Applied Clay Science 46 (2009) 1320

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Applied Clay Science

j o u r n a l h o m e p a g e : w w w. e l s ev i e r. c o m / l o c a t e / c l a y

Evaluation of bauxite residues (red muds) of different origins for

environmental applications
K. Snars, R.J. Gilkes
School of Earth and Environment, University of Western Australia, Crawley, Australia 6009

a r t i c l e i n f o a b s t r a c t

Article history: Bauxite residue (red mud) samples from 11 Australian and overseas Bayer process reneries and variously
Received 20 February 2009 treated red muds were investigated from the perspective of potential environmental uses for red muds. Red
Received in revised form 22 May 2009 muds had pH (1:5 H2O) values ranging from 8.4 to 12.6 and electrical conductivities of 0.7 to 18.2 mS/cm
Accepted 14 June 2009
(1:5 extract), surface area ranged from 15 to 30 m2/g and texture from sandy clay loam to clay. Red muds are
Available online 24 June 2009
mostly composed of crystalline compounds of Fe, Al, Si and Ca with some red muds containing moderate
Keywords:
amounts of Ti and Na. Most red muds contain hematite, goethite, quartz, calcite, desilication product
Iron oxides (sodalite), gibbsite, boehmite and anatase. Other minerals, including muscovite, halite and gypsum occur in
Sodalite some red muds. The acid buffering behaviour of red muds was investigated by incubation of red muds with
Calcite various amounts of hydrochloric acid. Buffering curves changed with time and each red mud gave a different
Buffering capacity buffering curve although curves could be grouped into ve different shapes. Most of the buffering occurs
between about pH 6 and 8 where the pH is buffered by dissolution of calcite, sodalite and tricalcium
aluminate (when present). X-ray diffraction (XRD) analysis of acid treated red muds at different pH values
indicate that sodalite and calcite buffer (i.e. dissolve) simultaneously. Buffering at lower pH values (b 4) is
due to dissolution of Fe oxides. Each red mud has different pH buffering characteristics so that the use of red
mud for liming of acid soil, water, sulphidic mining residues and manufacturing wastes will require detailed
characterisation of the buffering reactions for the particular system.
2009 Elsevier B.V. All rights reserved.

1. Introduction
Most alumina is extracted from bauxite using caustic soda in the
Bayer process. The residue is usually divided into two fractions with
the coarse fraction consisting mostly of quartz (red sand) and the ne
fraction (red mud) containing large amounts of ne iron oxides. Due
to residual caustic soda, red mud has a very high pH, usually N 11.
Although all alumina reneries routinely characterise their residue
there are few published reports on the characteristics of red muds and
particularly in relation to environmental applications. There is an
increasing demand for the use of red muds in environmentally
benecial applications (liming, phosphate retention, heavy metal
precipitation, etc) (Glenister and Thornber, 1985; Hofstede and Ho,
1992; McPharlin et al., 1994; Summers et al., 1996; Lombi et al., 2002)
rather than disposal into dumps.
The limited published data indicate that red muds consist mostly
of various mixtures of hematite, goethite, quartz, gibbsite, boehmite,
anatase, calcite, and desilication product (DSP) (Zambo, 1979;
Thornber and Hughes, 1986). DSP has been variously described by
these and other authors as sodalite, cancrinite and Na-aluminosilicate.
Various other compounds including muscovite, tricalcium aluminate,
Corresponding author. Fax: +61 8 6488 1050.
E-mail address: Bob.Gilkes@uwa.edu.au (R.J. Gilkes).
diaspore and maghemite occur in some red muds. For red muds
derived from lateritic bauxite from the Darling Range of Western
Australia both goethite and hematite are Al-substituted with less Al in
hematite (Thornber and Hughes, 1986). The specic surface area of
red muds ranges from 7.3 to 34.5 m2/g (Orban et al., 1976; Zambo,
1979; Thornber and Binet, 1999). The nature of the bauxite and
conditions of the Bayer process largely determine the properties of red
mud.
Neutralisation of red mud by acid, copperas (ferrous sulphate),
gypsum and seawater has been investigated for red muds produced by
Alcoa World Alumina Australia (Thornber and Hughes, 1986; Ho,
1989; Thornber and Hughes, 1992). Neutralisation by progressive
addition of acid combined with XRD analyses of dissolution residues
allows investigation of the acid buffering contribution of individual
alkaline components, in particular, DSP, calcite, tricalcium aluminate
and free Fe oxides (Thornber and Hughes, 1992). Neutralising with
copperas, gypsum and seawater has also been investigated as
ameliorative methods to facilitate the environmental use and
rehabilitation of the red mud (Thornber and Hughes, 1986; Ho,
1989). In most studies of this type the forms of alkalinity in red mud
have not been quantitatively determined.
All published studies have investigated one red mud or a small
number of red muds from a single renery that used bauxite from a
single or few mines so that it is uncertain whether published results
are representative of most red muds. This study reports on the

0169-1317/$ see front matter 2009 Elsevier B.V. All rights reserved.
doi:10.1016/j.clay.2009.06.014
14 K. Snars, R.J. Gilkes / Applied Clay Science 46 (2009) 1320

Table 1 red mud/gypsum) (ARMG). A subsample of fresh Alcoa Kwinana red

Origins of red mud samples and the bauxites used at the reneries.
Sample Red Mud Sample origin
Kwinana Alcoa World Alumina Australia Kwinana
renery, Western Australia, Australia
Pinjarra Alcoa World Alumina Australia Pinjarra
renery, Western Australia, Australia
Wagerup Alcoa World Alumina Australia Wagerup
renery, Western Australia, Australia
Worsley Worsley Australia Pty Ltd, Western
Australia, Australia
Nabalco Nabalco, Northern Territory
(now Alcan Gove), Australia
QAL Queensland Alumina Ltd, Queensland,
Australia
Brazil Alunorte, Brazil
Germany Aluminium Oxid Stade GmbH, Germany
Italy Eurallumina, Italy
Spain Alcoa, Spain
USA Reynolds Metal Company, USA
CRM Carbonated red mud, Kwinana, Western
Australia, Australia
BRM Bitterns concentrate treated red mud,
Kwinana, Western Australia, Australia
RMG Kwinana red mud + 10% w/w gypsum
ARMG Kwinana red mud + 10% w/w gypsum
exposed to weather ~ 4 years
LRMG Pinjarra red mud + 5% w/w gypsum with
leaching to remove salts
LRM Pinjarra red mud leached with dilute acid
TKW Kwinana red mud treated with
formaldehyde as for quarantine
characteristics of red muds from 11 reneries utilising bauxite from
several mines and also on red muds which have been modied in
various ways.
Bauxite origin
Western Darling Range,
Western Australia, Australia
Western Darling Range,
Western Australia, Australia
Western Darling Range,
Western Australia, Australia
Eastern Darling Range,
Western Australia, Australia
Nhulunbuy, Northern
Territory, Australia
Weipa, Queensland, Australia
Para State, Brazil
Boke, Guinea
Weipa, Queensland, Australia
Boke, Guinea
Jamaica and Guyana
Western Darling Range,
Western Australia, Australia
Western Darling Range,
Western Australia, Australia
Western Darling Range,
Western Australia, Australia
Western Darling Range,
Western Australia, Australia
Western Darling Range,
Western Australia, Australia
Western Darling Range,
Western Australia, Australia
Western Darling Range,
Western Australia, Australia
mud was mixed with 10% w/w gypsum (red mud/gypsum) (RMG).
Subsamples of Alcoa Pinjarra red mud were ameliorated to reduce
alkalinity by (a) the addition of gypsum at 5% and thoroughly leached
to remove water soluble sodium sulphate (leached red mud/gypsum)
(LRMG); and (b) thorough leaching with dilute acid to remove most
alkaline salts (leached red mud) (LRM). These materials were air-dried
and crushed to pass a 2 mm mesh. All samples imported from overseas
were treated with formaldehyde in accordance with Australian
quarantine rules which may modify properties of red mud. A
subsample of the Kwinana red mud was treated with formaldehyde
(TKW) to compare its properties with those of the original.
3. Methods
The red muds were analysed as random powders on a Philips
PW3020 X-ray diffractometer tted with a graphite monochromator
using Cu K radiation at 1o/minute scan speed. The following
properties were determined using methods from Rayment and
Higginson (1992) except where indicated:
a) pH and electrical conductivity (EC) in a 1:5 soil : water ratio;
b) Fe and Al extracted by dithionite-citrate-bicarbonate (DCB)
(Mehra and Jackson, 1960) and ammonium oxalate (ox);
c) elemental analysis by X-ray uorescence spectrometry (XRF);
d) BET specic surface area;
e) elemental analysis by ICPMS after HF digestion and
f) Particle size analysis by wet sieving the samples and collecting the
fraction b 0.045 mm. The clay-sized fractions of the red muds
were determined using a Malvern Mastersizer analyser [Mastersi-
zer Microplus Ver. 2.18, c/o Malvern Instruments Ltd. 1995]. A
particle refractive-index (RI) of 2.59 was used in the analysis and a
particle density of 2.64 g/cm3 was assumed. Water was used as
dispersant (RI = 1.33).

2. Materials 3.1. Batch titration method

Red mud from the six Australian alumina reneries and ve over-
seas reneries was air-dried, crushed, and sieved to b 2 mm. Table 1
lists the sample identications and origins of the red muds and origins
of the bauxites that generated the red muds. A carbonated red mud
(CRM) and bitterns concentrate treated red mud (BRM) were also
supplied by Alcoa World Alumina Australia. Red mud with added
gypsum (10%) used for liming acid soils was collected from a stockpile
which had been exposed to the weather for 4 years (identied as aged
20 g samples of red mud were weighed into 120 ml plastic bottles.
Deionised water and 0.5 M HCl in several 5 ml increments were added
to bring solution additions to a total of 100 ml. These suspensions
were shaken by hand and pH was measured immediately, the samples
were next put on a shaker operating at 30 C and 130 rpm. Suspension
pH was measured after 4 hours, 1 day, 3 days, 7 days, 14 days and
28 days of shaking. Electrical conductivity (EC) was measured after
28 days. These measurements were taken on the suspensions in the

Table 2
XRF analyses of red muds expressed as % oxide.

Fe2O3 MnO TiO2 CaO K2O P2O5 SiO2 Al2O3 MgO Na2O SO3 LOI Total
Kwinana 28.5 0.02 3.11 5.26 0.94 0.14 18.8 24.0 0.43 3.4 0.69 15.5 100.8
Pinjarra 31.7 0.02 3.17 4.44 0.90 0.16 20.2 18.8 0.39 4.2 0.67 15.8 100.4
Wagerup 29.6 0.02 2.65 3.64 0.46 0.24 30.0 17.3 0.23 3.2 0.54 12.5 100.4
Worsley 56.9 0.04 4.46 2.39 0.26 0.22 3.0 15.6 0.12 2.2 0.39 14.3 99.9
Nabalco 34.8 0.01 8.03 2.25 0.69 0.16 9.2 23.2 0.04 7.1 0.27 13.8 99.6
QAL 30.7 0.03 7.01 2.51 0.78 0.18 16.0 18.6 1.01 8.6 0.48 13.8 99.8
Brazil 45.6 0.01 4.29 1.16 0.29 0.05 15.6 15.1 0.05 7.5 0.21 9.3 99.1
Germany 44.8 0.06 12.33 5.22 0.27 0.45 5.4 16.2 0.13 4.0 0.31 10.2 99.3
Italy 15.2 0.01 6.15 4.23 1.10 0.15 18.6 24.7 0.46 11.7 2.29 15.5 100.1
Spain 37.5 0.05 11.45 5.51 0.26 0.40 4.4 21.2 0.08 3.6 0.2 14.0 98.7
USA 35.5 0.57 6.31 7.73 0.47 1.19 8.5 18.4 0.09 6.1 0.48 14.2 99.6
CRM 28.3 0.02 3.00 5.80 0.94 0.16 19.1 20.5 0.51 4.4 0.68 16.5 99.9
SWC 28.5 0.01 2.97 4.95 0.95 0.14 18.7 19.8 1.18 4.3 0.8 17.9 100.2
RMG 29.6 0.01 2.84 6.88 0.76 0.21 18.0 18.1 0.40 4.3 4.6 16.1 101.8
ARMG 28.5 0.02 2.79 4.86 0.95 0.12 23.7 22.0 0.45 2.1 0.46 14.0 99.8
LRMG 31.1 0.02 3.11 6.21 0.79 0.16 19.5 19.4 0.39 2.6 2.46 15.8 101.6
LRM 34.5 0.02 3.49 2.29 0.82 0.18 21.6 21.5 0.28 0.9 0.33 14.3 100.2
TKW 27.5 0.02 2.96 5.27 1.13 0.15 19.9 23.8 0.44 3.5 0.59 15.1 100.5
 K. Snars, R.J. Gilkes / Applied Clay Science 46 (2009) 1320 15

Table 3 calcite. Muscovite, feldspar, rutile, gypsum, tricalcium aluminate (TCA)

Characteristics of red muds. and halite are present in some red muds. DSP as identied here has a
Sample pH EC BET SSA Particle Size Analysis (%) zeolite type structure and resembles sodalite and cancrinite (Thornber
(1:5 H20) (dS/m) (1:5 H20) (m2/g) b 2 m 220 m N 20 m and Hughes, 1992). Fig. 2 shows XRD patterns of seven red muds which
Kwinana 11.45 2.98 28 21 65 15 between them contain all the minerals which occurred in the red muds
Pinjarra 11.63 6.09 25 25 61 15 studied. Some of these minerals are produced during the Bayer process,
Wagerup 11.99 2.69 24 20 41 39 e.g. DSP and calcite, but most minerals are unaltered residual minerals
Worsley 12.56 6.28 25 29 50 21 from the original bauxite. Thus it is the nature of the bauxite which has
Nabalco 12.44 10.75 29 44 40 16
QAL 10.22 8.15 29 40 50 10
the greatest effect on the minerals present in red mud.
Brazil 12.21 3.26 15 22 65 13 Muscovite only occurred in red muds from Alcoa's Darling Range
Germany 12.08 2.57 23 57 28 15 Bauxite (Fig. 2 Kwinana, LRM and RMG) and is a persistent residual
Italy 9.75 18.17 25 29 38 33 mineral which is revealed by its strongest XRD reections (10 )
Spain 12.58 2.34 21 33 38 29
despite being a minor constituent (Anand and Gilkes, 1987a). Halite
USA 11.04 3.59 27 22 35 43
CRM 10.85 6.32 19 na na na (NaCl) occurred in samples which had been treated with seawater
SWC 9.86 6.72 27 na na na before disposal (Fig. 2 - QAL and Italy). Tricalcium aluminate and
RMG 11.36 8.45 23 20 66 14 calcite are products of causticisation which introduces lime into the
ARMG 10.66 0.72 24 20 46 35 Bayer liquid (Thornber and Hughes, 1992). Tricalcium aluminate
LRMG 9.18 2.44 26 na na na
LRM 8.44 0.67 30 na na na
appeared to be present in all samples, however its weak reections
TKW 11.00 1.69 26 31 61 8 (2.694, 2.720 and 1.920 ) were obscured by reections of dominant
minerals.
Gypsum was only present when it had been added to red mud and
bottles without removal of any sample. After the measurement at probably had not reacted fully in the given time (Fig. 2 - RMG). After
28 days the suspensions were centrifuged to separate solution from gypsum dissolves the Ca2+ reacts with CO2- 3 reducing the pH of red
solid and the solid was air dried. Samples at a range of nal pH values mud (Barrow, 1982; Thornber and Hughes, 1986). The chemical
were then analysed by XRD. Solutions were analysed by atomic reaction is
absorption spectrometry (AAS) for Ca, Na, Al, Si and Fe.
Na2 CO3 CaSO4 CaCO3 Na2 SO4
4. Results and discussion
The sodium sulphate may eventually leach out of the red mud
Comparison of formaldehyde treated Kwinana red mud (TKW) and when it is retained in a drained situation or applied to soils but none of
the original Kwinana red mud showed that there were no differences the red mud gypsum samples used in this study were sufciently
in XRD patterns and only minor differences in chemical composition leached to have dissolved all the gypsum and removed all the sodium
between the formaldehyde treated and untreated samples (XRF sulphate.
analyses Table 2). The main differences were in pH and EC values It was anticipated that there might be amorphous iron oxides in
which both decreased with formaldehyde treatment (Table 3). These the red muds but oxalate Fe values (= amorphous Fe oxide (Ross and
reductions appear to be due to removal of free alkali salts by the Wang, 1993)) were very small (Table 4). The much higher Fe (DCB)
formaldehyde wash. This effect is seen in the acid buffering curves for values (and also Al (DCB)) are due to dissolution of crystalline
TKW and Kwinana red muds (Fig. 1) which follow the same shape but aluminium substituted iron oxides (Singh and Gilkes, 1992).
the TKW curve is displaced as less acid was required to reduce the pH. To determine the Al substitution in iron oxides via displacement of
Thus formaldehyde treatment did not affect the mineral or chemical XRD reections (Schwertmann et al., 1979; Schulze, 1984), quartz was
composition of the samples other than decreasing the free alkalinity used an internal standard to correct XRD peak positions. Aluminium
which affects initial pH and EC and acid consumption to a minor extent. substitution for iron in goethite was calculated using the c dimension
of the unit cell for goethite determined from the 110 and 111
4.1. Texture reections using the equation: Mole % Al = 1730572.0 c (Schulze,
1984). For hematite, the a dimension was determined from d(110)
Particle size analyses of red mud are misleading due to iron oxides and the structural Al was determined using the equation: Mole %
existing as aggregates of nanometric particles. Malvern Mastersizer Al = 3109617.1 a (Schwertmann et al., 1979). The results from these
analyses of washed samples (Table 3) indicate that the texture of the
red muds ranges from a sandy clay loam to clay (McDonald et al.,
1998) with a substantial content of silt size (220 m) particles. BET
surface areas range from 15 to 30 m2/g which is consistent with a high
content of nano to micron meter size particles. Surface area values are
consistent with results of earlier workers (Thornber and Hughes,
1992; Thornber and Binet, 1999; Zambo, 1979). There are not strong
relationships between surface area and particle size due partly to
aggregation of nanometric iron oxide particles into silt size particles.
Most of the surface area of red muds is due to the iron oxides. Surface
area values are broadly consistent with predictions of the surface area
of iron oxides based on the crystallite size of the iron minerals
[derived from XRD line broadening (Table 4)] and the Fe2O3 content,
although there is no close relationship between these characteristics.

4.2. Mineralogy

The major minerals present in most red muds are hematite, goethite, Fig. 1. Comparison of buffering curves for an original Kwinana red mud and Kwinana
quartz, gibbsite, boehmite, anatase, desilication product (DSP), and red mud treated with formaldehyde (TKW).
16 K. Snars, R.J. Gilkes / Applied Clay Science 46 (2009) 1320

Table 4
Mineralogical and chemical characteristics of iron oxides in red muds.

Sample Fe (ox) Al (ox) Fe (DCB) Al (DCB) Crystallite size

(%) (%) (%) (%) ((110)) (nm) Mole % Al G/(G + H)
Hematite Goethite Hematite Goethite
Kwinana 0.10 1.74 15.79 3.57 25 20 9 34 0.44
Pinjarra 0.12 1.49 21.03 4.34 23 20 8 20 0.42
Wagerup 0.13 1.62 17.06 3.91 28 20 8 30 0.44
Worsley 0.34 0.93 29.04 3.53 25 26 12 28 0.48
Nabalco 0.09 4.05 23.74 4.37 23 16 12 na 0.05
QAL 0.09 4.19 19.58 5.58 21 17 10 na 0.04
Brazil 0.05 4.83 32.64 6.45 30 19 8 17 0.20
Germany 0.13 2.10 24.88 3.13 25 16 12 27 0.35
Italy 0.11 5.02 9.05 6.52 19 18 4 25 0.04
Spain 0.17 1.01 20.72 2.83 18 15 11 25 0.39
USA 0.07 3.77 23.58 3.99 28 18 12 28 0.24
CRM 0.25 1.22 13.51 3.76 30 23 6 38 0.44
SWC 0.22 1.40 12.62 4.01 23 21 12 25 0.45
RMG 0.11 1.45 17.72 4.18 32 21 11 30 0.47
ARMG 0.05 1.25 14.45 3.30 23 18 8 35 0.54
LRMG 0.18 1.50 21.23 4.61 28 23 9 30 0.47
LRM 0.14 1.62 22.83 4.61 20 20 8 25 0.57
TKW 0.10 1.76 17.70 4.64 30 18 10 31 0.46

calculations indicate that there was 4 to 12 Mole % Al substitution in
hematite and 17 to 35 mole % Al substitution in goethite in the red
muds (Table 4). The QAL and Nabalco red muds did not contain
sufcient goethite [i.e. G/ (G + H) 0.04, 0.05 (see below)] to enable
measurement of the 111 reection of goethite and calculation of Al
substitution. These values for Al substitution in iron oxides are
consistent with the range discussed by Anand and Gilkes (1987b) and
Bardossy and Aleva (1990) for the lateritic bauxites used to produce
the red muds investigated in this research. Aluminium substitution in
goethite and hematite appears not to have changed during the Bayer
process which is consistent with laboratory studies of residues of
alkali digests of soils by Schwertmann et al. (1979) although these
workers consider that the presence of substantial dissolved Si in the
caustic liquid may be necessary to prevent recrystallisation of goethite
during caustic digestion.
Crystallite sizes (i.e. mean coherently diffracting zone sizes (Klug
and Alexander, 1974)) were calculated from the width of the 110
reections of goethite and hematite in XRD patterns. Crystallite sizes
ranged from 18 to 30 nm for hematite and 15 to 26 nm for goethite
(Table 4). Goethite crystallites were smaller than hematite for most
red muds. These results are consistent with those of Anand and Gilkes
(1987b) and Singh and Gilkes (1992) who used an identical procedure
for measuring crystal size of iron oxides in lateritic soils.
To correct for differences in specic diffracted intensity for hema-
tite and goethite, the ratio of abundances of these minerals was cal-
culated from the XRD patterns as: G/G + H = Area Goethite d(110)/
(Area Goethite d(110) + 3*Area Hematite d(012)). The factor of 3
was derived from XRD patterns of mixtures of pure minerals. The
ratio (G/G + H) ranged from 0.04 to 0.57 (Table 4). The red muds
with the lowest G/G + H values were derived from bauxite from
Weipa and Gove in north-eastern Australia and processed at the
Nabalco, QAL and Italian reneries. The Darling Range bauxites tend
to have the highest (G/G + H) ratios and contain similar amounts
of hematite and goethite. The values of G/G + H are consistent with
the colours of the red muds with low values corresponding to very
dark red colours while higher values correspond to the light red and
yellowish red muds. Pure goethite is generally orange-yellow and
hematite is red (Torrent et al., 1983; Schwertmann and Taylor, 1989).

Fig. 2. XRD patterns of representative red muds. M Muscovite, S Sodalite, G Gypsum,

B- Boehmite, Gi Gibbsite, Go Goethite, Ha Halite, H Hematite, A Anatase, F Feldspar,
Q Quartz, C Calcite. Fig. 3. Buffering curves of the Kwinana red mud showing changes in pH over 28 days.
 K. Snars, R.J. Gilkes / Applied Clay Science 46 (2009) 1320 17

Table 5
Time taken to reach half the nal (28 day) change in pH for three rates of addition of acid, moles H+/kg red mud required to reach pH 7 after 28 days and pH at 28 days for addition of
2.5 moles H+/kg red mud.

Sample T1/2 (days to half change in pH) moles H+/kg red pH at 28 days for
mud to reach pH addition of 2.5 moles
7 (28 days) H+/kg red mud
0.5 moles 1 moles 2 moles
H+/kg red mud H+/kg red mud H+/kg red mud
Kwinana 0.58 0.42 1.85 0.75 3.6
Pinjarra 0.70 0.38 15.00 1.08 3.1
Wagerup 0.76 4.80 0.65 0.68 2.8
Worsley 0.57 1.96 0.52 0.88 1.7
Nabalco 0.10 0.30 0.48 1.64 5.1
QAL 0.30 1.44 9.20 0.92 3.8
Brazil 0.12 0.17 1.70 1.25 4.5
Germany 0.44 1.65 1.90 0.61 2.7
Italy 0.50 1.10 0.75 0.94 5.3
Spain 0.82 3.40 1.60 0.86 3.0
USA 0.25 0.94 10.65 0.77 5.9
CRM 1.28 0.56 0.35 1.05 6.1
SWC 1.00 0.25 5.00 1.30 6.0
RMG 0.55 0.22 0.10 1.04 3.0
ARMG 1.80 3.10 0.50 0.52 2.8
LRMG 0.54 0.60 1.94 0.88 5.8
LRM 0.36 6.20 1.50 0.45 3.3
TKW 0.10 0.15 3.65 0.81 3.2

4.3. Chemistry
The main elemental components of red mud are Fe with lesser Si
and Al (Table 2). The Italian red mud had more Si and Al than Fe and
the largest amounts of Si are in red muds derived from the Darling
Range high silica (quartz) bauxite (Bardossy and Aleva, 1990). German
and Spanish red muds contained more than 10% TiO2 due to these
reneries using bauxite from the Guinea Boke district which
contains much TiO2 (up to 14%) (Bardossy and Aleva, 1990). Most red
muds contained less than 5% Na2O although the Italian red mud had
the highest Na2O content as this red mud contains a large amount of
NaCl, presumably because it had been washed in sea water. There is a
close relationship (R2 = 0.73) between the Na2O and sodalite contents
[XRD measurement with linear X-ray absorption correction (Klug and
Alexander, 1974)] of red mud and this relationship improves
(R2 = 0.84) when the Italian red mud is removed. Thus it appears
that the sodium in red mud is mostly in sodalite and NaCl although
some Na is also present as NaOH and/or NaCO3.
The abundances of CaO (XRF) and calcite (XRD) were correlated
and by removing the German and Spanish red muds from the data set
the R2 value increases from 0.42 to 0.67. Both these red muds had
small amounts of calcite and larger amounts of tricalcium aluminate
(co-precipitated with the calcite during the causticisation process), so
would not be expected to conform to the CaO versus calcite
relationship. Several weak XRD reections could not be identied
for some red muds but do not correspond to compounds that are usual
constituents of bauxite (Bardossy and Aleva, 1990). These reections
are absent for acid treated red mud.

Fig. 5. Buffering curves of red muds containing various amounts of sodalite and calcite.
Fig. 4. Five buffering curve shapes drawn from the measured starting pH (a) and when (Relative amounts of sodalite and calcite: HS high sodalite, LS low sodalite, HC high
all are displaced horizontally to start at the same pH (b). calcite, LC low calcite).
18 K. Snars, R.J. Gilkes / Applied Clay Science 46 (2009) 1320

4.4. Acid buffering behaviour
The buffering curves created by addition of increments of acid (i.e.
pH versus H+ added) differ between samples and pH increases over
time (Fig. 3) due to slow chemical reactions although most of the
increase in pH occurred by 7 days. The nal pH (28 days) for 2.5 moles
H+/kg solid varied from 1.7 to 6.1 (Table 5). The initial pH of red mud
varied from 8.4 to 12.6 (Table 3). However, red muds with the highest
starting pH values do not have the highest nal pH values. The time
taken to reach half the maximum change in pH (T1/2) was calculated
for additions of 0.5, 1.0 and 2.0 moles H+/kg red mud (Table 5). T1/2
values were not related to any other red mud characteristic. The moles
of H+/kg solid required to reach pH 7 (Table 5) was calculated and has
a systematic relationship with the nal pH (R2 = 0.69) and the change

Fig. 6. XRD patterns at different nal pH values after 28 days of shaking with acid for (a) Kwinana, (b) Brazilian, (c) LRM and (d) LRMG red mud. S sodalite, H/S overlapping
hematite and sodalite peaks, C calcite, Q/C overlapping quartz and calcite peaks, G gypsum.
 K. Snars, R.J. Gilkes / Applied Clay Science 46 (2009) 1320 19

in pH (28 days) (R2 = 0.61). The nal pH (28 days), change in pH

(28 days) and moles of H+/kg solid to reach pH 7 are not related to
any of the T1/2 values.
The buffering curves for red mud conform to one of ve shapes.
Examples of these ve curve shapes are shown in Fig. 4(a) and can be
explained as follows. Firstly there are different amounts of free
alkalinity in red muds which is the major cause of the differences in
starting pH. To remove these differences buffering curves have been
plotted to commence at pH 8.5 and zero H + addition or at their
starting pH where this was lower than 8.5. Even with this correction
for free caustic the curves are still distinctly different (Fig. 4(b)). The
main difference between the curves appears to be the length of the
buffering section occurring at pH 6 8 (i.e. the upper nearly horizontal
section of the curves). Some of this buffering will be due to hydroxyls
on the surfaces of iron oxides in the red mud. Much of this buffering is
associated with dissolution of calcite and sodalite and the length of
the buffering region reects the contents of these constituents in the
red muds.
Calcite and sodalite do not buffer at distinctly different pH values.
Fig. 5 shows the buffering curves for four red muds which contain
different amounts of sodalite and calcite. The LRM sample contains
little calcite and sodalite and provides little pH buffering. The Brazilian
red mud contains little calcite and large amounts of sodalite, LRMG
had small amounts of sodalite and large amounts of calcite and
Kwinana red mud had large amounts of both sodalite and calcite. The
latter three red muds provide considerable buffering at pH b 8. XRD
patterns of red mud removed at different pH values shows that the
near horizontal region of the buffering curves is due to dissolution of
both calcite and sodalite.
Once pH had decreased to 6 all sodalite and calcite had dissolved
(Fig. 6) thus both calcite and sodalite dissolved at pH 6 8.5 to provide
pH buffering. Where much sodalite and calcite were present both
dissolved and provided a long buffering curve (Fig. 5 Kwinana and
Fig. 6 (a)). Where there was little calcite and much sodalite was present
the calcite had completely dissolved before the sodalite was completely

Fig. 8. (a) Calculated buffering curve for a red mud composed of contributions from
buffering curves for NaOH (0.5%) (b), calcite (8%) (c), sodalite (7%) (d) and hematite
(~ 85%) (d). The buffering curve for German red mud is shown in (a) for comparison.

Fig. 7. Concentrations of Na, Ca, Fe, Si and Al in solution at different nal pH values for
Pinjarra red mud shaken with various amounts of acid.
exhausted (Fig. 6 (b)). In this case the nearly horizontal section of the
buffering curve is short (Fig. 5 Brazil) and pH was not maintained
between 7 and 8 as occurred for Kwinana red mud. Where sodalite is
absent the near horizontal portion of the buffering curve is short with
the little buffering occurring between pH 6 and 8 (Fig. 5 LRM) being
due to the small amount of calcite present as indicated by the XRD
patterns for different nal pH values (Fig. 6 (c)). The LRMG material had
the longest buffering section (Fig. 5 LRMG) and this red mud contained
little sodalite and relatively large amounts of calcite. XRD patterns of
LRMG removed at various parts of the buffering curve indicate that
dissolution of sodalite and calcite simultaneously provided buffering
and that as calcite dissolved gypsum precipitated (Fig. 6 (d)). In the
original LRMG the gypsum which had been initially added to red mud
had dissolved and calcite had precipitated, however sufcient sulphate
remained in the LRMG, possibly in exchange sites in the zeolite sodalite
lattice or adsorbed onto iron oxides, so that as calcite and sodalite
20 K. Snars, R.J. Gilkes / Applied Clay Science 46 (2009) 1320
dissolved on addition of acid the liberated Ca and sulphate precipitated
as gypsum.
Evidence for dissolution of the calcite and sodalite providing most
of the buffer capacity of red mud can also be seen in the Ca, Na, Si, Al
and Fe contents of solutions removed at different pH values (Fig. 7).
Between pH values of approximately 12 and 8 only Na dissolved and
this presumably came from free Na2CO3 and NaOH (Fig. 7 (a)).
Between pH values 8 to 4 ~ 5 considerable amounts of Na, Ca and Si
dissolved due to dissolution of sodalite and calcite. The Al that
dissolved from sodalite probably precipitated in this pH range so that
dissolution of sodalite appeared to be incongruent (Fig. 7 (b)). Below
pH 4 or 5 sodalite dissolution was congruent and Fe oxides also started
to dissolve increasing the amounts of dissolved Fe and Al.
A composite buffering curve is shown in Fig. 8(a). This has been
synthesised by addition of buffering curves of the individual
compounds present in red mud (Fig. 8 (bd)). The synthesised
buffering curve is for a red mud that contains approximately 0.5%
NaOH, 8% calcite, 7% sodalite and 85% hematite. The NaOH causes the
initial high pH (14) which decreases rapidly on addition of acid to the
plateau region where buffering is provided by dissolution of calcite
and sodalite (pH 68). Buffering by sodalite and calcite are shown as
separate sections on this curve but in practice they overlap and buffer
simultaneously. Once the buffering capacity of the sodalite and calcite
is exhausted pH decreases until the iron and aluminium oxides start to
dissolve and buffer pH values below 2. The buffering curve for the
German red mud is also shown on this diagram and is quite similar to
the synthesised curve. The buffer curve for German red mud does not
start with as high a pH (i.e. the buffering by NaOH, since it was
removed by the sterilization procedure), it conforms to the calcite and
sodalite buffering section but pH does not decrease as quickly once
this buffering is exhausted possibly due to dissolution of tricalcium
aluminate.
No single characteristic of red mud could be used to discriminate
the red muds into afnity groups. Principle component and canonical
variate statistical analyses were used to divide the red muds into three
groups based on their sodalite, calcite, SiO2, Na2O, TiO2, Fe2O3, K2O and
MgO contents and goethite : hematite ratio. These groups are
essentially based on the origins of the bauxites used to generate the
red muds.
Group 1. Alcoa Darling Range Bauxites - Kwinana, Pinjarra, Wagerup,
ARMG, RMG, LRMG, LRM, SWC, CRM, TKW;
Group 2. North-eastern Australia Bauxites QAL, Italy, Nabalco; and
Group 3. Other bauxites USA, Brazil, Spain, Germany and Worsley.
Although the Worsley bauxite is from south-western Australia it is
mostly derived from the Mt Saddleback deposit which is located east
of the Darling Range deposits mined by Alcoa and has developed from
different rock types (i.e. mac volcanics, Ball and Gilkes, 1987).
Furthermore Worsley red mud contains relatively more sand as the
Bayer process residue fractions (sand and mud) are recombined
before disposal at this renery.
5. Conclusions
All red muds are different although those produced at different
reneries from bauxites from the same deposit are quite similar. The
origin of the bauxite, conditions used in the Bayer process and any
further treatment of the residue inuence the mineralogy and
chemistry of the red muds. Amounts of hematite, goethite, quartz,
gibbsite, boehmite, muscovite, anatase and feldspar are usually
inherited from the bauxite and thus are related to the origin of the
bauxite. Calcite, sodalite, tricalcium aluminate, halite and gypsum in
red muds are usually produced in the Bayer process or by treatment of
the red mud after processing. Most of the acid buffering of red mud is
due to calcite, sodalite and tricalcium aluminate (where present)
which dissolve between pH values of 6 to 8. Buffering at lower pH
values (b 4) can be attributed to dissolution of Fe oxides. Clearly the
use of red muds to buffer acidic environmental materials (e.g. soils,
wastes, water) at values near neutrality will relate strongly to the
calcite and sodalite contents of red mud. Similarly interactions of red
mud with environmental contaminants including phosphate and
heavy metals will depend on these and other properties of the red
mud.
Acknowledgements
Staff at Alcoa World Alumina Australia, Worsley, QAL, Nabalco,
Reynolds Metal Company, Alunorte, Aluminium Oxid Stade GmbH,
Alcoa Spain, Eurallumina for supplying the red mud samples.
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