Wat. Res. Vol. 32, No. 4, pp.

1314±1322, 1998
# 1998 Elsevier Science Ltd. All rights reserved
Printed in Great Britain
PII: S0043-1354(97)00326-6 0043-1354/98 $19.00 + 0.00

ADSORBENT PROPERTIES OF RED MUD AND ITS USE

FOR WASTEWATER TREATMENT
E. LOÂPEZ*, B. SOTO, M. ARIAS, A. NUÂNÄEZ{, D. RUBINOS and M. T. BARRAL
Departamento de EdafologõÂ a y QuõÂ mica AgrõÂ cola. Facultad de Farmacia. 15706, Santiago de
Compostela, Spain

(First received March 1996; accepted in revised form March 1997)

AbstractÐWith a view to simultaneously conserving the environment and an important natural

resource, we assessed the feasibility of using red mud (RM), a residue from bauxite re®ning, for waste-
water treatment. Moistened mixtures of RM and 8% (w/w) CaSO4 form aggregates which are stable in
aqueous media. Batch experiments examining adsorption of phosphorus (P) by these aggregates for
contact times of 3, 6, 24 and 48 h indicated that adsorption occurred by both fast and slow reactions.
Likewise, comparison of experimental breakthrough curves (BTCs) for P retention on a column of RM
aggregates (residence time 3 h) with MCMFIT-simulated BTCs indicated that fast and slow adsorption
reactions were occurring. Actual P retention was predicted, taking into account both kinetics of fast
and slow adsorption reactions. The RM aggregates had maximum adsorption capacities (evaluated
from ®ts (0.90 < R2<0.99) of the Langmuir isotherm to batch adsorption data for contact time 48 h)
for Cu2+, Zn2+, Ni2+ and Cd2+ of 19.72, 12.59, 10.95 and 10.57 mg gÿ1, respectively. In continuous
adsorption experiments in which secondary e‚uent from an urban sewage treatment plant was perco-
lated through RM aggregates packed into columns, puri®cation eciencies for P, Ni2+, Cu2+ and
Zn2+ were 100, 100, 68 and 56% respectively. Aggregated RM is suitable for treatment of wastewaters,
in particular those whose principal contaminants are P or heavy metals. # 1998 Elsevier Science Ltd.
All rights reserved

Key wordsÐred mud, aggregation, adsorption, metals, phosphorus, column experiments, wastewater,
puri®cation

NOMENCLATURE INTRODUCTION

C concentration in solution (mg lÿ1) The search for uses for industrial wastes and by-
C0 initial concentration (mg lÿ1) products and ecient methods of wastewater recov-
Ce concentration in the e‚uent (mg lÿ1)
Ci in¯uent concentration (mg lÿ1) ery, is motivated by the need for economically
V Pore water velocity (cm hÿ1) viable industrial and wastewater treatment processes
D axial dispersion coecient (cm2 sÿ1) with protection of the environment and public
z coordinate (l)
X adsorbed concentration (mg gÿ1) health. With the aim of addressing all these pro-
X1 adsorbed concentration in equilibrium sites (mg gÿ1) blems at a single stroke, we assess the feasibility of
X2 adsorbed concentration in non-equilibrium sites (mg gÿ1)
X2(eq) adsorbed concentration in non-equilibrium sites at using red mud for wastewater treatment.
equilibrium (mg gÿ1) Utilization of iron oxides for waste treatment has
X0 initial adsorbed concentration (mg gÿ1) been succesfully tested by several researchers.
X(t) adsorbed concentration in function of time (mg gÿ1)
Xm maximum capacity of adsorption (Langmuir equation) (mg Anderson et al. (1982), and Anderson and Priestley
gÿ1) (1983) described a new technology for the treatment
K Langmuir constant (l mgÿ1)
K' Freundlich constant [mg gÿ1 (l mgÿ1)1/n]
of drinking water by means of a suspension of
1/n Freundlich exponent (dimensionless) ®nely milled natural magnetite. Later, Hencl et al.
a ®rst order kinetic parameter (dayÿ1) (1994) succesfully replaced the natural magnetite by
b fraction of sites at equilibrium (dimensionless)
Kv generic kinetic constant chemically precipitated magnetite or ferrite derived
t time from industrial e‚uents.
S.D. standard deviation
R2 coecient of determination
Red mud (RM) is a ®ne-textured residue from
w2 chi square statistic bauxite re®ning that is currently dumped in holding
* P < 0.1 ponds, for which large areas of land are required.
** P < 0.01
*** P < 0.001 Its texture and composition (its principal com-
ponents are oxides of Fe, Al and Ti), confer upon
RM a high surface reactivity, but as yet it has scar-
cely been exploited as a means of removing the
*Author to whom correspondence should be addressed. microorganisms and inorganic and organic contami-
{Member IQWM. nants found in wastewaters. Indeed, to our knowl-
1314
 Adsorbent properties of red mud 1315

Table 1. Properties of red mud

Chemical composition (%) (air dried samples)

SiO2 Al2O3 Fe2O3 TiO2 CaO MgO Na2O K2O

6.10 20.10 31.80 22.60 4.78 0.20 4.70 0.03
Mineral composition (%)
Rutile Hematite Magnetite Ilmenite Sodalite
>50 30±50 3±10 3±10 traces
Particle size distribution data (%)
2.0±0.2 mm 0.8
0.2±0.05 mm 11.2
0.05±0.02 mm 10.6
0.02±0.002 mm 39.7
<0.002 mm 37.8

edge, the only references to wastewater treatment
using RM in the literature are those by Weaver and
Ritchie (1987), who examined phosphorus elimin-
ation from piggery e‚uent using RM, and those by
Ho et al. (1991, 1992a,b), who removed bacteria
and viruses and diminished wastewater N (NH+ 4
and NOÿ 3 ) and phosphate contents (by 74% and
>90%, respectively) by ®ltering primary sewage
e‚uent through mixtures of RM and sandy soil
packed into plastic columns; and diminished waste-
water N (NH+ ÿ
4 and NO3 ) and phosphate contents
(by 45% and 94%, respectively) using in®ltration
basins containing these mixtures for groundwater
recharge.
In this work we examine the use of RM as an
adsorbate for wastewater treatment. Since RM des-
tined for dumping in holding ponds has a high pH
and tends to form stable suspensions in water, pre-
treatment was necessary to neutralize alkaline com-
ponents and thereby induce formation of stable
aggregates suitable for use as a ®ltration medium.
We then determined those physico-chemical and
surface properties of the aggregated RM that might
in¯uence its ability to retain contaminants, and, by
means of batch and continuous experiments, in the
latter case employing packed columns, its adsorp-
tion capacity for a selection of contaminants.
MATERIALS AND METHODS
Properties of the red mud
Red mud was obtained from Alumina-Aluminio of San
CipriaÂn (Lugo, Spain). Freshly sampled RM had a water
content 47% and pH 10.2, and X-ray ¯uorescence revealed
its principal chemical components to be Fe2O3 (31.8%),

Fig. 1. Di€erential (pecked line) and cumulative pore size distribution curves for red mud aggregates.
1316 E. LoÂpez et al.

TiO2 (22.6%) and Al2O3 (20.1%) (Table 1). Analysis by
X-ray di€raction showed a predominance of poorly sol-
uble minerals (Table 1), which confer a high chemical
stability on the RM. A salt-free preparation of the RM
had speci®c surface 58 m2 gÿ1, a point of zero charge at
pH 6.9 (determined by potentiometric titration) and a cat-
ion exchange capacity of 108 10ÿ3 mol (+) kgÿ1 at pH 7
in ammonium acetate. The particle size data for this prep-
aration are included in Table 1.
Neutralization and aggregation
Because of the high sodium content and alkalinity of
the untreated RM, a pre-treatment step was necessary
before material suitable for use as ®ltration medium was
obtained. Pre-treatment entailed adding 8% (w/w) anhy-
drite (CaSO4) to dried, crushed RM and lightly kneading
the moistened mixture. The aggregates obtained had diam-
eter 0.01±5 mm and pH 8 (solid/water ratio 1:2.5), and
were stable in aqueous suspension over a broad pH range
(pH 2±12). The aggregates were physically characterized
using mercury intrusion porosimetry (Autopore II 9220)
with a pressure between 0 and 4 Mpa. The di€erential and
cumulative pore size distribution curves are shown in
Fig. 1. The porosity (pores ca. 0.002±6 mm; modal pore di-
ameter 3 mm) of the aggregates was 46.6%, their bulk den-
sity was 1.614 g cmÿ3, and their particle density was
3.025 g cmÿ3.
Batch adsorption experiments: adsorption of heavy metals
Adsorption of Ni2+, Cu2+, Cd2+ and Zn2+ by the RM
was examined as follows. Aggregated RM (1 g) and 25 ml
of 0.02 M Ca(NO3)2 were mixed and left for 3 h, stirring
them intermittently. This suspension was then adjusted to
pH 7 with NaOH 0.1 M, and 25 ml of a solution contain-
ing 250, 500, 1000, 1500 or 2000 mg lÿ1 of one of the diva-
lent metal ions (as its nitrate) was added. The suspension
was left stirring for 48 h, whereupon it was centrifuged at
4000 rpm for 15 min. The metal concentration in the
supernatant (C) was then determined by ¯ame atomic
absorption spectroscopy (Perkin-Elmer 2100 Spectro-
photometer), and the pH was measured.
Adsorption of phosphorus
Aggregated RM (1 g) was suspended in 25 ml of
KH2PO4 solution containing 20, 40, 80, 200 or 400 mg lÿ1
of phosphorus (P) and stirred for 3, 6, 24 or 48 h. At the
end of the contact time the suspension was centrifuged
and the P in the supernatant was determined colorimetri-
cally as the reduced phosphomolybdate (lmax =882 nm) by
comparison with standards of known concentration. The
amount of phosphorus adsorbed by RM was calculated by
the di€erence between the added P and P remaining in sol-
ution at the end of the incubation.
Adsorption kinetics
The data of adsorbed P at various time intervals were
®tted into six di€erent kinetic equations (zero, ®rst and
second order equations and the parabolic di€usion, two-
constant, and Elovich-type equations). The equations are
listed in Table 2.
Table 2. Equations used to ®t the various kinetic models to kinetic
data for phosphate adsorption
Equation Formula
Zero order X(t)=X0+Kv t
First order X(t)=X0+exp(Kv t)
Second order X(t)=1/((1/X0)-Kv t)
Two constant rate ln(X(t)) = ln(X0) + Kv lnt
Parabolic di€usion X(t)=X0+Kv sqrt(t)
Elovich equation X(t)=X0+Kv lnt
the column was re-weighed, thus allowing calculation of
the water content gravimetrically; the column was ¯ushed
with distilled water until the percolate was neutral (ca. pH
7) and had conductivity around 50 mS cmÿ1 at 258C. Then,
controlling the ¯ow with peristaltic pump (Gilson M312),
a solution initially containing 5.2 mg lÿ1 (Ci) of P as
H2POÿ 4 (adjusted to pH 7 with KOH) was allowed to per-
colate through the column at a rate of 1.24 ml hÿ1 so that
the mean residence time of the solution on the column
was 3 h. The samples were collected in average fractions
of 45.8 pore volume of the column. The concentration of
P in the percolate (Ce) was determined colorimetrically, as
described in the batch experiments.
Column II was used to examine adsorption of P and
heavy-metal, ammonium and nitrate ions from the e‚uent
of an urban sewage treatment plant following a secondary
aeration treatment. The chemical composition of this e‚u-
ent (including the initial concentrations, Ci, of the con-
taminants of interest) is given in Table 4.
Column II was prepared in much the same way as col-
umn I, except that this column was ®lled with aggregates
ranging from 1 to 2 mm of diameter and the percolate
procured in the ¯ushing stage had a pH between 7.5 and
8, and conductivity 390 mS cmÿ1, which was similar to that
of the e‚uent to be treated. E‚uent ¯ow onto the column
was controlled by a peristaltic pump so that the mean resi-
dence time was 3 h (¯ow rate 51.8 ml hÿ1). Percolate was
collected in fractions with volume equal to half the total
pore volume of the packed column (ca. 78 ml for each
0.5 displacement). The ®nal concentrations (Ce) of Cu2+,
Ni2+ and Zn2+ in the percolate were determined by
atomic absorption spectroscopy as before; and those of
NH+ 4 and NOÿ 3 were determined by titration as per
Bremmer and Keeney (1965), the total organic carbon
(TOC) was analyzed by measuring CO2 produced after the
total combustion of the organic matter using a Shimadzu
TOC-5000 total carbon analyzer.
In order that the mass balances for the wastewater con-
taminants could be compared with that for the inert tracer
ion Brÿ, a solution of KBr (523.4 mg lÿ1 Brÿ) was allowed
to percolate through the column. Bromide was determined
using an ion-selective electrode (Metrohm 702 SM
Titrino).
Table 3. Characteristic properties of the two columns used in the
adsorption experiments
Col. I Col. II

Continuous adsorption experiments Mass of red mud 5.0 191.8 g

Aggregate diameter 0.3±0.5 1±2 mm
These experiments examined percolation of a phosphate Column length 21.2 355.0 mm
solution and wastewater through RM aggregates packed Column diameter 15.0 28.0 mm
into two di€erent plastic columns. Characteristic proper- Total volume 3.75 218.6 cm3
ties of the columns used are given in Table 3. Bulk density 1.34 0.87 g cmÿ3
Column I was used to examine P adsorption, and was Intraaggregate
prepared bearing in mind the maximum adsorption ca- porosity 0.39 0.39 cm3 cmÿ3
pacity of the RM for P determined in the batch exper- Interaggregate
porosity 0.17 0.32 cm3 cmÿ3
iments. Speci®cally, the column was packed with RM
Total porosity 0.56 0.71 cm3 cmÿ3
aggregates of diameter 0.3±0.5 mm and its total mass was Residence time 3.0 3.0 h
recorded; the RM was saturated with distilled water and
 Adsorbent properties of red mud 1317

Table 4. Chemical composition of the secondary e‚uent of an and non-equilibrium. Also it was used for obtaining opti-
urban sewage treatment plant mal parameter values of the Freundlich equation.
The breakthrough curve (BTC) obtained for P in the
pH 7.09
C.E.(25oC)
_
484.1 mS cmÿ1
continuous experiment (column I) was used as objective
N-NH+ 4 12.18 mg lÿ1 data of the ®tting process. The Freundlich constants and
N-NOÿ 3 1.36 mg lÿ1 kinetic parameters for P adsorption were used as initial
P(soluble) 0.74 mg lÿ1 values in the parameter searching program.
P(total) 0.95 mg lÿ1
TOC 42.1 mg lÿ1
Cu2+ 20.7 mg lÿ1
Zn2+ 76.1 mg lÿ1 RESULTS AND DISCUSSION
Ni2+ 11.3 mg lÿ1
Batch adsorption experiments: adsorption of heavy
Description of MCMFIT metals
MCMFIT (Bajracharya and Barry, 1997) uses a mixing The experimental points in Fig. 2 show the vari-
cell method to simulate the physical dispersion by control- ation of the amount of each heavy metal ion (Ni2+,
ling the numerical dispersion induced by the ®nite di€er- Cu2+, Cd2+ or Zn2+) adsorbed per unit mass of
ence representation of the pure advective transport
equation. the aggregated RM (X) with the ®nal concentration
This is a two-site adsorption model which describes (C) of that ion in solution after 48 h. The curves
both equilibrium and non equilibrium adsorption (slow correspond to the best ®ts of the Langmuir iso-
adsorption). The two-site adsorption model has been dis- therm (Equation (4)) to the experimental data,
cussed by Cameron and Klute (1977), and Rao et al.
(1979). The governing one-dimensional transport describ- KXm C
ing two-site adsorption is Xˆ …4†
1 ‡ KC
dC dX1 dX2 dC d2 C where K is a constant related to the energy of the
‡ ‡ ˆV ‡D 2 …1†
dt dt dt dz dz adsorption-desorption process, and Xm is the maxi-
with the non equilibrium adsorption process de®ned by mum capacity of the substrate for adsorption of the
dX2 metal ion. Table 5 lists the values of K and Xm
ˆ a‰…1 ÿ b† f …C † ÿ X2 Š …2†
dt together with the corresponding coecients of de-
At equilibrium, adsorption on both the equilibrium and termination (R2). This equation gave better ®t than
non equilibrium sites is described by a non linear isotherm the Freundlich equation.
f(C) given by The high anities RM showed for these heavy
X1 ˆ b f …C † metal ions are attributable to chemisorption reac-
tions at the surfaces of the oxide components which
X2…eq† ˆ …1 ÿ b† f …C † …3† principally constitute RM. Owing to the hetero-
geneous nature of RM, it was not possible to ident-
At equilibrium the total concentration of adsorbed solute
is X1+X2. ify the oxide (e.g. Fe2O3, Al2O3, TiO2) with the
The terms dX1/dt and dX2/dt of the equation (1) highest anity for a given metal ion.
describe the fast and kinetically controlled reaction pro- The pH of the supernatant varied according to
cesses, respectively. When the fraction of adsorption sites the metal ion added and decreased as its concen-
(b) equals unity, the model becomes an equilibrium advec-
tive transport equation and when (b) equals zero, it
tration increased, oscillating between 7.5 and 7.9
reduces to a fully kinetic model. for Ni2+, 6.9 and 7.8 for Zn2+, 5.6 and 6.2 for
Given the initial conditions, such as the initial solute Cu2+ and 4.7 and 6.2 for Cd2+. These pH changes
concentration in both solid and liquid phases are assumed will have had some e€ect on the capacity of the
to be zero, equations (1) through (3) constitute the two- RM for adsorption of the metal ions.
site adsorption model. The linear two-site adsorption
model is mathematically identical to the problem of physi-
cal non-equilibrium (Parker and van Genuchten, 1984).
Also the two-site model is macroscopically indistinguish-
able from the double porosity and ®lm transfer processes.
MCMFIT is capable of dealing with linear, Freundlich
and Langmuir adsorption isotherms in equilibrium and
non-equilibrium, the simulation of non equilibrium
adsorption is simulated only by a ®rst order kinetic.
Nonlinear least-squares minimization is the curve ®tting
technique for parameter estimation in this model.
MCMFIT includes a random search of the parameter
space in order to ®nd a suitable set of initial parameter
values. User-de®ned parameter values were also included
because of physical considerations. Further details of the
model are explained in Bajracharya and Barry (1997).

Modelling and simulation

The program MCMFIT was used for the estimation of Fig. 2. Adsorption of Ni2+, Cu2+, Cd2+ and Zn2+ on
the kinetic constant of phosphorus adsorption rate at non- aggregated red mud; curves show the best ®ts of the
equilibrium sites and the fraction of sites of equilibrium Langmuir isotherm to the experimental data.
1318
Table 5. Maximum capacities (Xm) of the substrate for adsorption
of each metal ion, adsorption constant (K; 48 h contact time), and
coecients of determination (R2) for the best ®ts of the Langmuir
isotherm to the experimental data for heavy metal adsorption by
red mud
Xm (mg gÿ1) K(L gÿ1)
Copper 19.72 2.029 101
Zinc 12.59 1.195 102
Cadmium 10.57 2.634 102
Nickel 10.95 7.193 101
Adsorption of phosphorus
Nonlinear Langmuir (4) and the Freundlich (5)
equations were ®tted to the experimental adsorption
data using the Levenberg-Marquardt least squares
parameter estimation method. The experimental
data and isotherms ®tted to them are shown in
Fig. 3.
X ˆ K 0 C 1=n
where X is the mass of P adsorbed per unit mass of
the aggregated RM, C is the concentration of P in
solution at the end of the contact time, and K' and
n are constants.
The experimental data and the isotherms ®tted to
them are shown in Fig. 3, and the values of K', 1/n,
Xm and K together with the corresponding determi-
nation coecients (R2), are listed in Table 6. In all
cases, good ®ts of the Freundlich equation to the
experimental data were obtained. Values of determi-
nation coecients corresponding to the Langmuir
equation were also good, however, the standard
error of the parameter estimates are too high,
because of the lack of sensitivity of the Langmuir
equation to the K parameter. The amount of P
adsorbed increased slowly with contact time. The
curves for the shorter times were quite similar,
while P adsorption increased markedly between
contact times of 24 and 48 h, suggesting that both
fast and relatively slow P adsorption reactions are
Fig. 3. Adsorption of phosphorus on aggregated red mud
for four di€erent contact times; curves show the best ®ts
of the Freundlich equation to the experimental data.
E. LoÂpez et al.
Table 6. Fitting constants, and coecients of determination (R2)
for the best ®ts of the Freundlich and Langmuir equations to the
experimental data for phosphorus adsorption by red mud
Freundlich isotherm
R2 Time K' 2S.D. 1/n 2S.D. R2
3 0.1222 0.01 0.627 20.02 0.991
0.905 6 0.1732 0.02 0.593 20.02 0.998
0.943 24 0.2442 0.01 0.532 20.02 0.997
0.969 48 0.2892 0.01 0.532 20.02 0.999
0.986
Langmuir isotherm
Time Xm 2 S.D. K 2 S.D. R2
3 6.8202 1.06 0.012 0.004 0.975
6 6.3392 1.12 0.012 0.004 0.963
24 7.0272 1.15 0.012 0.002 0.947
48 58.11 227.39 0.012 0.009 0.941
occurring, as it has been commonly reported for P
sorption on iron oxides (Torrent et al., 1992).
…5† Best results obtained with the Freundlich iso-
therm have been interpreted as the number of sorp-
tion sites are not limited; instead, the adsorption
capacity depends on the initial concentration of
phosphorus in solution.
Kinetics of adsorption of phosphorus
The results of ®tting the kinetic equations
(Table 2) to the observed data are shown in
(Table 7). For zero order kinetic equation, the reac-
tion rate is only dependent on the initial concen-
tration of adsorbable P. Several authors consider it
inappropriate to describe adsorption or desorption,
where it was found that for initial concentrations in
the liquid phase below 10 mg P lÿ1, zero order
equation gave a satisfactory ®t.
Kinetic data (Fig. 4) for P adsorption were also
well ®tted by a ®rst order equation for low initial
concentrations, indicating that sorption processes
occur at a rate proportional either to P concen-
tration, or to the number of vacant sorption sites.
Second order kinetics are thought to derive from
sorption processes in which the rate controlling step
is an exchange reaction. The goodness of ®t of this
equation was very poor in all cases, consequently it
cannot be considered.
The rate controlling step of P adsorption pro-
cesses with kinetics conforming to the parabolic dif-
fusion law is thought to be the di€usion of the
phosphate ions, either to the interior of red mud
particles from their surface or from the solution to
the surface. The goodness of ®t was satisfactory for
all initial concentrations.
Elovich equation also describes a di€usion step
controlling the adsorption process. The goodness of
®t was better than for the parabolic difussion.
The experiments of P adsorption reveals that the
adsorption kinetis depends on the initial concen-
tration of phosphorus in solution, for concen-
trations ranging from 2.5 to 10 mg lÿ1 the zero and
®rst order kinetic are addecuate, which means that
 Adsorbent properties of red mud 1319

Table 7. Parameters of ®tted kinetic models and statistics (chi square and determination coecients (chi square and coecient of determi-
nation) for ®ve di€erent initial concentrations (C0)
C0 X02S.D. Kv 2S.D. w2 R2 sig.(R2)

Zero order
250 4.010 20.097 0.018 20.003 0.0667 0.868 **
200 2.303 20.108 0.013 20.004 0.0828 0.746 **
100 1.165 20.012 0.0069 20.000 0.0010 0.981 ***
10 0.709 20.025 0.0036 20.000 0.0045 0.719 *
2.5 0.412 20.007 0.0008 20.000 0.0004 0.685 *
First order
250 4.010 20.097 0.018 20.003 0.0657 0.870 **
200 2.303 20.108 0.013 20.004 0.0900 0.724 *
100 1.165 20.012 0.0069 20.000 0.0009 0.983 ***
10 0.709 20.025 0.0036 20.001 0.0047 0.706 *
2.5 0.412 20.007 0.0008 20.000 0.0004 0.682 *
Parabolic difussion
250 3.742 20.145 0.160 20.032 0.0705 0.861 **
200 2.083 20.136 0.124 20.030 0.0624 0.808 **
100 1.071 20.027 0.057 20.006 0.0025 0.956 ***
10 0.656 20.027 0.028 20.006 0.0025 0.841 **
2.5 0.397 20.009 0.0081 20.002 0.0003 0.776 **
Elovich equation
250 3.646 20.177 0.297 20.065 0.0823 0.837 **
200 1.980 20.129 0.242 20.047 0.0438 0.866 **
100 1.041 20.048 0.103 20.017 0.0061 0.894 ***
10 0.630 20.019 0.056 20.007 0.0009 0.939 ***
2.5 0.390 20.008 0.015 20.003 0.0002 0.864 **

there is a reaction of sites where the reaction rate is
very fast. As the initial concentration of phosphorus
increases, more adsorption sites appearÐaccording
with the nonlinear isotherm.
For more concentrated dissolutions the kinetic
equations that best describe the experimental
adsorption kinetics, are those in which the slowest
reaction is controlled by di€usion processes, namely
parabolic difussion and Elovich.
The increase of adsorption sites is related to a
di€usion mechanism that could be either liquid or
solid phase. The di€usion model in liquid phase
agree with the microscopic structure of the red mud
in which a particle of micrometric dimensions (10±
50 microns) is formed by other minor particles or
domains.
Continuous adsorption experiments: column I
The KH2PO4 solution was allowed to percolate
through the column for 63 days, during which time
1859 ml of percolates, equivalent to 870.8 pore
volume displacements, were collected in 19 frac-
tions. The relative concentration data (Ce/Ci) are
shown as points in Fig. 5, which also shows the

Fig. 4. Kinetics of adsorption of P to RM, lines show the best ®ts of four kinetic equations (0th, 1st
order, parabolic di€ussion and Elovich) to each experimental data corresponding to four di€erent in-
itial concentrations in solution ranging from 250 to 2.5 mg P lÿ1.
1320 E. LoÂpez et al.
Fig. 5. Relative concentration (Ce/Ci) of phosphorus in the
e‚uent as a function of displacement volume following
percolation through column I; the curve show MCMFIT
simulations of the experimental data using the Freundlich
constants for adsorption (K' and 1/n) obtained in batch
experiments for contact times of 3 h (continuous line).
BTCs ®tted by the MCMFIT program using the
experimentally derived Freundlich constants K' and
1/n for the shortest contact time (Table 5) as initial
values, the kinetic parameters (Table 6) were also
obtained from nonlinear ®tting with MCMFIT
using the estimated kinetic parameters X0 and Kv of
the ®rst order equation (Table 7) as initial asump-
tions.
Figure 5 shows that actual retention of P on the
column is similar than that simulated by the
MCMFIT program for the dispersion coecient
(D) of 0.2 10ÿ2 cm2 sÿ1 using the optimal
Freundlich constants (1/n 0.53 K' 0.36 mg gÿ1 (l
mgÿ1)1/n) and the kinetic parameters (a 2.85 10ÿ3
dayÿ1 and b 0.154 dimensionless). The optimal
Freundlich parameters di€ers from those obtained
in the batch experiments for a contact time of 3 h.
These results indicate that optimal degree of non
linearity (1/n) corresponds to the isotherms
observed at 24 and 48 h of contact time, neverthe-
less the optimal K' value is greater than the
observed values for the same contact times. This
fact suggests that the adsorption in the column does
not attain the equilibrium.
Table 8 shows the best ®t parameters of the
BTC. The fraction of equilibrium sites is only a
15% (standard error 0.8%) of the all adsorption
sites, the other sites (85%) which are not in equili-
brium undergo a kinetic control.
Table 8. Input parameters for the
MCMFIT program and coecient of de-
termination of observed and predicted
values
Ci 5.18 mg lÿ1
V 0.382 cm hÿ1
D 0.20 10ÿ2 cm2 sÿ1
1/n 0.53 dimensionless
K' 0.36 mg gÿ1(l mg ÿ1)1/n
a 2.85 10ÿ3 dayÿ1
b 0.154 dimensionless
R2 0.9851
Table 9. Phosphorus mass balance for experiments examining per-
colation of the e‚uent through column I, and the corresponding
simulated data produced by the MCMFIT model using the opti-
mized values of K' and 1/n
Retention Eluted
ÿ1
BTC (mg mg ) (mg P)
Observed 0.38 6.07
Simulated 0.39 5.98
Variation coecient 0.75%
(Amount of phosporus applied 9.8 mg P)
The experimental and simulated mass balance
data for column I are shown in Table 9.
Consequently, from 0 to approximately 300 pore
volume displacements, the out¯ow concentration is
controlled mainly by fast equilibrium adsorption,
however once the fast adsorption sites are occupied,
the calculated kinetic constant of the adsorption in
non-equilibrium sites governs the concentration of
phosphorus in the out¯ow.
The shape of the curve beyond the point of 300
pore volume displacements (Fig. 5) corresponds to
the ratio of sorption velocity to solute mass ¯ux at
the input boundary. The adsorption rate at this
stage is 8.4 10ÿ3 mg gÿ1 dayÿ1 with an input concen-
tration of 5.2 mg lÿ1.
During the experiment of solute transport in the
column, the adsorption process is di€erent from
batch adsorption. One di€erence is that the concen-
tration in solution never reaches the equilibrium,
since there is a constant supply of phosphorus to
the column. The second di€erence is that the red
mud in the column forms aggregates of size of di-
ameter 0.5 to 0.3 mm, therefore the di€usion pro-
cesses predominates more than in the batch
experiments.
Column II
In Fig. 6 the ratios of the relative concentrations
(Ce/Ci) in the percolate of several of the contami-
nants present in the sewage e‚uent (Cu2+, Zn2+,
NOÿ +
3 , NH4 , and total organic carbon, TOC), and
Fig. 6. Breakthrough curves for the indicated components
of the e‚uent following percolation through column II.
 Adsorbent properties of red mud
Table 10. Puri®cation eciencies (%) for the indicated contami-
nants after passage of 86.5 displacements of the e‚uent through
column II of red mud; bromide was used as an inert tracer ion
Bromide 1.7
Nitrate 2.3
Ammonium 18.1
TOC 19.2
Copper 68.5
Zinc 56.2
Nickel 100.0
Ortophosphate 100.0
also that of the inert tracer ion (Brÿ), are plotted
against the volume of percolated e‚uent, expressed
in displacements of the pore volume of the packed
column.
These BTCs show that nitrate is very weakly
retained by the aggregated RM, while ammonium
ions and organic matter were retained more
strongly. Neither phosphorus nor nickel, both pre-
sent in the e‚uent (Table 4), were detected in the
percolate, even after 86.5 displacements.
Puri®cation eciencies for these contaminants of
the percolated wastewater are included in Table 10.
Taking into account the maximum adsorption ca-
pacities calculated in the batch experiments and the
volume of wastewater percolated, the predicted
puri®cation eciencies for Cu2+ and Zn2+ were
100%. The low puri®cation eciencies observed for
Cu2+ and Zn2+ may be due to the formation of
complexes of these ions with organic matter, for
which both have high anity (Schnitzer and
Skinner, 1966; GranÄa et al., 1991). Retention of
such complexes would be weak in comparison with
that of the uncomplexed ions, in keeping with the
greater mobility of metal-organic matter complexes.
The observed similarity between the BTCs for cop-
per, zinc and TOC, which all show oscillating
values of Ce/Ci, con®rm that adsorption of these
complexed metals is strongly dependent on the
adsorption of organic matter. Oscillation of the
BTC for total organic carbon is usual when a sol-
ution containing organic components with di€ering
mobilities is percolated through a ®ltration medium
(Hoeks et al., 1979).
CONCLUSIONS
Moistened mixtures of red mud and 8% (w/w)
CaSO4 form aggregates which are stable in aqueous
media. Batch experiments examining the adsorption
of heavy metals by this aggregated red mud indi-
cated that it has strong anities for Cu2+, Zn2+,
Ni2+ and Cd2+. The maximum adsorption ca-
pacities, evaluated from ®ts of the Langmuir iso-
therm to the experimental data for a contact time
of 48 h, were 19.72 mg gÿ1 for Cu2+, 12.59 mg gÿ1
for Zn2+, 10.95 mg gÿ1 for Ni2+ and 10.57 mg gÿ1
for Cd2+.
In laboratory-scale experiments in which second-
ary e‚uent from an urban sewage treatment plant
1321
was percolated through aggregated red mud packed
into a plastic column, the order of puri®cation
eciencies (values in parenthesis) for the indicated
contaminants were: P (100%) = Ni2+ (100%)>
Cu2+ (68%)>Zn2+ (56%)>NH+ 4 (18%)>NOÿ 3
(2.5%).
Batch experiments examining P adsorption by
aggregated red mud for contact times of 3, 6, 24
and 48 h suggested that ®xation occurs by fast and
slow reactions. Likewise, a slow adsorption reaction
which does not attain equilibrium within 3 h was
suggested when the experimental breakthrough
curve (BTC) for phosphorus retention on a column
of aggregated red mud (residence time 3 h) was
compared with a BTC, ®tted using the Freundlich
constants for adsorption (K' and 1/n) obtained with
MCMFIT. Satisfactory retention of phosphorus
was predicted using a two site (equilibrium and
non-equilibrium) adsorption model with a ®rst
order adsorption kinetics for the non equilibrium
sites.
These experiments suggest that, after pre-treat-
ment to neutralize alkaline components and induce
formation of stable aggregates, red mud is suitable
for use as a ®ltration medium for treatment of
wastewaters, particularly those whose principal con-
taminants are phosphorus or heavy metals.
AcknowledgementsÐWe thank D. A. Barry for the
MCMFIT codes, Xunta de Galicia and the FundacioÂn
Caja Madrid for ®nancial support.
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