacter sp. Strain 1ST 103 of bacterial consortium for removal of
chromium from tannery effluent. A mixed microbial community obtained from
pulp and paper mill and tannery effluent was enriched in a chemostat in the
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presence of potassium chromate as sole source of carbon and energy. The
microbial community of pulp and paper mill indicated significant reductien of
chromium (70 per cent) in comparison to tannery community (60 %) in batch
culture in the presence of potassium chromate and sodium acetate as additional
carbon source. The community comprised three bacterial strains, identified as CP
1, CP2 and CP3, were further applied for reduction of chromium indicated higher
removal of chromium (68 %) by strain CP3 followed by CP2 and CPl. The strain
CP3 was identified as Acinetobacter sp. by biochemical test. The bacterial strain,
CP3, applied for the removal of chromium in tannery effluent in a sequential
bioreactor indicated the reduction of chromium (80 %).
Sibel Tunali et al [98] have studied on chromium (VI) biosorption characteristics
of Neurospora crassa fungal biomass. The effect of pH on the biosorption rate of
Cr (VI) on fungal biomass was investigated by equilibrating the sorption mixture
containing dried biomass (0.1 g) and Cr (VI) solutions (50 ml of 100 mg/L) in the
pH range 1.0–6.0. The greatest capacity of heat inactivated N. crassa biomass
was obtained at pH 1.0 using Cr (VI) concentration of 100 mg/L at 25 ± 0.1 ◦C.
biosorption capacity of acetic acid pretreated biomass was found to be 15.85 
0.94 mg/g biomass under optimum conditions. The adsorption constants were
found from the Freundlich isotherm model at 25 ◦C. The biosorbent was
regenerated using 10 mM NaOH solution with up to 95 % recovery and reused
five times in biosorption–desorption cycles successivelly.
Srinath et al [99] have studied on chromium (VI) biosorption and accumulation
by chromate resistant bacteria. In this study, strains that are capable of
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bioaccumulating Cr (VI) were isolated from treated tannery effluent of a common
effluent treatment plant. The growth response curve of strains H and A at various
concentrations of Cr (VI) (0, 25, 50, 100 and 150 mg/L) showed that the lag phase
as well as the optical density attained by the strains depended greatly on the
concentration of Cr (VI) in the medium. At the concentration of 100 mg/L Cr
(VI) and above, the lag phase was extended and the maximal cell density reduced
below 90 % of the control. Two strains, identified as Bacillus circulans and
Bacillus megaterium were able to bioaccumulate 34.5 and 32.0 mg/g Cr dry
weight, respectively and brought the residual concentration of Cr (VI) to the
permissible limit in 24 h when the initial concentration was 50 mg/L Cr (VI).
Sudha Bai et al [100] have made Studies on enhancement of Cr (VI) biosorption
by chemically modified biomass of Rhizopus nigricans. For biosorption
experiments, Cr solution having 50–500 mg/L was prepared and used. Treatment
of the biosorbent with mild alkalies (0.01 N NaOH and ammonia solution) and
formaldehyde (10 %, w/v) deteriorated the biosorption efficiency. However,
extraction of the biomass powder in acids (0.1N HCl and H2SO4), alcohols (50 %
v/v, CH3OH and C2H5OH) and acetone (50 %, v/v) improved the Cr uptake
capacity. Biomass modification experiments conducted using Cetyl Trimethyl
Ammonium Bromide (CTAB), Polyethylenimine (PEI), and Amino Propyl
Trimethoxy Silane (APTS) improved the biosorption efficiency to exceptionally
high levels. The FTIR spectroscopic analysis of the native, Cr bound and the
other types of chemically modified biomass indicated the involvement of amino
groups of Rhizopus cell wall in Cr binding.
126
Sujoy K. Das et al [101] have studied on biosorption of hexavalent chromium by
Termitomyces clypeatus biomass: Kinetics and transmission electron microscopic
study. Biosorption of Cr+6 by Termitomyces clypeatus has been investigated
involving kinetics, transmission electron microscopy (TEM) and Fourier
transform infrared spectroscopic (FTIR) studies. Kinetics experiments reveal that
the uptake of chromium by live cell involves initial rapid surface binding followed
by relatively slow intracellular accumulation. Of the different chromate analogues
tested, only sulfate ion reduces the uptake of chromium to the extent of 30 %
indicating chromate ions accumulation into the cytoplasm using sulfate transport
system. Metabolic inhibitors, e.g. N,N-dicyclohexylcarbodiimide, 2,4-ditrophenol
and sodium azide inhibit chromate accumulation by 30 % in live cell. This
indicates that accumulation of chromium into the cytoplasm occurs through the
active transport system.
Sujoy K. Das et al [102] have studied on biosorption of chromium by
Ermitomyces clypeatus. The influence of hydrogen ion concentration on the
sorption of chromium was monitored at pH values 2.0–7.0 by suspending 0.2 g of
dry live TC biomass in 25 mL 50 mM acetate buffer containing either 100 mg/L
Cr6+ or Cr3+, varying Cr6+ concentration from 10 to 1000 mg/L. The sorption of
hexavalent chromium by live TCB depends on the pH of the solution, the
optimum pH value being 3.0. The process follows Langmuir isotherm (regression
coefficient 0.998, χ2-square 5.03) model with uniform distribution over the
surface which gets strong support from the X-ray elemental mapping of chromium
adsorbed biomass. Desorption and FTIR studies also exhibited that Cr6+ is
reduced to trivalent chromium on binding to the cell surface. The level of
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chromium concentration present in the effluent of tannery industries’ is reduced to
a permissible limit using TCB as adsorbent.
Vieira et al [103] have studied on biosorption of chromium (VI) using a
Sargassum sp. packed-bed column. The objective of the study was to examine
chromium (VI) removal from an aqueous solution using a packed-bed column
with Sargassum sp. algae as a biosorbent. The kinetic and equilibrium results for
a biomass of 4 g and a flow rate of 0.015 mL/s for several initial chromium
concentrations from 200 to 1240 mg/L and different tme intervals from 0 to 210
min. The capacity of removal obtained at optimum conditions was 19.06 mg of
metal/g biosorbent.
Vinoda et al [104] have studied on biosorption of nickel and total chromium from
aqueous solution by gum kondagogu (Cochlospermum gossypium) The optimum
conditions of biosorption were determined by investigating pH, contact time, and
initial metal ion and biosorbent concentrations. The maximum biosorption
capacity of gum kondagogu as calculated by Langmuir model were found to be
50.5 mg/g for nickel at pH 5.0 ± 0.1 when the range is maintained from (2.0–6.0)
and 129.8 mg/g for total chromium at pH 2.0 ± 0.1 when the range is maintained
from (2.0–6.0), respectively. It was observed the adsorption capacity of nickel
(Ni2+) and chromium by gum kondagogu was increased as the contact time
increased and the equilibrium was reached after 120 min. The result shows that
with the increase in the gum kondagogu concentration, the metal removal
efficiency also increased. The % metal biosorption increased from 55 ± 1.4 to
82.2 ± 2.8 % for Ni2+ and 58.9 ± 1.54 to 87.5 ± 3.05 % for total chromium.
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However, the adsorption capacity decreased from 55 ± 1.4 to 16.4 ± 0.45 mg/g for
Ni2+ and 58.9 ± 1.54 to 7.5 ± 0.49 mg/g for total chromium, when gum kondagogu
concentration was increased from 1000 to 5000 mg/L.
Xu Han et al [105] have studied on biosorption and bioreduction of Cr (VI) by a
microalgal isolate, Chlorella miniata. Cr (VI) removal was determined under
different initial pH (from 1.0 to 4.0) and biomass concentrations (from 1.0 to 5.0
g/L) at an initial Cr (VI) concentration of 100 mg/L. The biosorption capacity of
total Cr [Cr (III) and Cr (VI)] reached the maximum at initial pH of 3.0. The
spectrum of Fourier Transform Infrared Spectrometer analysis (FTIR) further
confirmed that amino group on the algal biomass was the main adsorption site for
Cr (VI) biosorption in acidic pH while the reduced Cr (III) was mainly
sequestered by carboxylate group.
Yasemin S ahin et al [106] have studied on biosorption of chromium (VI) ions
from aqueous solution by the bacterium Bacillus thuringiensis. Batch
experiments were done as a function of pH, initial metal ion concentration and
temperature. When the initial chromium (VI) ions concentration varied from 25.0
to 250.0 mg/L, the loading capacity of B. thuringiensis’vegetative cell has
increased from 14.3 to 54.7 mg/L while its spore–crystal mixture’s uptake has
increased from 20.6 to 61.5 mg/L. The optimum pH value for the biosorption of
chromium (VI) ions was determined as 2.0 for both of the spore– crystal mixture
and the vegetative cell. In this work, the maximum initial adsorption percentage
yields were found to be 38.3 % for the vegetative cells and 59.3 % for the spore–
crystal mixture at 25 oC Chromium (VI) ions uptake of B. thuringiensis’ spore–
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crystal mixture at 250 mg/L was 24.1 %, whereas its vegetative cell metal uptake
was 18.0 %. Chromium (VI) biosorption experiments were carried out at three
different temperatures, 15, 25 and 35 0C. The best temperature for biosorption
was 25 0C.
Yasmin Khambhaty et al [107] have studied on kinetics, equilibrium and
thermodynamic studies on biosorption of hexavalent chromium by dead fungal
biomass of marine Aspergillus niger. The present study was carried out in a batch
system using dead biomass of marine Aspergillus niger for the sorption of Cr (VI).
The removal rate of Cr (VI) was increased with a decrease in pH and an increase
in Cr (VI) and biomass concentration. A. niger exhibited the highest Cr (VI)
uptake of 117.33 mg/g of biomass at pH 1.0 in the presence of 400 mg/L Cr at
50oC.
Yetis et al [108] determined the heavy metal biosorption potentials of two white-
rot fungi, Poloporous versicolor and Phanarochaete chrysosporium, which were
commonly used in wastewater treatment. Biosorption studies were performed for
Cu (II), Cr (III), Cd (II), Ni (II) and Pb (II) at the same operational conditions and
the effectiveness of both fungi at removing these heavy metals was compared. It
was found that both P. versicolor and P. chrysosporium were the most effective in
removing Pb (II) from aqueous solutions with biosorption capacities of 57.5 and
110 mg Pb (II)/g dry biomass, respectively. With P.versicolor, the adsorptive
capacity order was determined to be Pb (II) > Ni (II) > Cr (II) > Cd (II) > Cu (II)
whereas the order was Pb (II) > Cr (III) > Cu (II) = Cd (II) > Ni (II) with P.
chrysosporium. It was observed that, as a general trend, the metal removal
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efficiency with these fungi decreased as the initial metal ion concentration
increased.
Ziagova et al [109] have worked on Comparative study of Cd (II) and Cr (VI)
biosorption on Staphylococcus xylosus and Pseudomonas sp. in single and binary
mixtures. In tis study Langmuir and Freundlich models were applied to describe
metal biosorption and the influence of pH, biomass concentration and contact time
was determined. Biosorption experiments were conducted at initial Cd (II)
concentrations from 10 to 1000 mg/L. The effect of pH was investigated in the
range of 3.0–7.0. Maximum uptake capacity of cadmium was estimated to 250
and 278 mg/g, whereas that of chromium to 143 and 95 mg/g for S. xylosus and
Pseudomonas sp., respectively. In binary mixtures with Cd (II) ions as the
dominant species, there is a profound selectivity for cadmium biosorption,
reaching 96 % and 89 % for Pseudomonas sp. and S. xylosus, respectively, at 10
mg/L Cd (II) and 5 mg/L Cr (VI). Interesting, when chromium (VI) ions are the
dominant species, there is selectivity towards chromium around 92 % with S.
xylosus only.
Zumriye Aksu et al [110] have studied on biosorption of chromium (VI) ions by
Mowital®B30H resin immobilized activated sludge in a packed bed: comparison
with granular activated carbon. The effect of operating parameters such as flow
rate and inlet metal ion concentration on the sorption characteristics of each
sorbent was investigated in a continuous packed bed column. From the batch
system studies the working sorption pH value (1-7) was determined as 1.0 for both
sorbents and packed bed sorption studies were performed at this pH value.
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Saturation was reached within 210-/1800 min at different flow rates from 0.8 to
3.2 mL/min and prolonged exposure time did not increase removal of chromium
(VI). The sorption breakthrough curves obtained by changing inlet chromium
(VI) concentration from 50 to 500 mg/L at 0.8 ml/min flow rate. At 50 mg/L of
inlet chromium (VI) concentration and at the lowest flow rate of 0.8 ml/min, the
sorption, although continuous with time, was very efficient in the initial steps of
the process.
Zumriye Aksu et al [111] have studied on single and binary chromium (VI) and
Remazol Black B biosorption properties of Phormidium sp. In this study
biosorption of chromium (VI) and Remazol Black B reactive dye by dried
Phormidium sp., a thermophilic cyanobacterium, was studied as a function of
initial chromium (VI) concentration and temperature in no dye and 100mg/L dye
containing media at an initial pH value of 2.0 at which the biomass exhibited the
maximum chromium (VI) and dye uptakes. Experiments were performed at five
different initial pH values ranging from 1.0 to 6.0 in single 100 mg/L chromium
(VI) and in single 100 mg/L dye-containing media. The highest uptake values
were found at pH 2.0 for both situations tested. The adsorption of chromium (VI)
and dye has been studied over a range of 25–45 oC. At 25 oC, 22.8 mg/g
chromium (VI) and 91.3 mg/g dye were sorbed by the biomass in binary 100mg/L
chromium (VI) and 100 mg/L dye-containing medium. At 25 oC, on changing the
initial chromium (VI) concentration from 10 to 100 mg/L, the amount of
biosorbed chromium (VI) increased from 3.5 to 15.2 mg/g and from 5.1 to 22.8
mg/g in the absence and in the presence of 100 mg/L dye, respectively.
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3.2 LEAD (Pb):
Adil Hammaini et al [112] investigated the effect of the presence of Pb on the
biosorption efficiency of Cu, Cd and Zn by activated sludge was investigated. The
interference of Pb with the Zn uptake was very pronounced. The amount of Zn
adsorbed [Cf [Zn] = 1mM] when Pb was present at 0.2 mM was 87 % less than
when Cf [Pb] = 0.05 mM. At Cf [Pb] = 0.2 mM and when 0.5 and 2 mM of Zn
were present in the system (final equilibrium Zn concentration), the Pb uptake was
0.5 and 0.48 mmol/g, respectively. When the residuals of Pb and Zn were the
same,about 99 % of the total metal uptake was due to Pb uptake. The equilibrium
concentration of Zn would have to be 70 times greater than that of Pb to obtain the
same proportion of uptake for each metal. When the residuals of Pb and Cd were
the same, about 88 % of the total metal uptake was due to Pb.
Ahmet Cabuk et al [113] studied the Pb (II) biosorption properties of
immobilized Bacills sp.ATS-2 cells were investigated in the fixed bed column and
batch system. The maximum Pb (II) biosorption capacity of the immobilized
biosorbent was obtained at the initial pH of 4.0.The effect of initial pH on the
biosorption of Pb (II) onto silica gel-immobilized Bacillus sp. ATS-2 was
investigated at a constant flow rate of 180 ml/h, fixed bed column with the bed
length of 10 cm and the initial Pb (II) concentration of 100 mg/L. The lower
biosorption yield under the initial pH values of 4.0 has been attributed to the
competition of the metal ions with the protons for the available binding sites on
the immobilized biosorbent. The FTIR spectra of the immobilized biosorbent
before and after Pb (II) sorption in the range of 400–4000 cm−1 were taken and
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compared with each other to find out which functional groups are responsible for
the Pb (II) biosorption
Ahmet Cabuk et al [114] suggested that the S. cerevisiae immobilized on cone
biomass of P. nigra appears as a low cost possible biosorbent and to be used for
treatment of Pb (II) bearing solutions. The maximum biosorption capacity was
determined to be 30.04 mg/g at pH 5.0, 2.0 g/L biosorbent dosage and 30 min.
The experimental data were evaluated by Langmuir, Freundlich and Dubinin–
Radushkevich isotherms and fitted well to all of the isotherm models with good
regression coefficients. The Pb (II) biosorption capacity of biosorbent increased
with increasing pH from 1.0 to 5.0. It is well known that, at low pH values, cell
wall ligands were closely associated with the hydronium ions and restricted the
approach of positively charged metal ions as a result of the repulsive force. The
mechanism of the process was evaluated by FT-IR and EDAX analysis.
Alaa H. Hawari et al [115] investigated the feasibility of anaerobic granules as a
novel type of biosorbent, for lead, copper, cadmium, and nickel removal from
aqueous solutions. Over the pH range 4–5.5, pH-related effects were not
significant. Meanwhile, at the pH values of 3.5 and 3, the q values started to
decrease. At low pH, protons would compete for active binding sites with metal
ions. The protonation of active sites thus tends to decrease the metal sorption. At
a low pH, of almost 2.0, all the binding sites may be protonated, thereby desorbing
all originally bound metals from the biomass. Water was the most abundant
single compound in the cell and it makes almost 70 % of the total weight of the
cell. Inorganic salts and mineral elements were found to be 25 % of the total dry
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weight (TFS). Organic matter (TVS), on the other hand, constitute 75 % of the
solid fraction of the biomass.
Ankit Balaria et al [116] investigated the study on biosorption of lead (Pb) from
aqueous solution using citrus peels can provide an efficient and cost-effective
solution for lead removal from industrial wastewaters. These peels contain the
biopolymer pectin that has a strong affinity formetal ions. A plateau can be
observed for pH 6–9 at surface charge values of 0.8 meq/g for LM pectin and 0.4
meq/g for HM pectin. LM pectin contains fewer methoxylated carboxylic groups
and more free carboxylic groups than HM pectin, which explains the higher
negative charge for LM pectin.For the LM pectin, 91 % of the carboxyl groups
should be free (based on a methoxyl content of 9 %) in contrast to 36 % of the
HM pectin. If only free carboxyl groups contribute to the charge, one would
expect the LM pectin to have a charge 2.5 times higher than the HM pectin, which
is similar to the observed factor of two. The FTIR spectra comparisons of pure
versus Pb–laden pectins reveal that the absorption peak corresponding to the
carboxylate (–COO−) groups shifted significantly from 1627 cm−1 to 1636 cm−1 in
the case of the HM pectin after treatment with Pb. A similar shift in the same
peak from 1624 cm−1 to 1635 cm−1 can be observed for LM pectins. This shift in
wave number corresponds to a change in bonding energy corresponding to the
functional group, which further reflects that the bonding pattern of carboxylate
groups changes after biosorption. This result confirmed the involvement of
carboxylic acid groups in binding of Pb in the case of pectin.
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Anushree Malik et al [117] observed a set of studies that demonstrated the
feasibility of employing rotating biological contactor (RBC), supporting the
immobilized growing bio films for removal of Cu, Zn and Cd from synthetic
wastewater. The inoculum consisted of the enrichment cultures out of the sewage
activated sludge and the nutrient broth concentration had been judiciously chosen
to avoid metal complexation. The disc rotation speed (10 rev/min) and flow rate
(6.9 ml/min) had to be previously optimized for maximum biofilm growth and
metal removal.Candida spp. isolated from sewage samples could accumulate
significant amount of Ni (57–71 %) and Cu (52–68 %), but the process was found
to be affected by initial metal concentration and pH (optimum 3–5) of the
medium. This method of uptake is independent of the biological metabolic cycle
and is known as ‘‘biosorption’’ or ‘‘passive uptake’’. The three strains of bacteria
isolated from industrial effluents (Enterobacter cloacae and Klebsiella spp.) were
resistant to high concentrations of Cd, Pb and Cr in the growth media and could
remove approximately 85 % Cd during growth.
Arzu Y. Dursun et al [118] investigated the kinetics and thermodynamics of
copper (II) and lead (II) biosorption onto Aspergillus niger pretreated with NaOH
were studied with respect to pH, temperature and initial metal ion concentration.
The optimum pH values were determined as 5.0 and 4.0 for copper (II) and lead
(II) at 25 oC, respectively. Maximum biosorption capacities were obtained at pH
5 and 4 for Cu (II) and Pb (II), respectively. An increase or decrease in the pH
from these optimum pH resulted in a reduction in the biosorption of metal ions.
Little biosorption took place for pH less than 3.0.Solution pH influences both cell
surface metal binding sites and metal chemistry in water. It was shown that the
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removal of both metal ions increased with increasing temperature up to 35 ◦C.
22.5 mg/g Cu (II) and 27.1 mg/g Pb (II) of dried microorganism were adsorbed at
equilibrium at 35 ◦C.
Aysegul Seker et al [119] studies has demonstrated that S. platensis is an
effective biosorbent for the adsorption of Pb2+, Cd2+, and Ni2+ ions from aqueous
solution. The uptake of metal ions by S.platensis seemed to be quite rapid and the
experimental data obeyed well the pseudo-second-order model. Faster adsorption
kinetics was observed for Pb (II) ions in comparison to Cd2+ ions. Aqueous Pb2+,
Cd2+, and Ni2+ ions were prepared from analytical reagent grade lead nitrate,
Pb(NO)3 (Riedel, 99 %, product code: 31137, CAS no. [10099-74-8]) cadmium
chloride, CdCl2 ( Fluka, > 99, product code: 20899, CAS no. [10108-64-2]) and
nickel chloride, NiCl2·6H2O (Carlo Erba, 99 %, product code: 464645, CASno.
[7791-20-0]) respectively. According to the thermodynamic parameters such as
G◦, H◦and S◦ calculated, the sorption process was endothermic and largely
driven towards the products. Sorption activities in a three metal ion system were
studied which indicated that there is a relative selectivity of the biosorbent
towards Pb2+ ions.
Bahadir et al [120] investigated the effects of the media conditions (pH,
temperature, biomass concentration) on the biosorption of Pb (II) ions to Rhizopus
arrhizus in a batch reactor. In order to determine the effect of biomass
concentration on Pb (II) removal, stock solutions of 10.0 g/L were prepared for
different microorganism particle size ranges, such as 0.045–0.063, 0.063–0.090
and 0.090–0.125 mm. These stock solutions were diluted to 0.1–1.0 g/L standard
137
solutions in order to find the effect of microorganism concentration on
biosorption. To determine the effect of pH of the biosorption medium on the
initial biosorption rates of Pb (II) ions, the pH was varied between 2.0 and 5.0.
The optimum initial pH of the biosorption medium was found to be 4.5. Results
of removal of Pb (II) ions from storage battery industry wastewater experiments
carried out at different temperatures ranging from 20 to 45 C. The optimum
biomass concentration was obtained at 1.0 g/L dose. It may be possible to
consider the biomass dose as 0.5 g/L but it may take time to reach at equilibrium
conditions at this dose. After the treatment of wastewater, the Pb (II)
concentration was measured as 0.157 mg/L which was far from the maximum
discharge limit of legacy.
In this study, biosorption of lead (Pb) from aqueous solution using citrus peels can
provide an efficient and cost-effective solution for lead removal by Balaria and
Silke [116] from industrial wastewaters. These peels contain the biopolymer
pectin that has a strong affinity for metal ions. A plateau can be observed for pH
6–9 at surface charge values of 0.8 meq/g for LM pectin and 0.4 meq/g for HM
pectin. LM pectin contains fewer methoxylated carboxylic groups and more free
carboxylic groups than HM pectin, which explains the higher negative charge for
LM pectin. For the LM pectin, 91 % of the carboxyl groups should be free (based
on a methoxyl content of 9 %) in contrast to 36 % of the HM pectin. The FTIR
spectra comparisons of pure versus Pb–laden pectins reveal that the absorption
peak corresponding to the carboxylate (–COO−) groups shifted significantly
from1627 cm−1 to 1636 cm−1 in the case of the HM pectin after treatment with Pb.
A similar shift in the same peak from 1624 cm−1 to 1635 cm−1 can be observed for
138
LM pectins. This shift in wave number corresponds to a change in bonding
energy corresponding to the functional group, which further reflects that the
bonding pattern of carboxylate groups changes after biosorption. This result
confirmed the involvement of carboxylic acid groups in binding of Pb in the case
of pectin.
Chang et al. [121] studied the biosorption kinetics of lead (Pb), copper (Cu) and
cadmium (Cd) ions on the biomass of pseudomonas aeruginosa PU21 (Rip64)
was investigated. Effects of environmental factors and growth conditions on the
biosorption were studied. The biomass originated from different growth phases
exhibited different adsorption capacities for Pb and Cd whereas the effect of
growth phase on biosorption of Cu was negligible. The saturation uptake capacity
and metal-cell affinity tended to increase as pH increased, until metals precipitated
as metal hydroxides when the pH exceeded some threshold values. Adjusting the
pH value to about 2.0 resulted in 98, 98 and 82 % recovery of Pb, Cu and Cd
respectively. The biomass resulted from desorption processes was able to retain
approximately 80 % of original adsorption capacity for Pb and Cu with four
repeated adsorption and recovery runs. The maximal adsorption capacity of
resting cells was nearly 110 mg Pb/g dry cell, whereas for the inactivated cells its
around 70 mg Pb/g dry cell.
Changzhou Yan et al [122] stated that the experimental results showed the
biosorption of lead and was adversely affected by low acidic pH values and the
presence of high concentrations of other metal ions. The removal efficiency of
lead ions was 37 % at a solution pH of 2.0, and it increased when solution pH
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increased from 2.0 to 5.0. At pH 5.0, the removal rate was 76 %. It showed that
the sorption amount of lead rose markedly with increasing solution pH and that
the sorption process was pH dependent. The rise in lead biosorption value with
increasing pH can be explained by the presence of a strong relation between
biosorption and the number of negatively charged sites, which is highly dependent
on the dissociation of functional groups. In order to characterize the interference
by the Langmuir competitive model, another experiment was carried out at room
temperature (25 ± 1 ◦C) with initial pH of 5.0 for three metal solutions: Pb (II)
with varies concentration of Cu(II), 10, 30 and 50 mg/L, respectively. In all cases,
the Pb (II) concentration was varied from 10 to 250 mg/L and the samples were
placed on the shaker for a period of 120 min. Overall, this study suggested that
biosorption of Pb (II) ions by M. spicatum can be an inexpensive and effective
way of metal-ion treatment.
Comte et al [123] presented the influence of pH on the metal biosorption of
extracellular polymeric substances (EPS) extracted from two different activated
sludges called A and B. All samples were treated in exactly the same way in
order to obtain the polarographic titration curve. The polarographic measurements
were performed at 25 ± 1 oC under a nitrogen atmosphere and with a 20 mL total
volume of solution containing EPS. The pH of the different samples in the
analysis cell was continuously measured using a CRISON pH meter. The pH was
adjusted to 4.0, 6.0, 7.0 and 8.0 ± 0.1 by the addition of micro quantities of a
dilute solution of sodium hydroxide or nitric acid. Two pKa values were found
for each EPS. pKa1 are 6.6 and 5.7 and pKa2 are 8.7 and 9.4 for EPS A and B,
respectively.
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Cynthia Urdaneta et al [124] studied, after a preliminary physical and chemical
characterization of the vermicompost, the optimal parameters for the heavy metal
adsorption. A synthetic multielemental solution of Pb, Cr and Ni and a solution of
NH4VO3 for vanadium were evaluated. The effect of pH on the adsorption
efficiency was evaluated in a range of 3.5 to 7.0 using aqueous solution of NaOH
or HNO3 of 0.10 mol/L. The effects of the agitation time were evaluated using 5,
10, 15, 30, 45 and 60 min. The solution volume was fixed to 75 mL, the pH to
5.00, the vermin compost mass was1g and the particle size ranging between 841
and 75 μm. Removing levels for Pb, Cr andNi are in the order of 95 % showing
that vermicompost is adequate for this removing process. Metal adsorption for Ni,
Pb and Cr in real wastewater from Barquisimeto city was 100, 65 and 40 %,
respectively.
Durali Mendil et al [125] experimented Bacillus thuringiensis var. israelensis
immobilized on Chromosorb 101 that is a new solid phase extractor has been
presented in his work for the preconcentration and separation of cadmium(II),
lead(II), manganese(II), chromium(III), nickel(II) and cobalt(II) in environmental
samples. The influences of the some metal ions as concomitant were investigated.
Under the optimized conditions, the detection limits by 3 sigma for analyte ions
were in the range of 0.37–2.85 g/L. The presented biosorption procedure is an
easy, safe, rapid, and inexpensive for the preconcentration and separation of trace
metals in aqueous solutions. The limits of detection (LOD) of the proposed
method for the determination of investigated elements were studied by passing
250 mL of blank solutions from the column under the optimal experimental
141
conditions. The LOD, defined as the concentration equivalent to three times the
standard deviation (N = 11) of the reagent blank were found as: Co(II): 2.11 g/L,
Cd(II): 0.37 g/L, Pb(II): 2.85 g/L, Mn(II): 0.71 g/L, Cr(III): 1.15 g/L and Ni(II):
1.67 g/L. The method was also applied successfully to the determination of
analytes in microwave digested red wine, rice and canned fish samples and sea
water, spring water and urine samples.
El-Naas et al [126] studied and the experimental results showed that the uptake
increased with increasing pH from 3.0 to an optimum value of 5.0. The
biosorption of Pb (II)was found to be adversely affected by the presence of Cu (II)
ions, while Zn (II) ions seemed to have negligible effect on the process. The
results also revealed that biosorption mechanism does not depend only on the
presence of active sites, and that it may involve a combination of complexation
and nucleation at cellar wall of the biosorbent. Modeling of the controlling
mechanism indicated that both intrinsic kinetics and mass transfer played major
roles in controlling the process. The results indicated that the uptake of lead ions
was significantly affected by solution pH and that the biosorption capacity of C.
vulgaris increased with increasing pH as shown in. At pH values of less than 3,
there seemed to be negligible uptake of lead; however, as the pH is increased to 4.
Fang Luo et al [127] investigated in his paper that marine brown algae Laminaria
japonica was chemically-modified by crosslinking with epichlorohydrin (EC1,
EC2), or oxidizing by potassium permanganate (PC), or only washed by distilled
water (DW). They were used for equilibrium sorption uptake studies with lead.
The biosorption is solution pH dependent and the highest removal of lead is
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occurred at pH 4.0–5.3 for EC1 and EC2. With regard to PC and DW, the
maximum Pb2+ uptakes are obtained in pH range of 3.0–5.3. L–F isotherm model
is in good agreement with all the experimental data compared with the results of
Langmuir and Freundlich isotherm models. The adsorption characteristics of lead
with various pH in the range of 1.4–5.3 are examined using four biomasses. The
initial concentration of Pb2+ solution is 1.0 mmol/L and the investigation of pH
values above 5.5 was not possible since lead precipitation appeared. The
maximum lead uptakes were 1.67 mmol g/L, 1.62 mmol g/L, 1.54 mmol/g and
1.21 mmol/g, respectively for EC1, EC2, PC and DW. The order of maximum
lead uptakes for different pretreated and raw alga was EC1 > EC2 > PC > DW
Flavio A. Pavan et al [128] experimented and from the study, it can be concluded
that natural ponkan peel is an effective and efficient biosorbent for removing Pb
(II) ions from aqueous solution. The effects of initial pH on biosorption capacity
of Pb (II) ions using ponkan peel were evaluated within the pH range of 2.0–8.0
Electron micrographs and EDX spectra of the ponkan peel before and after
biosorption with 1000 mg/L of solution contained Pb (II) ions. The broad and
intense absorption with a maximum at 3400 cm−1 was assigned to O–H stretching
group, originally bonded to organic polymeric structure. In order to evaluate the
influence of pH parameter on biosorption, experiments were carried out at
different pH values between 2.0 and 8.0. For this experiments the initial Pb (II)
concentration used was 15.0 mmol/L, pH of the solution was 5.0 and contact time
120 min.
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Francesca Beolchini et al [129] investigated that the experimental data of single
and binary metal biosorption in membrane reactor and is reported in this work
denoted by the effect of metal competition for the active sites on the biosorbent.
Biosorption tests using single and binary metallic solutions (Cu, Pb and Cu–Pb)
denoted the biomass affinity (PbNCu), the competition among metals
simultaneously present in the system, the filtrate flux decline and the change of
metal retention coefficient on the membrane for pore plugging by cell fragments.
Dynamic modelling is developed considering the unsteady mass balances of the
metal in the system and the equilibrium parameters obtained by biosorption batch
tests using Langmuir models.
Francisco W. Sousa et al [130] investigated that green coconut shells can be used
as adsorbent for the removal of toxic metal ions from aqueous effluents using
column adsorption. Using HNO3 1.0 mol/L, the adsorbent can be reused, but
removal efficiencies decrease from the first cycle. Investigation of a real sample,
containing Ni (2.787 mg/L); Zn (98.02 mg/L) and Cu (320.4 mg/L), showed that
the fixed-bed technology can be applied, provided that the pH of the sample is
adjusted to 5.0. It can be observed that the reuse of the adsorbent decreases the
removal efficiency for all metal ions from the first cycle. Removal capacities
were reduced more than 50 % for Pb, 70 % for Ni; 67 % for Cd; 76 % for Zn and
75 % for Cu.
Gulsad Uslu et al [131] studies include the biosorption of lead (II) and copper (II)
ions, in single and binary systems using P. putida in the batch system. The lead
(II) and copper (II) ions binding capacity of microorganism was shown as a
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function of initial pH, temperature and single–binary-pollutant concentrations.
The single and binary component sorption phenomena were expressed by the
single component (noncompetitive) and multicomponent (competitive) Langmuir
and Freundlich adsorption models and adsorption isotherms were developed for
both single and binary component systems at different temperature. For binary
lead (II) and copper (II) ions mixture studies, desired combinations of lead (II) and
copper (II) ions were obtained by diluting 1.0 gd/m3 of stock solutions of
component and mixing them in the test medium before mixing with the bacterial
suspension. Adsorption data were well described by the Langmuir model,
although they could be modeled by the Freundlich equation. The thermodynamics
constants of the adsorption process: H◦, S◦ and G◦ were evaluated.
Gabr et al [132] investigated the optimum conditions for biosorption and
bioaccumulation of lead and nickel using a tolerant bacterial strain isolated from
El-Malah canal, Assiut, Egypt, and identified as Pseudomonas aeruginosa ASU
6a. The optimal pH values for Ni (II) and Pb (II) adsorption were, respectively,
7.0 and 6.0. The maximum adsorption uptake (qmax) of nickel and lead
calculated from Langmuir equation for biosorption by heat-dried cells and
lyophilized cells or accumulated by living cells is 113.6, 77.5, 70 and 123, 93, 79
mg/g for both metals, respectively. The appropriate equilibrium time for
measurements was taken at 30 min. Here it is worth mentioning that the
correlation coefficients for all the lead and nickel Pseudomonas systems were
found to be close to unity.
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García-Rosales et al [133] investigated the removal of Pb (II) from aqueous
solutions by a maize (Zea mays) stalk sponge. The sorption process was found to
be influenced by the pH of the solution; the percentage of sorbed lead increased
with the pH value, with maximum sorption percentage of 70 % at pH 7. Specific
metal uptake was found to decrease with an increase in pH (after pH > 7). The
adsorption capacities increased with increasing pH, but pH 7.0 was too high for
Pb because it precipitates at pH > 5. The results obtained showed that Zea may
stalk sponge was a useful biomaterial for Pb (II) sorption and that pH has an
important effect on metal biosorption capacity.
Groudeva et al [134] found that the Tulenovo oil deposit, Northeastern Bulgaria,
waters contaminated with crude oil and toxic heavy metals Cd, Cu, Pb, Mn, Fe
and were treated by a passive system of the type of the constructed wetlands. The
oil content in the fluid recovered from the different wells varies in the range of
about 0.1–0.5 %. The oil is heavy, rich in asphalthene-resinous substances and
with a high viscosity. The total ion concentration in the brine is about 2–4 g/L
and the pH is in the range of 6.8–7.7. The oil content of the waters after treatment
was decreased to less than 0.2 mg/L, and the concentrations of heavy metals were
decreased below the relevant permissible levels. The waters had a pH of about
5.3–6.8 and contained about 2–10 mg/L oil.
Gupta et al [135] conducted the batch studies to provide significant information
regarding biosorption of lead on green algae Spirogyra species in terms of
optimum pH and biomass dose for maximum removal of Pb (II) from the aqueous
solution. It has been observed that maximum adsorption took place within first
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100 min. As the pH of the lead solution (100 and 200 mg/L) increased from 2.99
to 7.04, the adsorption capacity of lead was changed, i.e. it first increased from
2.99 pH to pH 5.0 and then dramatically decreased up to pH 7.04. The extent of
lead biosorption was 31.2 % for 0.05 g/L of algal biomass, while it was greatly
increased to 80 % for 10 g/L of adsorbent. For an increase in temperature from
298 to 318 K, an increase in the adsorption of lead was observed. The maximum
amount adsorbed increased from 96.4 to 104 mg/g at 150 mg/L, initial lead
concentration.
The biosorption of different metals (Cu2+, Cd2+, Zn2+, Ni2+ and Pb2+) was
investigated using activated sludge by Hammaini et al [136]. The optimum pH
was 4 for Cd, Cu and Pb sorption and 5 for Ni and Zn. Biomass metal uptake
clearly competed with protons present in the aqueous medium, making pH an
important variable in the process. Protons consumed by biomass in control tests
versus protons exchange in biosorption tests confirmed a maximum exchange
between metal cations and protons at pH 2. pH had a clear influence on the
sorption capacity of activated sludge for Cu, Cd, Ni, Zn and Pb. The competition
between metal and protons sorption was greater at pH 2. At very low pH values
(pH 1–2) metal uptake was negligible. Metal uptake increased with pH up to 4–5,
beyond these pH values no improvement in the sorption capacity was observed.
The most adequate sorption pH was 4 for Cd, Cu and Pb, 5 for Ni and 6 for Zn. In
the latter case, the pH was also set at 5 to avoid its precipitation, especially in
those experiments carried out to draw the sorption isotherms in which the initial
metal concentration was higher.
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The effect of the presence of Pb on the biosorption efficiency of Cu, Cd and Zn by
activated sludge was investigated by Hammaini et al. [137]. The interference of
Pb with the Zn uptake was very pronounced. The amount of Zn adsorbed [Cf [Zn]
= 1mM] when Pb was present at 0.2 mM was 87 % less than when Cf [Pb] = 0.05
mM. At Cf [Pb] = 0.2 mM and when 0.5 and 2 mM of Zn were present in the
system (final equilibrium Zn concentration), the Pb uptake was 0.5 and 0.48
mmol/g respectively. When the residuals of Pb and Zn were the same, about 99 %
of the total metal uptake was due to Pb uptake. The equilibrium concentration of
Zn would have to be 70 times greater than that of Pb to obtain the same proportion
of uptake for each metal. When the residuals of Pb and Cd were the same, about
88 % of the total metal uptake was due to BP.
This work confines to biosorption of copper and lead ions on waste beer yeast, a
byproduct of brewing industry by Han et al. [138]. Batch biosorption tests were
done at different contact time at the initial concentration of 0.315 mmol/L for Cu
(II) and 0.393 mmol/L for Pb (II) respectively, and waste beer yeast dose
concentration is 8 g/L in 10 mL solution. The temperature was controlled with a
water bath at the temperature of 293 K. Experiments could not be performed at
higher pH values due to hydrolysis and precipitation of the lead ions. Flasks were
agitated on a shaker for 60 min to ensure that equilibrium was reached. There was
an increase in biosorption capacity of biomass with increasing pH from 2.0 to 6.0
for both metal ions. The lowest metal uptake values were determined at pH < 2.0
for both metal ions. The adsorption quantity of Pb (II) decreased with the
increasing of Cu (II) concentration. The biosorption quantity of Pb (II) decreased
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from 0.0218 to 0.0140 mmol/g when the concentration of Cu (II) ranged from 0 to
0.472 mmol/L.
Biosorption of lead (II) onto a cone biomass of Pinus syivestris was studied by
Handan Ucun et al [139] with variation in the parameters of pH, initial metal ion
concentration and impeller speeds. The biosorption medium was stirred at
constant speed for 1 h at 25 oC.The role of contact time on biosorption of lead by
cone biomass was studied under shake flask conditions at pH 4.0, 150 rpm, using
50 mg/L lead ion concentration. The pH of the biosorption medium affects the
biosorption rate on biomass. The pH solution ranging from 2.0 to 5.5 was studied.
Biosorption studies of lead with cone biomass was carried out in a shaker working
at pH = 4.0 using a lead solution of 50 mg/L lead solution. By varying the
impeller speed from 100 to 240 rpm in different sets, keeping biomass constant,
the effect of contact time on the biosorption capacity.
The results of the study given by Harikishore Kumar Reddy et al [140] revealed
that MOL wastes could be converted into an innovative low-cost biosorbent with
good biosorption capacity by modifying it with NaOH and citric acid. The
biosorption of Pb (II) by CAMOL from aqueous solution was found to be greatly
dependent on solution pH. Moringa oleifera leaves (MOL); an agro-waste
material has been used as a precursor to prepare a new biosorbent. The leaves
were washed with base and citric acid, and obtained new chemically modified
MOL biosorbent (CAMOL) for sequestration of Pb (II) from aqueous solution.
The biosorbent was characterized by SEM, FTIR spectral and elemental
analyses.The equilibrium data were analyzed using Langmuir, Freundlich,
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Dubinin–Radushkevick and Temkin isotherm models. Langmuir model provided
the best correlation with biosorption capacity of 209.54 mg/g at 313 K. The
thermodynamic properties showed that biosorption of Pb (II) onto CAMOL was
spontaneous, endothermic and feasible in the temperature range of 293–313 K.
Desorption experiments showed feasibility of regeneration of the biosorbent for
further use after treating with dilute HCl.
Ilhami Tuzun et al [141] studied the biosorption of lead with cone biomass was
carried out in a shaker working at pH 4.0 using a lead solution of 50 mg/L lead
solution. By varying the impeller speed from 100 to 240 rpm in different sets,
keeping biomass constant, the effect of contact time on the biosorption capacity.
The biosorption of Hg (II), Cd (II) and Pb (II) ions by microalgae biomass
increased as the initial concentration of Hg (II), Cd (II) and Pb (II) ions increased
in the biosorption medium. The maximum biosorption capacities of microalgae
for Hg (II), Cd (II) and Pb (II) ions were 72.2 G 0.67, 42.6 G 0.54 and 96.3 G 0.86
mg/g dry biomass, respectively. The biosorption of Hg (II), Cd (II) and Pb (II)
ions by microalgae biomass increased as the initial concentration of Hg (II), Cd
(II) and Pb (II) ions increased in the biosorption medium. The maximum
biosorption capacities of microalgae for Hg (II), Cd (II) and Pb (II) ions were 72.2
G 0.67, 42.6 G 0.54 and 96.3 G 0.86 mg/g dry biomass, respectively.
Immobilized Microcystis aeruginosa in a flow-through sorption column was
evaluated for the potential to remove Pb2+, Cd2+ and Hg2+ from aqueous solutions
by Jianhua Pan et al [142]. M. aeruginosa showed high affinity for the three
heavy metals with removal efficiency of 90 % for Cd2+ and Hg2+, and 80 % for
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Pb2+ at saturation conditions. The removal efficiency reached 90 % for Cd2+ and
Hg2+, and 80 % for Pb2+ when the biosorption attained a plateau. Competitive
uptake experiments carried out in binary and ternary systems revealed a high
selectivity for Pb2+ over Cd2+ and Hg2+. Pb2+ and Hg2+ interfered slightly with the
uptake of Cd2+. As such, lower interference of Cd2+ on Hg2+ was also observed in
this study. In contrast, the influence of Pb2+ on Hg2+ adsorption was significant at
certain time. Cooperation of Pb2+ and Hg2+ significantly interfered with the
uptake of Cd2+ in the first 10 min, and thereafter the cadmium removal efficiency
remained lower than that for Cd2+ added individually and paired with Pb2+ and
Hg2+ during the experimental timeframe except for 70 min.
To elucidate the potential mechanisms involved in the biosorption of metal ions,
atomic force microscopy (AFM) and Fourier transform infrared (FTIR)
spectroscopy were used to characterize the interaction between Pb2+ and Bacillus
cereus by Jianhua et al. [4]. The scanning speed and the loop gain factors were
varied during the imaging process. Changes in the spectra are attributed to the
interaction of Pb2+ with the carboxyl, hydroxyl and amino groups present on the
surface of the biosorbent. The shift of peak at 1455.6 cm−1 transposing to lower
frequencies up to disappearance is due to the complexation of amino and hydroxyl
groups with Pb2+. Kinetic studies demonstrate that the biosorption of Pb2+ by B.
cereus biomass is a rapid process and follows the pseudo-second-order rate law.
The AFM imaging of B. cereus biomass surfaces after Pb2+ biosorption indicates a
major morphological difference on mica, the assembly structures changing from
rod-like to spindle-like. Among the rest, the Redlich–Peterson model yielded the
best fit of experimental data.
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Ji Bing et al. [143] investigated the potential of Sedum alfredii hance for the
biosorption of some metals from synthetic wastewater. S. alfredii hance was
grown in synthetic wastewater in 2.5 L capacity containers contaminated with
(mg/L) 19.20 Zn, 11.24 Cd, 3.27 Cu and 0.53 Pb respectively. The initial Pb
concentration of in the control solution (without plants) was 0.53 mg/L that is
decreased to 0.23 ± 0.04 mg/L after the experiment with a removal rate of 56.32 ±
8.28 %, likely resulting from precipitation. The removal efficiencies of Zn, Cd,
Cu and Pb were 94.07 %, 82.03 %, 96.03 % and 69.61 % respectively. Both root
surface adsorption and plant absorption contributed to the removal of metals from
contaminated water. The amounts of heavy metals removed by root surface
adsorption accounted for 67.74 %, 24.03 %, 66.53 % and 70.77 % of the total
plant removal for Zn, Cd, Cu and Pb respectively. The supplied metal
concentrations were comparable with those in plating industrial wastewater. The
results indicated that heavy metal removal was mostly contributed by adsorption
on root surface in case of Zn, Cu and Pb but less for Cd than root absorption.
The study experimented by Jose T. Matheickal et al [144] indicated that
abundantly and cheaply available brown marine algae from the Australian marine
environment can be used for the development of efficient biosorbent materials for
heavy metal recovery from wastewater. A two stage modification process
substantially improved the leaching characteristics of the biomass. Batch
equilibrium experiments showed that the maximum adsorption capacities of
DP95Ca for lead and copper were 1.6 and 1.3 mmol/g, respectively. The
corresponding values for ER95Ca were 1.3 and 1.1 mmol/g. These capacities are
152
comparable with those of commercial ion exchange resins and are much higher
than those of natural zeolites and powdered activated carbon. The heavy metal
uptake process was found to be rapid with 90 % of the adsorption completed in
about 10 min in batch conditions. Heavy metal adsorption was observed at pH
values as low as 2.0 and maximum adsorption was obtained approximately at a pH
of 4.5.
Jo-Shu Chang et al [145] investigated the biosorption kinetics of lead (Pb),
copper (Cu) and cadmium (Cd) ions on the biomass Pseudomonas aeruginosa
PU21 (Rip64) was investigated. Effects of environmental factors and growth
conditions on the biosorption were studied. The biomass originated from different
growth phases exhibited different adsorption capacities for Pb and Cd, whereas
the effect of growth phase on biosorption of Cu was negligible. The saturation
uptake capacity and metal-cell affinity tended to increase as pH increased, until
metals precipitated as metal hydroxides when the pH exceeded some threshold
values. Adjusting the pH value to about 2.0 resulted in 98, 98 and 82 % recovery
of Pb, Cu and Cd, respectively. The biomass resulted from desorption processes
was able to retain approximately 80% of original adsorption capacity for Pb and
Cu with four repeated adsorption and recovery runs. Regeneration of biomass
appears to enhance the uptake capacity of Cd by nearly 35% after four
adsorption/desorption cycles.
Junxia Yu et al [146] studied a simple method was used to prepare modified
biomass to improve its adsorption capacity for Cd2+ and Pb2+. This study showed
that grafting effective groups on the biomass could result in a biosorbent with high
adsorption capacity for metal ions.the dependence of Cd2+ and Pb2+ uptake with
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the solution pH. It could be seen a fast increase in lead and cadmium uptake with
increasing pH from 2.5 to 3.5, while around pH 4.5, the Cd2+ and Pb2+ adsorption
capacity leveled off at a maximum value reaching a plateau. In these experiments,
the Cd2+ and Pb2+ concentration were 150 mg/L and 250 mg/L, respectively. After
0.0500 g of the biomass was used to adsorb Cd2+ at 80 mg/L in 50 mL solution
over 0.5 h, the adsorbent was regenerated, and then rinsed with distilled water and
used in subsequent adsorption experiments. The adsorption capacity and
desorption efficiency of the modified biomass for Cd2+ over six successive
adsorption–desorption cycles. It could be seen that little loss of uptake capacity of
the biomass was observed after using for six times, and the desorption efficiency
was above 90 %.
Biosorption of lead (II) and cadmium (II) from aqueous solutions by protonated
Sargassum glaucescens biomass was studied in a continuous packed bed column
by Kazem Naddafi et al [147]. The selective biosorption capacities of Pb2+ and
Cd2+ at complete exhaustion point were determined to be 1.18 and 0.22 mmol/g,
respectively; therefore, the biosorbent exhibited much higher relative affinity for
Pb2+ than for Cd2+. The efficiency of biosorbent regeneration by 0.1MHCl was
achieved about 60 %, so that the maximum uptake capacity of Pb2+ by the
regenerated biomass was determined to be 0.75 mmol/g while the same value for
the original biomass was 1.24 mmol/g.the effluent pH decreased to about 2.3 by
the most replacement of hydrogen ions in the binding sites with Pb2+ and then by
reduction of protonated binding sites as well as decrease of Pb2+ biosorption rate,
the effluent pH increased gradually until the effluent pH became equal to the
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influent pH at complete exhaustion of the biosorption bed, so the rate of metal ion
biosorption was proportionate to release of hydrogen ions.
Kılıc et al [148] studied adsorption of Pb (II) and Hg (II) on nonviable activated
sludge biomass at both batch and continuous-flow operational conditions.
Equilibrium concentration, equilibrium period, optimum pH and temperature for
adsorption were found out to be 0.387 mmol/g, 3.5 and 30 oC for Pb (II) and 0.097
mmol/g, 105 min, 5.8 and 20 oC for Hg (II), respectively. Optimum pH’s for both
metal ions were investigated using solutions containing 0.05 g dried raw biomass
and 1mg metal ion within 50 ml of deionized water. The equilibrium was reached
around 90 min though 62 % of the biosorption capacity for Pb (II) was completed
in first 15 min. In the tests, the highest biosorption capacity was observed at 30oC
as 0.091 mmol Pb (II) per g biomass. Optimum temperature for Pb (II) and Hg
(II) biosorption were found out to be 30 oC and 20 oC, respectively.
Lalhruaitluanga et al [149] demonstrated that the charcoal biomass could be
used as adsorbents for the treatment of Pb (II) from aqueous solution. The effect
of chemical pretreatment on the adsorption of Pb (II) ions by MBRC and MBAC
showed that 60 % KOH pretreatment shows highest percentage of adsorption.
The maximum biosorption of Pb (II) was found at pH 5. In order to determine the
functional groups involved in metal adsorption, the unloaded biomass, MBRC-Pb
(II) loaded and MBACPb (II) loaded with 50 mg/L Pb (II) ions were analyzed
using Fourier Transform Infrared Spectroscopy (JASCO FTIR-5300) in a range of
400–4000 cm−1. Chemical activation was carried out using phosphoric acid
(Qualigens) and potassium hydroxide (Himedia) at various concentrations (20, 40,
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60 and 80 %, w/w). In the activation system, the charcoal powder with a mass
concentration of 40 g/L was in contacted with the above various concentrations of
chemical reagents, respectively, for 24 h by shaking on an orbital shaker with a
speed of 150 rpm.
Lawal et al [150] showed that the uptake of the metal ions increased with increase
in initial metal ion concentration. The lead ion was optimally adsorbed at pH 4,
and its uptake was rapid in the first 10 min of adsorption after which adsorption
decreased. Pseudo-secondorder kinetics explained the biosorption of the metal ion
better than the pseudo-first-order. The pH of the Pb (II) solution was first adjusted
to a desired value, from 1.0 to 6.0 with HNO3 or NaOH. It was observed that the
biosorption process reached equilibrium after 75 min when the biosorption of the
Pb (II) ions on C. inophyllum seed husk was 95 %.It is reasonable that increase in
metal ion concentration facilitated enhanced displacement of hydrogen ions on the
surface of the biomass at pH 4 because of high concentration of the metal ions.
The stretching vibrations of OH group shifted from 3391 to 3385 cm−1 after Pb
(II) ions adsorption.
Lenka Svecova et al [151] studied the evaluation of the impact of pH on the
sorption of selected metals and continued with the sorption isotherms
determination. The maximum uptake capacity is close to 270 mg/g mercury (i.e.
1.34 mmol/g) and the affinity coefficient is quite low (about 0.07 L/mg, or 14.04
L m/mol). The optimum pH for sorption of mercury is obtained at initial pH close
to pH 5; however, during the sorption process the pH rises to 6.5 and the sorption
is not increased when controlling the pH at the initial value; the fluctuation of pH
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reveals favorable to metal recovery.Results obtained at pH lower than 3 are not
presented since the material was partially dissolved in acidic pH region. For
biosorbent P3, the sorption efficiency remained almost constant between pH 4 and
6. After the treatment with ethanol (P2), Penicillium biomass lost a significant
percentage of C (from 48 % to 43 %) while the percentage of nitrogen slightly
increased (from 4.4 % to 5 %). Hydrogen content slightly decreased (from 7.6 %
to 7.1 %).
Biosorption potential of Penicillium simplicissimum (Penicillium sp.) immobilized
within loofa sponge (PSILS) for lead and copper from aqueous media was
explored by Li et al. [152]. The effect of pH on the biosorption capacity was
investigated at initial pH values range of 2.0–6.0 and the desired pH of the
suspensions was maintained by adding HCl or NaOH at the beginning of the
experiment and not controlled afterwards. Results showed that the biosorption of
Pb (II) and Cu (II) on PSILS increased significantly as the pH increased from 2.0
to 5.0. The low Pb (II) and Cu (II) biosorption capacity at pH values below 3.0
may be attributed to hydrogen ions that compete with metal ions on the sorption
sites. The contact time of approximately 60 min was required to reach the
equilibrium. The effect of initial single metal ion concentration was investigated
in the range of 10–500 mg/L. sites. According to Langmuir isotherm, the
monolayer saturation capacity of PSILS is 144.9 mg/g for Pb (II) and 106.4 mg/g
Cu (II).
Luo et al. [153] studied about marine brown algae Laminaria japonica which was
chemically-modified by crosslinking with epichlorohydrin (EC1, EC2) or
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oxidizing by potassium permanganate (PC) or only washed by distilled water
(DW) and are used for equilibrium sorption uptake studies with lead. The
biosorption is solution pH dependent and the highest removal of lead is occurred
at pH 4.0–5.3 for EC1 and EC2. With regard to PC and DW, the maximum Pb2+
uptakes are obtained in pH range of 3.0–5.3. Langmuir and Freundlich isotherm
models are in good agreement with all the experimental data. The adsorption
characteristics of lead with various pH in the range of 1.4–5.3 are examined using
four biomasses. The initial concentration of Pb2+ solution is 1.0 mmol/L and the
investigation of pH values above 5.5 was not possible since lead precipitation
appeared. The maximum lead uptakes were 1.67 mmol/g, 1.62 mmol/g, 1.54
mmol/g and 1.21 mmol/g, respectively for EC1, EC2, PC and DW. The order of
maximum lead uptakes for different pretreated and raw alga was EC1 > EC2 > PC
> DW.
Response surface methodology was applied to optimize the removal of lead ion by
Aspergillus niger in an aqueous solution by Malihe Amini et al [154].
Optimization of biosorption from aqueous solution by response surface
methodology resulted in 96.21 % lead removal than that of the pre-optimized
condition. The level of the three variable, initial solution pH, 4.27; initial ion
concentration, 30 mg/L; A. niger dosage, 2.17 g/l, were found to be optimum for
maximum lead ion removal.A minimum level of biomass dosage (1.6 g/l),
maximum levels of initial lead ion concentration (30 mg/L) and lead removal
(96.21 %) and level of initial solution pH within range of 2.8–7.2 were set for
maximum desirability. The importance of each goal was changed in relation to the
other goals.
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Gymnogongrus torulosus adsorption efficiency for cadmium (II), copper (II), lead
(II) and zinc (II) were studied in batch mode in different acidic conditions by
María Mar Areco et al [155]. Lead biosorption exhibits a slight dependence on
pH. Both zinc (II) and copper (II) have a similar profile with a higher dependence
on pH, while cadmium shows moderate pH dependence. Initial solution pH plays
a significant role on metal biosorption, with maximum uptake at pH values above
5. Temperature can influence the sorption process rate. An increase in temperature
from 7 to 25 oC at pH 5.5 increases the pseudo-second-order kinetic constant by a
factor of 2.1, 17.3, 13.6 and 10.5 for lead (II), cadmium (II), zinc (II) and copper
(II), respectively. Increasing the temperature from 25 to 55 oC decreases the
pseudo-second-order kinetic constant by a factor of 0.1, 0.2 and 0.6 for lead (II),
cadmium (II) and copper (II), respectively. The sea weed was washed thoroughly
with deionized water, then dried overnight at 60 oC and finally stored in
desiccators before being used. Afterwards, the dried seaweed was blended in a
homogenizer into finer particles. A stainless steel standard sieve was used to
obtain fine particles (0.5–2 mm) of sea weed. Biosorption capacities were affected
by solution parameters. The maximum metal uptake (qmax) increased with
increasing pH.
Mata et al [156] determined the effect of immobilized brown alga Fucus
vesiculosus in the biosorption of heavy metals with alginate xerogels. Calcium in
the xerogels was displaced by heavy metals from solution according to the “egg-
box” model, creating a more uniform and organized structure. The Langmuir
maximum biosorption capacity increased two fold for cadmium, 10 times for lead,
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and decreased by half for copper. According to this model, the affinity of the
metals for the biomass was as follows: Cu > Pb > Cd without alga and Pb > Cu >
Cd with alga. Tests were run for 24 h, time enough to reach the equilibrium, at the
initial pH values previously mentioned, with 0.5 g/l initial biomass concentration
and 50 ml of different initial metal concentration solutions: 10, 25, 50, 100 and
150 mg/L.
Meral Yurtsever I. Ayhan Sengil et al [157] investigated the effect of
temperature, pH and initial metal concentration on Pb (II) biosorption on modified
quebracho tannin resin (QTR) was investigated. The specific BET surface area of
QTR was found to be 0.820 m2/g.The adsorption of Pb (II) increases with time
from 0 to 10 min and then becomes almost constant up to the end of
experiment.The analysis is carried out through an adsorption of N2 gas (gas
effluent temperature = 75 oC versus bath temperature = 77.35 oC). The measured
BET specific surface area for QTR was 0.820 m2/g.The kinetic data was tested
using pseudo-first-order, pseudo-second-order, Elovich and intraparticle diffusion
model. The results suggested that the pseudo-second-order model (R2 > 0.999)
was the best choice among all the kinetic models to describe the adsorption
behavior of Pb (II) onto QTR. Langmuir, Freundlich and Tempkin adsorption
models were used to represent the equilibrium data.
Mohammad Mehdi Montazer-Rahmati et al [158] studied the biosorption of Cd
(II), Ni (II) and Pb (II) from aqueous solutions using brown algae, C. indica, S.
glaucescens, N.zanardini and P. australis in batch systems indicates that the
adsorption of metal ions is significantly dependent on the pH of solution. The
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results are best fitted by the Freundlich model among two-parameter models and
the both, Khan and Radke-Prausnitz models among three-parameter isotherm
models for Cd (II), Ni (II) and Pb (II), respectively. The kinetic data were fitted
by models including pseudo-first-order and pseudo-second-order. The adsorption
characteristic of metal biosorption at various pH values in the range of 2.5–7.0
was examined. Experiments were not conducted beyond a pH of 7.0 to avoid
metal precipitation. The adsorption rate tests were performed on an equilibrium
batch basis. 0.06 g/L of the biomass was contacted with a solution bearing a metal
concentration of 0.25, 1 and 0.5 mmol/L for Cd (II), Ni (II) and Pb (II),
respectively at 25 oC and the optimum pH. The pseudo second-order kinetic
model fits the experimental data well (R2 : 0.99 for all metals).
Mustafa Tuzen et al [159] investigated the biosorption of copper (II), lead (II),
iron (III) and cobalt(II) on Bacillus sphaericus-loaded Diaion SP-850 resin for pre
concentration–separation of them have been investigated. Biosorption on B.
sphaericus for the atomic absorption spectrometric determination of copper (II),
lead (II), iron (III) and cobalt (II) ions at trace level is described. In order to study
the adsorptive capacity of B. sphaericus loaded Diaion SP-850, batch method was
used. To 0.1 g resin was added 50 mL of solution containing 1.0 mg of metal ion
at pH 6.0. After shaking, the mixture was filtered. To estimate the accuracy of the
procedure, different amounts of the investigated metal ions were spiked in natural
waters and urine sample. The detection limits by 3 sigma for analyte ions were in
the range of 0.20–0.75 µg/L for aqueous samples and 2.5–9.4 mg/g for solid
samples.
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Nabanita Chakraborty et al [160] studied the lead accumulation by free and
immobilized cyanobacteria, Lyngbya majuscula and Spirulina subsalsa. The
column packed with glass wool only retained 18–20 % Pb from 5 mg/L solution,
but 95.8 % Pb was adsorbed by the column packed with growing cyanobacteria
filaments and only 4.2 % Pb was found in Elute I. After the first wash with 0.1 M
EDTA, 92.5 % of accumulated Pb was recovered in Elute II. A second exposure
to 5 mg/L Pb solution showed 59–60 % removal of Pb (40 % remaining in Elute
III) indicating its ability to be used in repeated Pb removal process. In L.
majuscula accumulation of Pb was 3.5, 3.0 and 2.89 mg/g at pH 6, 7 and 8
respectively. The corresponding values were 1.07, 1.05 and 0.9 mg/g for S.
subsalsa. The absorption was concentration dependant. L. majuscule accumulated
15 times more Pb when exposed to 20 mg/L Pb solution for 3 h than that to 1
mg/L while a 2.5 to 3-fold increase in accumulation of Pb was observed in S.
subsalsa under the same experimental conditions. A 92.5 % recovery of
accumulated Pb from the immobilized biomass suggests that repeated absorption–
desorption is possible.
Biosorption of lead (II) and cadmium (II) from aqueous solutions by protonated
sargassum glaucescens biomass was studied by Naddafi et al. [161] in a
continuous packed bed column. The selective biosorption capacities of Pb2+ and
Cd2+ at complete exhaustion point were determined to be 1.18 and 0.22 mmol/g
respectively. Therefore, the biosorbent exhibited much higher relative affinity for
Pb2+ than for Cd2+. The efficiency of biosorbent regeneration by 0.1 M HCl was
achieved about 60 %, so that the maximum uptake capacity of Pb2+ by the
regenerated biomass was determined to be 0.75 mmol/g while the same value for
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the original biomass was 1.24 mmol/g. The effluent pH decreased to about 2.3 by
the most replacement of hydrogen ions in the binding sites with Pb2+ and then by
reduction of protonated binding sites as well as decrease of Pb2+ biosorption rate,
the effluent pH increased gradually until the effluent pH became equal to the
influent pH at complete exhaustion of the biosorption bed, so the rate of metal ion
biosorption was proportionate to release of hydrogen ions.
Several number of biosorption experiments have been done considering dead
biomass, weeds as biosorbents until now but, in this Nadeem et al. [162] stepped
away from conventional methods and took another form, a locally available fish
(Labeo rohita) scales for Pb (II) removal from aqueous solutions under different
experimental conditions. Sorption experiments beyond pH 5 were not conducted
since insoluble precipitates appeared beyond this pH. Stock Pb (II) solution (1000
mg/L) was prepared by dissolving 1.598 g of Pb(NO3)2 in 100 mL deionized water
shaking it for 15 min on a magnetic stirrer to obtain complete dissolution and then
diluting quantitatively to 1000 mL using deionized water. Sorption capacities
(mg/g) of fish scales pretreated using bases were in the following order: Ca(OH)2
(200.76) > nontreated (196.8) > Al(OH)3 (192.76) > NaOH (149.14). The two
factors are responsible for increase or decrease in sorption capacity of a particular
biomass after basic pretreatment. The highest removal capacities 196.80 mg/g of
Pb (II) ions by fish scales were obtained at pH 3.5 and the overall removal
capacity of Pb (II) decreased to 86.96 mg/g as pH increased up to 5.
Nurbas Nourbakhsh et al [163] investigated the biosorption of various metal
ions onto Bacillus sp. (OGUB 001). At 27 oC, pH values of 2.0, 4.5 and 4.5 were
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determined for Cr6+, Pb2+ and Cu2+ ions, respectively. At pH 4.0, 71.8 % of the
capacity was used by lead, while 16.3 and 11.9 % were used by copper and
chromium ions, respectively ; and, at pH 7.0, 75.42 % of the capacity was used by
lead while 0.9 and 23.68 % by copper and by chromium ions, respectively. The
multi-metal ions, containing different concentrations of Cr6+, Pb2+ and Cu2+ ions
together were prepared and partial competitive adsorptions of these mixtures were
investigated at 27 oC and for the pH values of 4.0 and 7.0 that are the most
frequently seen conditions in industrial waste waters.
Ofomaja et al [164] investigated the kinetic modeling is frequently performed on
both raw and modified biosorbents and changes in model parameters. Kinetic
experiments were carried out by agitating 100 cm3 of lead (II) solution of
concentration ranging from 60 to 120 mgd/m3 with 0.40 g of pine cone and base
modified pine cone powder in a 250 cm3 beaker at 291K at an optimum pH of 5.0
and at a constant agitation speed of 160 rpm for 15 min. Samples (3.0 cm3) were
pipette out at different time intervals, centrifuged and the concentration of lead
(II) analyzed using a Perkin-Elmer model 2100 atomic absorption spectrometer
(AAS). To a series of 100 cm3 conical flasks, 45 cm3 0.01 mol/dm3 of KNO3
solution of known concentration was transferred. The pH values of the solution
were roughly adjusted from pH 2 to 12 by adding ether 0.10 mol/dm3 HCl or
NaOH on a pH meter. It was observed that for two stages a total of 3.82, 2.30 and
1.57 kg of PCP Raw, PCP 0.01 and PCP 0.05 is required to remove 99 % of 120
mg/dm3 lead (II) from 2.5 m3 solution.
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Ofomaja et al [165] studied the biosorption of lead and copper onto Mansonia
wood sawdust. Biosorbents usually contains organic functional groups such as
alcohol, aldehydes, ketones, carboxylic, phenolic and ether groups on their
surface. These groups have been shown to participate in cation binding due to
their ability to ionize in aqueous solution. The temperature dependence of copper
and lead ion biosorption onto Mansonia wood sawdust was studied at a
concentration range of 60–140 mg/dm3 at 200 rpm with Mansonia sawdust dose of
2.0 g/dm3 at temperatures ranging from 299 to 329 K. Accurately weighed
amount (0.25 g) of Mansonia sawdust was added to five 250 ml beakers
containing 100 ml of 120 mg/dm3 of lead and copper ion solutions, each adjusted
to pH of 2.0, 3.0, 4.0, 5.0, and 6.0 using either 0.1 MHCl or NaOH solutions. The
solutions were stirred at 200 rpm for 4 h at 299 K. The optimization procedure
requires an error function to be defined in order to evaluate the fit of the equation
to the experimental data. In this study, linear coefficient of determination and
nonlinear chi-square were examined.
Ozgur Dogan Uluozlu et al [166] focused on the biosorption of Pb (II) and Cr
(III) ions onto P. tiliaceae biomass from aqueous solution. The effect of pH on the
biosorption of Pb (II) and Cr (III) ions onto P. tiliaceae biomass was studied by
changing pH values in range of 2–8. Negligible biosorption could be found when
the pH values were lower than 2.0 and also at pH < 5 the biosorption yield was in
range of 30–60 % for both Pb (II) and Cr (III) ions. The maximum biosorption
was found to be 100 % for Pb (II) and 95 % for Cr (III) ions at pH 5. Therefore,
all the biosorption experiments were carried out at pH 5.It can be seen that the
biosorption yield of Pb (II) and Cr (III) increases with rise in contact time up to 90
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min at 20–50 oC. After this time there was no considerable increase. For instance,
at 20 oC and during 90 min, when the biosorption efficiency for Pb (II) and Cr
(III) was 99 % and 96 %, respectively. Experimental data were also tested in
terms of biosorption kinetics using pseudo-first-order and pseudo-second-order
kinetic models. The results showed that the biosorption processes of both metal
ions followed well pseudo-second-order kinetics.
Pagnanelli et al [167] studied the experimental data of lead, copper, zinc and
cadmium biosorption onto Sphaerotilus natans at different equilibrium pH. The
amount of metal adsorbed per gram of biomass weight at the equilibrium, Ceq is
the residual (equilibrium) metal concentration left in solution after binding, qmax is
the maximum possible amount of metallic ion adsorbed per unit of weight of
adsorbent and b is the equilibrium constant related to the affinity of the binding
sites for the metals. In his research a Sphaerotilus natans biomass was used as a
potential adsorbent for heavy metal removal from aqueous solutions. This
bacterium was isolated from a biological depuration plant where it is usually
present as a characteristic component of activated sludge. An original empirical
model was proposed to represent the effect of pH on heavy metal biosorption
inserting qmax vs pH empirical functions into the classical Langmuir isotherm.
Pan Jian-hua et al [168] studied the surface chemical functional groups of
Bacillus cereus biomass were identified by Fourier transform infrared (FTIR)
analytical technique. The Langmuir isotherm can yield the best fit to absorption
experimental data for two metals on the biomass. A certain amount of 3 g/L
biomass stock suspension was added to a 100 ml flask, and 1 mol/L NaNO3 was
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used to stabilize the system at a fixed ionic strength. Bacteria cells were cultured
in 600 ml of nutrient broth for 72 h with growth condition: pH 7.2–7.5,
temperature 30 °C, and stirring speed of 160 r/min. The bacteria were then
harvested from the growth media by centrifugation at 7000 r/min for 30 min,
rinsed 4–6 times in DDI water. The mixture was then agitated on a shaker at 25°C
for 24 h, which was more than ample time for adsorption equilibrium, based on
the results of the previous kinetics experiments. After 24 h of equilibration, the
bacterial suspensions were separated by centrifugation and the supernatant was
analyzed for dissolved metal content via flame atomic absorption
spectrophotometer.
The biosorption of lead (II) by fruiting bodies of Pleurotus ostreatus immobilized
in calcium alginate was studied by Pan Xiangliang et al [4]. The kinetic
biosorption experiment was carried out as follows: 10 g of beads (wd) were added
to flasks containing 100 ml of lead-bearing solution with pH adjusted to a value of
6.5 with 0.01 M HCl and 0.01 M NaOH. Flasks were shaken at 150 rpm at 25 0C.
Aliquot amounts (2 ml) of solution were collected, periodically. Samples were
filtered and lead concentrations in filtrate were determined by AAS. The
biosorption tests were replicated twice and the standard error values ranged from
1.5 to 4 %. The maximum adsorption capacity (qmax) onto P. ostreatus
immobilized in calcium alginate based on Langmuir isotherm model was up to
121.21 mg/g for Pb (II).
Puranik et al [169] evaluated the infuence of co-cations (cadmium, copper,
cobalt and nickel) on lead and zinc biosorption by Streptoverticillium
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cinnamoneum and Penicillium chrysogenum in binary and multimetal systems.
On the basis of the covalent index we may prepare a `covalent series' of the
cations used in the present investigation as: Pb2+ > Cu2+ > Ni2+ > Co2+ > Cd2+ >
Zn2+. The results of metal biosorption by S. cinnamoneum and P. chrysogenum
from the solutions containing mixture of cations at pH 4.0. The results of the
present studies also indicated that there was preferential uptake of lead in addition
to the direct competition effect for the binary metal systems used; Pb2+- Cd2+, Pb2+
- Zn2+, Pb2+ - Cu2+, Pb2+ - Ni2+ and Pb2+ - Co2+. The metal cations used in the
studies can be classified into three classes on the basis of the extent of metal
biosorption from multi metal solutions as; high affinity (Pb2+), intermediate affnity
(Cd2+, Cu2+ and Zn2+), and low affinity (Ni2+ and Co2+). The order of metal
biosorption in multimetal systems could be predicted well for P. chrysogenum on
the basis of Langmuir parameters evaluated in binary metal systems.
Puranik et al [170] studied the linear transformation of the adsorption data using
Freundlich and Langmuirian models that allowed the computation of the metal
adsorption capacities (r2= 0.97 for both the models). The results indicate that
0.1M sodium carbonate, 0.1 M sodium bicarbonate and 0.1 M potassium chloride
were poor desorbing agents for both lead and zinc. Among the eluents tried for
lead desorption, 0.1 M hydrochloric acid, 0.1 M nitric acid and 0.1 M EDTA were
found to be most efficient with 90 % desorption efficiency in the first desorption
cycle. In the case of zinc, in addition to these three eluents, 0.05 M sulphuric acid
could also desorb 90 % of the metal. The results obtained indicated that the
optimum pH range for the biosorption of lead and zinc by S. cinnamoneum
biomass was between 3.5–4.5 and 5.0–6.0, respectively. It has been reported
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previously that the biosorption requires a few min to reach > 90 % of the total
metal uptake.
Rajesh Singh et al [171] studied that biosorption has been found to be
spontaneous and relatively fast process. The pure colony was preserved on the
slants at 4◦C and identified from Microbial Type Culture Collection on the basis of
spore’s morphology. The fungal biomass was prepared in the nutrient broth by
inoculating the spore suspension in the 250 ml flasks containing 100 ml of
nutrient broth on the rotary shaker cum incubator at 35 oC and 125 rpm. The
results are obtained with the experimental design that was aimed at identifying the
best levels of the selected variables, i.e.temperature (20–40 oC), adsorbent loading
(0.5–2.5 g/L), pH (2–6) and initial metal ions concentration (20–100 ppm). The
effects of temperature, adsorbent loading, pH and initial metal ions on the
biosorption were studied.
Raziya Nadeem et al [172] evaluated the biosorption of Pb (II) using dried
untreated and pretreated distillery sludge biomass. The sorption of Pb (II) ions
rapidly occurred within first 30 min followed by slow diffusion controlled step till
the equilibrium was reached. Maximum biosorption capacity of untreated and
pretreated distillery sludge was observed at pH 5. The maximum Pb (II)
adsorption was achieved with a biomass concentration of 0.5 g/L and sorption
capacity declined smoothly with increase in biomass level. The parameters such
as contact time (24 h), volume of solution (100 mL), particle size (0.250 mm) and
biomass loading (0.5 g/L) were kept constant. A significant increase in Pb (II)
uptake per weight of biomass was obtained as the pH increased from 2 to 5. The
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spent wash is acidic in character having very high BOD (40,000–50,000 mg/L)
and COD (10,000–125,000 mg/L). The most of solid waste generated by sugar
mills are used for land fills.
Raziya Nadeem et al [173] used the locally available fish (Labeo rohita) scales
for Pb (II) removal from aqueous solutions under different experimental
conditions. Sorption experiments beyond pH 5 were not conducted since
insoluble precipitates appeared beyond this pH. The highest removal capacities
196.80 mg/g of Pb (II) ions by fish scales were obtained at pH 3.5 and the overall
removal capacity of Pb (II) decreased to 86.96 mg/g as pH increased up to 5.
Stock Pb (II) solution (1000 mg/L) was prepared by dissolving, 1.598 g of
Pb(NO3)2 in 100mL deionized water shaking it for 15 min on a magnetic stirrer to
obtain complete dissolution and then diluting quantitatively to 1000mL using
deionized water. For chemical pretreatment, 10 g of powdered sample was soaked
in 150 mL of 0.1 M HCl, H2SO4, H3PO4, NaOH, Ca(OH)2 and Al(OH)3 for 2 h at
30 oC and 100 rpm at an orbital shaker while for physical pretreatment 10 g
powdered sample was heated at 100 oC for 24 h, boiled and autoclaved at 121 oC
and 15 Psi for 30 min in 150 mL of deionized water.
Renmin Gong et al [174] studied the biosorption of lead by using intact biomass
and pretreated biomass of S. maxima. The external pH significantly influenced
lead biosorption and maximum adsorption was observed approximately at pH 5.5.
The biosorption rate of lead was rapid and equilibrium was reached at 60 min.
The removal percentage of lead was increased along with increase in sorbent dose.
At a pH below 2, the amount of lead biosorption was less. As pH increases, the
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amount of biosorption observably increased at the range of pH 2–5.5 and the
maximum adsorption of lead ions was observed at pH 5.5. Experiments were not
conducted beyond pH 5.5 to avoid heavy metal precipitation. Among all four
eluent solutions studied, more then 90 % of lead adsorbed were desorbed from
biosorbents with nitric acid and EDTA. The lead adsorbed could be desorbed
effectively by 0.1 M nitric acid, EDTA and hydrochloric acid.
P. chrysosporium has been successfully used as the sorbing agent for removal of
metals ions from artificial wastewaters by Rõdvan Say et al [175]. The
maximum biosorption of heavy metal species on the biomass was observed at
around pH 6.0. The amounts of adsorbed heavy metal ions (Cd (II), Pb (II) and
Cu (II)) on the dry fungal biomass at pH 6.0 were found to be 13.24, 45.25 and
10.72 mg/g dry biomass, respectively. There was an increase in metal ions
adsorption per unit weight of fungal biomass with increasing pH from 2.0 to 6.0,
but it seemed to level at pH greater than 6.0. Each heavy metal ion (100 mg/L
was prepared in 150 mM NaCl solution (50 ml) and dry fungal biomass (0.2 g)
was transferred to this medium and agitated magnetically at 100 rpm. Once
inoculated, asks were incubated on an orbital shaker at 150 rpm for 7 days at
30°C. After incubation, the biomass was harvested from the medium and washed
with distilled water; it was then dried at 90 °C in an oven for 24 h.
Rong Pan et al [176] investigated the effects of single and multiple heavy metals
on the growth and uptake of consortium of two types of fungal strains, Penicillium
sp. A1 and Fusarium sp. A19. The biomasses of A1 + A19 cultivated in PDB
absorbed more metals than A1 or A19 under the different treatments of heavy
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metals. Nevertheless, the metal concentrations absorbed by the biomass of A1 +
A19 cultivated in CDM were not significantly higher than those by A1 or A19.
However, in PDB, the fungal biomasses of A1, A19, and A1 + A19 reached the
highest values in the presence of Cu2+ compared with other treatments. The fungal
biomass cultivated in PDB in the presence of single Pb2+ was lower than those
cultivated in the media containing multimetals. Then 1 g (fresh weight) of the
washed biomass was added into each of 25 ml heavy metal solution containing
100 mg/L of Cd2+, Cu2+, Zn2+, and Pb2+, respectively, in a conical flask. The
flasks were shaken on a rotatory shaker (160 rpm) for 45 min at 25 oC. The
biomass was separated by the filteration, dried at 80 oC, and weighted. The
filtrate was digested in 67 % HNO3. The HNO3 solution was evaporated and the
solids were redissolved in 0.1 M HCl.
Ruhan Altun Anayurt et al [177] studied the use of L. scrobiculatus as a
biosorbent for removing of Pb (II) and Cd (II) ions from aqueous solution. The
biosorption efficiency was increased from 60 % to 96 % for Pb (II) and from 52 %
to 95 % for Cd (II) ion as pH was increased from 2 to 5. The maximum
biosorption was found to be 98 % for Pb (II) and 96 % for Cd (II) ions at pH 5.5.
Therefore, the remaining all biosorption experiments were carried out at this pH
value. The biosorption yield steeply increases with concentration as the biomass
concentration was increased from 0.1 to 4 g/L. The biosorption yield of Pb (II)
and Cd (II) increased considerably until the contact time reached 60 min. The
biosorption decreased from 98 % to 90 % for Pb (II) and from 95 % to 88 % for
Cd (II) as temperature was increased from 20 to 50 oC during the equilibrium
time, 60 min.
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Runping Han et al [178] worked on the biosorption of copper and lead ions on
waste beer yeast. Batch biosorption tests were done at different contact time at the
initial concentration of 0.315 mmol/L for Cu (II) and 0.393 mmol/L for Pb (II),
respectively, and waste beer yeast dose concentration is 8 g/L in 10 mL solution.
The temperature was controlled with a water bath at the temperature of 293 K.
Experiments could not be performed at higher pH values due to hydrolysis and
precipitation of the lead ions. Flasks were agitated on a shaker for 60 min to
ensure that equilibrium was reached. There was an increase in biosorption
capacity of biomass with increasing pH from 2.0 to 6.0 for both metal ions. The
lowest metal uptake values were determined at pH < 2.0 for both metal ions. The
adsorption quantity of Pb (II) decreased with the increasing of Cu (II)
concentration. The biosorption quantity of Pb (II) decreased from 0.0218 to
0.0140 mmol/L when the concentration of Cu (II) ranged from 0 to 0.472 mmol/L.
Runping Han et al [179] studied the adsorption potential of MOCS for the
removal of Cu (II) and Pb (II) from single (noncompetitive) and binary
(competitive) aqueous systems. A volume of 20 ml of Cu (II) and Pb (II) solution
with initial concentrations ranged from 0.077 to 1.27 mmol/L and 0.097 to 1.54
mmol/L were placed in 125 ml conical flasks, respectively. The initial pH was
4.0. An accurately weighed MOCS sample (20 g/L) with particle size range from
0.99 to 0.67 mm was then added to the solution. In another binary system, the
initial concentration of Pb (II) was constant in 0.386 mmol/L, and the
concentration of Cu (II) were varied from 0 to 1.57 mmol/L. The adsorption
capacities qe obtained from the experiment results for the binary component
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system at described conditions were ranging from 0.162 to 2.94 mol/g and 2.82 to
7.14 mol/g for Cu (II) and Pb (II), respectively
Safa Özcan et al [180] investigated the biosorption of lead (II) ions onto
Phaseolus vulgaris L. waste with the variation in the parameters like pH, contact
time, biosorbent and lead (II) concentrations and temperatures. The nature of the
possible biosorbent and metal ion interactions was examined by the FTIR
technique. The lead (II) biosorption equilibrium was attained within 20 min. This
study has shown that an agricultural byproduct, P. vulgaris L., can be used to
remove lead (II) ions from aqueous solution as a function of pH, contact time and
temperature. The maximum biosorption capacity of biosorbent for the removal of
lead (II) was obtained at pH 5. Biosorption of lead (II) ions onto P. vulgaris L.
waste followed by the Langmuir and Dubinin–Radushkevich isotherm models.
Sarabjeet Singh Ahluwalia et al [181] has desired to develop biosorbents
(microbial and plant derived biomass) with a wide range of metal affinities that
can remove a variety of metal cations. These will be particularly useful for
industrial effluents, which carry more than one type of metals. Copper
biosorption by non-living wood rotting fungus Ganoderma lucidum was studied
and it was found that protein interaction with metals did not play a significant role
in copper (II) uptake. At pH 4–5, the saturated uptake capacity for lead sorption
was higher than that of activated charcoal and that reported for some other
organisms. Dead cells of Saccharomyces cerevisiae removed 40 % more uranium
or zinc than live cultures and biosorption rapidly reached 60 % of the final uptake
value within 15 min of contact.Dried Caulerpa lentillifera was shown to have
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adsorption potential for Cu, Cd, Pb and Zn. The adsorption of metals from binary
mixture of heavy metal was competitive and the adsorption capacity of any single
metal decreased by 10– 40 % in the presence of the other metallic species and the
overall adsorption capacity of the algae decreased by 30–50 %. Further,
adsorption capacities for these metals were found to in the order of Cr (VI) > Cd
(II) > Co (II) > Cr (III) > Ni (II) > Cu (II) > Pb (II), respectively.
Selatnia et al [182] examined that this method of eliminating Pb2+ ions is very
promising and confirm the technical and economic interest compared to the
conventional processes such as the ion exchange on resins. The quantity of
adsorbed Pb2+ per unit mass of biosorbent increased when the initial Pb2+ ions
concentration increased. In our study, initial Pb2+ concentration varies from 10 to
800 mg/L. After pretreatment of biomass at the ambient temperature, optimum
conditions of biosorption were found to be: a biomass particle size between 50
and 160 µm, an average contact time of 3 h, a biomass concentration of 3 g/L and
a stirring speed of 250 rpm. The equilibrium data could be fitted by Langmuir
isotherm equation. Under these optimal conditions, 135 mg Pb2+/g biomass was
obtained.
Senthilkumar et al [183] utilized T. conoides as a suitable biosorbent to be
utilized for lead removal in batch and column mode of operations. In column
experiments, 35.1 g of T. conoides was packed in the column to yield 25 cm bed
height with a packing density of 447.1 g/L. Sorption isotherms, obtained at
different pH (4–5) and temperature (25–35 oC) conditions were fitted using
Langmuir and Sips models. According to the Langmuir model, the maximum lead
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uptake of 439.4 mg/g was obtained at optimum pH (4.5) and temperature (30 oC).
The influence of co-ions (Na+, K+, Mg2+ and Ca2+) on lead uptake was well
pronounced in the case of divalent ions compared to monovalent ions. The
solution of 0.1 M HCl performed well in eluting lead from the biomass, with
elution efficiency of 99.7 %.
Shihabudheen M. Maliyekkal et al [184] reported that physisorption plays a
dominant role in Pb (II) adsorption by both NMO and C–NMOC in his work with
the use of a novel cellulose-nano scale manganese oxide composite (C–NMOC)
for removing Pb (II) ions from contaminated water. The performance of C–
NMOC was compared with unsupported nanoscale-manganese oxide (NMO)
prepared through a similar route. The studies report: (i) the synthesis and detailed
characterization of NMO and C–NMOC, (ii) application of these materials for Pb
(II) ions removal from aqueous medium, and (iii) spectroscopic and microscopic
studies to probe the mechanism of Pb (II) removal by NMO and C–NMOC. Pb
(II) adsorption by C–NMOC is less sensitive to pH variations compared to NMO.
Optimum removal of Pb (II) by NMO was achieved at pH 5 whereas C–NMOC
removed more than 90 % of the Pb (II) even at an initial pH of 2.5. It is apparent
that adsorption of Pb (II) onto NMO and C–NMOC is a fast process and most of
the adsorption happened in a short period (< 10 min) and the system achieved
pseudo equilibrium at 60 min of contact time from the commencement of the
adsorption process.
Sibel Tunali et al [185] examined the biosorption of lead (II) onto
Cephalosporium aphidicola at constant temperatures of 20, 30 and 40 oC for the
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pseudo-first-order and pseudo-second-order kinetic models and for the biosorption
isotherms at 20 oC. With an increase in biosorbent concentration, from 0.4 to 2.0
g/dm3 the percentage of lead (II) removal increased from 14.58 to 62.48 %, as the
number of binding sites would be increased, but the amount of lead (II) biosorbed
decreased from 35.80 to 31.24 mg/g. It was observed that there was almost no
change in adsorption capacity with increasing pH of the metal solution during the
biosorption process up to pH’s 4–6 and the maximum lead (II) removal was
observed at pH 5.
Sibel Tunali Akar et al [186] reported the results of lead (II) binding by the
natural and low cost biosorbent Symphoricarpus albus. A stock solution of lead
(II) was prepared by dissolving appropriate amount of anhydrous Pb(NO3)2 in 1 L
of deionized water, and the concentrations of lead (II) used in this study (50–500
mg/L) were obtained by dilution of the stock solution. The pH of the solutions
was adjusted to the desired value by adding a small quantity of 0.1 mol/L HCl, or
0.1 mol/L NaOH. The batch equilibrium studies were carried out with different
initial pH values ranging from 1.0 to 5.5 in order to study the effect of initial pH
on the biosorption capacity of S. albus biomass. The batch equilibrium studies
were carried out with different initial pH values ranging from 1.0 to 5.5 in order to
study the effect of initial pH on the biosorption capacity of S. albus biomas. The
biosorption yield for lead (II) onto S. albus biomass increased from 15.34 to
88.55% when the biomass dosage was increased from 0.6 to 4.0 g/L. In order to
determine the biosorption equilibrium time for lead (II) ions, the contact time was
varied from 10 to 70min at different temperatures
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Sıtkı Baytak et al [187] employed the analysis of environmental water and
vegetable samples, P. digitatum immobilized on pumice stone as solid phase
extraction material. The sample solutions were adjusted to the desired pH with
diluted hydrochloric acid and/or a diluted ammonia solution. The resulting
solution was passed through the preconditioned column at a flow rate about
1mL/min and the retained metal ions were eluted with 10 mL of 1 mol/L HCl
solution. The quantitative recovery (> 95 %) was obtained at pH 6 for Cu (II) and
6–8 for Zn (II) and Pb (II).The time required for preconcentration of 500 mL of
sample solution (125 min, at flow rate of 4 mL/min), elution (10 min,at flow rate
of 1mL/min) and conditioning the column (about 5 min) was approximately 2 h.
The mean recovery of the analytes with their standard deviation (N = 5) were
found as to be 97 ± 2, 98 ± 2 and 98 ± 2% at 95 % confidence level for Cu (II), Zn
(II) and Pb (II), respectively.
Sudhir Dahiya et al [188] explored the sorption potential of pretreated crab and
arca shell biomass for lead and copper from aqueous media. The removal was
40% within 60 min and thereafter removal was slightly slow and attained
equilibrium after 4 h. Sorption behaviour of biosorbent at different dosages from
0.2 g/L to 25 g/L have been studied in 100 g/mL of solution under optimised
condition of pH and contact time. The residual concentration of lead was
decreased from 92.4 g/mL at pH 1 to less than one microgram per liter at pH 5.5
with a 99.1 % removal. For the Sorption of lead and copper on arca shell biomass
the percentage removal of copper increased from 7.7 % at pH 1 to 88.2 % at pH
4.5. The treated crab and arca shell biomasses are waste material from the fishing
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industry can be converted in a biosorbent, which exhibit good sorption for both
the metals lead and copper.
Ting Fan et al [189] reported a very high potential for P. simplicissimum to
remove Cd (II), Zn (II) and Pb (II) from aqueous solution in his study. Maximum
biosorption capacities were obtained at pH 4.0, 6.0 and 5.0 for Cd (II), Zn (II) and
Pb (II), respectively. At low pH (< 1.0) the biosorption capacity for all metal ions
is very low, because large quantity of hydrogen ions competes with metal ions at
sorption sites. The influences of biomass dose and initial metal ion concentration
on biosorption were studied at temperature of 28 oC and pH 5.0. Equilibrium was
reached in 3 h for Cd (II), 4 h for Zn (II) and Pb (II), respectively. After the
equilibrium time, no more Cd (II), Zn (II) and Pb (II) were adsorbed. The
maximum Cd (II), Zn (II) and Pb (II) uptake capacity were determined as 52.50,
65.60 and 76.90 mg/g, respectively.
Tolga Bahadir et al [190] studied the effects of the media conditions (pH,
temperature, biomass concentration) on the biosorption of Pb (II) ions to R.
arrhizus in a batch reactor. In order to determine the effect of biomass
concentration on Pb (II) removal, stock solutions of 10.0 g/L were prepared for
different microorganism particle size ranges, such as 0.045–0.063, 0.063–0.090
and 0.090–0.125 mm. These stock solutions were diluted to 0.1–1.0 g/L standard
solutions in order to find the effect of microorganism concentration on
biosorption. To determine the effect of pH of the biosorption medium on the
initial biosorption rates of Pb (II) ions, the pH was varied between 2.0 and 5.0.
The optimum initial pH of the biosorption medium was found to be 4.5. Results
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of removal of Pb (II) ions from storage battery industry wastewater experiments
carried out at different temperatures ranging from 20 to 45 oC.
Urdaneta et al. [191] obtained the optimal parameters for the heavy metal
adsorption after a preliminary physical and chemical characterization of the
vermicompost. A synthetic multielemental solution of Pb, Cr and Ni and a
solution of NH4VO3 for vanadium were evaluated. The effect of pH on the
adsorption efficiency was evaluated in a range of 3.5 to 7.0 using aqueous solution
of NaOH or HNO3 of 0.10 mol/L. The effects of the agitation time were
evaluated using 5, 10, 15, 30, 45 and 60 min. The solution volume was fixed to
75 mL, the pH to 5.00, the vermicompost mass was 1.0 g and the particle size
ranging between 75 and 841 μm. Removing levels for Pb, Cr and Ni are in the
order of 95 % showing that vermicompost is adequate for this removing process.
Metal adsorption for Ni, Pb and Cr in real wastewater from Barquisimeto city was
100, 65 and 40 % respectively.
Vimala et al [192] studied the sorption capacity of oyster mushroom (Pleurotus
platypus), button mushroom (Agaricus bisporus) and milky mushroom (Calocybe
indica). When the pH values increased, biosorbent surfaces were more negatively
charged and the biosorption of metal ions (positive charge) increased and reached
equilibrium at pH 6.0 for cadmium and pH 5.0 for lead. Decrease in biosorption
at higher pH (pH > 6.0 and > 5.0) is due to the formation of soluble hydroxylated
complexes of the metal ions the removal efficiency reached equilibrium at 60 min
and that by A. bisporus and C. indica reached equilibrium at 240 min. The
respective removal efficiencies of lead by P. platypus, A. bisporus and C. indica
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reached at 120, 240 and 180 min. Langmuir isotherm model exhibited better fit to
the sorption data of both cadmium (II) and lead (II) for all the three mushrooms
than the Freundlich isotherm model. Higher values of qmax (34.96 mg/g) and Kf
(4.9980) in case of P. platypus for cadmium sorption and qmax (33.78 mg/g) and Kf
(4.9522) for lead sorption of A. bisporus indicate their greater suitability for
removal for cadmium (II) and lead (II) ions, respectively from wastewater.
Vinod K. Gupta et al [193] reported the ability of two non-living (dried) fresh
water algae, Oedogonium sp. and Nostoc sp. to remove lead (II) from aqueous
solutions in batch system. It has been observed that maximum adsorption took
place within first 90 and 70 min for Oedogonium sp. and Nostoc sp., respectively.
The extent of lead removal was found to be 11.1 and 16.4 % for 0.1 g/L of algal
biomass Oedogonium sp. and Nostoc sp., respectively. It greatly increased to 63.5
and 70 % for 0.5 g/L of biosorbent, respectively. As the pH of the lead solution
(200 mg/L) increased from 2.99 to 7.04, the adsorption capacity of lead increased
upto pH 5.0 and then dramatically decreased at pH 7.04 for both the algae. For an
increase in temperature from 25 to 45 oC, an increase in the adsorption of lead was
observed (111.4 mg/g at 25 oC to 124.8 mg/g at 45 oC at 200 mg/L, initial lead
concentration
Wei-Bin Lu et al [194] studied the biosorption kinetics and equilibria of lead
(Pb), copper (Cu) and cadmium (Cd) ions using the biomass of Enterobacter sp.
J1 isolated from a local industry wastewater treatment plant. The biosorbent was
suspended in 50 ml of heavy metal solutions (100 mg/L) in a glass container to
reach a cell concentration of 1.5–2.5 g/L. Metal loaded and metal free (control)
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biosorbents were treated with glutaraldehyde for 1 h and were dehydrated by
acetone (50–100 %) for 30 min. Both models had a good agreement with the data
for Cu and Cd biosorption, evidenced by the high r2 values (all greater than
0.978). However, prediction of Pb adsorption by Langmuir isotherm was less
precisely with a lower r2 value of 0.883, in contrast to better fits of the Pb
adsorption data by Freundlich model (r2 = 0.970).Desoprtion of Cd was nearly
complete for pH 3, while desorption efficiency of Cu and Pb reached 90 % when
pH was decreased to below 2.0.
The biosorption of lead (II) by fruiting bodies of pleurotus ostreatus immobilized
in calcium alginate was studied by Xiangliang et al. [4]. The kinetic biosorption
experiment was carried out as follows: 10 g of beads (wd) were added to flasks
containing 100 mL of lead-bearing solution with pH adjusted to a value of 6.5
with 0.01 M HCl and 0.01 M NaOH. Flasks were shaken at 150 rpm at 25 C.
Aliquot amounts (2 mL) of solution were collected, periodically. Samples were
filtered and lead concentrations in filtrate were determined by AAS. The
biosorption tests were replicated twice and the standard error values ranged from
1.5 to 4 %. The maximum adsorption capacity (qmax) onto P. ostreatus
immobilized in calcium alginate based on Langmuir isotherm model was up to
121.21 mg/g for Pb (II).
Xiao-ming Li et al [152] reported that PSILS is an efficient biosorbent for
removal of heavy metal ions from aqueous solution. The effect of pH on the
biosorption capacity was investigated at initial pH values range of 2.0–6.0 and the
desired pH of the suspensions was maintained by adding HCl or NaOH at the
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beginning of the experiment and not controlled afterwards. The results showed
that the biosorption of Pb (II) and Cu (II) on PSILS increased significantly as the
pH increased from 2.0 to 5.0, however, the increase was slightly on NLS, and then
decreased at pH 5.0–6.0. The low Pb (II) and Cu (II) biosorption capacity at pH
values below 3.0 may be attributed to hydrogen ions that compete with metal ions
on the sorption sites. The contact time of approximately 60minwas required to
reach the equilibrium. The effect of initial single metal ion concentration was
investigated in the range of 10–500 mg/L. sites. According to Langmuir isotherm,
the monolayer saturation capacity of PSILS is 144.9 mg/g for Pb (II) and 106.4
mg/g Cu (II).
Yasemin Bakircioglu et al [195] studied the filamentous fungal biomass loaded
TiO2 nano particles were used for the biosorption of lead (II) ions. Maximum
retention was maintained within the pH of 4.0–10.0 which is quite a wide range.
Therefore, a precise pH adjustment above 4 was not necessary. Nevertheless, the
pH of the solutions was adjusted to 4.0–4.5 throughout this study. In this study,
various concentrations of HCl and HNO3 (0.5–2.0 mol/L) were used for
desorption of the lead ions from the biosorbent following the on-line
preconcentration procedure. The highest signal was obtained with 1.0 mol/L HCl
whereas relatively lower signals and incomplete elution of the lead from the
biosorbent column was observed with HNO3 solutions. Results showed that the
absorbance was higher at flow rate of 4.3 mL/min by using distilled-deionized
water as a carrier.
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Yongwen Liu et al [196] studied the biosorption behavior of the solid waste
Chinese herb Pang Da Hai (seeds of Sterculia lychnophera Hance) as a sorbent for
trace lead and cadmium. The optimum pH ranges for metal adsorption were 5.0–
8.0 for Pb and 6.0–8.0 for Cd. So pH 6.5 was selected for the recommended
procedure. It was observed that temperature changes between 15 and 45 ◦C have
slightly influence on the rate of biosorption, but did not affect the biosorption
capacity. The reproducibility of the proposed procedure was also measured using
model solution. The relative standard deviations (n = 10) were 7.2 % for Pb and
4.6 % for Cd.
Yurtsever and Ahyan [197] investigated the effect of temperature, pH and initial
metal concentration on Pb (II) biosorption on modified quebracho tannin resin
(QTR). The specific BET surface area of QTR was found to be 0.820 m2/g. The
adsorption of Pb (II) increases with time from 0 to 10 min and then becomes
almost constant up to the end of experiment. The analysis is carried out through
an adsorption of N2 gas (gas effluent temperature = 75 C versus bath temperature
= 77.35 C). The kinetic data was tested using pseudo-first-order, pseudo-second-
order, Elovich and intraparticle diffusion model. It was found that the kinetics Pb
(II) ions adsorption onto QTR followed by the pseudo-second-order rate equation.
Langmuir, Freundlich and Temkin adsorption models were used to represent the
equilibrium data. Langmuir model best describes the lead adsorption process (R2
> 0.999). Using the Langmuir model equation, the monolayer adsorption capacity
of QTR was found to be 86.207 mg/g for Pb (II) ions.
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Yus Azila et al [198] investigated about response surface methodology (RSM) for
obtaining optimum process condition for Pb (II) removal using immobilized cells
of P. sanguineus as a biosorbent. It was observed that more than 90 % removal
was achieved with the initial Pb (II) ions concentration increased from 50 to 350
mg/L at pH 4. The interaction shows that for a higher biomass loading more than
9 g/L, the percentage of Pb (II) ions removal was more than 97 % with initial Pb
(II) ions concentration in the range of 50–350 mg/L. At solution pH lower than 3,
less than 80 % removal was achieved due to competition between hydrogen and
metal ions on the binding sites of biosorbent. As the solution pH increased more
than pH 4.0, which resulted in precipitation of Pb (II) ions thus, lower the
biosorption efficiency.
Zhexian Xuan et al [199] studied about preparation of a new biosorbent using
chemically modified orange peel and its biosorption of lead ion. As the pH
increases, the amount of lead uptake increases and the sharpest increase is
observed between pH 4.5 and 6.0 for all the biosorbents. When the final lead
concentrations are increased from 0.5 to 10.0 mmol/L, the uptake of lead
increased. But it has no change when the final concentrations are more than 10.0
mmol/L. The maximum removal rate is more than 90 % when the s/l ratio is 3.0–
5.0 g/L. Thus the optimum s/l ratio is 3.0 g/L in terms of the cost effect.
3.3 RESPONSE SURFACE METHODOLOGY (RSM):
Aleboyeh et al [200] studied the decolorization of C.I. Acid Red 14 (AR14) azo
dye by electro coagulation (EC) process in a batch reactor. Response surface
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methodology (RSM) was applied to evaluate the simple and combined effects of
the three main independent parameters, current density, and time of electrolysis
and initial pH of the dye solution on the color removal efficiency and optimising
the operating conditions of the treatment process. A 23 full factorial central
composite face centred (CCF) experimental design was employed. Analysis of
variance (ANOVA) showed a high coefficient of determination (R2 =0.928) and
satisfactory second-order regression model was predicted. Maximum color
removal efficiency was predicted and experimentally validated. The optimum
current density, time of electrolysis and initial pH of the dye solution were found
to be 102 Am-2, 4.47 min and 7.27, respectively. Under optimal value of process
parameters, removal of > 91 % was obtained for Acid Red 14. This study clearly
showed that response surface methodology was one of the suitable methods to
optimize the operating conditions and maximize the dye removal. Graphical
response surface and contour plots were used to locate the optimum point.
Antonio et al [201] employed a factorial design to evaluate the quantitative
removal of an anionic red dye from aqueous solutions to epichlorohydrin-cross-
linked chitosan. The experimental factors and their respective levels studied were
the initial dye concentration in solution (25 to 600 mg/L), the absence or the
presence of the anionic surfactant sodium dodecylbenzenesulfonate (DBS) and the
adsorption temperature (25 or 55 oC). The adsorption parameters were analyzed
statistically using modeling polynomial equations. The results indicated that
increasing the dye concentration from 25 to 600 mg/L increased the dye
adsorption whereas the presence of DBS increased it. The principal effect of
temperature did not show a high statistical significance. The factorial results also
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demonstrated the existence of statistically significant binary interactions of the
experimental factors. The adsorption thermodynamic parameters, namely AadsH,
AadsG and AadsS, were determined for all the factorial design results.
Exothermic and endothermic values were found in relation to the AadsH. The
positive AadsS values indicated that entropy was a driving force for adsorption.
The AadsG values were significantly affected by an important synergistic effect of
the factors and not by the temperature changes alone.
Antonio et al [202] employed a 23 factorial design to evaluate the quantitative
removal of the indigo carmine (IC) dye from aqueous solutions on glutaraldehyde
cross-linked chitosan. The variables were chitosan masses of 100 and 300 mg, IC
concentrations of 2.0 and 5.0 x 10-5 mol/L and temperatures of 25 and 350 ºC.
The quantitative and energetic adsorption parameters were analyzed statistically
using modeling with bilinear equations. The results indicated that increasing the
chitosan mass from 100 to 300 mg decreased the IC adsorption/mass ratio (mol/g)
whereas a temperature increase of 25-35 ºC increased it. The principal effect of
the IC concentration did not show statistical significance. The factorial
experiments demonstrated the existence of a significant antagonistic interaction
effect between the chitosan mass and temperature. The adsorption
thermodynamic parameters, namely AadsH, AadsG, and AadsS, were determined
for all the factorial design results. Endothermic values were found in relation to
the AadsH. The positive AadsS values indicated that entropy was a driving force
for adsorption. The AadsG values were also significantly affected by important
antagonistic and synergistic effects involving all principal and interactive factors.
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The thermodynamically spontaneity of the IC adsorption parameters were greatly
influenced by the interactive factors and not by the temperature changes alone.
Ayla Ozer et al [203] investigated the biosorption of copper (II) ions on
Enteromorpha prolifera, green seaweed, in a batch system. The effects of
operating parameters such as initial pH, temperature, initial metal ion
concentration and biosorbent concentration on the copper (II) biosorption were
analysed using response surface methodology (RSM). The proposed quadratic
model for central composite design (CCD) fitted very well to the experimental
data that it could be used to navigate the design space according to ANOVA
results. The optimum biosorption conditions were determined as initial pH 4.0,
temperature 25 oC, biosorbent concentration 1.2 g/L and initial copper (II) ion
concentration 200 mg/L. The Langmuir and Freundlich isotherm models were
applied to the equilibrium data at different temperatures and initial pH values.
The maximum monolayer coverage capacity of E. prolifera for copper (II) ions
was found to be 57.14 mg/g at 25 ºC and initial pH 4.0 indicating that the
optimum biosorption temperature and initial pH. The external and intraparticle
diffusion models were also applied to biosorption data of copper (II) ions with E.
prolifera and it was found that both the external diffusion as well as intraparticle
diffusion contributes to the actual biosorption process. The pseudo-second order
kinetic model described the copper (II) biosorption process with a good fitting.
The thermodynamics of copper (II) biosorption on E. prolifera indicated its
spontaneous and exothermic nature.
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Ayla Ozer et al [204] investigated the biosorption of nickel (II) ions on
Enteromorpha prolifera, a green algae, in a batch system. The single and
combined effects of operating parameters such as initial pH, temperature, initial
metal ion concentration and biosorbent concentration on the biosorption of nickel
(II) ions on E. prolifera were analyzed using response surface methodology
(RSM). The optimum biosorption conditions were determined as initial pH 4.3,
temperature 27 ºC, biosorbent concentration 1.2 g/L and initial nickel (II) ion
concentration 100 mg/L. At optimum biosorption conditions, the biosorption
capacity of E. prolifera for nickel (II) ions was found to be 36.8 mg/g after 120
min biosorption. The Langmuir and Freundlich isotherm models were applied to
the equilibrium data and defined very well both isotherm models. The monolayer
coverage capacity of E. prolifera for nickel (II) ions was found as 65.7 mg/g. In
order to examine the rate limiting step of nickel (II) biosorption, such as the mass
transfer and chemical reaction kinetics, the intraparticle diffusion model, external
diffusion model and the pseudo second order kinetic model were tested with the
experimental data. It was found that for both contributes to the actual biosorption
process. The pseudo second order kinetic model described the nickel (II)
biosorption process with a good fitting.
Azharul Islam et al [205] dealt with the multiple response optimization for the
removal of organ phosphorus pesticide quinalphos [QP: O, O-diethyl O-2-
quinoxalinyl phosphorothioate] from the aqueous solution onto low-cost material
and tried to overcome the drawbacks of univariate optimization. Used tea leaves
were used as low-cost adsorbent and batch equilibration method was followed for
this study. A Box-Behnken design was used to develop response model and
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desirability function was then used for simultaneous optimization of all affecting
parameters in order to achieve the highest removal % of quinalphos. The
optimum conditions of factors predicted for quinalphos removal % were found to
be: pH 8.83, concentration 7 mg/L and dose 0.40 g. Under these conditions,
maximum removal % of quinalphos was obtained 96.31 %. Considering the
above optimum conditions, the adsorption isotherms were developed and provided
adsorption capacity of 196.07 (mg/g) by using Langmuir equation, indicating that
used tea leaves may be applied as a low-cost material for pesticides removal from
aqueous matrices.
Bala Kiran et al [206] presented the chromium adsorptive potential of
polysaccharide produced by a novel cyanobacterium Lyngbya putealis HH-15.
Batch mode experiments were performed to determine the adsorption equilibrium
and the equilibrium data was applied to different two-parameter models
(Langmuir, Freundlich, Temkin, Dubinin-Radushkevich, Flory-Huggins, and
Brunauer, Emmer & Teller (BET) model). The highest coefficient of
determination (0.9925) for Langmuir and BET models indicates best fitness of
these models in explaining the sorption as a multilayer process. Effect of different
variables like initial metal ion concentration (10-100 mg/L), pH (2-6) and
temperature (25-45 ºC) on chromium adsorption of exopolysaccharides (EPS)
were also examined, using Box-Behnken design model. Very high value of
regression coefficient between the variables and the response (R2 = 0.9982)
indicates excellent evaluation of experimental data by second-order polynomial
regression model. The response surface method indicated that 30-40 mg/L initial
chromium concentration, pH = 2 and 45 ºC temperature were optimal for
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biosorption of chromium by the cyanobacterial exopolysaccharides. Adsorption
capacity of EPS increased from 45 to 157 mg/g of EPS as initial Cr (VI)
concentration increased from 10 to 30 mg/L. Surface adsorption of the metal at
surface of EPS was confirmed through scanning electron microscopy.
Bala Kiran and Anubha Kaushik [207] investigated the potential use of alginate
immobilized algal beads for the removal of chromium from aqueous solution
under optimized conditions using a novel cyanobacterium, Lyngbya putealis
isolated from metal contaminated soil. Batch mode experiments were performed
to determine the adsorption equilibrium and kinetic behavior of chromium in
aqueous solution allowing the computation of kinetic parameters and maximum
metal adsorption capacity. Influences of other parameters like initial metal ion
concentration (10-100 mg/L), pH (2-6) and temperature (25-45 ºC) on chromium
adsorption were also examined, using Box-Behnken design. Very high regression
coefficient between the variables and the response (R2 = 0.9984) indicates
excellent evaluation of experimental data by second-order polynomial regression
model. The response surface method indicated that 50-60 mg/L initial chromium
concentration, 2-3 pH and a temperature of 45 ºC were optimal for biosorption of
chromium by immobilized L. putealis, when 82 % of the metal is removed from
the solution.
Baral et al [208] studied the Cr (VI) adsorption efficiency of the seaweed,
Hydrilla verticillata, in batches. The adsorbent was characterized using SEM,
BET surface area analyzer, Malvern particle size analyzer, EDAX and FT-IR. Cr
(VI) removal efficiency of the adsorbent was studied as a function of different
191
adsorption parameters such as contact time, stirring speed, pH, adsorbent dose,
particle size, adsorbate concentration, and temperature. Langmuir, Freundlich,
and Temkin adsorption isotherm equations were used in the equilibrium modeling.
The adsorption process followed pseudo second-order kinetics and intra-particle
diffusion was found to be the rate-controlling step. Experimental data follow
Langmuir adsorption isotherm. Thermo-dynamic parameters such as Gibbs free
energy and enthalpy of the adsorption process were evaluated to find out the
feasibility of the adsorption process. The negative values of Gibb's free energy
and positive enthalpy values show the feasibility and endothermic nature of the
process. The significance of different adsorption parameters along with their
combined effect on the adsorption process has been established through a full 24
factorial design. Among the different adsorption parameters, pH has the most
influential effect on the adsorption process followed by adsorbate concentration
and combined effects of all the four parameters were tested. The correlation
among different adsorption parameters were studied using multi-variate analysis.
Corneliu et al [209] investigated the ability of dried yeast Saccharomyces
biomass to remove Cu (II) ions from aqueous solutions by using of batch
techniques. The influence of different parameters on copper uptake by dried
yeast, such as initial Cu (II) concentration, initial pH of solution and temperature,
was studied. The Freundlich, Langmuir, Redlich-Peterson and Sips isotherms
were applied to the obtained experimental data. According to Langmuir isotherm
the maximum adsorption capacity of investigated non-living biomass was found to
be 2.59 mg/g. The thermodynamic parameters (e.g. free energy and enthalpy)
were calculated and discussed. The adsorption of Cu (II) onto the dried cells of
192
Saccharomyces cerevisiae is an endothermic process and become more favorable
with the increasing of temperature in pH range from 3 to 4. Optimization studies
by means of response surface methodology were carried out, which resulted in
improvement of the efficiency of sorption removal by using of biomass. The
removal efficiency of real wastewater originating from electroplating industry
which contains Sn (II) ions was determined and compared with synthetic
wastewater obtained in laboratory.
Farshid Ghorbani et al [210] Optimized cadmium biosorption process was
performed by varying three independent parameters (initial pH, initial cadmium
ion concentration, Saccharomyces cerevisiae dosage) using a central composite
design (CCD) under response surface methodology (RSM). For the maximum
biosorption of cadmium ion in an aqueous solution by S. cerevisiae, a total of 20
experimental runs were set and the experimental data fitted to the empirical
second-order polynomial model of a suitable degree. The potential of S.
cerevisiae as a bioadsorbent was evaluated as a pretreated material with 700 g/L
of ethanol. Furthermore, the quantitative relationship between the heavy metal
uptake (q) and different levels of these factors was used to work out optimized
levels of these parameters by a full factorial design (23). The analysis of variance
(ANOVA) of the quadratic model demonstrates that the model was highly
significant. The best set required 5 as initial pH, 3.8 g/L S. cerevisiae and 19
mg/L cadmium ion concentration within 240 min of contact time. Three
dimensional plots demonstrate relationships between the cadmium ion uptake with
the paired factors (when other factor was kept at its optimal level), describing the
behavior of biosorption system in a batch process. The model showed that
193
cadmium uptake in aqueous solution was affected by all the three factors studied.
An optimum cadmium uptake of 6.71 mg/g biomass was achieved at initial
cadmium ion concentration of 26.46 mg/L and S. cerevisiae dosage of 2.13 g/L.
The process kinetics were also evaluated by isotherm, pseudo-second-order and
intra-particle diffusion models. It showed that both monolayer adsorption and
intra-particle diffusion mechanisms were effective in the cadmium biosorption
process. Therefore, it is apparent that the response surface methodology not only
gives valuable information on interactions between the factors but also leads to
identification of feasible optimum values of the studied factors.
Harapriya and Rani Gupta [211] reported biosorption of Zn (II), Cu (II) and Co
(II) onto O. angustissima biomass from single, binary and ternary metal solutions,
as a function of pH and metal concentrations via Central Composite Design
generated by statistical software package Design Expert 6.0. The experimental
design revealed that metal interactions could be best studied at lower pH range i.e.
4.0, 5.0, which facilitates adequate availability of all the metal ions. The sorption
capacities for single metal decreased in the order Zn (II) > Co (II) > Cu (II). In
absence of any interfering metals, at pH 4.0 and an initial metal concentration of
0.5 mM in the solution, the adsorption capacities were 0.33 mmol/g Zn (II), 0.26
mmol/g Co (II) and 0.12 mmol/g Cu (II). In a binary system, copper inhibited
both Zn (II) and Co (II) sorption but the extent of inhibition of former was greater
than the latter; sorption values being 0.14 mmol/g Zn (II) and 0.27 mmol/g Co (II)
at initial Zn (II) and Co (II) concentration of 1.5 each, pH 4.0 and 1 mM Cu (II) as
the interfering metal. Zn (II) and Co(II) were equally antagonistic to each other’s
sorption; Zn (II) and Co (II) sorption being 0.23 and 0.24 mmol/g, respectively, at
194
initial metal concentration of 1.5 mM each, pH 4.0 and 1 mM interfering metal
concentration. In contrast, Cu (II) sorption remained almost unaffected at lower
concentrations of the competing metals. Thus, in binary system inhibition
dominance observed was Cu (II) > Zn (II), Cu (II) > Co (II) and Zn (II) > Co (II),
due to this the biosorbent exhibited net preference/ affinity for Cu (II) sorption
over Zn (II) or Co (II). Hence, the affinity series showed a trend of Cu (II) > Co
(II) > Zn (II). In a ternary system, increasing Co (II) concentration exhibited
protection against the inhibitory effect of Cu (II) on Zn (II) sorption. On the other
hand, the inhibitory effect of Zn (II) and Cu (II) on Co (II) sorption was additive.
The model equation for metal interactions was found to be valid within the design
space.
Hasan et al [212] successfully utilized the biomass of Aeromonas hydrophila for
the removal of lead from aqueous solution. The effects of process variables such
as pH, initial Pb (II) concentration, biomass dose and temperature on the uptake of
lead were investigated using two level four factor (24) full factorial central
composite designs with the help of MINITAB version15 software. The predicted
results thus obtained were found to be in good agreement (R2 = 98.6 %) with the
results obtained by performing experiments. The multiple regression analysis and
analysis of variance (ANOVA) showed that the concentration has positive and
temperature and biomass dose have negative whereas pH has curved relationship
with the uptake of Pb (II). The maximum uptake of Pb (II) predicted by
optimization plots was 122.18 mg/g at 20 oC, initial Pb (II) concentration of 259
mg/L, pH 5.0, temperature 20 oC and biomass dose 1.0 g. Langmuir isotherm
model was applicable to sorption data and sorption capacity was found to be 163.3
195
mg/g at 30 ºC, pH 5.0 and Pb (II) concentration range 51.8-259 mg/L indicate that
the biosorbent was better in comparison of the biosorbent reported in the
literature. Dubinin-Radushkevich (D-R) isotherm model was also applied and it
was found that sorption was chemisorptions (E = 12.98 kJ/mol). FT-IR studies
indicate the involvement of various functional groups present on biomass surface
in the sorption of Pb (II).
Helen Kalavathy et al [213] investigated adsorption capacity of Cu2+ from
aqueous solution onto H3PO4 activated carbon using rubber wood sawdust
(RSAC) in a batch system. Kinetic and isotherm studies were carried out, the
thermodynamic parameters like standard Gibb's free energy (ΔG), enthalpy (ΔH)
and entropy (ΔS) were evaluated. The pseudo-second-order model was found to
explain the kinetics of Cu2+ adsorption most effectively. The process optimization
was performed through Central Composite Rotary Design using response surface
methodology (RSM) by Design Expert Version 5.0.7 (STAT-EASE Inc.,
Minneapolis, USA). An initial concentration of 35 mg/L, temperature of 260 ºC,
carbon loading of 0.45 g (100 mg/L), adsorption time 208 min and pH of 6.5 was
found to be the optimum conditions for the maximum uptake of copper ions of 5.6
mg/L in batch mode.
Javad Zolgharnein et al [214] in their study introduced Robinia tree leaves as a
novel and efficient biosorbent for removing Pb (II) from aqueous solutions. In
order to reduce the large number of experiments and find the highest removal
efficiency of Pb (II), a set of full 23 factorial design with two blocks were
performed in duplicate (16 experiments). In all experiments, the contact time was
196
fixed at 25 min. The main interaction effects of the three factors including sorbent
mass, pH and initial concentration of metal-ion were considered. By using
Student's t-test and analysis of variances (ANOVA), the main factors, which had
the highest effect on the removal process, were identified. Twenty-six
experiments were designed according to Doehlert response surface design to
obtain a mathematical model describing functional relationship between response
and main independent variables. The most suitable regression model, that fitted
the experimental data extremely well, was chosen according to the lack-of-fit-test
and adjusted R2 value. Finally, after checking for possible outliers, the optimum
conditions for maximum removal of Pb (II) from aqueous solution were obtained.
The best conditions were calculated to be as: initial concentration of Pb (II) = 40
mg/L, pH = 4.6 and concentration of sorbent equal to 27.3 g/L.
Junkal Landaburu et al [215] conducted removal of cadmium and zinc from
their respective water samples by micellar-enhanced ultra filtration (MEUF),
using sodium dodecyl sulfate (SDS) as the surfactant. Response surface
methodology (RSM) was used for modeling and optimizing the process, and to
gain a better understanding of the process performance. Face Centered Composite
(CCF) Design was used as the experimental design. The factors studied were
pressure (P), nominal molecular weight limit (NMWL), heavy metal feed
concentration (CZn, CCd) and SDS feed concentration (CSDS). Using RSM the
retention of heavy metals was maximized while olarizati the surfactant to metal
ratio (S/M). Response surface plots improved the understanding the effect of the
factors on permeate flux. Concentration olarization was negligible and
therefore, high NMWL membranes with high pressure provided high flux with
197
negligible effect on the retention of heavy metals. The optimal conditions of zinc
removal were CSDS = 13.9 mM, CZn = 0.5 mM, NMWL = 10 kDa and P = 3.0
bar, and for cadmium removal CSDS = 14.2 mM, CCd = 0.5 mM, NMWL = 10
kDa and P = 3.0 bar. The retentions achieved were 98.0 ± 0.4 % for zinc and 99.0
± 0.4 % for cadmium. To improve resource efficiency, the surfactant was
reclaimed after use; 84 % of the initial SDS was recovered by precipitation.
Kaan et al [216] employed a three factor, three-level Box-Behnken experimental
design combining with response surface modeling (RSM) and quadratic
programming (QP) for maximizing Pb (II) removal from aqueous solution by
Antep pistachio (Pistacia vera L.) shells based on 17 different experimental data
obtained in a lab-scale batch study. Three independent variables (initial pH of
solution) pH ranging from 2.0 to 5.5, initial concentration of Pb (II) ions (C0)
ranging from 5 to 50 ppm, and contact time (t) ranging from 5 to 120 min were
consecutively coded as x1, x2 and x3 at three levels (-1, 0 and 1), and a second-
order polynomial regression equation was then derived to predict responses. The
significance of independent variables and their interactions were tested by means
of the analysis of variance (ANOVA) with 95 % confidence limits (a = 0.05). The
standardized effects of the independent variables and their interactions on the
dependent variable were also investigated by preparing a Pereto chart. The
optimum values of the selected variables were obtained by solving the quadratic
regression model, as well as by analysing the response surface contour plots. The
optimum coded values of three test variables were computed as x1 = 0.125, x2 =
0.707, and x3 = 0.107 by using a LOQO/AMPL optimization algorithm. The
experimental conditions at this global point were determined to be pH = 3.97, Co
198
= 43.4 ppm, and t = 68.7 min, and the corresponding Pb (II) removal efficiency
was found to be about 100 %.
Khattar and Shailza [217] used Response surface methodology (RSM) to
optimize the critical parameters responsible for higher Cd2+ removal by a
unicellular cyanobacterium Synechocystis pevalekii. A three-level Box-Behnken
factorial design was used to optimize pH, biomass and metal concentration for
Cd2+ removal. A coefficient of determination (R2) value (0.99), model F-value
(86.40) and its low p-value (F < 0.0001) along with lower value of coefficient of
variation (5.61 %) indicated the fitness of response surface quadratic model during
the present study. At optimum pH (6.48), biomass concentration (0.25 mg protein
ml-1) and metal concentration (5 gm/L) the model predicted 4.29 gm/L Cd2+
removal and experimentally, 4.27 gm/L Cd2+ removal was obtained.
Malihe et al [218] investigated the effects of biosorbent Aspergillus niger dosage,
initial solution pH and initial Ni (II) concentration on the uptake of Ni (II) by
NaOH pretreated biomass of A. niger from aqueous solution. Batch experiments
were carried out in order to model and optimize the biosorption process. The
influence of three parameters on the uptake of Ni (II) was described using a
response surface methodology (RSM) as well as Langmuir and Freundlich
isotherm models. Optimum Ni (II) uptake of 4.82 mg/gbiomass (70.30 %) was
achieved at pH 6.25, biomass dosage of 2.98 g/L and initial Ni (II) concentration
of 30.00 mg/L Ni (II). Langmuir and Freundlich were able to describe the
biosorption isotherm fairly well. However, prediction of Ni (II) biosorption using
Langmuir and Freundlich isotherms was relatively poor in comparison with RSM
199
approaches. The biosorption mechanism was also investigated by using Fourier
transfer infrared (FT-IR) analysis of untreated, NaOH pretreated, and Ni (II)
loaded A. niger biomass.
Malihe et al [219] investigated, the process of cadmium biosorption on NaOH
pretreated Aspergillus niger biomass in the batch mode. The effect of three
independent variables, initial pH of solution (1.3-8.7), biomass dosage (0.1-7.5
g/l) and initial cadmium ion concentration (0.5-37.5 mg/L) on the biosorption
process was determined and the process was then optimized by means of response
surface methodology (RSM). The process was evaluated by cadmium removal
efficiency as the process response. Twenty experiments designed by central
composite design (CCD) were carried out and the process response was modeled
using a polynomial equation as function of the variables. The optimum values of
the variables were found to be 5.96, 30.0 mg/L and 1.6 g/L for initial pH, initial
cadmium ion concentration and biomass dosage, respectively, at contact time of
1440 min. At optimal conditions, a biosorption capacity of 10.14 mg/g biomass
was obtained corresponding to 82.2 % cadmium removal efficiency. Under this
condition, a desirability value of 0.903 was obtained, showing that the estimated
function may represent the experimental model and give the desired conditions.
According to these observations, biomass A niger fungus particles with clean
surface and high porosity may have application as biosorbent for heavy metal
removal from industrial wastewater effluents.
Mevra et al [220] applied response surface methodology to optimize the removal
efficiency of Ni (II) using Pinus sylvestris ovulate cones. A 23 full-factorial
200
central composite design was employed for experimental design and analysis of
the results. The initial Ni (II) concentration (10-30 mg/L), pH (2.5-6.5) and
biomass concentration (5-25 g/L) were the critical components of the removal
optimized. The optimum pH, m (biomass concentration) and Co (initial Ni (II)
concentration) were found to be 6.17, 18.8 g/L and 11.175 mg/L, resp ectively.
Under these conditions, removal efficiency of Ni (II) was 99.91 %.
Mohammad et al [221] investigated the biosorption of Cd (II) and Ni (II) from
aqueous solution onto Saccharomyces cerevisiae and Ralstonia eutropha non-
living biomass. Biomass inactivated by heat and pretreated by ethanol was used in
determination of optimum conditions. The important process parameters, such as
initial solution pH (2-8), initial Ni (II) concentration (11-42 mg/L), initial Cd (II)
concentration (11-42 mg/L), and biomass dosage (0.2-4.7 g/L) were optimized
using design of experiments (DOE). A central composite design (CCD) under
response surface methodology (RSM) was applied to evaluate and optimize the
efficiency of removing each adsorbent. Moreover, the two responses were
simultaneously studied by using a numerical optimization methodology. The
optimum removal efficiency of Cd (II) and Ni (II) onto S. cerevisiae was
determined as 43.4 and 65.5 % at 7.1 initial solution pH, 4.07 g/L biomass dosage,
16 mg/L initial Ni (II) concentration and 37 mg/L initial Cd (II) concentration.
The optimum removal efficiency of Cd (II) and Ni (II) onto R. eutropha was
ascertained as 52.7 and 50.1 % at 5.0 initial solution pH, 2.32 g/L biomass dosage,
28 mg/L initial Ni (II) concentration and 37 mg/L initial Cd (II) concentration.
The present analysis suggests that the predicted values were in good agreement
with experimental data. The characteristics of the possible interactions between
201
biosorbents and metal ions were also evaluated by scanning electron microscope
(SEM) and Fourier transform infrared (FT-IR) spectroscopy analysis.
Olga Freitas et al [222] was used A Box-Behnken factorial design coupled with
surface response methodology to evaluate the effects of temperature, pH and
initial concentration in the Cu (II) sorption process onto the marine macro-algae
Ascophyllum nodosum. The effect of the operating variables on metal uptake
capacity was studied in a batch system and a mathematical model showing the
influence of each variable and their interactions was obtained. Study ranges were
10-40 ºC for temperature, 3.0-5.0 for pH and 50-150 mg/L for initial Cu (II)
concentration. Within these ranges, the biosorption capacity is slightly dependent
on temperature but markedly increases with pH and initial concentration of Cu
(II). The uptake capacities predicted by the model were in good agreement with
the experimental values. Maximum biosorption capacity of Cu (II) by A.
nodosum is 70 mg/g and corresponds to the following values of those variables:
temperature = 40 ºC, pH = 5.0 and initial Cu (II) concentration = 150mg/L.
Preetha and Viruthagiri [223] used Response surface methodology to study the
cumulative effect of the various parameters namely, initial copper ion
concentration, pH, temperature, biomass loading and to optimize the process
conditions for the maximum removal of copper. For obtaining the mutual
interaction between the variables and optimizing these variables, a 24 full factorial
central composite design using response surface methodology was employed. The
analysis of variance (ANOVA) of the quadratic model demonstrates that the
model was highly significant. The model was statistically tested and verified by
202
experimentation. A maximum copper removal of 98 % was obtained using the
biosorption kinetics of copper under optimum conditions.
Rajender Kumar et al [224] applied the Box-Behnken design matrix and
response surface methodology (RSM) to design the experiments to evaluate the
interactive effects of three most important operating variables: pH (2.0-6.0),
temperature (25-40 ºC) and initial concentration of metal ions (10.0-60.0 mg/L) on
biosorption of Cr (VI), Ni (II) and Zn (II) ions with immobilized bacterial strain
Bacillus brevis. The total 17 experiments were conducted in the present study
towards the construction of a quadratic model. Independent variables have
significant value 0.0001 which indicates the importance of these variables in the
biosorption process. Values of "Prob > F' less than 0.0500 indicate that model
terms are significant for the biosorption of Cr (VI), Ni (II) and Zn (II) ions. The
regression equation coefficients were calculated and the data fitted to a second-
order polynomial equation for removal of Cr (VI), Ni (II) and Zn (II) ions with
immobilized bacterial strains B. brevis.
Rajesh Singh et al [225] optimized various environmental conditions for
biosorption of Pb (II), Cd (II) and Cu (II) by investigating as a function of the
initial metal ion concentration, temperature, biosorbent loading and pH using
Trichoderma viride as adsorbent. Biosorption of ions from aqueous solution was
optimized in a batch system using response surface methodology. The values of
R2 0.9716, 0.9699 and 0.9982 for Pb (II), Cd (II) and Cu (II) ions, respectively,
indicated the validity of the model. The thermodynamic properties ΔG, ΔH, ΔE
and ΔS by the metal ions for biosorption were analyzed using the equilibrium
203
constant value obtained from experimental data at different temperatures. The
results showed that biosorption of Pb (II) ions by T. viride adsorbent are more
endothermic and spontaneous. The study was attempted to offer a better
understating of representative biosorption isotherms and thermodynamics with
special focuses on binding mechanism for biosorption using the FTIR
spectroscopy.
Sahu et al [226] presented application of RSM for optimizing the removal of Cr
(VI) ions from aqua solutions using activated carbon as adsorbent. All
experiments were performed according to statistical designs in order to develop
the predictive regression models used for optimization. The optimization of
adsorption of chromium on activated carbon was carried out to ensure high
adsorption efficiency at low adsorbent dose and high initial concentration of Cr
(VI). In the adsorption experiments a laboratory developed Tamarind wood
activated carbon made of chemical activation (zinc chloride) was used. A 24 full
factorial central composite design experimental design was employed. Analysis
of variance (ANOVA) showed a high coefficient of determination value (R2 =
0.928) and satisfactory prediction second-order regression model was derived.
Maximum chromium removal efficiency was predicted and experimentally
validated. The optimum adsorbent dose, temperature, initial concentration of Cr
(VI) and initial pH of the Cr (VI) solution were found to be 4.3 g/L, 32 ºC, 20.15
mg/L and 5.41 respectively. Under optimal value of process parameters, high
removal (> 89 %) was obtained for Cr (VI).
204
Umesh et al [227] investigated the effect of adsorbent dose, pH and agitation
speed on nickel removal from aqueous medium using an agricultural waste
biomass, Sugarcane bagasse. Batch mode experiments were carried out to assess
the adsorption equilibrium. The influence of three parameters on the removal of
nickel was also examined using a response surface methodological approach. The
central composite face-centered experimental design in response surface
methodology (RSM) by Design Expert Version 6.0.10 (Stat Ease, USA) was used
for designing the experiments as well as for full response surface estimation. The
optimum conditions for maximum removal of nickel from an aqueous solution of
50 mg/L were as follows: adsorbent dose (1500 mg/L), pH (7.52) and stirring
speed (150 rpm). This was evidenced by the higher value of coefficient of
determination (R2 = 0.9873).
Umesh et al [228] investigated the effect of adsorbent dose, pH and agitation
speed on the removal of chromium from aqueous medium using an agricultural
waste biomass (sugarcane bagasse treated with succinic acid). Batch mode
experiments were carried out to assess the adsorption equilibrium. The influence
of three parameters on the removal of chromium was examined using a response
surface methodological approach. The Central Composite Face-Centered
Experimental Design in Response (CCFD) Surface Methodology (RSM) by
Design Expert Version 6.0.10 (Stat Ease, USA) was used for designing the
experiments as well as for full response surface estimation and 20 trials as per the
model were run. The Chromium optimum conditions for maximum removal of
chromium from an aqueous solution of 50 mg/L were as it follows: adsorbent dose
205
(20 g/L), pH (2.0) and stirring speed (250 rpm). This was evidenced by the higher
Adsorption value of coefficient of determination (R2 = 0.9873).
Veglio et al [229] presented a study on the biosorption of toxic metals (copper,
manganese, nickel and lead) by a species of Arthrobacter. The equilibrium of the
process was in all cases well described by the Langmuir isotherm. The highest
values of specific uptake were 406 mg Mn/g, 148 mg Cu/g, 13 mg Ni/g and 130
mg Pb/g. Some factorial experiments were performed in order to investigate the
effect of operating and cultural conditions on the equilibrium. Experimental
results showed the influence of the biomass concentration on the specific uptake
(mg of metal/g of biomass as dry weight). A comparison with results reported in
the literature was made.
Yasar and Nuran [230] studied the effects of process parameters pH, adsorbent
dose and initial Cr (VI) concentration in the ranges 1.5-9.5, 1.8-24.2 g/L and 15-
95 mg/L, respectively. A predictive quadratic model was constructed by variance
analysis of data obtained from a total of 20 experimental runs with three replicates
each. Maximum removal was attained from a solution as concentrated as 30 ppm
at pH 3 with an adsorbent dosage of 13 g/L. The adsorption capacity of chitosan
flakes was determined as 22.09 mg/g at these specified conditions. However, the
adsorption capacity was recorded as high as 102 mg/g for 100 mg/L initial
concentration. Out of Langmuir, Freundlich and Dubinin-Radushkevich isotherm
models, adsorption data was best described by Langmuir isotherm with 0.99
consistencies. The process kinetics was evaluated by pseudo-first, pseudo-second
order and intra-particle diffusion models. Pseudo-second order kinetic model
206
exhibited the highest correlation with data. The results showed that both
monolayer adsorption and intra-particle diffusion mechanisms limited the rate of
Cr (VI) adsorption. Thermodynamic parameters revealed the feasibility,
spontaneity and exothermic nature of adsorption.
Yi- Ling Lai et al [231] tested the performance of a new biosorbent system,
consisting of a fungal biomass immobilized within an orange peel cellulose
absorbent matrix, for the removal of Zn2+ heavy metal ions from an aqueous
solution. The amount of Zn (II) ion sorption by the beads was as follows; orange
peel cellulose with Phanerochaete chrysosporium immobilized Ca-alginate beads
(OPCFCA) (168.61 mg/g) > orange peel cellulose immobilized Ca-alginate beads
(OPCCA) (147.06 mg/g) > P. chrysosporium (F) (125.0 mg/g) > orange peel
cellulose (OPC) (108.70 mg/g) > plain Ca-alginate bead (PCA) (98.26 mg/g). The
Zn2+ concentration was 100 to 1000 mg/L. The widely used Langmuir and
Freundlich isotherm models were utilized to describe the biosorption equilibrium
process. The isotherm parameters were estimated using linear and non-linear
regression analysis. The Box-Behnken model was found to be in close agreement
with the experimental values, as indicated by the correlation coefficient (R2) value
of 0.9999.
Yus Azila et al [232] employed central composite design (CCD) to optimize the
biosorption of Pb (II) ions onto immobilized cells of Pycnoporus sanguineus. The
independent variables were initial Pb (II) concentration, pH and biomass loading.
The combined effects of these variables were analyzed by response surface
methodology (RSM) using quadratic model for predicting the optimum point.
207
Under these conditions the model predicted a maximum of 97.7 % of Pb (II) ions
removal at pH 4, 200 mg/L of initial Pb (II) concentration with 10 g/L of
biosorbent. The experimental values are in good agreement with predicted values
within +0.10 to +0.81 % error.
Zulkali et al [233] investigated the effects of initial concentration of lead,
temperature, biomass loading and pH for an optimized condition of lead uptake
from the aqueous solution. The optimization process was analyzed using Central
Composite Face-Centered Experimental Design in Response Surface
Methodology (RSM) by Design Expert Version 5.0.7 (StatEase, USA). The
design was employed to derive a statistical model for the effect of parameters
studied on the removal of lead ion from aqueous solution. The coefficient of
determination, R2 was found to be 92.36 %. The initial concentration of 50.0
mg/L, temperature of 60 oC, biomass loading of 0.2 g and pH of 5.0 had been
found to be the optimum conditions for the maximum uptake of lead ions in 98.11
% batch mode. Under the optimum conditions, the lead uptake was attained to be
circa 8.60 mg/g.
It is evident from the above literature review that no research has been carried out
on biosorption of chrmomium and lead using Ageratum Conyzoides leaf powder
and Anacardium occidentale testa powder in batch study. Hence the author has
intended to follow up the present work.
208

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Chapter – III Literature Review

The major pollution for the present society is Environmental pollution.

3.1 CHROMIUM (Cr):

Agarwal et al [27] have studied on biosorption of aqueous chromium (VI) by

Hexavalent chromium sorption by TS decreased with increase in pH, and slightly

reduced with increase in ionic strength. Cr (VI) removal by TS seems to be

Ahmet Sarı et al [28] have studied on biosorption of total chromium from

aqueous solution by red algae (Ceramium virgatum): Equilibrium, kinetic and

thermodynamic studies. This study focused on the biosorption of total chromium

onto red algae (Ceramium virgatum) biomass from aqueous solution.

Experimental parameters affecting biosorption process such as pH, contact time,

removal efficiency of total chromium onto C. virgatum was studied by changing

value attained at pH 1.5. The biosorption capacity of C. virgatum biomass for

chromium was taken place by chemisorptions.

Annadural et al [29] examined the liquid-phase adsorption removal of Cu2+,

both adsorbents. The adsorption isotherms were better described by the

Freundlich equation. The amount of adsorption increased with increasing pH and

reached a plateau at pH > 7, which was confirmed by the variations of zeta

potentials. The application potential of such cellulose-based wastes for metal

and solution temperature on the removal of Cr (VI) from solution by waste

shown to be mainly governed by physico-chemical adsorption under the weak

model. The Langmuir constants were calculated at different temperatures and

temperature. The endothermic nature of the Cr (VI) adsorption was confirmed by

used as an effective adsorbent for removal of Cr (VI) from wastewater.

reduction of Cr (VI) to trivalent state occurred to lesser extent even in strong

acidic media, the Cr (VI) removal was mainly governed by physico-chemical

Langmuir find Freundlich isotherms.

solvent tolerant Pseudomonas fluorescens TEM08. The effects of pH, contact

temperature. According to the Q values, the biosorption capacity of the type I

mg/g) cells for Ni (II) biosorption.

their aqueous solutions using ordinary sand as an adsorbent. The experiments

phenomenon was illustrated on the basis of the interaction between surface

(containing low concentrations of metals), especially in the developing countries.

Bala Kiran et al [34] have studied on biosorption of Cr (VI) by native isolate of

biosorption of Cr (VI) by native isolate of Lyngbya putealis HH-15 in batch

(90.1 %) in the presence of 0.2 % salts. Adsorption equilibrium and kinetic

behavior of Cr (VI) in solution was also examined. Both Langmuir and

respectively) at 0.2 % salt concentration. Pseudo-second order kinetic model also

Balibek et al [35] studied the Chromium (VI) biosorption by dried Rhizopus

initial chromium (VI) concentration increased from 25 to 250 mg/L

optimum pH experiments were performed at different initial pH values (1.0–6.0)

obtained at pH 2.0 Equilibrium uptakes of chromium (VI) increased with

increasing chromium (VI) concentration and decreased considerably by the

presence of increasing concentrations of salt. And as the concentration of salt

increased from 0 to 50 g/L, the amount of chromium (VI) adsorbed by dried

and from 92.1 to 72.2 %.

metal concentration in solution and ash quality) on the removal at 20 ± 2 °C was

65.24 % for Afsin-Elbistan fly ash) at pH 7. The adsorption of Cd (II) increased

with an increase in the concentrations of these metals in solution while Cr (VI)

ash seemed to be a significant factor in influencing Cr (VI) and Cd (II) ions

6 ± 0.2 mg/I for Cd (II) as functions of solution pH (3.0-8.0). The adsorption of

Blázquez et al [37] have studied on the effect of pH on the biosorption of Cr (III)

sorbent, analysing the pH effect in the biosorption process. Removal of Cr (III)

Cr (III) removed reaches a maximum at range pH between 4 and 6, reaching

values close to 90 %. However, at pH 3 the retention of Cr (III) is less than 50 %.

The percentage of Cr (VI) removed is higher than 80 % when the pH is equal or

Cr (III) indicate that a combined effect of biosorption and reduction is involved in

the Cr (VI) removal specially when the pH value is lower than 3.

Calero et al [38] have made a study of Cr (III) biosorption in a fixed-bed column.

then qe remains constant. Column data obtained at different conditionswere

Response models. The breakthrough curve prediction by the Adams–Bohart and

Dose–Response models were found to be very satisfactory. In particular, the

Adams–Bohart model can be used to represent the initial region of breakthrough