Process Biochemistry 38 (2002) 175
/186

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Biosorption of chromium(VI) ions by Mowital† B30H resin

immobilized activated sludge in a packed bed: comparison with
granular activated carbon
Zümriye Aksu *, Ferda Gönen, Zafer Demircan
Hacettepe University, Chemical Engineering Department, Beytepe, 06532 Ankara, Turkey

Received 21 July 2001; received in revised form 24 January 2002; accepted 19 February 2002

Abstract

The potential use of Mowital† B30H resin immobilized dried activated sludge as a substitute for granular activated carbon for
removing chromium(VI) was examined in a continuous packed bed column. The effect of operating parameters such as flow rate
and inlet metal ion concentration on the sorption characteristics of each sorbent was investigated. From the batch system studies the
working sorption pH value was determined as 1.0 for both sorbents and packed bed sorption studies were performed at this pH
value. The total adsorbed quantities, equilibrium uptakes and total removal percents of chromium(VI) related to the effluent
volumes were determined by evaluating the breakthrough curves obtained at different flow rates and different inlet chromium(VI)
concentrations for each sorbent. Data confirmed that the total amount of sorbed chromium(VI) and equilibrium chromium(VI)
uptake decreased with increasing flow rate and increased with increasing inlet chromium(VI) concentration for both immobilized
dried activated sludge and granular activated carbon systems. The results also indicated that the sorption process could only deal
with lower flow rates and lower concentrations of chromium(VI) solutions if a high percentage removal was required for extended
periods for both sorbents. The suitability of the Freundlich and Langmuir adsorption models to the column equilibrium data was
also investigated for each chromium(VI)-sorbent system. The results showed that the equilibrium data for both the sorbents fitted
the Langmuir model best within the concentration range studied. # 2002 Elsevier Science Ltd. All rights reserved.

Keywords: Biosorption; Chromium(VI); Immobilized activated sludge; Mowital† B30H resin; Granular activated carbon; Packed bed column

1. Introduction for removing dissolved heavy metal ions include chemi-

The existence of copper, nickel, chromium, cadmium,
etc., in wastewaters may cause toxic and harmful effects
to living organisms in water and also to the consumers
of it. All of the reported metals are widely used materials
in daily life. For example, chromium compounds are
added to cooling water to inhibit corrosion. They are
employed in the manufacture of inks, industrial dyes
and paint pigments, in chrome tanning, aluminum
anodizing, leather and mining industries and other metal
cleaning, plating and electroplating operations. The
wastewaters from these industries contain undesirable
amounts of chromium(VI) ions. Conventional methods
* Corresponding author. Tel.: /90-312-2977434; fax: /90-312-
2992124.
E-mail address: zaksu@hacettepe.edu.tr (Z. Aksu).
0032-9592/02/$ - see front matter # 2002 Elsevier Science Ltd. All rights reserved.
PII: S 0 0 3 2 - 9 5 9 2 ( 0 2 ) 0 0 0 5 3 - 5
cal precipitation, chemical oxidation and reduction, ion
exchange, filtration, electrochemical treatment and eva-
porative recovery. However, these high-technology pro-
cesses have significant disadvantages, including
incomplete metal removal, requirements for expensive
equipment and monitoring systems, high reagent or
energy requirements or generation of toxic sludge or
other waste products that require disposal. New tech-
nologies are required that can reduce heavy metal
concentrations to environmentally acceptable levels at
affordable costs [1
/4].
The process of adsorption is a well established and
powerful technique for treating domestic and industrial
effluents. Activated carbon is the most widely and
effectively used adsorbent. A typical activated carbon
particle, whether in a powdered or granular form, has a
porous structure consisting of a network of intercon-
176 Z. Aksu et al. / Process Biochemistry 38 (2002) 175
/186
nected macropores, mesopores, and micropores that
provide a good capacity for the adsorption of heavy
metals due to its high surface area. The surface
chemistry of activated carbon and the chemical char-
acteristics of adsorbate, such as polarity, ionic nature,
functional groups and solubility determine the nature of
bonding mechanisms as well as the extent and strength
of adsorption. A variety of physicochemical mechan-
isms/forces, such as van der Waals, H-binding, dipole
/
dipole interactions, ion exchange, covalent bonding,
cation bridging and water bridging, can be responsible
for adsorption of heavy metal ions in activated carbon.
In spite of these characteristics, activated carbon suffers
from a number of disadvantages. It is quite expensive
and the higher the quality, the greater the cost. Both
chemical and thermal regeneration of spent carbon is
expensive, impractical on a large scale and produces
additional effluent and results in considerable loss of the
adsorbent [5,6].
Biosorption of heavy metals by microbial cells has
been recognized as a potential alternative to existing
technologies for recovery of heavy metals from indus-
trial waste streams and natural waters. Many aquatic
microorganisms such as bacteria, yeast and algae can
take up dissolved metals from their surroundings and
can be used to remove heavy metal ions successfully.
Since of this property, more economical, practical and
efficient techniques are being developed for the treat-
ment of industrial wastewaters. Metal ion binding to
non-living cells occurs rapidly by cell surface (passive)
adsorption and is called ‘biosorption’. The mechanism
of binding metal ions by inactivated biomass may
depend on the chemical nature of metal ion (species,
size, ionic charge), the species of microorganism and
environmental conditions (pH, temperature, ionic
strength, existence of competing organic or inorganic
metal chelators) [2
/4,7
/28]. Activated sludge is a well
known biomass used for the purification of some
industrial effluents and domestic wastes. Part of the
microorganisms over grown in such wastewater systems
can be separated and utilized for removal of heavy metal
ions as an abundant and cheaper biosorbent. Activated
sludge from wastewater systems contains both bacteria
and protozoa. The cell wall of bacteria essentially
consists of various organic compounds such as carboxyl,
acidic polysaccharides, lipids, amino acids and other
components. The protozoa are unicellular, motile,
relatively large eucaryotic cells that lack cell walls.
They can absorb components through their outer
membranes that contain proteins and lipids [4,24].
The use of dead microbial cells in biosorption is more
advantageous for water treatment in that dead organ-
isms are not affected by toxic wastes, they do not require
a continuous supply of nutrients and they can be
regenerated and reused for many cycles. However, the
use of dead biomass in powdered form has some
problems, such as difficulty in the separation of biomass
after biosorption, mass loss after regeneration and low
strength and small particle size, which make it difficult
to use in column applications [2,3,13,19,27]. To solve
these problems, dead biomass can be immobilized in a
supporting material. Much of the bioremoval literature
deals with artificially immobilized biomass. Researchers
have recognized that immobilizing nonliving biomass in
a biopolymeric or polymeric matrix may improve
biomass performance, biosorption capacity, increase
mechanical strength and facilitate separation of biomass
from metal-bearing solution. Immobilization also allows
higher biomass concentration, resistance to chemical
environments and column operations and immobilized
systems may be well suited for non-destructive recovery.
Indeed, the use of immobilized biomass has a number of
major disadvantages. In addition to increasing the cost
of biomass pre-treatment, immobilization adversely
affects the mass transfer kinetics of metal uptake.
When biomass is immobilized the number of binding
sites easily accessible to metal ions in solution is greatly
reduced since the majority of sites will lie within the
bead. So a good support material used for immobiliza-
tion should be rigid, chemically inert and cheap, should
bind cells firmly, should have high loading capacity and
should have a loose structure for overcoming diffusion
limitations. In most biomass immobilization processes
described in the literature, the cells are embedded in a
gelatinous biomatrix such as sodium or calcium algi-
nate, agarose or polymers such as polypropylene,
polyacrylamide, polysulfone or cross-linked copolymer
of ethyl acrylide-ethylene glycol dimethacrylate,
poly(hydroxyethyl methacrylate) or silica for selective,
efficient and low-cost metal removal [2,3,7
/
13,15,16,18
/20,23,26
/28].
Mowital† B30H resin (a polyvinyl butyral based
polymer) is a well known polymer used extensively in
painting and coating industries. While it is abundant,
extremely cheap than other immobilizing agents, non
toxic and chemically inert, more suitable for preparation
of porous beads, the solid and rigid support, showing
little change in volume under any conditions, with
dimensional stability under pressure, produced in the
desired size and thus highly competitive with ion
exchange resins and activated carbon [30] so it can be
used for immobilization of microorganisms for biosorp-
tion. Activated sludge has been immobilized in Mowi-
tal† B30H resin in order to produce a biosorbent
material with proper characteristics for use in typical
chemical engineering operations such as fixed beds. It
has been used to demonstrate the potential for removal
of chromium(VI) ions from waste streams and to
compare the chromium(VI) sorption characteristics of
granular activated carbon in a continuous packed bed
column as a function of flow rate and inlet metal ion
concentration and to describe the column chromium(VI)
 Z. Aksu et al. / Process Biochemistry 38 (2002) 175
/186
sorption equilibrium by the use of Langmuir and
Freundlich models. To our knowledge, this is the first
attempt to immobilize biomass in Mowital† B30H resin
in a fixed column and to test its use as an biosorbent for
the removal of metal ions.
2. Mathematical description
For continuous operation with granular activated
carbon or immobilized biomass, the most convenient
configuration is that of a packed column, much like that
used for ion exchange. Continuous packed bed sorption
has a number of process engineering advantages includ-
ing high yield operations and relatively easy scaling up
from a laboratory scale procedure. The stages in the
separation protocol can also be automated and high
degrees of purification can often be achieved in a single
step process. A large volume of wastewater can be
continuously treated using a defined quantity of sorbent
in the column. Reuse of microorganism is also possible.
After metal loading the metal may be concentrated in a
small volume of solid material or desorbed into a small
volume of eluant for recovery, disposal or containment
[2,11,13,16,17,19,23,26].
Much of the information needed to evaluate column
performance is contained in plots of adsorbed metal ion
concentration (Cad /inlet metal ion concentration
(Co)/outlet metal ion concentration (C )) or normalized
concentration defined as the ratio of effluent metal ion
concentration to inlet metal ion concentration (C /Co) as
a function of flow time (t) or effluent volume (Veff)
calculated from Eq. (1).
Veff  Qt total
where ttotal and Q are the total flow time (min) and
volumetric flow rate (ml min 1). The general position of
the breakthrough curve along the volume axis depends
on the capacity of the column with respect to the feed
concentration and flow rate. The breakthrough curve
would be a step function for favorable separations, i.e.
there would be an instantaneous jump in the effluent
concentration from zero to the feed concentration at the
moment the column capacity is reached [2,23,27,29].
The area under the breakthrough curve (A ) can be
obtained by integrating the adsorbed concentration
(Cad) versus t plot. Total adsorbed metal ion quantity
(qtotal) in the column for a given feed concentration and
flow rate is calculated from Eq. (2):
tttotal
QA Q
g
qtotal   Cad dt
1000 1000
t0
Total amount of metal ion sent to column (mtotal) is
calculated from Eq. (3).
177
Co Qttotal
mtotal  (3)
1000
Total removal percent of metal ion (column perfor-
mance) with respect to flow volume can be also found
from the ratio of total adsorbed quantity of metal ion
(qtotal) to the total amount of metal ion sent to column
(mtotal; Eq. (4)).
qtotal
Total Removal % 100 (4)
mtotal
Adsorption is also a well-known equilibrium separa-
tion process for wastewater treatment. Equilibrium
studies on adsorption give information about the
capacity of the sorbent or the amount required to
remove a unit mass of pollutant under the system
conditions. Equilibrium metal uptake (qeq) in the
column is defined by Eq. (5) as the total amount of
metal ion sorbed (qtotal) per g of sorbent (X ) at the end
of total flow time.
qtotal
qeq  (5)
X
Unadsorbed metal ion concentration at equilibrium in
the column can be defined by Eq. (6):
mtotal  qtotal
Ceq  1000 (6)
Veff
The most widely used isotherm equation for modeling
the equilibrium is the Langmuir equation which is valid
for monolayer sorption on to a surface a finite number
of identical sites [2,11,22,25,29]. The empirical Freun-
dlich model based on sorption on a heterogeneous
surface is also more widely used but provides no
(1) information on the monolayer adsorption capacity, in
contrast to the Langmuir model [2,11,22,25,29].
3. Experimental
3.1. Microorganism
The waste activated sludge collected from the waste-
water treatment system of Meteksan Company
/Ankara
Paper and Board Mill, Turkey was used in this study.
The harvested cells were washed thoroughly with sterile
distilled water, centrifuged at 5000 rpm for 5 min, dried
at 60 8C for 24 h and then powdered before immobi-
lization.
3.2. Granular activated carbon
(2)
A commercial, 18
/20 mesh (within the particle range
of 0.84
/1.00 mm) granular activated carbon (Sigma)
with a specific surface area of 600
/650 m2 g1 was used
178 Z. Aksu et al. / Process Biochemistry 38 (2002) 175
/186
for packed bed column studies. The particles were oven
dried at 110 8C for 24 h and stored in a desiccator until
used.
3.3. Preparation of Mowital† B30H resin immobilized
activated sludge
The method used for the immobilization is based on
solvent evaporation. For each batch immobilization, 1 g
Mowital† B30H (Hoechst) was dissolved in 8 ml of
chloroform (Merck). When Mowital† B30H resin was
completely dissolved in this solution, 1 g of dried and
powdered activated sludge biomass was added to this
medium mixed continuously by means of an agitator. 4
g of polyvinyl alcohol (Sigma) used as the stabilizator
was solved in 500 ml of distilled water. After that, 0.3 g
of sodium dodecyl sulphate (Sigma) used as the emulsi-
fier was added to this mixture and mixed thoroughly. At
the last step, the first prepared mixture was added to this
mixture. The mixing operation was continued for 6 h at
750 rpm to obtain the porous, uniform and spherical
immobilized particles and to evaporate chloroform.
Finally, the particles were removed from the immobili-
zation medium and washed with distilled water. These
particles had 1.0 mm of mean diameter and contained
50% dried activated sludge by weight [30].
3.4. Preparation of chromium(VI) solutions
Chromium(VI) solutions were prepared by diluting 1
g l 1 of stock chromium(VI) solution which was
obtained by dissolving exact quantity of K2Cr2O7
(Merck) in double distilled and de-ionized water. The
range in concentrations of chromium(VI) prepared from
stock solution varied between 50 and 500 mg l 1. Before
the adsorption/biosorption in the continuous column
system, the pH of each test solution was adjusted to the
required value with diluted and concentrated H2SO4 and
NaOH solutions.
3.5. Sorption studies in the batch and column systems
The effect of initial pH on chromium(VI) adsorption/
biosorption by granular activated carbon and Mowi-
tal† B30H resin immobilized activated sludge were
examined in a batch system. For the batch system
studies, 0.05 g of granular activated carbon or immobi-
lized particles containing 0.05 g of dried activated sludge
were contacted with the known concentration of 100 ml
metal-bearing solution in Erlenmayer flasks at the
desired pH. The flasks were agitated on a shaker for
120 h which is more than ample time for sorption
equilibrium. Three milliliter samples of solution were
taken in definite intervals and analyzed for the residual
chromium(VI) ions. The equilibrium chromium(VI)
uptake value (qeq) was determined as mg of sorbed
chromium(VI) per g of sorbent.
Continuous fixed bed column studies were performed
in a fixed bed mini column reactor with an inside
diameter of 0.96 cm, a bed depth of 6 cm and 3 g of
immobilized cells containing 1.5 g of dried activated
sludge biomass. For the adsorption of chromium(VI) to
granular activated carbon, a fixed bed mini column
reactor with an inside diameter of 0.96 cm, a bed depth
of 10.4 cm and 4.2 g of granular activated carbon was
used. The column was preconditioned to pH 1.0 for
chromium(VI) (by eluting the column with 1 M H2SO4).
The metal ion solution at a known concentration and
flow rate was passed continuously through the station-
ary bed of sorbent. The flow rate was regulated with a
variable speed pump by a Masterflex L/S digital drive
and easy-load pump head. Samples were taken from the
effluent at timed intervals and analyzed for chro-
mium(VI) ions as described below. The experiment
was continued until a constant concentration of metal
ion was obtained. The experiments showed that no
chromium(VI) was taken up by Mowital† B30H beads
in the absence of entrapped biomass.
For both the sorption systems, the studies were
performed at a constant temperature of 25 8C to be
representative of environmentally relevant conditions.
All the experiments were carried out in duplicates and
the average values were used for further calculations.
3.6. Analysis of chromium(VI) ions
The concentration of free chromium(VI) ions in the
effluent was determined spectrophotometrically by
using diphenyl carbazide as the complexing agent. One
milliliter of a 0.2% (w/v) of diphenyl carbazide solution
prepared in 95% ethyl alcohol and 1 ml of 1/5 H2SO4
solution was added to the sample (1 ml) containing less
than 100 mg l 1 of chromium(VI) ions and diluted to
100 ml with double-distilled water. The absorbance of
the purple colored solution was read at 540 nm after 10
min [31].
4. Results and discussion
4.1. Effect of initial pH
The most important single parameter influencing the
sorption capacity is the pH of adsorption medium. The
initial pH of adsorption medium is related to the
adsorption mechanisms onto the adsorbent surface
from water and reflects the nature of the physicochem-
ical interaction of the species in solution and the
adsorptive sites of adsorbent. The variation of equili-
brium chromium(VI) uptake with initial pH obtained
from batch system studies was given in Fig. 1. It was
 Z. Aksu et al. / Process Biochemistry 38 (2002) 175
/186
Fig. 1. The effect of initial pH on the equilibrium chromium(VI) uptake in the batch system (Temperature, 25 8C; initial pH 1.0; Co, 100 mg l 1; X ,
0.5 g l 1; agitating rate, 150 rpm).
observed that the removal of chromium(VI) ions from
aqueous solution was more efficient with decreasing pH
and was the greatest at pH 1.0. The equilibrium
chromium(VI) uptakes were 72.2 and 61.0 mg g1 for
granular activated carbon and immobilized activated
sludge, respectively, at this pH value. Packed bed
column studies were also performed at the same pH.
pH affects the surface properties of the sorbent, i.e.,
surface charge of the cells used as biosorbent. The
isoelectric point of activated sludge, is usually between
pH 1 and 3. From Fig. 1, as the pH is lowered, the
overall surface charge on the cells will become positive
and the interaction of metal ions such as chromium(VI),
in anionic form, with the biosorbent will be primarily
electrostatic in nature. At very low pH values, the
surface of sorbent would also be surrounded by the
hydronium ions which enhance the chromium(VI)
interaction with binding sites of the biosorbent by
greater attractive forces. As the pH increased, however,
the overall surface charge on the cells became negative
and biosorption decreased [2,4].
Chromium(VI) anions were bound to positively
charged sites on activated carbon surface which is a
collection of organic functional groups such as carboxyl,
phenolic, alcoholic and quinone groups at pH 1. In
addition, hydrogen bonding by the metal anion with the
oxygen present on the carbon surface is also quite
probable. The adsorption decreased with further in-
creasing of pH due to repulsive forces between the
negative surface charge of the activated carbon and
anionic chromium(VI) ions [6,32].
179
4.2. Effect of flow rate
In the first stage of removal studies in the continuous-
flow fixed column with granular activated carbon and
Mowital† B30H resin immobilized activated sludge, the
flow rate was changed from 0.8 to 3.2 ml min1 while
the inlet chromium(VI) concentration in the feed was
held constant at 100 mg l 1 at pH 1.0. The plots of
comparative normalized chromium(VI) concentration
versus effluent volume at different flow rates are given in
Fig. 2 for both sorbents. As the flow rate increased the
effluent volume (or indirectly contact time) required for
complete column saturation decreased for both sorbents
due to less interaction between the metal ion and
sorbent. The sorption data were evaluated for each
sorbent and total amounts of chromium(VI) sent to
column (mtotal), total sorbed quantities of chromium(VI)
(qtotal), equilibrium chromium(VI) uptakes (qeq) and
total removal percentages of chromium(VI) with respect
to the volume of flow passed at different flow rates are
presented in Table 1. In general mtotal values increased;
qtotal, qeq and total chromium(VI) removal percentage
values decreased with increasing flow rate and max-
imum values were obtained at 0.8 ml min 1 for each
sorbent. When compared with the values of equilibrium
uptake, total sorbed quantity and removal percentage of
immobilized activated sludge beads, granular activated
carbon particles showed higher uptake and yield values.
The equilibrium uptakes and total chromium(VI) re-
moval percentages were 96.5 mg g1 and 42.2% and
16.4 mg g1 and 22.4% by the activated carbon and
180 Z. Aksu et al. / Process Biochemistry 38 (2002) 175
/186

Fig. 2. The breakthrough curves obtained at different flow rates for chromium(VI) biosorption/adsorption to Mowital† B30H resin immobilized
activated sludge (open symbols) and granular activated carbon (filled symbols). (Temperature, 25 8C; initial pH, 1.0; Co, 100 mg l 1).

immobilized activated sludge beads, respectively, at 0.8
ml min 1 flow rate and 100 mg l1 inlet chromium(VI)
concentration.
As may be seen from Fig. 2, the lowest flow rate gave
a more gentle breakthrough curve for granular activated
carbon. The breakthrough curves became steeper and
the breakpoint time decreased with increasing flow rate.
Early saturation and lower chromium(VI) removal were
observed at the highest flow rate. The two main reasons
for this behavior are the unsufficient adsorption equili-
brium time in the column and the diffusion limitations
of the solute into the pores of granular activated carbon.
For all flow rates studied, after the breakpoint, chro-
mium(VI) removal was maintained over a long period
showing approximately constant uptake. Apparently,
the intraparticular uptake was still in progress long after
the breakpoint. Fig. 2. also illustrated that break-
through for granular activated carbon occurred much
later because of its higher chromium(VI) uptake capa-
city and, therefore, the saturation time of activated
carbon was also longer than that of immobilized
biomass.
As indicated in Fig. 2, much sharper breakthrough
curves were obtained by immobilized activated sludge at

Table 1
The effect of flow rate on total amount of chromium(VI) sent to column (mtotal), total adsorbed quantity of chromium(VI) (qtotal), equilibrium
chromium(VI) uptake (qeq) and total removal percentage of chromium(VI) for chromium(VI) adsorption to Mowital† B30H resin immobilized
activated sludge and granular activated carbon

Q (ml min 1) t total (min) Veff (ml) mtotal (mg) qtotal (mg) Total chromium(VI) removal (%) qeq (mg g 1)

Mowital† B30H resin immobilized activated sludge

0.8 1800 1440 145.8 32.7 22.4 16.4
1.6 660 1056 107.5 20.3 18.9 10.1
3.2 210 672 69.3 9.6 22.4 4.8
Granular activated carbon
0.8 11700 9360 961.1 405.4 42.2 96.5
1.6 4950 7920 801.7 221.8 27.7 52.8
3.2 1065 3408 351.3 79.2 22.5 18.9
 Z. Aksu et al. / Process Biochemistry 38 (2002) 175
/186
all studied flow rates. The breakpoint time and total
adsorbed chromium(VI) quantity also decreased with
increasing flow rate. Unlike for chromium(VI) adsorp-
tion on granular activated carbon, saturation was
reached within 210
/1800 min at different flow rates
from 0.8 to 3.2 ml min 1 and prolonged exposure time
did not increase removal of chromium(VI) by Mowi-
tal† B30H resin immobilized activated sludge. At the
lowest flow rate of 0.8 ml min 1, relatively higher
uptake values were observed for chromium(VI) biosorp-
tion to the immobilized activated sludge at the beginning
of column operation could be due to the magnitude of
concentration driving force. But, as solution continued
to flow, the concentration of chromium(VI) in the
effluent rapidly increased, the bed became saturated
with chromium(VI) and the concentration of solute in
the effluent suddenly rose to inlet chromium(VI) con-
centration. This behavior can be explained that chro-
mium(VI) biosorption by activated sludge biomass is
also affected by insufficient residence time of the solute
in the column, the diffusion of the solute into the pores
of biosorbent and limited number of active sites and
ionic groups of biomass for biosorption in the matrix.
4.3. Effect of inlet chromium(VI) concentration
In the sorption of chromium(VI) to both the sorbents,
a change in inlet chromium(VI) concentration affected
the operating characteristics of the packed column. The
sorption breakthrough curves obtained by changing
inlet chromium(VI) concentration from 50 to 500 mg
l 1 at 0.8 ml min1 flow rate for granular activated
carbon and Mowital† B30H resin immobilized activated
sludge are given in Fig. 3. The breakpoint time
decreased with increasing inlet chromium(VI) concen-
tration as the binding sites became more quickly
saturated in both the systems. The equilibrium chro-
mium(VI) uptakes, total sorbed chromium(VI) quanti-
ties and chromium(VI) removal percentages of both
systems related to the feed chromium(VI) concentration
are also compared in Table 2. Although the equilibrium
chromium(VI) uptake and amount of total sorbed
chromium(VI) increased with increasing inlet chro-
mium(VI) concentration from 50 to 500 mg l 1, the
total chromium(VI) removal percentages for both the
sorbents showed opposite trend. The removal efficiency
was higher at low influent chromium(VI) concentration.
Table 2. shows that for the inlet chromium(VI) con-
centrations of 50 and 500 mg l 1, 55.7 and 30.3 and 25.8
and 17.0% of total chromium(VI) applied to the column
was adsorbed by the granular activated carbon and
Mowital† B30H resin immobilized activated sludge
beads, respectively. The equilibrium chromium(VI)
uptake increased from 71.8 to 135.8 mg g1 for
activated carbon and from 15.3 to 18.5 mg g1 for the
immobilized biomass with an increase of inlet chro-
181
mium(VI) concentration from 50 to 500 mg l 1. The
equilibrium chromium(VI) uptakes, total sorbed chro-
mium(VI) quantities and adsorption yields were highest
for the granular activated carbon, which was expected,
because of the greater specific surface area and the
porous structure of granular activated carbon. The
biosorption of chromium(VI) to the immobilized acti-
vated sludge appeared to be significantly lower com-
pared with the adsorption to granular activated carbon.
The relatively low chromium(VI) retention for immobi-
lized activated sludge can be attributed to the difference
in the surface morphology. Immobilized activated
sludge particles do not have many micro or macropores,
so its low surface area also results in lower sorption
capacity.
As seen from Fig. 3 at lower inlet chromium(VI)
concentrations breakthrough curves were dispersed,
breakthrough occurred very late and the surface of the
adsorbent was saturated with chromium(VI) after a
longer time for granular activated carbon. At 50 mg l 1
of inlet chromium(VI) concentration and at the lowest
flow rate of 0.8 ml min 1, the sorption, although
continuous with time, was very efficient in the initial
steps of the process. This fact is probably associated to
the availability of reactional sites around or inside the
granular activated carbon particles, able to capture
chromium(VI) and sufficient retention time. In a second
stage, with the gradual occupancy of these sites, the
uptake become less effective. Even after the break-
through occurred, the column was still capable of
accumulating chromium(VI), although at a progres-
sively lower efficiency. In continuous-flow column,
equilibrium chromium(VI) uptake level was higher
than the batch uptake value at 100 mg l 1 inlet
chromium(VI) concentration and at 0.8 ml min 1 flow
rate.
The sorption behavior of immobilized cells for
chromium(VI) was different from that of chromium(VI)
adsorption by granular activated carbon. The beads
adsorbed chromium(VI) very rapidly at the beginning of
the biosorption but as the experiment continued, the
concentration of chromium(VI) in the effluent increased
rapidly, the bed became saturated with chromium(VI)
and the concentration of solute in the effluent rose to the
inlet chromium(VI) concentration Fig. 3 shows that
much sharper breakthrough curves so very low chro-
mium(VI) uptakes and removal yields were obtained
especially at higher inlet chromium(VI) concentrations
for the chromium(VI) biosorption to immobilized
activated sludge. At 100 mg l1 inlet chromium(VI)
concentration when compared with the batch system
biosorption, it was observed that equilibrium metal
uptake level decreased from 61.0 to 16.4 mg g1 in
continuous packed bed studies at 0.8 ml min1.
182 Z. Aksu et al. / Process Biochemistry 38 (2002) 175
/186

Fig. 3. The breakthrough curves obtained at different inlet chromium(VI) ion concentrations for chromium(VI) biosorption/adsorption to
Mowital† B30H resin immobilized activated sludge (open symbols) and granular activated carbon (filled symbols) (Temperature, 25 8C; initial pH
1.0; Q , 0.8 ml min1).

4.4. The application of the Langmuir and Freundlich
models
Analysis of the isotherm data is important in order to
develop an equation which accurately represents the
results of the column and which could be used for
column design purposes. Two kinds of several isotherm
equations have been applied for this study, Langmuir
and Freundlich isotherms. The linearized Freundlich
and Langmuir adsorption isotherms of chromium(VI)
obtained at 25 8C were shown in Figs. 4 and 5 for both
sorbents. The Freundlich and Langmuir adsorption

Table 2
Total amounts of chromium(VI) sent to column (mtotal), total adsorbed quantities of chromium(VI) (qtotal), equilibrium chromium(VI) uptake (qeq)
and total removal percentages of chromium(VI) for chromium(VI) adsorption to Mowital† B30H resin immobilized activated sludge and granular
activated carbon at different inlet chromium(VI) concentrations

Q (ml min 1) t total (min) Veff (ml) mtotal (mg) qtotal (mg) Total chromium(VI) removal (%) qeq (mg g 1)

Mowital† B30H resin immobilized activated sludge

51.4 2880 2304 118.4 30.6 25.8 15.3
101.2 1800 1440 145.8 32.7 22.4 16.4
251.5 840 672 169.0 34.4 20.4 17.2
503.1 540 432 217.3 36.9 17.0 18.5
Granular activated carbon
51.2 13200 10560 541.0 301.6 55.7 71.8
102.7 11700 9360 961.1 405.3 42.2 96.5
251.5 7800 6240 1569.6 527.9 33.6 125.7
502.3 4680 3744 1880.6 570.2 30.3 135.8
 Z. Aksu et al. / Process Biochemistry 38 (2002) 175
/186 183

Fig. 4. The linearized Langmuir adsorption isotherms for chromium(VI) biosorption/adsorption to Mowital† B30H resin immobilized activated
sludge and granular activated carbon.

constants evaluated from the isotherms with the correla-
tion coefficients were also presented in Table 3. In view
of the values of linear regression coefficients in the table,
the Langmuir model exhibited a little better fit to the
sorption data of both the chromium(VI)-sorbent sys-
tems than the Freundlich model in the studied concen-
tration ranges. However, the Freundlich model also
seemed to agree well with the experimental data of
chromium(VI) considering that obtained linear regres-
sion coefficients are greater than 0.972.
An adsorption isotherm is characterized by certain
constants the values of which express the surface
properties and affinity of the sorbent and can also be
used to compare the sorptive capacity of sorbents for the
chromium(VI) in the fixed column. KF and n , the
Freundlich constants, are indicators of adsorption

Fig. 5. The linearized Freundlich adsorption isotherms for chromium(VI) biosorption/adsorption to Mowital† B30H resin immobilized activated
sludge and granular activated carbon.
184 Z. Aksu et al. / Process Biochemistry 38 (2002) 175
/186
Table 3
The comparison of the Langmuir and Freundlich adsorption constants evaluated from the Langmuir and Freundlich isotherms for chromium(VI)
adsorption to Mowital† B30H resin immobilized activated sludge and granular activated carbon
Freundlich model
1 n
KF [(mg g 1
)(mg l ) ]
Immobilized activated sludge 11.6
Granular activated carbon 35.4
capacity and adsorption intensity, respectively. The
closer the n value of Freundlich is to zero the more
heterogeneous is the system. From Table 3, the high
values of KF showed easy uptake of chromium(VI) ions
from wastewater with high adsorptive capacities of these
sorbents. Table 3 also indicates that n is greater than
unity, indicating that chromium(VI) ions are favorably
adsorbed by the sorbents. The obtained data in Table 3
also pointed out that granular activated carbon had a
higher biosorption capacity than that of Mowi-
tal† B30H resin immobilized activated sludge and re-
presented a greater heterogeneity than immobilized
activated sludge.
The Langmuir constants, Qo and b have been
determined from Ceq/qeq versus Ceq plots obtained for
each sorbent and the results are also tabulated in Table
3. The maximum capacity Qo defines the total capacity
of each sorbent for chromium(VI) ions. The maximum
sorption capacities of granular activated carbon and
immobilized biomass were determined as 147.1 and 18.9
mg g1, respectively, in the packed bed column. The
value of Qo appears to be significantly higher for the
chromium(VI)-granular activated carbon system in
comparison with the uptake of chromium(VI) on
immobilized activated sludge. But a large value of b ,
related to binding energy, implied strong bonding of
chromium(VI) on to Mowital† B30H resin immobilized
activated sludge.
The Langmuir model makes several assumptions,
such as monolayer coverage and constant adsorption
energy while the Freundlich equation deals with hetero-
geneous surface adsorption. The applicability of both
Langmuir and Freundlich isotherms to the chro-
mium(VI)-granular activated carbon and immobilized
activated sludge systems implies that both monolayer
adsorption and heterogeneous surface conditions exist
under the experimental conditions used.
It was shown that Mowital† B30H resin immobilized
dried activated sludge can be used as an adsorbent in the
same way as granular activated carbon in a continuous
packed bed column to separate chromium(VI) ions from
aqueous solutions. The immobilized biomass was pre-
ferable over native biomass in packed column opera-
tions as the dried, powdered biomass was not rigid and
strong enough to use in downtlow packed bed column
operations and presents an unacceptable pressure drop
Langmuir model
2
n R Qo (mg g 1) b (l mg1) R2
13.2 0.988 18.9 0.0799 0.999
4.2 0.972 147.1 0.0370 0.999
to flow. Diffusion limitations causing a decrease in
biosorption capacity is one of the major disadvantages
of immobilized systems. Considerable research has been
focused on reducing diffusion limitations, but no gen-
erally satisfactory solution has been found. The major
requirement is to develop immobilization systems which
are more open to hydraulic flow but still provide large
contact areas and which have good mechanical proper-
ties for large-scale systems. The beads must be mechani-
cally strong, chemically resistant, inexpensive and easy
to regenerate and they must not swell and contract
during use as do many ion exchange resins. The
production of the beads must be examined in the hope
of increasing the yield in the desired size range,
improving porosity, and increasing capacity. The per-
formance of polymer, which have been used to immo-
bilize activated sludge must be significantly improved by
modifying bead fabrication procedure to improve sur-
face and/or interior properties. Mowital† B30H resin
immobilized activated sludge can be used in continuous
packed bed columns for chromium(VI) removal from
waste waters because they satisfy most of the specifica-
tions defined above. They can be hardened, formed into
beads and used highly efficiently in packed-bed bior-
eactors that resemble the column processes used with
ion exchange resins and activated carbon systems. This
suggests that if the porosity of the beads could be
increased by modification of the biosorbent preparation
method, then the contact time necessary for maximal
biosorption could be significantly reduced.
5. Conclusion
The breakthrough curves for column sorption of
chromium(VI) from dilute solutions using granular
activated carbon and Mowital† B30H resin immobilized
activated sludge have been measured at 25 8C. The
obtained results showed that the sorption of chro-
mium(VI) is dependent on the flow rate, the inlet
chromium(VI) concentration and time and these para-
meters affect the saturation capacity of both sorbents
directly. The breakpoint time and total sorbed chro-
mium(VI) quantity and chromium(VI) removal yield
decreased with increasing flow rate and chromium(VI)
concentration in both systems. Although granular
 Z. Aksu et al. / Process Biochemistry 38 (2002) 175
/186
activated carbon had a higher adsorption capacity for
chromium(VI) (147.1 mg g1), the experimental results
indicated that dried activated sludge has also a con-
siderable potential for the removal of chromium(VI)
over a wide range of chromium(VI) concentration (18.9
mg g1). Consequently, it can be said that for a given
type of immobilized biosorbent, the saturation capacity
is greater under conditions of lower concentrations of
chromium(VI) and lower flow rates. By adjusting the
operating characteristics of the packed column, for
example the flow rate, inlet chromium(VI) concentra-
tion, particle size, biomass quantity very rapid and
efficient chromium(VI) uptake can be achieved for the
system.
The Freundlich and Langmuir adsorption models
were used for the mathematical description of the
adsorption of chromium(VI) ions to granular activated
carbon and Mowital† B30H resin immobilized activated
sludge in a continuous packed bed column and the
isotherm constants were determined to compare the
adsorption capacity of granular activated carbon and
Mowital† B30H resin immobilized activated sludge for
chromium(VI) ions. It was seen that the adsorption
equilibrium data fitted very well to Langmuir adsorp-
tion model.
It seems that although the immobilization process
decreased the metal biosorption properties of the
biomass, the use of Mowital† B30H immobilized acti-
vated sludge technology for wastewater treatment will
offer an attractive alternative for various industries. If
processing time is important, recycle or linked-column
series may be also employed in order to obtain higher
chromium(VI) removal yields at higher flow rates and
higher inlet chromium(VI) concentrations. If the quan-
tity of biomass per unit volume of the column is
increased (decrease of the void fraction of the column)
chromium(VI) uptake also will be higher for concen-
trated chromium(VI) solutions because of the increasing
of active adsorption sides.
Appendix A: Nomenclature
Co inlet (feed) chromium(VI) concentration in
the column (mg l 1)
C effluent chromium(VI) concentration in
the column (mg l 1)
Cad( /Co/ adsorbed chromium(VI) concentration in
C) the column (mg l 1)
Ceq nonadsorbed chromium(VI) concentration
at equilibrium in the column (mg l1)
mtotal total amount of chromium(VI) ions sent to
column (mg)
qeq equilibrium chromium(VI) uptake in the
column or in the batch system (mg g1)
185
qtotal total adsorbed quantity of chromium(VI)
in the column (mg)
Q flow rate ( ml min 1)
t flow time (min)
ttotal total flow time (min)
Veff effluent volume (ml)
X amount of sorbent in the column (g) or
sorbent concentration in the batch system
(g l 1)
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