See discussions, stats, and author profiles for this publication at: https://www.researchgate.

net/publication/47786198

Effect of Structure on the Geotechnical Properties of Bauxite Residue

Article  in  Journal of Geotechnical and Geoenvironmental Engineering · February 2006

DOI: 10.1061/(ASCE)1090-0241(2006)132:2(143) · Source: OAI

CITATIONS READS
55 471

4 authors, including:

Tom Dyer Tim Newson

University of Dundee The University of Western Ontario
67 PUBLICATIONS   726 CITATIONS    86 PUBLICATIONS   1,063 CITATIONS   

SEE PROFILE SEE PROFILE

Some of the authors of this publication are also working on these related projects:

The contribution of microbial biotechnology to the SDGs View project

Biodeterioration View project

All content following this page was uploaded by Tom Dyer on 29 May 2014.

The user has requested enhancement of the downloaded file.

 Effect of Structure on the Geotechnical Properties
of Bauxite Residue
Tim Newson1; Tom Dyer2; Chris Adam3; and Sandra Sharp4

Abstract: This paper describes a laboratory program to investigate the mechanical and physicochemical properties of bauxite residue
共red mud兲 at a site in the United Kingdom. The red mud storage facility has been recently decommissioned and has been considered for
future rehabilitation and construction activity. Based on a suite of laboratory tests conducted on the red mud, the material has compression
behavior similar to clayey soils, but frictional behavior closer to sandy soils. The red mud appears to be “structured” and has features
consistent with sensitive, cemented clay soils. Chemical testing suggests that the agent causing the aggregation of particles is hydroxy-
sodalite and that the bonds are reasonably strong and stable during compressive loading. Exposure of the red mud to acidic conditions
causes dissolution of the hydroxysodalite and a loss of particle cementation. Hydration of the hydroxysodalite unit cells is significant, but
does not affect the mechanical performance of the material. The shape, size, and electrically charged properties of the hydroxysodalite,
goethite, and hematite in the red mud appear to be causing mechanical behavior with features consistent with clay and sand, without the
presence of either quartz or clay minerals.
DOI: 10.1061/共ASCE兲1090-0241共2006兲132:2共143兲
CE Database subject headings: Cementation; Soil properties; Tailings; Triaxial tests; Zeolite; United Kingdom.

Introduction Sodalite is a feldspathoid mineral whose structure consists of

Bauxite Processing and Waste Products
Bauxite is a weathered rock containing two forms of hydrated
aluminum oxide. These oxides are either predominantly mono-
hydrate 关AlO共OH兲兴 or trihydrate 关Al共OH兲3兴, and the bauxite will
usually have additional Fe2O3 as the main impurity. The process-
ing of bauxite ore to produce aluminum leads to the production of
caustic waste material. The Bayer process is commonly used in
this purification process and it involves digesting the bauxite ore
in a solution of sodium hydroxide at temperatures between 150
and 230° C under pressure. During the digestion process, alumi-
num reacts with the sodium hydroxide to form soluble sodium
aluminate, leaving behind the Fe2O3 and other impurities. Where
silicates are also present in the ore, some dissolution of these
minerals can occur; these often react with sodium aluminate
in solution to form silicate minerals such as sodalite
关Na4共Si3Al3兲O12Cl兴.
1 minerals in this waste. The waste is differentiated into two grades:
Associate Professor, Geotechnical Research Centre, Dept. of Civil
and Environmental Engineering, The Univ. of Western Ontario, London
ON, Canada N6A 5B9. E-mail: tnewson@eng.uwo.ca
2
Lecturer, Dept. of Civil Engineering, Univ. of Dundee, Dundee,
Scotland DD1 4HN, U.K.
3
Senior Geotechnical Engineer, Jacobs Babtie, 95, Bothwell St.,
Glasgow G2 7HX, U.K.
4
Assistant Geotechnical Engineer, Jacobs Babtie, 95, Bothwell St.,
Glasgow G2 7HX, U.K.
Note. Discussion open until July 1, 2006. Separate discussions must
be submitted for individual papers. To extend the closing date by one
month, a written request must be filed with the ASCE Managing Editor.
The manuscript for this paper was submitted for review and possible
publication on December 8, 2003; approved on May 25, 2005. This paper
is part of the Journal of Geotechnical and Geoenvironmental Engineer-
ing, Vol. 132, No. 2, February 1, 2006. ©ASCE, ISSN 1090-0241/2006/
2-143–151/$25.00.
an alumino-silicate framework of cavities occupied by sodium
and chloride ions. It has a “cagelike” structure affording it many
of the properties characteristic of zeolite minerals, such as a high
ion-exchange capacity and water retention capabilities 共Breck and
Flanigen 1968兲. The net negative charge of sodalite is usually
balanced by extra-framework exchangeable cations loosely held
within the central cavities of the structure and surrounded by
water molecules. Zeolites typically have cation exchange capaci-
ties between 100 and 400 meq/ 100 g. Where chlorine is absent,
the compound hydroxysodalite forms, with hydroxyl ions present
in the positions usually occupied by the chloride.
Geotechnical Properties of Red Mud
The Bayer process results in a highly alkaline 共pH = 11– 13兲 waste
material, whose mineral components can include hematite,
goethite, gibbsite, rutile, calcite, sodalite, and complex silicates
共Parekh and Goldberger 1976; Somogyi and Gray 1977; Li 1998兲.
Notably, there is usually a complete absence of quartz or clay
fine-grained “red mud” and coarse “red sand.” Typical red mud
gradings show up to 20–30% clay sized, with the majority of
particles in the silt range 共e.g., Miners 1973; Somogyi and Gray
1977兲. Some red muds have been found to have greater than 50%
of the particles less than 2 ␮m 共Li 1998兲, but this is a function of
the processing and the ore body. These materials tend to have low
plasticities 关e.g., WL = 45%, I P = 10%, after Vick 共1981兲兴 and rela-
tively high specific gravity 共Gs = 2.8– 3.3兲. In spite of their plas-
ticity indices and lack of clay minerals, these wastes show many
geotechnical properties similar to clayey tailings found in other
mineral processing 关e.g., mineral sands, gold, etc. 共Vick 1981兲兴.
Consolidation and settling of red muds has been found to be
a function of the type and quantity of iron minerals 共i.e.,
Al-goethite, goethite, and hematite兲. In particular, very fine
goethite can cause problems due to its relatively high specific

JOURNAL OF GEOTECHNICAL AND GEOENVIRONMENTAL ENGINEERING © ASCE / FEBRUARY 2006 / 143

gravity 共Gs = 3.2兲 and high surface area compared to the other
oxide minerals 共Li 1998兲. One-dimensional compression tests
indicate compression indices Cc = 0.27– 0.39, permeabilities
k = 共2 – 20兲 ⫻ 10−7 cm/ s and coefficients of consolidation
cv = 共3 – 50兲 ⫻ 10−3 cm2 / s and are therefore similar to silty-clay
soils 共Somogyi and Gray 1977; Newson and Fahey 1998兲. In situ
undrained shear strengths are typically very high compared to
uncemented, clayey soils at equivalent liquidity indices 共i.e.,
Su Ⰷ 2 kPa for IL ⬎ 1兲 and sensitivities from 5 to 15 are commonly
found. Thixotropy has been observed with these materials 共e.g.,
Vogt 1974兲 and apparent preconsolidation pressures in excess of
actual overburden pressures are found. Hence there is a strong
indication that some red muds are cemented or aggregated. Inter-
estingly, very high friction angles 共␾⬘兲 of 38–42° are also found
for these materials, which are more typical of sandy soils. Leach-
ing by freshwater and acid neutralization has been found to
reduce in situ void ratios and compression indices. The cation
exchange capacities of red muds are comparable with kaolin or
illite minerals 共Li 1998兲.
Disposal and Storage of Red Mud
Bauxite waste storages are required to be permanent structures
that contain large volumes of material. Residues are typically de-
posited as slurries 共with 15–40% solids兲 into above ground ring
dyke disposals of large lateral extent. Mixed streams of waste
共fine and coarse兲 are deposited on some sites, whereas other
facilities have purely red mud streams. The fine particles of red
mud tend to consolidate very slowly and can be a source of con-
tamination for the surrounding environment for long periods.
Problems range from leakage of alkaline supernatant and leachate
into the groundwater, overtopping and spillage of material, dust-
ing of dry surfaces, and slow consolidation and drying interfering
with rehabilitation 共Li 1998兲. Subaerial deposition of red mud can
also present problems due to the formation of a surface crusting
of dissolved solids 共left by evaporation兲 drastically reducing ef-
fective evaporation rates and the benefits of desiccation to dewa-
tering. Synthetic and organic flocculants are commonly used prior
to dewatering and deposition, and thickened tails are often used as
part of the tailings management schemes 共Fahey et al. 2002兲.
Irrespective of the site, the selection of the dewatering scheme
and disposal method requires a sound knowledge of the geotech-
nical properties of these materials. Following decommissioning,
facilities must continue to store the material in a safe and eco-
nomic manner, while minimizing any disturbance to the local
environment. In recent years, environmental awareness in the
mining industry has increased, with legislation being developed to
ensure that disturbed areas return, as closely as possible, to their
original states or to acceptable alternative usage. The satisfactory
postdecommissioning performance of many of these materials and
structures has yet to be proven and is currently impeded by a lack
of suitable case studies.
Overview of Study
This paper describes a laboratory program to investigate the me-
chanical and physicochemical properties of bauxite residue 共red
mud兲 at a site in the United Kingdom. The storage facility has
operated for approximately 40 years and has been recently de-
commissioned and is now being considered for redevelopment
and rehabilitation. The bauxite on the site was extracted using the
Bayer process. The coarse fraction of the waste was separated and
formed approximately 23% of the total residue by weight. The
144 / JOURNAL OF GEOTECHNICAL AND GEOENVIRONMENTAL ENGINEERING © ASCE / FEBRUARY 2006
fines residue remaining was coagulated using starch 共Akers 1975兲
and later dewatered using a rotating vacuum filter. Material was
tipped at approximately 65% moisture content.
A number of site investigations conducted on the site over the
last 30 years have found two distinct materials: silty-clay 共red
mud兲 and fine to medium sand. These materials were interlayered
in both horizontal and vertical directions, which may reflect the
deposition history of the waste at the site. The deposit was up to
20 m deep and material ranged considerably in age through the
depth of the facility. The results of the investigations showed the
red mud to have high undrained shear strengths 共determined from
field vane tests兲 from 30 to 130 kPa; variations were observed
with depth and age. The sensitivity of the red mud was found to
be 2–12 共St = ratio of the peak to remolded undrained shear
strength兲, suggesting a high sensitivity material in many parts of
the facility.
Extremely high friction angles were measured in a range of
triaxial and shear box laboratory tests 共␾⬘ = 37– 45° 兲 and very
little variation in peak and residual friction angles were found.
Comparison of the undrained shear strengths of the red mud with
clays of similar plasticity and moisture content suggest that the
shear strength should be much lower. Hence it has been postu-
lated that the material is aggregated or cemented. The origin of
this particle aggregation was unknown and the purpose of this
study was to determine the agent共s兲 causing this phenomenon and
to estimate the potential for this structure to breakdown during
subsequent construction loading.
Experimental Methods
Initial Characterization of the Material
During the study, a range of characterization, stress-strain, and
chemical tests were conducted on thin-walled piston samples of
red mud from the site. The sample quality was assessed using
measured volumetric strain due to reconsolidation to the in situ
stress state in triaxial tests; this was found to be in the range of
2 to 3%, which suggests minimal sampling disturbance and high
quality samples 共Lunne et al. 1997兲. Intact and disturbed speci-
mens were taken from the various boreholes across the site;
where possible samples were taken for both materials. For the
purposes of this paper only data from a single borehole and depth
共9.5– 10.5 m兲 will be described, but this material is reasonably
representative of that across the site. Moisture contents were con-
ducted on the intact material from the core and the red mud was
found to have an in situ moisture content of 57% and the sand a
moisture content of 20%. The in situ bulk density of the red mud
was 1.75 t / m3 and the specific gravity of the particles was found
to be Gs = 3.05, which reflects the high iron content of the
minerals. The red mud was found to be highly alkaline with a
pH = 11.6. Atterberg limit tests were also conducted on the red
mud; the liquid limit was found to be 54% and the plastic limit
40%. Hence the material had a plasticity index of 14% and a
liquidity index close to unity. It would therefore lie below the
“A”-line and would be classified as high plasticity silt. The grad-
ing of the red mud is shown in Fig. 1, which indicates 20% of the
material was clay sized and the remainder in the silt range. Par-
ticle size distributions for acid-washed red mud and pure sodalite
are also shown in this figure.

Fig. 1. Particle size distribution curves for red mud, acid-washed red
mud, and hydroxysodalite material
Testing Program
Specimens of the red mud were taken and a series of chemical
and mechanical laboratory tests were conducted to ascertain the
origin of the particle aggregation. Isotropic consolidated und-
rained triaxial compression tests were conducted to characterize
the intact material and provide parameters for design purposes.
Oedometer tests were also used to quantify the compression and
swelling indices of the intact material and to identify any yield
points and subsequent postyield destructuration 共i.e., breakdown
of cemented/aggregated structure兲 that may occur. Reconstituted
and acid washed clay specimens were also tested in the oedom-
eter at the same in situ moisture content.
X-ray powder diffraction was carried out on the samples for
qualitative identification of the mineral phases and quantitative
estimates of mineralogical composition were obtained using
Rietveld refinement methods. Elemental composition was also
determined using x-ray fluorescence spectrometry. Scanning elec-
tron microscopy was used to examine the material structure.
Chemical and Morphological Analysis
The samples were dried at 105° C and pulverized in a ball mill to
yield fine powders. X-ray powder diffraction was initially carried
out on the powders for qualitative identification of mineral
phases. An internal standard 共5% by mass of spectrometer-grade
corundum兲 was mixed into portions of each sample using a mor-
tar and pestle, and these mixtures analyzed again using a Philips
diffractometer with a Cu K␣ radiation source and a single crystal
graphite monochromator. An angular range of 3 – 70° 2␪ in
0.1° 2␪ increments was used throughout.
Quantitative estimates of mineralogical composition were
obtained using Rietveld refinement methods. This was conducted
on the entire x-ray diffraction traces, using the computer pro-
grams X-FIT and KOALARIET 共Marquardt 1963; Berger 1986;
Nash 1990; Cheary and Coelho 1992, 1998兲. Noncrystalline
phases in the material could not be quantified directly using
Rietveld refinement. However, the corundum internal standard al-
lowed quantification of the total amorphous content of each
sample.
Separate samples were also pressed into pellets and elemental
composition determined using x-ray fluorescence spectrometry.
The sample of red mud was spread onto the top surface of an
aluminum scanning electron microscope 共SEM兲 stub and dried
JOURNAL OF GEOTECHNICAL AND GEOENVIRONMENTAL ENGINEERING © ASCE / FEBRUARY 2006 / 145
under ambient conditions. The specimen was then sputtered with
a layer of carbon before presention to the scanning electron
microscope.
One-Dimensional Compression
Specimens of the intact red mud were taken and placed in a
standard 70 mm diameter oedometer and loaded in small incre-
ments from a 12.5 kPa vertical effective stress to 800 kPa, and
then unloaded with the same increments to 25 kPa. These speci-
mens were then taken and dried, and reconstituted into a homo-
geneous paste with deionized water 共at the in situ moisture
content of 57%兲 using a paddle mixer. The oedometer tests were
then repeated over the same stress range as the intact specimens.
To better establish the role of sodalite in the compressive behav-
ior of the red mud, a portion of the red mud was treated to remove
this phase. One-hundred grams of red mud was dispersed in 1 L
of dilute nitric acid 共10% by volume兲 and stirred for 24 h. After
this period, the slurry was filtered and the residue washed repeat-
edly on the filter with distilled water. The washed residue was
then dried at 105° C for 24 h. Again the oedometer test was re-
peated with this material reconstituted at 57% moisture content
and tested over the same stress range.
Sodalite constitutes a high percentage of this particular red
mud 共⬃17.5% 兲, thus it was decided to investigate the compres-
sive properties of this material in isolation. Pure hydroxysodalite
was synthesized for testing in the oedometer. This was prepared
with the aid of reaction composition diagrams devised by Breck
and Flanigen 共1968兲. A slurry comprising 66 g of NaAlO2, 14.2 g
NaOH, 109 g of Na2Si2O5, and 200 g of distilled water was pre-
pared and divided into a series of thick-walled 15 ml capacity
Teflon containers, which were tightly sealed and transferred to a
105° C environment for 24 h. After this period, the containers
were cooled, their contents filtered, and the residue repeatedly
washed on the filter using distilled water. The residue was then
dried in an oven at 105° C for 24 h. The residue was confirmed as
being hydroxysodalite using x-ray diffraction. The liquid limit of
the sodalite was found to be WL = 96%, and the sodalite was
mixed at 1.2 times the liquid limit and loaded/unloaded over the
same stress range as the red mud in the oedometer. Particle size
distributions of the sodalite were also performed before and after
loading.
The aforementioned tests were conducted to quantify the effect
that the cemented/aggregated structure had on the mechanical be-
havior of the red mud, and to provide a “reference,” uncemented
material for comparison with the intact material. The oedometer
tests on the hydroxysodalite were conducted to provide the com-
pression properties of the pure material and give an indication of
the potential for hydration and particle fracture or crushing of the
material at different stresses.
Undrained Triaxial Compression
Intact specimens of the red mud were taken from the piston
samples and prepared for standard isotropic triaxial compression
tests 共BS1377: Part 8 1990兲. Cylindrical specimens of 38 mm
diameter and 76 mm height were cut from the piston samples
and saturated at 10 kPa in the triaxial cell. The specimens were
drained from one end and from the radial boundary. Skempton’s
pore-pressure parameter “B” was identified after saturation for
48 h. Values of “B” were found to be in the range of 0.97–1.0,
hence the samples were essentially saturated. A back-pressure of
300 kPa was used and specimens subject to effective consolida-

Fig. 2. 共a–c兲 X-ray powder diffractograms obtained from the red
mud, sand, and acid-washed samples
tion pressures of 50, 100, and 300 kPa for 24 h. The specimens
were then sheared to failure under undrained compression condi-
tions at a rate of 0.015 mm/ min to ensure adequate equilibration
of pore pressures through the specimens.
Laboratory Testing Results
Chemical Analysis
The x-ray powder diffraction traces obtained from the materials
are shown in Fig. 2. Both samples 关red mud and sand, see
146 / JOURNAL OF GEOTECHNICAL AND GEOENVIRONMENTAL ENGINEERING © ASCE / FEBRUARY 2006
Figs. 2共a and b兲兴 were found to contain significant quantities of
iron, present mainly as hematite 共Fe2O3兲 and goethite
关␣-FeO共OH兲兴. The main distinguishing features between the two
materials were the presence of large quantities of the zeolite min-
eral sodalite in the red mud, and the presence of gibbsite
关Al共OH兲3兴 in the “sand” sample. Sodalite 共Na8关Al6Si6O24兴Cl2兲
has a cubic habit, a hardness of 5.5–6, and a specific gravity of
2.20–2.35 共Deer et al. 1992兲. Its composition can vary signifi-
cantly, and while the low chloride content of the red mud suggests
that pure hydroxysodalite is formed, this is not necessarily the
case. The Rietveld refinement results are shown in Table 1. The
results of XRF analysis are shown in Table 2. Composition is
expressed in terms of the oxides of each species, with the excep-
tion of anionic species 共chloride and sulfate兲.
The x-ray diffraction trace obtained from the acid-washed red
mud is shown in Fig. 2共c兲 and indicates that all hydroxysodalite
共plus calcite兲 was removed by the washing process. The mineral-
ogical composition of the acid-washed material estimated using
Rietveld refinement is also given in Table 1 and the chemical
composition of the acid-washed material is given in Table 2, in-
dicating appropriately reduced levels of SiO2, Al2O3, Na2O, and
CaO.
Scanning Electron Microscopy
The microstructure of the red mud specimen was observed to be
relatively consistent over its entire surface, being composed of a
collection of small, apparently aggregated particles 关Fig. 3共a兲兴.
Closer inspection of the particles shows a layer of material coat-
ing most of the particle surfaces 关Fig. 3共b兲兴. Energy-dispersive
x-ray analysis of this coating shows spectral peaks for silicon,
aluminum, sodium, and iron 共Fig. 4兲. This suggests that the coat-
ing is composed largely of hydroxysodalite which, of the com-
pounds identified using x-ray diffraction, is unique in containing
sodium, and also contains silicon and aluminum 共see Table 1兲.
Further magnification of the coating 共Fig. 5兲 shows it to be com-
posed of crystals with a cubic habit, which further supports the
hypothesis that the substance is hydroxysodalite.
Oedometer Testing
The compression behavior of the intact, reconstituted, and acid-
washed red mud specimens is shown in Fig. 6. The intact speci-
mens vary from a void ratio of approximately 1.76 to 1.45 over
the stress range of 12.5– 800 kPa. The intact specimens show an
initially overconsolidated response, with yield occurring at ap-
proximately 200 kPa vertical effective stress 关determined using
the bilogarithmic method of Butterfield 共1979兲兴. The compression
index 共Cc兲 was found to be 0.41 and the swelling index 共Cs兲 was
0.015. The reconstituted specimens have very similar compres-
sion behavior, with void ratio varying from 1.75 to 1.45 over the
same stress range, and yield occurring again at approximately
200 kPa vertical effective stress. However, the compression index
共Cc兲 was found to have reduced to 0.34, while the swelling index
共Cs兲 remained the same at 0.015. Acid washing the specimens
caused a marked reduction in the yield stress to approximately
100 kPa, but the same compression and swelling indices as the
reconstituted specimens 共i.e., Cc = 0.34 and Cs = 0.02兲.
The compression data for the pure sodalite is shown in Fig. 7.
A specific gravity of 2.3 has been assumed for the calculation of
the void ratio. The compression indices of this material are com-
parable with those of the red mud, with Cc = 0.4 and Cs = 0.02.
There is no discernable yield and the material appears to be
Table 1. Mineralogical Analysis—Intact, Reconstituted, and Acid-Washed Material
Red mud Red mud
Mineral 共intact and reconstituted兲 Sand 共acid washed兲
phase Formula 共%兲 共%兲 共%兲
Quartz SiO2 1.2 1.8 1.3
Hematite Fe2O3 13.5 22.0 16.1
Goethite FeO共OH兲 21.8 22.7 23.8
Rutile TiO2 4.6 1.2 5.4
Sodalite Na4共Si3Al3兲O12Cl 17.5 1.8 —
Calcite CaCO3 0.7 — —
Muscovite KAl2共Si3Al兲O10共OH , F兲2 2.4 — —
Siderite FeCO3 0.1 — —
Perovskite CaTiO3 — 0.6 —
Gibbsite Al共OH兲3 — 15.7 —
Amorphous 38.2 34.2 51.0

already on the virgin compression line at 12.5 kPa. Particle crush- Deviatoric stress 共q兲 against axial strain 共␧a兲 is shown in
ing is unlikely to have occurred during compression; the particle Fig. 9. In general, the curves show the material behaving in a
size distributions conducted before and after testing showed no frictional manner, with peak deviatoric stresses increasing with
discernable difference. In addition, the compressive strength of confining pressures. There appears to be no evidence of strain
sodalite is 33 MPa, and this is comparable with that of silica softening and therefore little chance of progressive failure of this
sand grains with 42– 147 MPa 共McDowell 2001兲. Hence the ob- material. Excess pore-pressure 共⌬u兲 development with axial strain
served compression was assumed to be due purely to particle is shown in Fig. 10. The higher confining pressures 共100 and
rearrangement. 200 kPa兲 show positive pore-pressure development, with a
continuous rise up to the peak values and a slight drop in pore
Undrained Triaxial Compression Tests pressure as the material approached critical state. The specimens
consolidated to the lower pressure of 50 kPa show negative
The stress-strain behavior of the intact red mud was investigated excess pore-pressure development, after reaching a positive pore-
using the triaxial data shown in Figs. 8–10. Stress paths for the pressure peak at approximately 1 to 2% axial strain. Values of
six tests 共RM1 to 6兲 are shown in Fig. 8 in deviatoric stress Skempton⬙s pore-pressure parameter “A” 共=⌬u / ⌬q兲 at failure are
共q = ␴⬘1 − ␴⬘3兲: mean normal effective stress 共p⬘ = 关␴⬘1 + 2␴⬘3兴 / 3兲 quite low and in the range of 0.07–0.41, which would normally be
space. The initial quasi-elastic phase for these curves lies to the associated with heavily overconsolidated clays or sands.
right of the vertical and suggests an anisotropic material with a
higher vertical stiffness than horizontal stiffness 共Graham and
Houlsby 1983兲. The specimens consolidated at 50 and 100 kPa
Analysis of Results and Discussion
appear to yield at approximately 100– 125 kPa deviatoric stress,
and the specimens consolidated at 200 kPa yield at 150– 175 kPa
deviatoric stress. As the material yields, the stress path follows Effect of Structure on Mechanical Behavior
the state boundary surface and deviates towards the left, and
The triaxial data shows a material with a very high friction angle
eventually reaches a unique critical state line with a stress ratio
共␾⬘ = 42° 兲, which is usually associated with sandy soils. This was
M = q / p⬘ = 1.72 共which corresponds to a friction angle of 42°兲.
also confirmed with direct shear box testing. Apparent cohesion
共c⬘兲 of 10– 20 kPa was also suggested from the triaxial and shear
box data, which reinforces the hypothesis that the material is
Table 2. Bulk Oxide Analysis—Intact, Reconstituted, and Acid-Washed cemented. The shape of the triaxial stress paths 共shown in Fig. 8兲
Material
is also consistent with a cemented material. Initially the stress
Red mud Red mud paths lie to the right of the vertical, as the cementitious bonds
共intact and reconstituted兲 Sand 共acid washed兲 begin to break down, the stress path begins to deviate to the left,
Oxide 共%兲 共%兲 共%兲 which indicates the material is collapsing and trying to compress
SiO2 18.25 6.93 21.02 causing positive pore-pressure development. As the specimens
TiO2 5.97 3.69 8.36 approach critical state, the stress paths again deviate towards the
Al2O3 23.43 25.13 17.04 right, suggesting negative pore-pressure generation and an at-
Fe2O3 36.31 62.44 51.75 tempt by the material to dilate; thus the effect of the bonding is
MnO 0.14 0.38 0.17 lost at this stage. Nagaraj et al. 共1998兲 suggested that the resis-
MgO 0.03 0.12 0.32
tance to loading offered by cemented soils was the sum of the
resistance of the unbonded soil skeleton and the resistance of the
CaO 4.38 0.11 0.19
cementation bonds. Once the soil is subject to loads greater than
Na2O 12.36 3.45 0.67
the bond strength 共i.e., yielding兲 load is transferred from the ce-
K 2O 0.20 0.09 0.21
mentitious bonds to the “frictional bonds.” Hence under low con-
SO32− 0.74 0.13 0.17
fining stresses the cementitious bonds will dominate and there
Cl− 0.20 0.04 0.04 will be little frictional resistance after the bonds break. At higher
confining pressures, sufficient frictional resistance exists after the

JOURNAL OF GEOTECHNICAL AND GEOENVIRONMENTAL ENGINEERING © ASCE / FEBRUARY 2006 / 147


Fig. 3. 共a兲 Aggregated particles making up the red mud sample; and
共b兲 detail of particles in the red mud sample
bonds break for the deviatoric stress to continue to rise. The pore
pressure development of the specimens with the lowest confining
pressures suggest that once the peak pressure is reached 共presum-
ably where the cementitious bonds begin to break down兲, the
material attempts to dilate significantly and negative pore pres-
sures develop. The yielding and breakdown of the cementitious
bonds occurs at approximately 1 to 2% axial strain for all of the
specimens. This suggests that the material is not metastable and
this strain is unlikely to be reached under typical construction
Fig. 4. Energy-dispersive x-ray analysis spectrum obtained from the
material coating the aggregated particles
148 / JOURNAL OF GEOTECHNICAL AND GEOENVIRONMENTAL ENGINEERING © ASCE / FEBRUARY 2006
Fig. 5. Crystals of cubic habit on the surface of a particle
loads. Inspection of the specimens after failure revealed distinct
failure planes for all of the specimens, which is another typical
feature of cemented materials.
In comparison, the compression behavior of the intact, recon-
stituted, and acid-washed red mud appears to be more consistent
with typical silty-clay soils 共e.g., Newson and Fahey 1998兲; the
compression indices are reasonable when compared with empiri-
cal estimates of Cc using the liquid limit 共Terzaghi and Peck
1967兲. The yield stress for the intact specimen appears to be twice
as high as would be expected from previous overburden 共i.e.,
depth= 10.5 m, ␴⬘y = 100 kPa兲, assuming no material has been re-
moved from the current ground level or desiccation has occurred.
This is consistent with the observations of Somogyi and Gray
共1977兲, who found apparent preconsolidation pressures up to four
to five times previous overburden pressures. The intact specimens
also appear to be quite firm to the touch, which would not be
expected for an insensitive soil so close to its liquid limit
共IL ⬎ 1兲 and suggest a significant sensitivity; indeed a hand vane
on the core sample indicated a shear strength of approximately
20 kPa 共undrained unconsolidated triaxial compression tests sug-
gested that cu = 26 kPa兲. Hence the compression and strength data
seem to confirm that the intact soil is aggregated or cemented,
Fig. 6. Compression behavior from the intact, reconstituted,
and acid-washed red mud material
 Fig. 7. Compression behavior of pure hydroxysodalite material
leading to increased peak strengths. Interestingly, the triaxial data
shows little sensitivity, which suggests very high strain is required
to fully destructure the material.
The reconstituted specimens have similar compression and
yield behavior to the intact material 共although with some reduc-
tion in compression index兲, which suggests that either there is no
cementation/aggregation occurring in the intact specimen, or the
agent causing this phenomenon has quickly reestablished the par-
ticulate bonds after reconstitution. Although the yield stress of the
two materials is similar, the initial gradients of the two curves are
different 共the intact material is close to horizontal兲 and the slope
of the apparent normal compression lines is different. This sug-
gests that a proportion of the compression of the intact material is
due to breakdown of bonds 关or destructuration; Leroueil et al.
共1979兲兴. Removal of the hydroxysodalite from the red mud by
acid washing shows a reduction in yield stress to 100 kPa, no
change in compression index compared to the reconstituted ma-
terial, and the initial portion of the curve again has a much higher
gradient than the intact specimen. The initial portion of the recon-
stituted and acid-washed material curves may also be an artifact
of the preparation process, since apparent initial overconsolida-
tion in compression curves is commonly observed when the ma-
terial is reconstituted well below the sedimented void ratio 共Pane
and Schiffman 1997兲.
Fig. 8. Undrained triaxial compression stress paths for the intact
red mud
JOURNAL OF GEOTECHNICAL AND GEOENVIRONMENTAL ENGINEERING © ASCE / FEBRUARY 2006 / 149
Fig. 9. Stress-strain relationships from undrained triaxial tests on the
intact red mud
Factors Controlling Mechanical Behavior
The chemical analyses show the two materials 共sand and red
mud兲 to be predominantly hematite and goethite 共compounds of
iron兲, with significant quantities of sodalite in the red mud, and
gibbsite 共a hydrated aluminum decomposition product of plagio-
clase feldspar, often associated with bauxite deposits兲 in the
“sand” sample. While these are still particulate materials, the clas-
sical mineralogy of quartz and sheet silicates 共clay兲 of typical
soils is not present with any significant quantities. In particular,
the red mud has virtually no clay minerals present and yet pre-
sents “claylike” behavior.
Zeolite materials 共similar to hydroxysodalite兲 crystalize in
three-dimensional framework structures, where oxygen atoms are
shared between tetrahedra containing silicon and/or aluminum.
This gives a negatively charged framework that encloses cavities
and pores of molecular dimensions that can be occupied by
charge balancing cations and loosely held water molecules 共Lee
et al. 2002兲. Clay minerals and zeolites share a number of prop-
erties, which include high cation exchange capacities, small par-
ticle size, and the ability to reversibly hydrate and dehydrate.
However, there are significant differences in crystal structure;
clay minerals having two-dimensional layer structures, which can
Fig. 10. Excess pore-pressure–strain relationships from undrained
triaxial tests on the intact red mud
be disordered in stacking dimension. The hydration of both ma-
terials is a function of temperature and the partial pressure 共i.e.,
relative humidity兲 around the particles. Unlike some clay miner-
als, which may undergo essentially infinite swelling, zeolites have
a fixed upper hydration limit, although limited expansion of their
unit cells occurs with hydration.
The specific surface areas of the goethite 共45– 169 m2 / g兲, he-
matite 共1.8– 3.1 m2 / g兲, and sodalite 共810 m2 / g兲 共Langmuir 1997兲
are comparable with those of kaolinite 共10– 38 m2 / g兲 共Langmuir
1997兲. The cation exchange capacities 共CEC兲 of these materials:
goethite 共20– 470 meq/ 100 g兲, hematite 共1.5– 11 meq/ 100 g兲,
and sodalite 共100– 400 meq/ 100 g兲 are also comparable with
kaolinite 共2 – 21 meq/ 100 g兲 共Hsi 1981; Davis and Kent 1990兲.
The CEC of zeolites is permanent and independent of solution;
the CEC of kaolin and metal oxyhydroxides 共i.e., goethite and
hematite兲 are pH dependent 共net negative at low pH兲. Hence the
sorptive surface properties of the minerals in the red mud sample
are similar or greater than kaolinite and even comparable with
illite and smectite clays; it would therefore be expected that red
mud would attract water molecules and other red mud particles in
a similar manner to clay minerals and share similar mechanical
properties.
Zeolite materials such as sodalite, where the framework
structure remains unchanged after dehydration, will rehydrate by
internal pore filling and the usual concepts of surface area as
applied to other solid adsorbents cannot be used. However, a
limiting adsorption value may be estimated using Gurvitsch’s
pore filling rule 共Breck and Flanigen 1968兲. Hence the sorption of
water molecules at a relative humidity of 98% is approximately
13.5– 14.5 g / 100 g solid. Thus for red mud at a moisture content
of 60% 共e.g., for a case of mass of water= 60 g, mass of solid
100 g兲 with a sodalite content of approximately 20%, a maximum
of 3 g of water will be held within the sodalite unit cells, with the
remaining 57 g in the voids between the particles. In the pure
sodalite material, 100 g solid at 104% moisture content 共i.e., mass
of water= 104 g兲, 15 g of water will lie within the unit cell frame-
works. Although in both cases the actual moisture content within
the particles voids is reduced due to the presence of intracell
moisture, this is not sufficient to alter significantly the mechanical
properties of the material 共e.g., liquidity index兲.
Observations of extremely high friction angles for red mud are
most likely related to the rotund shape of the red mud particles;
most of the minerals have cubic or prismatic habits 共shapes兲. In-
creases in peak shear strengths 共and friction angles兲 have been
also noted for cemented and “structured” clay soils 共e.g., Graham
and Li 1985; Cotecchia and Chandler 1997兲 but these increases
are not sufficient to explain the very high angles found. Hence it
can be anticipated that the red mud will behave physicochemi-
cally in a manner similar to clay, but mechanically may share
some properties with sands or silts.
Stability of Cementitious Bonds
Based on the chemical analyses, the cementing/aggregating agent
is hydroxysodalite. Hydroxysodalite is only very slightly soluble
in water, but becomes more soluble in alkaline conditions 共which
occur in the red mud兲. It is therefore likely that as the red mud
settles in the storage, the dissolved hydroxysodalite is playing a
cementing role due to its precipitation over mineral surfaces and
at contact points between hydroxysodalite crystals. It is unlikely
that the starch flocculent has survived the filtration and deposition
process, and the bond strength of the polymer bridges between
particles is much less than that of the sodalite 共Akers 1975兲, so
150 / JOURNAL OF GEOTECHNICAL AND GEOENVIRONMENTAL ENGINEERING © ASCE / FEBRUARY 2006
this potential source of bonding has been ignored. Across the site,
yield stresses 共and hence bond strength兲 are very similar even for
materials at different depths. Nagaraj et al. 共1998兲 found that the
stress-carrying capacity of bonds in cemented soils does not
change during compressive loading and is approximately con-
stant. It is not clear why the bond strength is similar at different
load levels 共although this is predominantly a chemical process兲,
since it would be expected that disruption of bonds could occur
during loading 共e.g., construction or deposition兲. However, if the
number of bonds per unit volume was the same at different
depths, then the capacity would not change. The cementation will
be influenced by the void ratio at the time of bonding, the stress
history after bonding, the distribution of cementing agent, and the
time required for full bond strength to develop. Li 共1998兲 found
that the presence of low concentrations of sodalite had no effect
on the settling properties of red mud, which suggests that relative
stability of the structure is required for this bonding process to
occur.
The oedometer and triaxial data suggests that the hydroxy-
sodalite bonds appear to be quite strong and stable over the range
of stresses and strains normally encountered during deposition
and construction. Acid washing the red mud was found to break
down the hydroxysodalite bonds and change the mechanical prop-
erties of the material. Preliminary geochemical calculations using
Gibbs energy of formation coefficients 共Weber 2001兲 have found
that of the water solubility of hydroxysodalite is pH dependent; at
high pH there is a very slight increase in solubility, but at low pH
this becomes much more significant. Therefore if the red mud on
the site remains alkaline or neutral, it is unlikely that seasonal
wetting and drying cycles under loading would affect the red mud
structure and properties. However, there have been recent sugges-
tions in the literature 共e.g., Poulin et al. 1996兲 to comingle acid
mine generating wastes with alkaline red muds, which may affect
the long-term geotechnical performance of this material.
Conclusions
A suite of laboratory tests investigating the mechanical and physi-
cochemical properties of bauxite residue 共red mud兲 have been
described. Based on the results of the tests conducted the follow-
ing conclusions have been drawn:
• The red mud on this site has compression behavior similar to
clayey soils and frictional behavior similar to sandy soils;
• The intact material appears to be “structured” and has me-
chanical behavior consistent with sensitive, cemented soils;
• The agent causing the cementation/aggregation of particles is
the feldspathoid hydroxysodalite;
• The hydroxysodalite bonds appear to be strong and stable,
with little destructuration occurring over a range of normal
construction loads;
• The hydroxysodalite bonds can be broken down by subjecting
the red mud to an acidic environment;
• Hydration of the hydroxysodalite unit cell is significant, but
does not affect the mechanical performance of the red mud;
and
• The shape, size, and electrically charged properties of the
hydroxysodalite, goethite, and hematite in the red mud appear
to be causing mechanical behavior with features consistent
with clay and sand, without the presence of either quartz or
clay mineral.
Acknowledgments
Thanks are due to the staff of the Division of Civil Engineering at
the University of Dundee. The writers would also like to thank
Alcan Chemicals Europe and Ritchies for use of the data from the
ground investigation.
References
Akers, R. J. 共1975兲. Flocculation, The Institute of Chemical Engineering,
London.
Berger, H. 共1986兲. “Study of the k-alpha emission-spectrum of copper.”
X-Ray Spectrom., 15, 241–243.
Breck, D. W., and Flanigen, E. M. 共1968兲. Molecular sieves, Society of
Chemical Industry, London, 47.
British Standard. 共1990兲. “Methods of test for soils for civil engineering
purposes.” BS1377.
Butterfield, R.. 共1979兲.“A natural compression law for soils 共an advance
on e-log p 兲, Geotechnique, 29共4兲, 469–480.
⬘
Cheary, R. W., and Coelho, A. A. 共1992兲. “A fundamental parameters
approach of x-ray line-profile fitting.” J. Appl. Crystallogr., 25,
109–121.
Cheary, R. W., and Coelho, A. A. 共1998兲. “Axial divergence in a conven-
tional x-ray powder diffractometer: I. Theoretical foundations.”
J. Appl. Crystallogr., 31, 851–861.
Cotecchia, F., and Chandler, R. J. 共1997兲. “The influence of structure on
the pre-failure behavior of a natural clay.” Geotechnique, 47共3兲,
523–544.
Davis, J. A., and Kent, D. B. 共1990兲. “Surface complexation models in
aqueous geochemistry In Mineral-Water Interface Geochemistry.”
Rev. Mineral., 23, 177–160.
Deer, W. A., Howie, R. A., and Zussman, J. 共1992兲. An introduction to
rock-forming minerals, 2nd Ed., Longman, 696.
Fahey, M., Newson, T. A., and Fujiyasu, Y. 共2002兲. “Engineering with
tailings.” Invited Lecture, Proc., 4th Int. Conf. on Environmental
Geotechnics, Rio de Janeiro, Brazil, 2, 947–973, Balkema, Lisse.
Graham, J., and Houlsby, G. 共1983兲. “Elastic anisotropy of a natural
clay.” Geotechnique, 33共2兲, 165–180.
Graham, J., and Li, E. 共1985兲. “Comparison of natural and remoulded
plastic clay.” J. Geotech. Eng., 111共7兲, 865–881.
Hsi, C. D. 共1981兲. “Sorption of uranium 共VI兲 by iron oxides.” Ph.D.
thesis T-2514, Colorado School of Mines, Golden, Colo.
Langmuir, D. 共1997兲. Aqueous environmental geochemistry, Prentice-
Hall, Englewood Cliffs, N.J., 601.
Lee, Y. J., et al. 共2002兲. “Non-framework cation migration and irrevers-
JOURNAL OF GEOTECHNICAL AND GEOENVIRONMENTAL ENGINEERING © ASCE / FEBRUARY 2006 / 151
View publication stats
ible pressure induced hydration in a zeolite.” Nature (London), 420,
485–489.
Leroueil, S., Roy, M. La Rochelle, P., Brucy, F., and Tavenas, F. 共1979兲.
“Behavior of destructured natural clay.” Proc., ASCE Geotech. Div.,
105共6兲 759–778.
Li, L. Y. 共1998兲. “Properties of red mud tailings produced under varying
process conditions.” J. Environ. Eng., 124共3兲, 254–264.
Lunne, T., Berre, T., and Strandvik, S. 共1997兲. “Sample disturbance in
soft low plastic Norwegian clay.” Recent developments in soil and
pavement mechanics, M., Almeida, ed., Balkema, Rotterdam, 81–102.
Marquardt, D. W. 共1963兲. “An algorithm for least squares estimation of
non-linear parameters.” J. Soc. Ind. Appl. Math., 11, 431–331.
McDowell, G. K. 共2001兲. “Statistics of soil particle strength.”
Geotechnique, 51共10兲, 897–900.
Miners, K. 共1973兲. “Alcan’s experience of the disposal of red mud from
the Bayer ore process.” Proc., 1st Int. Tailings Symposium, Miller
Freeman, San Francisco, 553–562.
Nagaraj, T. S., Pandian, N. S., and Narasimha, P. S. 共1998兲. “Compress-
ibility behaviour of soft cemented soils.” Geotechnique, 48共2兲,
281–287.
Nash, J. C. 共1990兲. Compact numerical methods for computers, Adam
Hilger, Bristol.
Newson, T. A., and Fahey, M. 共1998兲. “Saline tailings disposal and
decommissioning.” MERIWA Rep. No. M241, Vol. 1, Univ. of Western
Australia, Perth.
Pane, V., and Schiffman, R. L. 共1997兲. “The permeability of clay suspen-
sions.” Geotechnique, 47共2兲, 273–288.
Parekh, B., and Goldberger, W. 共1976兲. “An assessment of technology for
possible utilization of Bayer process muds.” US EPA, EPA-600/2-76-
301.
Poulin, R., Hadjigeorgiou, J., and Lawrence, R. W. 共1996兲. “Layered
mine waste co-mingling for mitigation of acid rock drainage.” Trans.
Inst. Min. Metall., Sect. C, 105, A55–A62.
Somogyi, F., and Gray, D. 共1977兲. “Engineering properties affecting dis-
posal of red mud.” Proc., Conf. on Geotechnical Practice for Disposal
of Solid Waste Materials, ASCE, 1–22.
Terzaghi, K., and Peck, R. B. 共1967兲. Soil mechanics in engineering
practice, Wiley, New York.
Vick, S. G. 共1981兲. Planning, design and analysis of tailings dams, Wiley,
New York, 369.
Vogt, M. F. 共1974兲. “Development studies on dewatering of red mud.”
103rd Annual Meeting of AIME, Dallas, Tex., 73–91.
Weber, C. F. 共2001兲. “Phase equilibrium studies of Savannah River tanks
and feed streams for the salt waste processing facility.” ORNL/TM-
2001/109, Oak Ridge National Laboratory Report, Computational
Physica and Engineering Division, 62.