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Hydrometallurgy 52 1999 189197


A comparative study of the mass transfer kinetics of
metal biosorption by microbial biomass
P.R. Puranik
a
, J.M. Modak
b
, K.M. Paknikar
a,)
a
Diision of Microbial Sciences, Agharkar Research Institute, G.G. Agarkar Road, Pune 411 004, India
b
Department of Chemical Engineering, Indian Institute of Science, Bangalore 560 012, India
Received 30 October 1998; received in revised form 18 February 1999; accepted 22 February 1999
Abstract
A comparative study of the kinetics of lead and zinc biosorption was carried out using the
biomass of Streptoerticillium cinnamoneum, Penicillium chrysogenum and Citrobacter sp. The
uptake of metals in all cases was found to be rapid in the first 10 min, reaching an equilibrium
within 30 min of contact. The rate of metal uptake was independent of initial metal concentration.
The metal concentration profiles could be well predicted using a batch kinetic model. q1999
Elsevier Science B.V. All rights reserved.
Keywords: Mass transfer kinetics; Metal biosorption; Microbial biomass
1. Introduction
The toxic effects of heavy metals such as lead and cadmium on biota necessitate their
removal from the aquatic environment. The removal and recovery of heavy metals such
as zinc, copper, silver and gold is important from the point of resource recovery as
metals are non-renewable. The most recent development in environmental biotechnology
is the use of microbial biomass for removal and recovery of heavy metals from
industrial effluents. Different kinds of microbial biomass have been identified and
w x
studied extensively for their use in metal removalrrecovery processes 1 . The mecha-
nisms associated with metal removal by microorganisms are complex and include
metabolism-dependent and independent metal uptake.
)
Corresponding author. Tel.: q91-20-354357; Fax: q91-20-351542; E-mail: paknikar@vsnl.com
0304-386Xr99r$ - see front matter q 1999 Elsevier Science B.V. All rights reserved.
.
PII: S0304- 386X 99 00017- 1
( )
P.R. Puranik et al.rHydrometallurgy 52 1999 189197 190
The potential application of the biosorption process for the recovery of metal values
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from waste streams has been of considerable interest 2 . In order to obtain the
parameters for the design of the processing equipment and to determine the optimum
size and operating conditions, mathematical models describing the removal process must
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be developed 3 . The equilibrium of metal sorption has been studied by applying the
widely-used adsorption isotherm models of Langmuir and Freundlich to the experimen-
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tal data 1 . Several other complex mathematical models based on mass transfer
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reactions and the equilibrium of metal sorption have been proposed 24 .
Previous studies carried out using microbial biomass of Streptoerticillium cinna-
moneum, Penicillium chrysogenum and Citrobacter sp. MCM B-181 were directed
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towards detailed characterization of lead and zinc biosorption from solutions 5,6 . The
main objective of the work reported here is to compare the kinetics of metal sorption by
these microorganisms and attempt to interpret the experimental data with the help of a
mathematical model based on the equilibrium of metal sorption and mass transfer
kinetics. The application of such a model would help in understanding the biosorbent
behavior and aiding the scale-up of the process.
2. Materials and methods
2.1. Biomass
The waste mycelial biomass of S. cinnamoneum and P. chrysogenum from fermenta-
.
tion industry were used in these studies. The biomass samples 5 kg batches were
obtained in the form of cakes which were placed in shallow enamel trays in an electric
oven at 608C for 48 h. The dried biomass was then crushed in a blender and sieved to
.
obtain particles of 1416 BSS mesh 1.21.4 mm size.
Biomass of Citrobacter strain MCM B-181 was developed by growing in nutrient
. .
broth pH 7.0 at room temperature 28"38C for 24 h. The cells were harvested by
y1
.
centrifugation at 8000 min for 10 min Sorvall RC-5B plus centrifuge . The harvested
.
cells biomass were washed twice with sterile physiological saline. Cell suspensions of
Citrobacter strain MCM B-181 were prepared by re-suspending a cell pellet in distilled
water for use in the biosorption experiments. The biomass concentration in the cell
suspensions was determined by drying an aliquot to constant weight at 808C in a
pre-weighed aluminum foil.
2.2. Metal sorption studies

A set of 250 ml Erlenmeyer flasks containing 50 ml metal solution 0.5, 1 and 1.5
.
mM was used and 0.2 g biosorbent i.e., granulated waste biomass of S. cinnamoneum
.
and P. chrysogenum was contacted with the metal solutions by incubating the flasks on
a rotary shaker at 150 min
y1
. The period of contact between the biomass and the metal
solutions was varied for the determination of the rate of uptake. For this purpose, the
( )
P.R. Puranik et al.rHydrometallurgy 52 1999 189197 191
.
flasks from an experimental set were removed at an interval of 5 min up to 90 min ,
their contents were filtered and the filtrates were analyzed for the residual metal
.
concentration. In the case of Citrobacter, 2 ml cell suspension 0.1 g dry cell biomass
was contacted with 50 ml metal solution. The biomass from samples were removed by
y1
.
centrifuging at 10,000 min for 3 min using a microfuge Spinwin, India and the
supernatants were analyzed for residual metal concentration on an atomic absorption
.
spectrometer Unicam 929 AA Spectrophotometer, UK . All the above experiments
were carried out in triplicate and repeated twice to ensure accuracy of results.
.
The metal adsorbed by the biomass Q mg metalrg dry biomass was calculated as:
QsV C yC r1000M 1 . .
i f
.
where Q is the specific metal uptake mgrg biosorbent ; V is the volume of metal
. .
solution ml ; C is the initial concentration of metal in the solution mgrl ; C is the
i f
. .
final concentration of metal in solution mgrl and M is the dry weight of biomass g .
2.3. Metal solutions
.
Stock solutions of lead and zinc 20 mM were prepared by dissolving appropriate
quantities of pure metal powders in 1% nitric acid. The choice of nitric acid was made
on the basis of non-interference of nitrate ions on biosorption of lead and zinc by the
.
biomass used in the present study data not shown . The stock solutions were diluted
with de-ionized distilled water to obtain working solutions of 0.5, 1 and 1.5 mM
concentrations. The solutions were adjusted to desired pH values with 0.1 M sodium
hydroxide and 0.1 M nitric acid.
2.4. Modeling of the metal biosorption in batch flask experiments
A mathematical model was used in the present studies on metal sorption by three
different kinds of microbial biomass. The following assumptions were made for
.
developing the model: i the particles are considered to be spherical consisting of

uniform biosorptive surface the biomass particles used in this study were nearly
. .
spherical and of consistent size ; ii the concentration of the solute in the bulk is
.
considered to be homogeneous due to uniform mixing in the batch reactor; iii
.
intraparticle diffusion is neglected due to the consideration of surface adsorption; iv a
rapid equilibrium is established between the solute at the interface and that present on
.
the biomass particle; v volume of the liquid in the reactor is assumed to be equal to the
.
volume of content in the batch reactor; and vi the biosorption process is isothermal and
may be characterized by either a Langmuir or a Freundlich isotherm. Assumptions
. .
ii vi have been justified in many previous efforts for simplification of general
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adsorption process modeling 4 .
A total mass balance equation of the solute across the biosorbent surface can be
written as
W QqCsC 2 .
s 0
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P.R. Puranik et al.rHydrometallurgy 52 1999 189197 192
.
where W is biomass loading per unit volume of solution grl , Q is the specific metal
s
. .
uptake mgrg , C is the concentration of solute in the bulk mgrl , and C is the initial
0
.
concentration of solute in the bulk mgrl .
The rate of change in the bulk concentration is proportional to the driving force for
adsorption on the surface of the particle
dCrdt syK a CyC 3 . .
m p
.
where K is the external film mass transfer coefficient mrs , a is the specific surface
m

2 3
.
area of the biosorbent granules per unit volume of reactor m rm , and C is the
p
concentration of solute at the liquidbiomass interface.
Assuming equilibrium conditions exist at the liquidparticle interface, the Langmuir
adsorption equation yields
QsQ bC r 1qbC 4 . .
max p p
.
where Q is a maximum metal uptake mgrg biomass , and b is a Langmuir isotherm
max
.
constant lrmg .
. .
Combining Eqs. 2 and 3
W dQrdt sK a CyC 5 . . .
s m p
.
Differentiating Eq. 4 and simplifying we have
2
dQrdt s dC rdt Q br 1qbC 6 . . .
p max p
. .
Substituting Eq. 6 in Eq. 5 and simplifying we have
2
dC rdt s K arW Q b CyC 1qbC 7 . . . .
p m s max p p
. .
Thus, Eqs. 3 and 7 describe the batch kinetics of metal uptake. Using non-dimen-
sionless variables,
C
U
sCrC and C
U
sC rC
0 p p 0
. .
Eqs. 3 and 7 reduce to
dC
U
rdt syK a C
U
yC
U
8 . .
m p
2
U U U U U
dC rdt s K arW Q b C yC 1qbC C 9 . . . .
p m s max p 0 p
. .
Eqs. 8 and 9 represent first order ordinary differential equations for the batch
U
.
kinetic model, which can be solved simultaneously using the initial conditions C t s0
U
.
s1, C t s0 s0. The change of metal concentration in the bulk liquid with time can
p
. .
be predicted by applying the model Eqs. 8 and 9 to the experimental data. In order to
judge the applicability of the mathematical model, the experimental values obtained in
. .
the kinetic studies were fit by Eqs. 8 and 9 and solved using the ode45 routine from
the MATLAB package.
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P.R. Puranik et al.rHydrometallurgy 52 1999 189197 193
3. Results and discussion
3.1. Kinetics of metal uptake
The results obtained in the kinetic studies on lead and zinc biosorption by S.
cinnamoneum, P. chrysogenum and Citrobacter sp. biomass are shown in Fig. 1ac and
Fig. 2ac. It can be seen that in all cases the metal concentration was found to decrease
rapidly during the first 10 min and remained unchanged after 30 min of contact. This

suggested that the metal biosorption by microbial biomass of different origin i.e.,
.
wasterlaboratory grown and bacterialrfungal biomass was fast and reached a state of
equilibrium within 30 min of contact.
In order to see the effect of initial metal concentration on the rate of uptake the

experiments were carried out at different metal concentrations viz. 0.5, 1.0 and 1.5
.
mM . It can be seen that the rate of metal uptake during the entire course of biosorption
was independent of initial metal concentrations used. There was no significant change in
the time required to attain the equilibrium at various initial metal concentrations.
However, the amount of metal adsorbed was found to increase with increasing initial
. . .
Fig. 1. Lead biosorption kinetics by a S. cinnamoneum, b P. chrysogenum and c Citrobacter strain MCM
. . .
B-181 obtained at initial lead concentrations of B 0.5; ' 1.0; and I 1.5 mM. The solid lines are the
lead concentration profiles predicted by the batch kinetic model. Dotted line shows the concentration profile
used for estimation of K a.
m
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P.R. Puranik et al.rHydrometallurgy 52 1999 189197 194
. . .
Fig. 2. Zinc biosorption kinetics by a S. cinnamoneum, b P. chrysogenum and c Citrobacter strain MCM
. . .
B-181 obtained at initial zinc concentrations of B 0.5; ' 1.0; and I 1.5 mM. The solid lines are the
zinc concentration profiles predicted by the batch kinetic model. Dotted line shows the concentration profile
used for estimation of K a.
m
metal concentration. Similar observations were reported in the studies on copper uptake
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by Aspergillus carbonarius 7 and nickel biosorption by Pseudomonas sp. 8 for metal
concentrations ranging between 25400 mgrl and 0120 mgrl, respectively. In con-
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trast, Scott and Karanjkar 9 observed that as the cadmium concentration increased
.
from 25 to 500 mgrl the time required to reach equilibrium of biosorption by
Enterobacter aerogenes decreased because the sites available for direct cadmium
adsorption were rapidly taken up.
It is known that the rate of metal uptake is influenced by factors affecting mass
transfer from bulk solution to the binding sites. Various steps of metal transfer from bulk
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solution to the binding sites have been reported in the literature 10 . The first step, viz.
bulk transport of metal ions in the solution phase, is usually rapid because of mixing and
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advective flow 11 . The second step, i.e., the film transport, involves diffusion of the
metal through a hydrodynamic boundary layer around the biosorbent surface. The third
step, i.e., actual adsorption of metal ions by the active sites of the biomass is considered
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to be rapid, equivalent to an equilibrium reaction 10 . In the present study, experimental
conditions allowing good mixing of solutes and biomass in the system might have
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P.R. Puranik et al.rHydrometallurgy 52 1999 189197 195
suppressed the kinetic limitations due to the first and third steps. Therefore, it is likely
that the kinetics of the process were influenced only by the step of metal transfer from
.
solution to the binding sites i.e., second step and hence showed characteristic metal
binding with an equilibrium time unaltered over the range of metal concentrations used.
3.2. Application of the batch kinetic model
. .
The prediction of metal ion concentration using Eqs. 8 and 9 requires knowledge
of three parameters: equilibrium isotherm parameters, Q , b and mass transfer
max
coefficient, K a. The estimation of the values of Q and b was done by applying the
m max

Langmuir adsorption isotherm model to the data at varying metal concentrations 01.75
.
mM . For a given metalmicroorganism pair, experimental data at 1 mM concentration
were used for determining the mass transfer rate. A least square minimization between
.
experimental and model predicted values for 1 mM data was used to estimate K a.
m
. ..
Using the estimated value of K a, the model Eqs. 8 and 9 was used to predict the
m
metal ion concentration profiles. It can be seen that there was no difference in the values
of K a estimated for lead and zinc by the same biomass. This suggested that the mass
m
transfer coefficient was independent of the type of metal ion to be adsorbed for those
metals considered.
The comparison of the metal biosorption performance of the biomass can be made on
the basis of Q values. It can be seen that S. cinnamoneum exhibited higher metal
max
.
sorption capacity values Q for both lead and zinc than other types of biomass. A
max
sorption series of biomass could be prepared on the basis of their metal uptake capacity
.
Q , as follows: S. cinnamoneum)Citrobacter sp.)P. chrysogenum.
max
The sorption performance could also be compared on the basis of process kinetics.
The sorption series of biomass prepared on the basis of values of mass transfer
.
coefficient K a and hence, kinetic efficiency was as follows: Citrobacter sp.)S.
m
cinnamoneum)P. chrysogenum.
The difference seen in the position of the S. cinnamoneum and Citrobacter sp. can be

attributed to the difference in size the former was a granular preparation while the latter
. .
was a cell suspension and concentration of the biomass used Table 1 . This indicated
that the mass transfer of metals was affected by change in the size and concentration of
biomass in the reactor. Similar effect of biosorbent size on the biosorption kinetics has
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been reported in the studies on uranium removal by immobilized Rhizopus arrhizus 2 .
Table 1
Model parameters
Parameter Biomass type and metal sorbed
S. cinnamoneum P. chrysogenum Citrobacter sp.
Lead Zinc Lead Zinc Lead Zinc
.
Q mgrg 74.6 10.1 49.8 6.0 68.8 7.6
max
.
b lrmg 0.026 0.06 0.013 0.1 0.11 0.16
.
W grl 4.0 4.0 4.0 4.0 2.0 2.0
s
y1
.
K a min 0.06 0.06 0.03 0.03 0.1 0.1
m
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P.R. Puranik et al.rHydrometallurgy 52 1999 189197 196
The model was applied to lead and zinc sorption data. Figs. 1 and 2 show a good
match of the experimental data with the values predicted by the model. In order to
evaluate the applicability of the model in response to change in process conditions, one
of the parameters, viz. initial metal concentration was varied. The metal concentration
.
profiles obtained at varying initial metal concentrations 0.5 and 1.5 mM using the
batch kinetic model defines well the actual system for Citrobacter. However, minor
deviations with regard to the experimental data were seen in the case of S. cinnamoneum
and P. chrysogenum biomass. These deviations may be due to the heterogenous nature
of the biomass procured as waste material from industry.
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Tsezos et al. 2 studied the kinetics of adsorption of uranium by the immobilized
fungal biomass of R. arrhizus. They reported that the overall rate of biosorption was
significantly affected by the size of the immobilized biomass particle. They also found
that the diffusion of uranium in the particle interior was as significant as the mass
transfer resistance in the non-biomass layer. In the present study it was observed that the
.
dried dead waste biomass was hard and non-porous. Therefore, transport of solute
inside the particle was neglected and it was assumed that the biosorption mainly
occurred at the particle surface. In the present study, successful prediction of metal
concentration profile with respect to the time using the new model indicated that there
was no uptake of the metals inside the cell surface.
. .
The applicability of the model, as evidenced by the derivation of Eqs. 1 9 , was
independent of the nature of the adsorbate. Therefore, the model can be applied to the
biosorption of different metals and types of biosorbent provided the equilibrium
isotherm is available and the model assumptions described earlier are valid.
Acknowledgements
The authors thank the Director, Agharkar Research Institute for the facilities pro-
vided. PRP is thankful to the Council of Scientific and Industrial Research, New Delhi
for the award of a Senior Research Fellowship.
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