Wat. Res. Vol. 35, No. 5, pp.

11251134, 2001
# 2001 Elsevier Science Ltd. All rights reserved
Printed in Great Britain
PII: S0043-1354(00)00389-4 0043-1354/01/$ - see front matter

PROCESS DEVELOPMENT FOR THE REMOVAL OF LEAD

AND CHROMIUM FROM AQUEOUS SOLUTIONS USING
RED MUD}AN ALUMINIUM INDUSTRY WASTE
VINOD K. GUPTA*, MONIKA GUPTA and SAURABH SHARMA
Department of Chemistry, University of Roorkee, Roorkee-247 667 UP, India

(First received 1 June 2000; accepted in revised form 10 August 2000)

Abstract}Red mud, an aluminium industry waste, has been converted into an inexpensive and efficient
adsorbent and used for the removal of lead and chromium from aqueous solutions. Effect of various
factors on the removal of these metal ions from water ( e.g. pH, adsorbent dose, adsorbate concentration,
temperature, particle size, etc.) has been studied and discussed. The effect of presence of other metal ions/
surfactants on the removal of Pb2+ and Cr6+ has also been studied. The material exhibits good adsorption
capacity and the data follow both Freundlich and Langmuir models. Thermodynamic parameters indicate
the feasibility of the process. Kinetic studies have been performed to understand the mechanism of
adsorption. Dynamic modelling of lead and chromium removal on red mud has been undertaken and
found to follow first-order kinetics. The rate constant and mass transfer coefficient have also been
evaluated under optimum conditions of removal in order to understand the mechanism. Column studies
have been carried out to compare these with batch capacities. The recovery of Pb2+ and Cr6+ and
chemical regenertion of the spent column have also been tried. # 2001 Elsevier Science Ltd. All rights
reserved

Key words}lead, chromium removal, adsorption, red mud

INTRODUCTION Standard Institution, the tolerance limit for discharge

The presence of metal ions in the environment is
of major concern due to their toxicity to many life
forms. Unlike organic pollutants, the majority of
which are susceptible to biological degradation,
metal ions do not degrade into harmless end-
products. The metals of most immediate concern
are Cr, Mn, Fe, Zn, and Cd. These metals are widely
distributed in materials which make up the earths
surface (Dean et al., 1972). Lead is ubiquitous in the
environment and is hazardous at high levels. It comes
into water through the combustion of fossil fuels and
the smelting of sulfide ore, and into lakes and streams
by acid mine drainage. Process industries, such as
battery manufacturing and metal plating and finish-
ing are also prime source of lead pollution. Lead
accumulates mainly in bones, brain, kidney and
muscles and may cause, many serious disorders like
anaemia, kidney disease, nervous disorders and
sickness even death. Current EPA drinking water
standard for lead are 0.05 mg L1, but a level of
0.02 mg L1 has been proposed and is under review
(Groffman et al., 1992). According to Indian
*Author to whom all correspondence should be addressed.
Tel.: 0091-1332-85801; fax: 0091-1332-73560; e-mail:
vinodfcy@rurkiu.ernet.in
1125
of lead into drinking water is 0.05 mg L1 (I.S.I.
Specification IA: 2490, 1982) and in land surface
waters is 0.1 mg L1 (I.S.I. Specification IS 10500,
1991).
Chromium occurs in higher concentration in the
wastes from electroplating, paints, dyes, chrome
tanning, paper industries, etc. It is also added to
cooling waters to check corrosion. Over exposure of
chrome workers to chromium dusts and mists has
been related to irritation and corrosion of the skin
and the respiratory tract and, probably, to lung
carcinoma. Ingestion may cause epigastric pain,
nausea, vomiting, severe diarrhoea and haemorrhage
(Huang and Wu, 1977). Maximum contaminant level
of chromium for the drinking water is 0.05 mg L1
(Faust and Aly, 1987).
Increasingly strignent legislation on the purity of
drinking water has created a growing interest in the
development of conventional treatment processes.
Various methods of wastewater treatment were
examined and adsorption emerged as one of the
most promising technique (Cheremisinoff and Eller-
bush, 1979; Pollard et al., 1992). The use of activated
carbon is still very popular and different grades are
available, but are quite expensive and the regenera-
tion of the carbon is not always possible (Lalvani
et al., 1998). A considerable research work has been
1126 Vinod K. Gupta et al.
done in the search of inexpensive adsorbents
especially developed from various industrial waste
materials i.e. fly ash (Ferraiolo et al., 1990; Diama-
dopoulos et al., 1993), metal hydroxides (Namasi-
vayam and Ranganathan, 1998), blast furnace slag
(Dimitrova and Mehandgiev, 1998), biomass (Chang
et al., 1997), peanut hull (Periasamy and Namasi-
vayam, 1994), bagasse pith (Aly and Daifullah,
1998), carbonaceous material (Srivastava et al.,
1989, 1997; Srivastava and Tyagi, 1995), bagasse fly
ash (Park et al., 1999), etc.
Our earlier efforts on the utilization of solid waste
materials being generated in some prime industries
have been very successful (Gupta et al., 1997, 1998,
1998a; Gupta, 1998). In continuation it was decided
to undertake a study to assess the potential of red
mud, an aluminium industry waste material as an
adsorbent for the removal of toxic metal ions viz.
lead and chromium from aqueous solutions. Red
mud is a waste material formed through the bayer
process of alumina production in the aluminium
industries (Lopez et al., 1998). The toxicity and
colloidal nature of the red mud particles as well as the
relatively large quantities generated, create a serious
pollution hazard and needs a search out for an 150200 BSS mesh was then added into each test tube and
improved disposal technique (Akay et al., 1998).
There have been many proposals for red mud
utilization and is currently being used, in the
manufacture of building materials and ceramics, as
a filler in asphalt road, as iron ore and a source of
various minerals, but still a large volume is dumped
in holding ponds for which a large area of land is
required (Li, 1998).
MATERIALS AND METHODS
All the reagent used were of A. R. grade. Stock solutions
of the metal ions were prepared by dissolving Pb(NO3)2
(Aldrich Chemical Corp., Inc., Delhi, India) and K2Cr2O7
(Sigma Chemical Corp., Inc., Delhi, India) in doubly
distilled water. Hydrogen peroxide (H2O2) used for the
activation of red mud was supplied by BDH, Delhi, India.
HNO3 utilized in column studies was supplied by Merck,
Delhi, India.
Equipment
Atomic absorption spectra were recorded using an atomic
absorption/emission spectrophotometer (Perkin Elmer
Model 3100, USA). X-ray measurements were done by
a Phillips X-ray diffractometer (Model No. PW 1140/90,
Holland) employing nickel filtered Cu Ka radiations. The
surface area of the sample was measured by a surface-area
analyzer (Model QS-7; Quantasorb surface-area analyzer,
USA). pH measurements were made using a pH meter
(Model CT No. C L 46 ; Toshniwal, India). The constituents
of red mud were analyzed following the standard methods
of chemical analysis (Vogel, 1989). Scanning electron
microscopy was performed using a Phillips SEM 501
electron microscope (Holland). The density of the adsorbent
was determined by specific gravity bottles.
Material development
Red mud obtained from Hindustan Aluminium Com-
pany (HINDALCO) (Renukoot, India), is a clayesh waste
residue composed of a fine fraction (mud) and a relatively
coarse fraction (sand) with small granules. This material was
first treated with hydrogen peroxide at room temperature
for 24 h to oxidize the adhering organic impurities and
washed repeatedly with doubly distilled water. The resulting
product was dried at 1008C cooled and again activated in air
in a muffle furnace at 5008C for 3 h. The temperature and
time were optimized by observing the surface properties of
red mud obtained during the activation at different time
intervals and varying temperatures. Condition of activation
were carefully controlled to obtain the product of batch to
batch reproducibility. The activated red mud was crushed to
smaller particles and sieved to desired particle size such as,
100150, 150200, and 200250 B.S.S. mesh. The studies
were carried out with the red mud of particle diameter
(150200 B.S.S. mesh or 0.089 mm). Finally, the product
was stored in a vacuum desiccator until used.
Adsorption studies
Adsorption studies were mainly carried out by batch
technique to obtain rate and equilibrium data. For these
investigations, a series of test tubes containing equal volume
(10 mL in each case) of adsorbate solutions of varying
concentration were employed, at desired pH and tempera-
ture. A known amount of adsorbent (0.1 g) of particle size
agitated intermittently for 24 h. Preliminary studies showed
that equilibrium was attained in 810 h. Shaking for
anytime between 8 and 24 h gave practically the same
uptake. As such, all adsorption experiments were carried
out after equilibrating 10 mL of adsorbate solution with a
fixed amount of red mud (0.1 g) for 24 h. Initial adsorbate
concentration ranged from 4.80  104 to 4.83  103 M for
lead and 9.60  104 to 9.60  103 M for chromium.
To optimize the adsorbent concentration for the removal
of lead and chromium from the solution, adsorption studies
were carried out with different adsorbent doses. The effect of
pH was determined by studying the adsorption of metal ions
at a fixed concentration over a range of 1.06.0 pH. pH
adjustment was made by dilute base and dilute acid.
Adsorption experiments were run at 30, 40 and 508C to
assess the effect of temperature. The influence of both
cationic surfactant (cetyltrimethyl ammonium bromide) and
anionic surfactant (manoxol-1B) on the adsorption was
studied at optimum pH (4.0 for Pb2+ and 2.0 for Cr6+) as a
function of detergent concentration. Stoppered glass tubes
containing adsorbate solution along with the detergent and
a fixed amount of adsorbent (10 g L1 for both Pb2+ and
Cr6+) were equilibrated for 24 h. The supernatant solution
was centrifuged and analyzed for aqueous metals.
A similar procedure was adopted to study the inter-
ference caused by the presence of other metal ions.
Kinetic studies
The batch technique was selected for kinetic studies
because of its simplicity and reliability. A number of 50 mL
stoppered glass tubes containing a definite volume (10 mL in
each case) of solutions of metal ions of known concentra-
tion (3.38  103 M for Pb2+ and 5.77  103 M for Cr6+)
were placed in a thermostat cum shaking assembly. At
desired temperature, a known amount of adsorbent (0.1 g)
was added into each tube and the solutions were agitated
intermittently. At predecided interval of time, the test
solutions were centrifuged to separate the adsorbent
material and the supernatant was analyzed for aqueous
metal. The kinetic studies were also performed at different
adsorbate (2.41  1034.83  103 M for Pb2+ and
 Removal of lead and chromium from aqueous solutions
9.60  1049.60  103 M for Cr6+) and adsorbent
(5 g L120 g L1 for both Pb2+ and Cr6+) concentration.
Column studies
Adsorption isotherms are used for some primary studies
and obtaining the operational parameters before running
more costly experiments. Hence, the practical applicability
of the product for column operations has also been studied
to obtain some parameters necessary for a factual design
model. A glass column (40  0.5 cm) filled with a known
amount of red mud (mesh size 200250) was used for
different metal ions. Effluent flow was adjusted with a clip at
the bottom of the column. The columns were loaded with
solutions of Pb2+ (3.38  103 M) and Cr6+ (5.77  103 M)
at pH 4.0 and 2.0, respectively.
Regeneration
Regeneration of adsorbent as well as recovery of
adsorbate material is quite important, therefore, the same
have been achieved by using 1% HNO3. Simultaneous
regeneration of adsorbent was also tried.
RESULTS AND DISCUSSION
Characterization of the adsorbent material
Chemical constituents of the activated red mud as
determined by using standard methods of chemical
analysis are Fe2O3, 38.80%; TiO2, 18.80%; SiO2,
9.64%; Al2O3, 17.28%; Na2O, 6.86%; Loss on
ignition, 7.34% by weight. Porosity and density of
the product, as determined by a mercury porosimeter
and specific gravity bottles, are 0.45 fractions and
2.002 g/cm3, respectively. One gram sample of
activated red mud was stirred with deionized water
(100 mL, pH 6.8) for 2 h and left for 24 h in an air-
tight stoppered conical flask. An enhancement in pH
7.5 was noticed. Red mud is quite stable in water, salt
solutions, acids, bases, and organic solvents. Analysis
by X-ray diffraction showed a predominance of
poorly soluble minerals (Table 1) which shows a
high chemical stability of the red mud (Index to the
powder diffraction file, 1971; Gadsden, 1975). The
surface area of the adsorbent as calculated by BET
method was found to be 108 m2 g1. Surface structure
of activated red mud was observed by scanning
electron microscope (SEM). SEM photo-micro-
graphs of activated red mud, at four different
magnifications, helped in recognizing the texture of
aluminium silicates, distributed with the heavy
constituents like iron. The photo-micrographs also
Table 1. d-spacing values obtained from X-ray diffraction of the
activated red mud
d (A) Probable minerals d (A) Probable minerals
3.67 Cancrinite 2.69 Hematite
4.18 Goethite 1.69 Hematite
2.45 Goethite 2.51 Hematite
3.26 Rutile 3.52 Anataze
2.94 Rutile 1.89 Anataze
3.33 Quartz
1127
depict that red mud consist of fine particles, of
indefinite shape, at the same time, there were distinct
separate crystal having a shape of regular and
irregular quadrangle (Fig. 1(a)(d)).
Adsorption studies
Adsorption of the two metal ions was studied at
varying pH values to determine the optimum pH
range for their removal, and the results are shown in
Fig. 2. The percentage adsorption increased with
increasing pH up to a certain range in both cases and
then decreased with further increase in pH. The
maximum uptake took place at pH 4.0 and 2.0 for
lead and chromium, respectively. The variation in the
removal of lead and chromium can be explained by
considering the surface charge of the adsorbent
material, i.e., red mud. Among the various constitu-
ents of red mud the ZPC of silica is 2.3 and that of
Fe2O3 is 8.6. The composite ZPC of the adsorbent
is found to be 3.2. Thus below 3.2 pH the surface has
high positive charge density and under these condi-
tions the uptake of metal ions would be quite low due
to electrostatic repulsion. With increasing pH, i.e.,
beyond ZPC the negative charge density on the
surface of adsorbent increases, thereby resulting in a
sudden enhancement in metal adsorption. As such
lead get adsorbed at pH 4.0. However, the higher
adsorption of Cr6+ on red mud at low pH may be
due to the neutralization of surface charge by an
excess of hydrogen ions, thereby, facilitating the
diffusion of dichromate ions and their adsorption on
the prepared adsorbent. A significant reduction in the
adsorption of Cr6+ at higher pH is possibly due to
the abundance of OH ions resulting in an increased
hindrance to the diffusing species. These finding are
also supported by considering the composition of red
mud texture. Red mud is composed of clay minerals
having negative double layer at the planar surface,
and on broken edges (Van Olphen, 1963), the
polarity of the double layer is reversed, i.e., the fixed
part of the double layer is positive and counter ions
are anions. The positive double layer at broken edges
changes polarity with increasing pH and results in an
enhancement of negative adsorption sites at higher
pH. Significant adsorption of lead and chromium at
low pH values suggested that the process of metal ion
uptake is sufficient energetic to over come the net
electrostatic repulsion.
Various fractions of particle size, i.e., 100150,
150200, and 200250 B.S.S. mesh have been tried
and it was found that as the particle size decreases,
the extent of adsorption increases this may be
because of the enhanced surface area available for
the adsorption (Fig. 3(a) and (b)). However, a
uniform particle size of 150200 mesh was used
because of convenience and due to the fact that there
was very little difference in adsorption with particle
size of 200250 mesh and 150200 mesh.
1128 Vinod K. Gupta et al.
Fig. 1. S.E.M. microphotographs of activated red mud at different magnifications: (a) 1  5000;
(b) 1  2500; (c) 1  160; (d) 1  80.
Fig. 2. Effect of pH on the adsorption of metal ions on
activated red mud.
Further it is observed that the adsorption de-
creased with an increase in temperature indicating
that the process is exothermic in nature (Fig. 4(a) and
(b)). The adsorption isotherms are regular, positive
and concave to the concentration axis. The plot of
Pb2+ (Fig. 4(a)) shows that lead is 100% adsorbed at
lower concentrations (1.45  103 M) on red mud
and the adsorption decreases with concentration
(3.38  103 M) and finally becomes constant. In
case of chromium as depicted in Fig. 4(b) the uptake
is nearly 100% upto concentration 9.60  104 M
and decreases leading to a constant value with
concentration (5.77  103 M). These finding sug-
gest the efficacy of the red mud for the removal of
lead and chromium from wastewater in a wide range
of concentrations. Freundlich and Langmuir iso-
therms have been employed to study the adsorption
behaviour of Pb2+ and Cr6+. The adsorption of
Pb2+ and Cr6+ on red mud follows both these
models. The values of Freundlich and Langmuir
constants evaluated from the plots are listed in
Table 2.
The adsorption capacity KF is less for leadred
mud system than that for chromiumred mud
system. The slope (1/n) which reflects the intensity
of adsorption presents the same trend. The value of
Q0 (i.e. maximum uptake) decreases with the increase
in temperature, thereby indicating exothermic nature
of the process. The value of Q0 appears to be
significantly higher for chromiumred mud system in
comparison to leadred mud system.
The dimensionless separation factor RL (Weber
and Chakravorti, 1974) as calculated from equation
(1) was found to be 0.018 and 0.302, respectively, for
lead and chromium. This indicate a highly favourable
adsorption (RL 51):
1
RL 1
1 bC0
Thermodynamic parameters were calculated using
Langmuir isotherms and are given in Table 3. The
changes in standard Gibbs free energy (DG0 ),
enthalpy (DH 0 ), and entropy (DS0 ) for the processes
 Removal of lead and chromium from aqueous solutions 1129

Fig. 3. Effect of particle size on the adsorption of (a) Pb2+

and (b) Cr2+ on activated red mud.

were obtained using expressions as described earlier
(Gupta, 1998). The negative free energy values
indicate the feasibility of the process and its
spontaneous nature without any induction period.
The negative values of enthalpy change (DH 0 ) for the
processes confirm their exothermic nature and the
possibility of strong bonding between the metal ions
i.e. Pb2+ and Cr6+ and red mud. A negative entropy
of adsorption (DS0 ) reflects the affinity of the
adsorbent material towards lead and chromium.
As a result of effluent emission from commercial
and domestic sector, natural water bodies may be
contaminated by a large number of heavy metal ions
and surfactants. The competitive adsorption of Pb2+
and Cr6+ was studied in the presence of several metal
ions and surfactants. The effects of ionic interactions
on the adsorption process has been interpreted, using
Fig. 4. Effect of temperature on the adsorption of (a) Pb2+
and (b) Cr2+ on activated red mud.
the ratio of the adsorption capacity of the ion in a
single component system (q0 ) to that in a multi-
component system (qm ) (Tan et al., 1985). It was
observed that the removal of Pb2+ at 4.35  103 M
was reduced by 4.37, 7.81, 12.64, and 15.17% in the
presence of 1.0  105 M Na+, Cr6+, Zn2+, and
Cd2+, respectively, and the removal of Cr6+ at
concentration 8.65  103 M is reduced by 1.50, 2.78,
3.82, and 4.63% in the presence of 1.0  105 M
Na+, Zn2+, Cd2+, and Pb2+, respectively. Similarly
a decrease in the scavenging efficiency (qm =q0 51) of
the red mud in the presence of anionic surfactant
(manoxol 1B) and cationic surfactant (cetyltrimethyl

Table 2. Freundlich and Langmuir constants for adsorption of Pb2+ and Cr6+ on red mud

Metal ion Freundlich constants Langmuir constants

1/n KF  104 Q0  104 (mol g1) b  103 (L mol1)

308C 408C 508C 308C 408C 508C

2+
Pb 0.20 1.45 3.44 3.39 3.23 15.90 4.80 2.05
Cr6+ 0.31 2.24 4.36 4.15 4.05 0.40 0.371 0.316
1130 Vinod K. Gupta et al.

Table 3. Thermodynamic parameters for the adsorption of Pb2+ and Cr6+ on red mud

Metal ion DG0(kJ mol1) DH 0 (kJ mol1) DS0 (kJ mol1)

308C 408C 508C

2+
Pb 22.82 20.74 18.67 85.94 0.208
Cr6+ 23.39 20.62 19.72 78.50 0.183

ammonium bromide) takes place for the uptake of values of the rate constant, Kad , for each system were
lead and chromium. It is found that the removal calculated from the respective Lagergerns plot and
of Pb2+ and Cr6+ goes down by 6.67 and 1.85%, are listed in Table 4.
respectively, in the presence of cationic surfactant
(1.0  105 M). Similarly in the presence of manoxol Mass transfer study. McKay and coworkers (1981)
1B (1.0  105 M) uptake was reduced by 9.88 and proposed a mass transfer model as given below
4.16% for Pb2+ and Cr6+, respectively.  
Ct 1 mk 1 mk
ln ln bL 3
C0 1 mk 1 mk mk
Kinetic studies
where Ct and Co (both in mg L1) are the respective
Preliminary studies on the rate of removal of Pb2+ concentrations of the metal ion at time t and zero,
and Cr6+ by red mud (at the optimum pH and k(L g1) is a constant obtained by multiplying the
adsorbent concentration), indicate the process to be Langmuir constants Q0 and b, m (g L1) and Ss
quite rapid. Nearly 3045% of the adsorption (cm1) are, respectively, the mass and outer surface
capacity was realized within the first hour of contact. area of the adsorbent particles per unit volume of
The initial rapid adsorption gives way to a very slow particle free slurry and bL (cm s1) is the mass
rate of approach to equilibrium, and saturation is transfer coefficient. The straight line plots between
reached in 810 h. It was found that the rate of lnCt =C0 1=1 mk and t proved the validity of
removal of metal ions increases with an increase in
the amount of red mud. For both the metal ions
(Pb2+ and Cr6+) there was a significant increase in
adsorption when adsorbent amount is increased from
5 to 10 g L1. Any additional amount of red mud
does not cause any significant change. Taking into
account both the handling problems associated with
large quantities of red mud and the relatively smaller
solute removal with smaller amounts of adsorbent,
the amount of red mud taken in all subsequent
kinetic studies was 10 g L1, for both Pb2+ and Cr6+
ions.
The rate of uptake of adsorbates, in the first hour
of contact, increases with an increase in the con-
centration of adsorbate, while, the time required for
50% of the ultimate adsorption is independent of the
initial adsorbate concentration (Fig. 5(a) and (b)).

Adsorption dynamics
The adsorption dynamics of the present system
were studied as follows.

Adsorption rate constant study. Lagergrens rate

equation as cited by Ho and McKay (1999) was
employed for studying the rate constant for the
system.
Kad
logqe q log qe 2
2:303
where qe and q (both in mg g1) are the amount
adsorbed at equilibrium and time t, respectively. The
plots between log (qe q) and t were found to be
linear for both lead and chromium which show the Fig. 5. Effect of adsorbate concentration on the rate of
first-order nature of the processes involved. The uptake of (a) Pb2+ and (b) Cr2+.
 Removal of lead and chromium from aqueous solutions 1131

Table 4. Mass transfer cofficient (bL ) and rate constant of
adsorption (Kad ) values for Pb2+ and Cr6+
Metal ion bL  105 (cm s1) Kad  103 (min1)
Pb2+ 13.70
Cr6+ 5.770
the above model in the present study. The values of
bL for different systems were determined from these
plots and are given in Table 4. These values indicate
that the velocity of mass transfer of lead and
chromium ions on red mud is sufficiently rapid to
recommend its use in the treatment of wastewater
polluted by lead and chromium.
Rate expression and treatment of data. In order to
properly interpret the experimental data, it is
necessary to identify steps controlling the overall
removal rate in the adsorption process. Kinetic data,
as obtained by finite bath method has been treated by
expression 4 and 5 given by Boyd et al. (1947). This is
in accordance with the observations of Reichenberg
(1953).
 
6 X1
1 Di tp2 n2
F 1 2 exp 4 adsorbent) accounts for the faster one and the one
p n1 n2 r20
6 X 1
1  
F 1 exp n2 Bt
p2 n1 n2
where F is the fractional attainment of equilibrium at
time t and is obtained by
F Qt =Q1
B p2 Di =r20 time constant
where Qt is the amount of uptake at time t and Q1 is
the maximum equilibrium uptake, Di is the effective
diffusion coefficient of adsorbate in adsorbent
phases, r0 is the radius of the adsorbent particle
assumed to be spherical and n is an integer. The
linearity test of Bt vs. t are employed to distinguish
between the film and particlecontrolled mechanism.
The Bt vs. time plots (figure not shown) for Pb2+ at
lower concentrations (3.38  103 M) were linear
and did not pass through the origin indicating
the film diffusion to be the rate-determining
mechanism. However, an increase in the sorption
rate of the Pb2+ with decreasing temperature,
support the particle diffusion mechanism. But at
higher concentrations (4.83  103 M) initially the
Bt vs. time plot obtained were linear and passed
through the origin and the process seems to be
particle diffusion controlled and during the later
stages of reactor the film diffusion mechanism also
becomes operative which is apparent from the
1.080 deviation of the plots from linearity. The Bt vs.
0.615 time plots of Cr6+ were linear initially at higher
concentration and passed through the origin
indicating the process to be particle diffusion but at
lower concentrations ( 5.77  103 M) it was
divided into two distinct parts. Initial part of the
plot did not pass through the origin and the slope
was small and thus the process was film-diffusion
controlled. But in the later part of the plot the slope
increases and thus particle-diffusion mechanism also
operates simultaneously (plot not given).
The Di values for the lead-red mud and chro-
miumred mud systems at different temperatures are
listed in Table 5. It may be argued that the effective
diffusion coefficient, Di in these systems comprises
two components, which are due to the simultaneous
diffusion of the ingoing ions through the pores of
different widths and different electronic fields along
the diffusion path. The diffusion within the pores of
wider-widths and weaker retarding forces of electro-
static interaction (particularly at the surface of the
within the pores of narrower mesh widths and
stronger retarding forces, accounts for the slower
5 component of Di . As the temperature increases, the
contribution of the faster component of Di decreases.
It is due to the decreasing mobility of the ingoing ion
at higher temperature which to some extent over-
comes the influence of retarding forces along the
6 diffusion path.
The linear nature of log Di vs. 1=T plots for both
7 the metal ions permits the use of Arrhenius equation
for the determination of D0 and Ea from the
intercepts and the slopes of the linear plots
(Fig. 6(a) and (b)). D0 values are further used to
calculate the entropy of activation for the adsorption
of lead and chromium (Table 5). It is found that the
Ea values are higher for chromiumred mud system
than for the leadred mud system. The negative DS#
values reflect that no significant change occurs in the
internal structure of red mud during the adsorption
of Pb2+ and Cr6+.
Column studies
For a feasible adsorption processes a straight
forward approach of Weber (1972) has been adopted
for the design of fixed bed adsorbers for the removal

Table 5. Effective diffusion coefficients (Di ), D0 , Ea , and DS # values for Pb2+ and Cr6+ at different temperatures

Metal ions Di (m2 s1)  1012 D0 (m2 s1)  1013 Ea (kJ mol1) DS (J K1 mol1)

308C 408C 508C

2+
Pb 1.32 1.16 1.02 9.02 10.53 128.19
Cr6+ 1.15 0.955 0.794 6.58 15.12 130.82
1132 Vinod K. Gupta et al.
Fig. 6. Log Di vs. 1=T plots of (a) Pb2+ and (b) Cr2+ for
activated red mud.
of Pb2+ and Cr6+. The breakthrough curves (Figs
7(a) and (b)) were used to calculate the column
capacity at complete exhaustion and the same was
determined by taking the total area to the point
where the effluent plot joins the effluent and dividing
this value by the weight of adsorbent in the column.
The values for batch capacity as well as column
capacity are given in Table 6. It was found that the
column capacity are much higher than their batch
capacity for both adsorbates. Similar behaviour has
also been reported earlier (Davis and Ford, 1972) and
higher breakthrough capacity may be assigned to the
inherent difference in the nature of continuous and
batch operations.
Regeneration
Studies have been performed for the desorption
of Pb2+ and Cr6+ using mineral acids, salt solutions
Fig. 7. Breakthrough curves of (a) Pb2+ and (b) Cr2+ on
activated red mud.
and bases. The desorption of lead and chromium
were studied under identical conditions of flow rate
(0.5 mL min1 ), length of column (40 cm), etc. It was
observed that 100 mL of 1% of HNO3 is sufficient for
almost complete desorption of lead from the column.
The first aliqout of 50 mL removed about 60% of the
adsorbate and the rest is desorbed in four increments
of 10 mL each. The percentage recovery of the lead
was 89%.
For chromiumred mud system 80 mL of 1%
HNO3 was used. The first aliquot of 35 mL desorbed
about 50% of the chromium metal ion and rest is
desorbed in three increments of 15 mL each. The
percentage recovery is 95%.
After desorption red mud columns were loaded
with lead and chromium. The break through capacity
of leadred mud system was found to be 88.2, 82.0,
78.8, 76.6, and 77.0 mg g1 and for chromium on red
mud 75.0, 65.5, 61.5, 58.9, and 57.0 mg g1 in the
subsequent cycles.
Thus a fall in sorption capacity of various columns
during repeated cycles was observed. Many solvents
and oxidizing agents were tried to regenerate the
 Removal of lead and chromium from aqueous solutions
Table 6. Comparison of batch and column capacity
Adsorbate Batch capacity Column capacity
(mg g1) (mg g1)
Pb2+ 64.79 88.20
Cr6+ 35.66 75.00
spent columns. It was observed that a treatment with
1M HNO3 solution at a flow rate of 0.5 mL min1
restores the sorption capacity of columns of red mud.
This treatment is to be done after each cycle. With
this treatment only 210% loss is recorded in the
second cycle and no further decrease is observed in
subsequent cycles.
CONCLUSIONS
Red mud obtained from the aluminium industry is
an efficient adsorbent for the removal of lead and
chromium. The product, activated in air, holds
promising adsorption characteristics for lead and
chromium and can be used as a suitable adsorbent
for the treatment of wastewater of various industries.
The uptake of chromium is more than that of lead
and is comparable to other commercially available
adsorbents. The removal of metal ions by this
adsorbent takes place via particle diffusion and the
thermodynamic parameters reflect the feasibility of
the process. The results indicate that the red mud can
be successfully employed for the removal of Pb2+
and Cr6+ in a wide range of concentrations. The
studies on column operations show that the product
can also be used on an indsutrial scale. Metal ions
adsorbed on the column of this material can be
quantitatively eluted with 1% HNO3. The exhausted
column can be chemically regenerated by treating it
with 1 M HNO3 and no dismantling is required.
Other salts present in effluents do not cause any
disturbing effects.
Acknowledgements}The authors are thankful to CSIR
(Council of Scientific and Industrial Research), New Delhi,
India for supporting the work.
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