Ocean Engineering 32 (2005) 1133–1159

www.elsevier.com/locate/oceaneng

Technical Note

Sulphate attack and ettringite formation in the lime

and cement stabilized marine clays
G. Rajasekaran1
Aspecise Ltd, Singapore
Received 2 April 2004; accepted 25 August 2004
Available online 12 February 2005

Abstract

Swelling and shrinkage behaviour of marine clays impose foundation problems that may
sometimes results in excessive settlements. Improving the behaviour of soft clays using lime or
cement is not new. Recent studies reported the occurrence of high swelling and pavement failures in
lime and cement stabilized clays containing sulphates. The above phenomena resulted in the
formation of swelling minerals such as ettringite and thaumasite. In this paper, the earlier reported
case histories of sulphate attack in lime and cement stabilized clays have been reviewed, and a list of
precautionary measures to be adopted for controlling the ettringite formation have been suggested.
An attempt has been made to investigate the application of deep lime mixing technique in sulphate
enriched marine clays. Physico-chemical and engineering properties of the lime treated clays
containing ettringite have been examined. Test results indicate that lime and cement stabilization
techniques should be cautiously approached in sulphate enriched clays.
q 2004 Elsevier Ltd. All rights reserved.

Keywords: Sulphate attack; Cement; Lime; Stabilization; Ettringite; Marine clays

1. Introduction

The application of cement and lime to improve the characteristics of soft fine grained
soils is not new (Broms and Boman, 1975; Okumura and Terashi, 1975; Narasimha Rao
and Rajasekaran, 1996). However, recent studies on cement and lime treated soils showed

E-mail address: rajammu@hotmail.com.

1
Formerly, Department of Civil Engineering, National University of Singapore, 10 Kent Ridge Crescent,
Singapore, Singapore 119260.

0029-8018/$ - see front matter q 2004 Elsevier Ltd. All rights reserved.
doi:10.1016/j.oceaneng.2004.08.012
1134 G. Rajasekaran / Ocean Engineering 32 (2005) 1133–1159

swelling and pavement failures due to the formation of high swelling minerals such as
ettringite and thaumasite (Mitchell, 1986; Hunter, 1988; Rajasekaran, 1994). Ettringite
formation is a complex phenomenon, and there are many controversial issues regarding its
stability with time (Rajasekaran, 1994). So far, suitable guidelines have not been
developed for treating the soils containing sulphates. This has resulted in developing
various techniques to treat the clays using either chemical mixing or in situ techniques.
Before the application of cement and lime stabilized techniques, it is essential to
understand the nature of sulphates present in the soils, soil–lime reactions, mechanisms
involved in ettringite formation and its related problems. It is necessary to examine the
nature of lime or cement stabilized soils, and the adverse conditions of ettringite
formation. Limited information is available on ettringite formation in sulphate enriched
marine clays (Rajasekaran, 1994; Rajasekaran et al., 1997). Hence, studies on ettringite
should be critically investigated for the successful application of deep cement and lime
mixing techniques in marine clays (Rajasekaran, 1994). Also, it is necessary to understand
the various mechanisms of sulphate attack causing the failures so that suitable protective
measures could be taken in time. In the present investigation, a detailed study on the
ettringite formation and its adverse effect on the engineering behaviour of lime and cement
treated clays has been reviewed. The earlier reported case histories related to sulphate
attack in treated soil, and the preventative measures suggested by various authors have
been reviewed.

2. Sulphate in soils

The presence of sulphates either in the ground or mixing water may affect the cation
exchange and pozzolanic reactions of cement and lime treated soil systems. The nature of
above reactions depends on the type and concentration of metal ions present, and the
availability of alumina and silica that can influence the engineering behaviour of soil with
time. Sulphates of sodium (thenardite, NaSO4$10H2O), potassium (arcanite, K2SO4),
calcium (gypsum or selenite, CaSO4$2H2O) and magnesium (epsomite, MgSO4$7H2O)
are commonly present in the surface sediments, especially in regions of limited rainfall
(Grim, 1968; Wild et al., 1999). The oxidization of sulphide minerals such as pyrite results
in the transfer of sulphates to other sites through ground water movement (Sherwood,
1962). Fookes (1978) reported the presence of calcium sulphate and its phase
transformations with climatic and environmental conditions along the coastal region of
Arabian Gulf. The presence of sulphates either in the form of iron sulphite, Fe2S (pyrite) or
selenite (gypsum) can be seen in lime stabilized clays as reported by Littleton and
Willavise (1992) and Azam et al. (1998). It has been established that the use of industrial
wastes for pavement or other construction works may be contaminated with sodium and
magnesium sulphates (Obika and Freer-Hewish, 1990).
Serious structural damages including uplifting of tunnel floors, rocks under dams and
the foundations of offshore structures resting on marine clays due to heaving and
settlement during the hydration of different calcium sulphate phases have been reported
(Brune, 1965; Zanback and Arthur, 1986; Rajasekaran, 1994; Azam, 1997). The
replacement of Ca2C ions by Mg2C in marine environment results in the formation of
 G. Rajasekaran / Ocean Engineering 32 (2005) 1133–1159 1135

gypsum precipitates (Blyth and de Frietas, 1984). Also, the leaching process results in the
dissolution of gypsum induced cementation in clay, and decreases clay sensitivity
(Mitchell, 1986).

3. Soil–lime-sulphate reactions

It is important to know the lime–soil reaction mechanisms, and several investigators

brought out their beneficial effects in clays (Broms and Boman, 1975; Okumura and
Terashi, 1975; Rajasekaran, 1994). Lime–soil reactions can be classified into short term
and long term reactions. Short term reactions include flocculation, lime migration, pH and
cation exchange reactions, carbonation, and the above reactions affect the physical
properties of the soil system such as Atterberg limits and particle size distribution.
Whereas the long term pozzolanic reactions include the formation of various new reaction
products, which result in the growth of aggregates and affect the strength and
compressibility of clays.
Figs. 1 and 2 show the various reaction mechanisms involved in the hardening effect of
improved soil as brought out by Saitoh et al. (1985). There are several factors that
influence the lime treated soil properties such as cations, concentration of sulphates and
clay minerals composition (available alumina and silica). The anions of sulphates combine
with the available calcium and alumina, and form insoluble ettringite in the soil system.
The formation of ettringite increases the porosity and simultaneously decreases the free
moisture content during ettringite nucleation and its subsequent growth. Ogawa and Roy
(1982) and Uchikawa and Uchida (1986) brought out the schematic reaction mechanism of

Fig. 1. Reaction mechanisms of soil and hardening agents.

1136 G. Rajasekaran / Ocean Engineering 32 (2005) 1133–1159

Fig. 2. Cement reaction mechanisms in soil with time.

C3S-pozzolanic compounds, and ettringite development during pozzolanic reactions,

respectively (Figs. 3 and 4).
The formation of calcium silicate hydrate and calcium aluminate hydrate in crystalline
or semi-crystalline phases can be seen in lime stabilized clays (Croft, 1964; Wild et al.,
1993, 1995). But the presence of sulphates in the mixing water and ground water caused

Fig. 3. Reaction mechanism involved in the development of C3S-Pozzolana grains.

 G. Rajasekaran / Ocean Engineering 32 (2005) 1133–1159 1137

Fig. 4. Schematic development of ettringite formation.

adverse effects in the soil systems (Sherwood, 1962; Obika and Freer-Hewish, 1990;
Snedker and Temporal, 1990a). In view of cation exchange, the broken bonds of soil
particle edges and unbalanced ionic substitution within the clay mineral lattice result in
increasing negative charges of soil system (Grim, 1968). Lime dissociates into Ca2C and
OHK ions in the presence of water, and results in reduction of interparticle repulsive
forces and increases the soil alkalinity (George et al., 1992; Smith et al., 1994). The effect
of different cations such as NaC, KC, Ca2C and Mg2C on lime treated kaolinite clay
containing sulphates has been studied by Kinuthia et al. (1999). His test results indicated
that Ca2C and Mg2C enhance the beneficial effects, whereas NaC and KC induced
adverse effects in treated soil systems. The addition of lime to soil results in several
reactions including flocculation and aggregation, increases pore volume and optimum
moisture content, and lower dry density. The long term reactions result in the formation of
several cementitious products which results in aggregates of different sizes with time
(Wild et al., 1996, 1998).
Cation exchange reactions influence the Atterberg limits and compaction character-
istics of lime treated kaolinite clay containing sulphates (Leroueil and Le Bihan, 1996).
1138 G. Rajasekaran / Ocean Engineering 32 (2005) 1133–1159

The penetration of cations into the soil system results in neutralizing the negative charges
of soil particles, and change the soil particles flocculated structure to parallel arrangement.
This phenomenon results in increasing water flow as well as increasing liquid limit of clay.
Higher the cations concentration increases soil particles interparticle spacing due to
cations hydrolysis and reduces the liquid limit (Grimshaw, 1971; Yong and Warkentin,
1975; Vyalov, 1986; Kinuthia et al., 1999). Comparing with sodium ions, potassium ions
can be more strongly held into the hexagonal holes of the tetrahedral faces of clay
particles, and result in the reduction of consistency limits close to divalent cations. The
presence of divalent ions in the soil system increases the shear resistance between the
particles stronger than monovalent ions. The inherent repulsion between clay particles
with large hydro-sphere results in interparticle separation, in the presence of monovalent
ions. However, the increasing concentration of monovalent ions in the soil system results
in the reduction of diffused double layer thickness (due to inadequate negative charge
neutralization when compared with divalent ions), and prevents further reduction in liquid
limit. However, the formation of ettringite in the sulphates enriched soil systems affects
the cation exchange, consistency and compaction characteristics with time. The addition
of gypsum and magnesium sulphates lowers the liquid limit as well as plasticity index of
lime treated kaolinite system. Even though the presence of sodium sulphate initially
lowers the liquid limit and plasticity index values of treated soil systems, the trend was
stable over a period of time. In the case of potassium sulphate treated soil system, the
initial trend is similar to the above except that there is a slight increase in liquid limit and
plasticity values with time. The magnitude of the effect of sulphates on consistency values
follows the series such as Ca2C!Mg2C!KC!Na2C, as in the case of lyotropic series.
The presence of divalent metal sulphates lowers the optimum dry density and increases the
optimum moisture content by high magnitude when compared with monovalent ions
(Rajasekaran, 1994).
It has been established that the cation exchange and pozzolanic reactions of lime
treatment reduced the swelling potential of soils (Transportation Research Board, 1987;
Tsatsos and Dermatas, 1998). The pozzolanic reactions involved in the formation of
ettringite compounds, and strongly associated with the heavy metal immobilization. This
reaction further results in swelling as reported by Struble (1986) and Mitchell and
Dermatas (1992). A simplified geochemical reaction reported by Hunter (1988) for lime-
induced heave reactions can be summarized as follows:

CaO C H2 O/ CaðOHÞ2 ðhydration of quicklimeÞ (1)

CaðOHÞ2 / Ca2C C 2ðOHÞK ðionization of calcium hydroxide; pH rises to 12:3Þ

(2)

6Ca2C C 2AlðOHÞK
4 C 4OH C 3ðSO4 Þ
K 2K
C 26H2 O

/ Ca6 ½AlðOHÞ6 2 $ðSO4 Þ3 $26H2 O ðformation of ettringiteÞ ð3Þ

 G. Rajasekaran / Ocean Engineering 32 (2005) 1133–1159 1139

Ca6 ½AlðOHÞ6 2 $ðSO4 Þ3 $26H2 O C 2H2 SiO2K 2K

4 C 2CO3 C O2
2K
/ Ca6 ½SiðOHÞ6 2 $ðSO4 Þ2 $ðCO3 Þ2 $24H2 O C 2AlðOHÞK
4 C SO4 C 4OH
K

C 2H2 O ðisostructural substitution as ettringite changes to thaumasiteÞ ð4Þ

Sherwood (1993) explained that the presence of sulphate in soils induces detrimental
effects to materials strength due to the swelling. Dermatas and Meng (1994) brought out
the application of quicklime for immobilizing heavy metals contaminated soils. The
various problems associated with lime–soil reactions due to sulphate environment depends
on the type and solubility of sulphate, amount of sulphates present and clay content as
reported by Littleton (1995). Sridhran et al. (1995) reported that the presence of sodium
sulphate in the soil system converts lime into insoluble gypsum and sodium hydroxide
(Eq. (5)), and thus reduces the lime available for the reactions with soil. However, the
presence of sodium hydroxide increases the pH, and thus the dissolution of silica from the
soil.
CaðOHÞ2 C Na2 SO4 / CaSO4 C 2NaOH (5)
Ettringite formation in the soil system imbibe enormous amount of water which
increases the swelling potential of soil and affects the engineering behaviour of soil
(Mehta, 1973a). An increase in the Ca2C ions concentration of the soil system due to the
addition of gypsum accelerates the soil–lime reactions, and results in the better formation
of cementation compounds. The beneficial effect of gypsum on improving the behaviour
of soils has been reported by Holm et al. (1983) and Kujala (1983). The formation of
ettringite in the lime–gypsum treated kaolinite soil has been reported by Wild et al. (1993).
An attempt has been made to evaluate the mechanisms responsible for the formation of
ettringite in lime treated kaolinite as well as montmorillonite minerals, in the presence of
sodium sulphate (Tsatsos and Dermatas, 1998). Their test results indicated significant
swelling in the lime–kaolinite–sulphate system due to the high amount of alumina
available for ettringite formation. But in the lime–montmorillonite–sulphate system, the
swelling effect is minimal (due to the slow release of alumina), and the higher release of
Si/Al ratio induces the formation of calcium silicate hydrate (CSH) cementation
compound. Energy Dispersive X-ray (EDX) analysis of the above samples containing
ettringite showed similar phases of pure ettringite in kaolinite system, whereas in the
montmorillonite case, the composition was different from pure ettringite phase. Hence, it
is imperative to fully understand on circumstances of ettringite formation in the cement
and lime stabilized soils.

4. Soil–cement–sulphate reactions

The formation of calcium-sulpho-aluminate in cement treated soils is not new

(Kollman, 1978; Sherwood, 1995; Glasser, 1996; Gonzalez and Irasser, 1996; Nagataki
and Gomi, 1998). The reaction mechanisms involved in the formation of ettringite and
related effects in cement treated soils are similar to lime treated system. Several
investigators reported ettringite induced swelling in cement or concrete materials
1140 G. Rajasekaran / Ocean Engineering 32 (2005) 1133–1159

(Mehta, 1973b, 1983; Olda and Gasser, 1988; Ghorab and Kishar, 1985). Also, the
sulphate enriched minerals induced swelling in lime treated soils (Hawkins and Pinches,
1987a,b). Mehta (1983) mentioned that the adsorption of sulphate on CSH surfaces result
in the reduction of strength due to the decrease in cementation ability. The various
mechanisms involved in the reactions of hardening materials were indicated by Saitoh et
al. (1985). An additional increase in the strength of soils when using cement with slags has
been reported by the above investigators (Quigley et al., 1973; Prince and Permi, 1997).
The hydration mechanism of calcium hydrate in the presence of lime and gypsum has been
studied by Uchikawa and Uchida (1986). They reported that the initial rate of calcium
hydrate formation has been increased effectively by the use of pozzolans. Kawamura et al.
(1986) observed needle shaped ettringite formation in compacted fly ash mixtures, which
filled up large intergranular voids that result in the densification at microstructural level
and improve strength. Prince and Perami (1997) reported that the presence of alkali metal
type (Na2SO4) sulphate prevents ettringite formation due to the hydrolysis of aluminates.
But the hydrolysis of alkaline earth, gypsum (CaSO4) results in the formation of ettringite
easily.

5. Ettringite formation

Ettringite is a complex mineral that can be seen in cement and lime treated soils due to
the reaction between solid material containing calcium, aluminium and iron, especially in
the presence of sulphate enriched environment. The soil–lime reactions involve a large
increase in solid volume which causes severe cracking and failure of concrete. Ettringite
and Thaumasite belong to the sulphate group, and four out of every five atoms of these
minerals are present as a part of water molecule or hydroxide (Bolan et al., 1988; Bensted,
1999). They usually form as a precipitate under hydrothermal conditions. The earlier
literature reported the formation of ettringite under two different environmental
conditions. The primary form of ettringite usually forms as a result of sulphate–alumina
reactions in the presence of calcium ions. Its secondary form appears when the above
minerals dissolve and then deposit again in the cracks or voids of soil system. It has been
established that no harmful swelling effects were noticed initially due to the completion of
chemical reactions. However, care has to be taken in stabilizing hardened material
including concrete since the preliminary formation of ettringite causes severe problems.
X-ray diffraction (XRD) and scanning electron microscopy (SEM) can be used as vital
tools to identify the formation of ettringite in the stabilized materials (Rajasekaran, 1994).
The formation of needle shaped ettringite (Et) in sulphate dominated lime and cement
treated systems has been reported by few investigators (Figs. 5–8). Fig. 5 shows the needle
shaped crystals, ettringite in the cement stabilized sand base with 6% Portland cement
(Rollings et al., 1999), whereas Kamon and Nontananandh (1991) showed similar
ettringite structure in new cement like stabilizer (NCS) treated loam soil after 90 days of
treatment (Fig. 6). The formation of ettringite in the sulphate contained lime–kaolinite
(Tsatsos and Dermatas, 1998), and quicklime–sodium sulphate soil systems can be seen in
Figs. 7 and 8, respectively (Rajasekaran, 1994).
 G. Rajasekaran / Ocean Engineering 32 (2005) 1133–1159 1141

Fig. 5. Ettringite formation in the Portland cement stabilized sand base.

6. Ettringite in stabilized soils

Ettringite attributed beneficial effects in the Portland cement concrete or cement

stabilized materials have been earlier reported by few investigators. The activation of initial
strength improvement in cement-stabilized materials, retardation of C3A hydration, ability
to stabilize high water content soils and bind heavy metals have been established (Bogue and
Lerch, 1934; Nurse, 1964; Montgomary et al., 1981; Kujala, 1986; Kamon et al., 1988;
Kamon and Nontananandh, 1991; Abdi and Wild, 1993). The effective strength increase in a
loam stabilized with NCS was observed due to the non-expansive type ettringite formation

Fig. 6. Ettringite formation in loam stabilized with 12% New cement like stabilizer (NCS).
1142 G. Rajasekaran / Ocean Engineering 32 (2005) 1133–1159

Fig. 7. Ettringite formation IN koalinite–lime system (after 6 months curing).

(Kamon and Nontananandh, 1991). Also the above investigators reported that there is an
enormous improvement in the strength of NCS stabilized clays than cement treated system,
and it is directly proportional to the amount of ettringite formation. The strength
improvement was due to the removal of water by ettringite, and thus results in the increase of
soil dry density. The presence of alumina in lime treated kaolinite results in the formation of
various phases of calcium aluminate hydrates (CAH), including C3AsH6 and C4AsH13, and
calcium aluminate silicate hydrate (CASH) such as C2AsSH8 (Croft, 1964; Wild et al.,
1995). The absence of alumina results in CSH phase in lime or cement treated soils. The
formation of ettringite due sulphate attack in concrete was reported by several investigators
(Mehta and Klein, 1966; Nivelle, 1981; DePuy, 1994).
The beneficial as well as harmful effects of lime and cement treated soils with
sulphates enriched environment have been well brought out by several researchers
(Mehra et al., 1955; Lambe et al., 1960; Ladd et al., 1960; Sherwood, 1962, 1982).

Fig. 8. Ettringite formation in quicklime–sodium sulphate treated marine clay (after 45 days treatment).
 G. Rajasekaran / Ocean Engineering 32 (2005) 1133–1159 1143

The above researchers mentioned that sulphates presence in lime treated clays enhances
the swelling, and disintegrate the stabilized soils due to the formation of ettringite
(Cordon, 1962; Hollis and Fawcett, 1966; Mitchell, 1986). Clay minerals start to
deteriorate at a higher pH of 10.5, and the subsequent increase in pH (up to 12.3) causes
the dissolution of clay particles. This reaction increases the availability of siliceous and
aluminus pozzolans that reacts with calcium ions (Eades and Grim, 1960; Thompson,
1966). If sufficient soluble silica or alumina is not available, then calcium reacts with other
minerals to form calcite, gypsum and pozzolanic compounds.
Enhanced strength improvement by the addition of gypsum in the lime–clay, and lime–
slag–clay mixtures has been brought out by few researchers (Hasaba et al., 1982; Gupta
and Seera, 1989; Abdi, 1992; Wild et al., 1993, 1996). Portland cement results in the
growth of swelling mineral, ettringite in the presence of SOK4 2 ions in the soil (Regroud,
1980; Sneker and Temporal, 1990b). Even though ettringite has been observed in the
lime–kaolinite–gypsum system, the addition of ground granulated blast furnace slag
(GGBS) results in the reduction of deleterious heaving effects significantly (Wild et al.,
1993). The secondary mechanisms responsible for the development of CSH gel, that
enhanced strength development of ettringite and improves the engineering behaviour of
soil. The beneficial effects of slag in lime–gypsum mixture activate the hydration of slag
(Daimon, 1980; Smolczyk, 1980; Wu et al., 1990; Gollop and Taylor, 1996), and also
accelerate the growth of ettringite due to the rapid removal of alumina. The above process
reduces the porosity of the soil system due to the cementation gel development within the
pores (Bijen, 1996). Depending on the chemical environment, the lime stabilized material
characteristics can be affected with time, and it may deteriorate the strength of treated soil
systems.
The addition of lime in sulphate containing soil certainly increases cation exchange, i.e.
calcium ions concentration, but not to the expected level since some portion of calcium has
been leached away or tied up with insoluble minerals. The above compounds formation does
not affect the soil–lime reactions such as cation exchange, agglomeration and carbonation
except long term pozzolanic reaction. Hence, the sulphate induced heave in lime treated soil
should be observed for long duration. Hunter (1988) brought out the lime induced expansive
reactions in sulphate enriched soils due to the formation of ettringite (calcium–aluminium-
hydroxide–sulphate–hydrate), and thaumasite (calcium–silicate-hydroxide–sulphate–car-
bonate–hydrate). He reported the formation of ettringite in the presence of aluminium and
its conversion to thaumasite at a temperature below 15 8C. The presence of clay minerals
reacting with excess silica and alumina could results in the formation of ettringite
{Ca6[Al(OH)6]2$(SO4)3$26H2O}, and later change to thaumasite {Ca6[Si(OH)6]2$
(CO3)2$(SO4)2$24H2O}. In case of temperature above 15 8C, ettringite appears to be
more stable. The conversion of ettringite to thaumasite occurs by isostructural substitution
of silica, aluminium and carbonate for sulphate (Gouda et al., 1975; Kollman et al., 1977;
Kollman, 1978). The formation of above mentioned compounds may occur when the
percentage of clay is more than 10%, and hence the free flow of ions migrate through soils in
a saturated system where soluble sulphates exceed 1% (10,000 ppm). Raja (1990) reported
that sulphates present in the calcium bentonite affect the physical as well as engineering
behaviour of the soil. His results indicated an increase in liquid limit (20–25%) and
compression index values (from 2.7 to 3.3) of the soil. In this section, ettringite induced
1144 G. Rajasekaran / Ocean Engineering 32 (2005) 1133–1159

changes in the cement and lime stabilized soils have been discussed. However, the various
factors which influence the ettringite formation should be examined.

7. Factors influencing ettringite formation

It is essential to understand the various factors such as clay minerals, pH, water content,
sulphates content and temperature that influence the behaviour of ettringite with time.

7.1. pH, water content and temperature

It is expected that pH of the soil system increases due to the increase in alkalinity
originated from lime or cement reactions. The increase in pH above 9 dissolves silica and
alumina, and induces the formation of several reaction products including ettringite
(Rajasekaran, 1994). In the presence of high alkaline environment, lime or cement reacts
with alumina and sulphate to form ettringite. The presence of moisture encourages the
formation of ettringite and results in longitudinal and transverse joints in concrete
pavements. Hence, the penetration of water through the cracks or joints during rainfall or
water vapor movement further accelerates the ettringite reactions favorably. The
accumulation of water due to poor drainage or ponding induces significant swelling in
lime treated sulphate soils as reported by earlier investigators (Rajasekaran, 1994). Several
researchers brought out the influence of temperature on ettringite formation (Mehta and
Klien, 1966; Hunter, 1988; Mitchell and Dermatas, 1992). Temperature is the major cause
of swelling in kaolinite or montmorillonite mixtures under sulphate environments, and the
rate of ettringite formation and swelling would be greater during summer (Rollings et al.,
1999).

7.2. Clay content and sulphate levels.

The percentage of clay present in the soil system plays an important role in sulphate
induced heave of lime or cement stabilized soils. Sherwood (1982) reported that strength
loss due to the ettringite formation was insignificant for specimens containing less clay
content. Hunter (1988) observed less swelling even in soil (clay content !10%)
containing high level of sulphate such as 20,500 ppm. Mitchell and Dermatas (1992)
proposed that kaolinite (alumina rich soil) facilitates the higher formation of ettringite than
montmorillonite. Bush road cement stabilized sand indicated clay content as low as 6–13%
(Rollings et al., 1999), and the predominant clay mineral present in the clay is halloysite.
Even though there were few cases of sulphate attack reported earlier, no definite
conclusive statements have been so far reached regarding the sulphate levels caused
swelling. Sherwood (1962) reported 24% reduction in strength at 0.25% sulphate level,
and 67% at 2% level in lime stabilized London clay. These findings match well with
Hunter (1988) results, who proposed 1% as a limit for causing soil swelling. Whereas
Mitchell and Dermatas (1992), and Snedker (1996) mentioned that even a low level of
0.3% is enough to induce heaving problems. The presence of sodium sulphate in the soil
results in the formation of ettringite and thaumasite compounds, and results in the drop of
 G. Rajasekaran / Ocean Engineering 32 (2005) 1133–1159 1145

pH due to the depletion of available lime present in the soil system (Mitchell, 1986).
Hence, lime stabilization is not recommended for soils containing soluble sulphates more
than 0.05%. Raja (1990) reported that the presence of sulphates even at low level of
500 ppm is sufficient to induce significant swelling in bentonite–lime system. Petry (1994)
mentioned that sulphate level of 0.2% has the potential to induce swelling and 1% causes
severe damages to structures resting on lime treated soils. The laboratory results of
McCallister and Tidwell (1997) indicated that 0.01–0.50% cause low to moderate level of
heave, 0.5–1.2% pose moderate to serious heaving problem and excess level of 1.2% cause
enormous heave and significant damage.
Limited information on ettringite induced adverse effects is available in the case of
cement stabilized soils. Dunlap et al. (1975) suggested to use sulphate resistant cement for
soils containing sulphate level of 0.09%. For coarse grained soils, Sherwood (1962)
noticed that the compressive strength was unaffected in 10% cement stabilized sandy soils
containing 0.25–3% sulphate. But, soils containing clay particles has been a serious
concern since the presence of low sulphate (0.2%) in soil results in a strength loss of higher
than 50%. The cement-stabilized clay soils are highly susceptible to severe attack even at a
low sulphate concentration, and further research is needed to establish clear guidelines
regarding the concentration levels of sulphate attack in lime and cement stabilized soils.
The sulphate induced heave is a complex phenomenon, and it depends on several factors as
discussed in the earlier sections. However, there were some guidelines established from
the previous literature which has been summarized as shown in Table 1. From this table, it
is clear that ettringite formed in the lime and cement stabilized soils is a complex
phenomenon, and it depends on many influencing factors such as soil chemistry, clay
minerals, type of metal cations present and sulphate levels. Also, it can be seen that even a
sulphate content of 0.03–0.05% in soils can induces severe swelling under the favourable
conditions.

8. Case histories

This section explains the various case histories related to ettringite formation in the
lime and cement stabilized soils. In general, the chances of stabilized soils failure are less,
and the probability of occurrence is low in cement stabilized soils when compared with
lime treated soils. Even though Sherwood (1962) earlier highlighted the sulphate attack
problem in both cement and lime stabilized soils, it was recognized well only after the
recent established works of Mitchell (1986), Hunter (1988), Raja (1990), Rollings and
Rollings (1996), and Rajasekaran et al. (1997). The failure cases of sulphate attack on lime
stabilized soils includes Wichota parking lot (Mitchell, 1986), military runway near Del
Rio, Tex, (Petry and Little, 1992) and mine waste in UK (Thomas et al., 1989). Also severe
problems in cement stabilized soils [due to the formation of either ettringite or
combination of ettringite and thaumasite (CaCO3$CaSO4$CaSiO3$15H2O)] have been
observed in Las Vegas Streets (Hunter, 1988), pavements at Joe Pool Lake, Tex (Perrin,
1992) and UK Motor way (Snedker, 1996; Sneker and Temporal, 1990b). The effect of
sulphate on the consolidation behaviour of lime treated black cotton soil has been reported
by Sridhran et al. (1995). Their test results indicated a significant increase in
 1146
Table 1
Summary of sulphate attack on cement and lime stabilized soils
Reference Project Stabilizing Sulphate level Nature of Observed site con- Type of soil Clay minerals Safe criteria Remarks
details agent used present at site/ reaction dition/laboratory test used, and present of sulphate
type of sulphates products details about soil percentage of level
used formed behaviour clay content suggested
Unpublished Cedar Hill Lime Severe swelling High Illite and mon-
data Park tmorillonite

G. Rajasekaran / Ocean Engineering 32 (2005) 1133–1159

Unpublished Bush Road Cement Severe swelling 6–13% of clay Halloysite with
data present smectite and
kaolinite
Mehta (1973a) Cement with Ettringite Swelling in soil
slag
Brantley and Ettringite
Glynn (1983),
Unpublished
data
Sam Wong Mississippi Lime
(1982), unpub- highway
lished data
Bogue and Cement Ettringite
Lerch (1934),
Nurse (1964),
and Montgom-
ary et al. (1981)
Sherwood Lime stabil- Lime 24% Strength loss Clay percentage ! 0.25% Sand speci-
(1962) ised London varied from 0 to mens unaltered
clay 100% by sulphate
attack
Dunlap et al. Cement !0.09% If sulphates
(1975) content
O0.09%, use
sulphate resist
cement
Regroud (1980) Cement with Ettringite Swelling in soil
slag
Mitchell (1986) Wichita park- Lime 0.50% Thaumasite pHZ8–10.5 Silty clay
ing lot at Los (dominant)
Vegas, with traces
Nevida of ettringite
Kujala et al. Laboratory Cement and Ettringite pHZ4.8–4.9 Silty soils Illite, chlorite Less than
(1986) study gypsum 0.15–0.41%
Hawkins and Llandough Selenite Floor slab heaving
Pinches (1987b) Hospital,
Cardiff
Hunter (1988) Las Vegas Lime (4.5%) Ettringite More than 100% Sandy silt and Sepiolite domi- !1%

G. Rajasekaran / Ocean Engineering 32 (2005) 1133–1159

Streets and Thau- swelling noticed silty clay nant with mon-
masite with 9–30% nmc, (10–55% clay) tmorillolite,
pHZ7.8–10.5 kaolinite
Thomas et al. Mine waste, Cement
(1989) UK
Snedker and Bonbury IV Lime Clay soils
Temporal contract, Part
(1990a) of M40
Oxford to
Brimingham
Motorway
Raja (1990) Laboratory Lime (5%) 5% of Na, K, Mg, Sodium sulphate Calcium bento- !0.05%
study Al sulphates increases com- nite
pression index
Kamon and Laboratory 3, 6, 9, 12% Ettringite Improve engineering Volcanic ash Chlorite with NCS–CaSO4
Nontananandh study by bulk behaviour soils with 13.1% amorphous (6.3%)
(1991) weight of clay (!5 mm) material
NCS (new
cement like
stabilizer)
Perrin (1992) Joe Pool Lake Lime 0.02–0.09% Severe swelling 3–18% Smectite and !0.03%
Projects, kaolinite–mon-
Loyd Park tmorillonite
Cedar Hill Lime 2.12% Severe swelling High Illite and Mon-
Park tmorillonite
Laughin Lime 1.4–2.5% Moderate swelling 34–63% Smectite
Runway, Joe
Pool Lake,
Del Rio, Tex

1147
(continued on next page)
 1148
Table 1 (continued)
Reference Project Stabilizing Sulphate level Nature of Observed site con- Type of soil Clay minerals Safe criteria Remarks
details agent used present at site/ reaction dition/laboratory test used, and present of sulphate
type of sulphates products details about soil percentage of level
used formed behaviour clay content suggested
Petry and Little Denver air- Lime Severe swelling Smectite
(1992) port, and lab-
oratory study

G. Rajasekaran / Ocean Engineering 32 (2005) 1133–1159

Mitchell and Laboratory Lime 0.3–6.2% Slight to severe Sand mixed with Kaolinite !0.3%
Dermatas study 30% clay con-
(1992) tent
None to moderate Montmorillonite
Rajasekaran Laboratory Lime (3%) Lime with Ettringite Increase in Cc from Marine clay Montmorillo- !0.2%
(1994) study individual combi- presence in 0.85 (untreated) to with 52% clay nite, kaolinite,
nations of 3% lime– 0.84 for sodium fraction sepiolite, mon-
sodium sulphate sodium sulphate, and a tmorillonite-
& 3% calcium sulphate decrease of 0.44 for chlorite-vermi-
sulphate system has calcium sulphate culite
been
noticed
DePuy (1994) Cement
Petry (1994) Lime 0.20% ! 1%
Sridhran et al. Laboratory Lime (6%) Sodium sulphate For sodium sulphate Black cotton !0.5%
(1995) study (0.5–3%) !0.5% no effect soil
For 1, and 3%,
compressibility
increase signifi-
cantly
Rajasekaran Laboratory Lime (3%) 3% sodium, pot- Ettringite For soil 1, Cc of Marine clays Both soils con- !0.05%
et al. (1997) study, and assium, calcium untreated soil chan- tain montmoril-
used two and magnesium ged from 0.79 to 0. lonite, chlorite,
different mar- sulphates 82 (Na), 0.72 (K), 0. kaolinite and
ine clays (soil 53 (Ca), 0.59 (Mg) vermiculite
1 & soil 2)
For soil 2, Cc was
changed to 0.79
(Na), 0.69 (K), 0.51
(Ca), 0.57 (Mg) for
soil 2
McCallister and Lime 0.01–0.5%
Tidwell (1997) (low to med-
ium), 0.5–1.
2% (medium
to serious),
and O1.2%
(serious)
Tsatsos and Lime (10%) 5% sodium Ettringite Showed negligible Kaolinite and
Dermatas sulphate swelling montmorillonite
(1998)

G. Rajasekaran / Ocean Engineering 32 (2005) 1133–1159

Wild et al. Laboratory Lime (6%) Gypsum (2, 4 and Ettringite Plasticity and 70% kaolinite Kaolinite 1% SO3
(1998) study for kaolinite 6% by wt) expansion potential
has reduced
Lime–GGBS 1.73% of SO3 Kimmeride clay
(5, 6, 8 and (dickite with
10%) for mica, pyrite and
Kimmeride gypsum traces)
clay
Wild et al. Laboratory For Kaolinite, For kaolinite– Ettringite Plasticity and Kaolinite 84% kaolinite, 1% SO3 1.73% SO3
(1999) study the total bin- lime–GGBS, expansion potential 13% mica, 1%
der contentZ gypsum contents has reduced feldspar and 2%
6% (lime/ equivalent to 0.0. other minerals
slag) 93, 1.86 and
2.79% SO3
For Kimmer- For Kimmeride Kimmeride clay Dickite with
ide clay, the clay, gypsum mica, pyrite and
total binder contents vary gypsum traces
contentZ5% from 0, 2 6 and
(lime/slag) 8% SO3
Rollings et al. Clay Ric and Lime (5–6%) Surface bumps Ettringite Sand with clay Halloysite
(1999) Suman due to soil (8–13%), pH 9–12 (predominant)
swelling with kaolinite
and smectite

1149
(continued on next page)
 1150
Table 1 (continued)
Reference Project Stabilizing Sulphate level Nature of Observed site con- Type of soil Clay minerals Safe criteria Remarks
details agent used present at site/ reaction dition/laboratory test used, and present of sulphate
type of sulphates products details about soil percentage of level
used formed behaviour clay content suggested
Kinuthia et al. Laboratory 6% lime Na, K, Ca, Mg Ettringite pH 10–12, sulphate kaolinite 28.57% of clay
(1999) test (samples sulphates (1, 2, 3 level O1% present
cured for and 4% SO3)

G. Rajasekaran / Ocean Engineering 32 (2005) 1133–1159

70 8C at
100% relative
humidity)
Increase in omc for
divalent, decrease
for monovalent
Max. dry density
decreased for diva-
lent, and increased
for monovalent
system

omc, optimum moisture content.

 G. Rajasekaran / Ocean Engineering 32 (2005) 1133–1159 1151

the compressibility for the presence of 1–3% sodium sulphate in the soil system. The effect
of sulphate in both lime treated red earth (containing kaolinite) and black cotton soil is
qualitatively similar.
The formation of transverse bumbs in the cement-stabilized sand of a road in Georgia
has been reported by Rollings et al. (1999). He reported that the presence sulphates in the
well water used for mixing with cement-stabilized base resulted in the formation of
ettringite, and thus induces severe expansion. Examination of core specimens collected
from the affected areas indicated needle like crystals, calcium sulphoaluminate
(ettringite), which was not originally present in the samples.

9. Ettringite in marine clays

Oceans consist of 70% of earth, and it is enriched with various natural minerals such as
oil, gas, manganese nodules, etc. (Poulos, 1988). The necessity to tap these marine
resources has recently increased the construction of structures either at the offshore or
onshore. However the hostile wave conditions, presence of large depth of water and weak
marine clays at the potential locations pose severe foundation problems (Rajasekaran
et al., 1999). The application of deep lime mixing technique to improve the behaviour of
marine clays either lime column or lime grouting is not new (Okumura and Terashi, 1975;
Rajasekaran, 1994; Narasimha Rao et al., 1992; Rajasekaran and Narasimha Rao, 1996).
The presence of sodium sulphate in lime treated marine clay affects the properties of soil
system, whereas the presence of gypsum (calcium suphate) improves the marine clay
properties (Rajasekaran and Narasimha Rao, 1996; Narasimha Rao and Rajasekaran,
1996; Rajasekaran and Narasimha Rao, 1998a–c). Also, the marine clays sometimes
enriched with sulphates due to the discharge of nearby industries wastes containing
sulphates or by nature. Hence it is essential to study the sulphate induced changes on the
lime treated marine clays.
Dredging marine sediments or reclamation of bay areas containing heavy metals results
in ground water contamination due to oxidation of pyrite. The above mentioned reactions
in marine clays result in the production of iron hydroxide and sulphate ions as per the
following equations (Ohtsubo et al., 1991; Adachi et al., 1992; Ohtsubo, 1995; Hawkins
and Pinches, 1997)

4FeS2 C 15O2 C 14H2 O/ 4FeðOHÞ3 C 16HC C 8SO2K

4 (6)

CaCO3 C 2HC C SO2K

4 C H2 O/ CaSO4 $2H2 O C CO2 (7)
Also leaching of SO2K
4 and reduction of sulphate results in the production of gypsum
(CaSO4$2H2O), and calcite (CaCO3), which is quite common in marine clays (Kawasaki,
1988). The above research findings indicate the release of adsorbed zinc from marine clays
into soluble phase due to the exposure of soil surface to atmosphere. In the presence of
excess water, sulphates induce negative effects in the cement stabilized soils. Besides
sulphates, sulphides can also be present in the form of pyrites and thus the release of
sulphate attacks stabilized soils. Mixing dredged sediments with binding agents can
1152 G. Rajasekaran / Ocean Engineering 32 (2005) 1133–1159

Table 2
Untreated soil properties

S. no Physical and chemical properties Sea water system

1 Liquid limit (%) 85
2 Plasticity index 53
4 pH 7.3
5 Organic content (%) 1.41
6 Sulphates (%) 0.20
7 Chlorides (%) 1.8
8 Cation exchange capacity (m equiv./100 g of the soil) 42
9 Lime content (%) 0.21
10 Shear strength of the soil (kN/m2) 18
11 Compression index (Cc) 0.85

dissolve small quantity of sulphates and prevent ettringite formation even at higher
sulphate concentration and high water content (Boutouil et al., 1999).
The physico-chemical properties of marine clay collected from the east coast of India
are given in Table 2. A laboratory investigation has been carried out using lime and
sulphate additives such as sodium sulphate and calcium sulphate (in 1:1 ratio) to evaluate
the effect of sulphates on the behaviour of marine clays (Rajasekaran, 1994). A test tank of
600 mm diameter and 550 mm height was used, and columns were formed at the centre of
the test tank. Samples were taken at a radial distance of 80 and 200 mm away from the
centre of column and tested to examine the sulphates induced changes in the soil system
with time. The results showed that addition of sodium sulphates induced adverse effects
due to the formation of ettringite, whereas calcium sulphate improved the behaviour of the
soil significantly (Table 3). This may be due to the fact that exchangeable sodium ions are
dominating in the quicklime–sodium sulphate system, and this affects the adsorption of
calcium ions by the soil particles (Table 3). Also it has been confirmed that the lime-
sulphate induced changes are similar for both land and marine clays (Rajasekaran, 1994).
In the case of fully saturated marine clays under sea water, it is expected that the formation

Table 3
Effect of sulphates on lime treated marine clay (after 45 days treatment)

S. Properties of treated soil systems Quicklime–sodium Quicklime–calcium

no sulphate system sulphate system
1 Liquid limit (%) 84 64
2 Plasticity index 52 30
3 PH 8.25 8.65
4 Exchangeable NaC (m equiv./100 g of the soil) 9.78 0.98
5 Exchangeable Ca2C (m equiv./100 g of the soil) 26.09 35.87
6 Cation exchange capacity (m equiv./100 g of the soil) 52.34 52.61
7 Lime content (%) 2.38 1.62
8 Shear strength of the soil (kN/m2) 72 152
9 Compression index (Cc) 0.84 0.44
10 Ettringite formation (X-ray diffraction technique) Yes No

Rajasekaran (1994).
 G. Rajasekaran / Ocean Engineering 32 (2005) 1133–1159 1153

of ettringite does not produce any adverse effects. However the stability of ettringite with
time should be ascertained before the lime stabilization technique has been planned for
marine clays.

10. Precautionary or remedial measures

The preventive measures to be adopted for preventing ettringite formation in lime and
cement stabilized clays are given below.

† The use of sulphate resisting cement limits the available quantity of alumina for
ettringite formation. Sulphate resistance of concrete can be achieved by using low
permeability concrete, cement with low calcium aluminate (C3A) and adding
admixtures such as slag or fly ash (Rolling et al., 1999).
† Use of admixtures such as ground blast furnace slag or fly ash with cement helps to
prevent (not in all cases) sulphate attack on concrete (DePuy, 1994).
† The use of industrial product, ground granulated blast furnace slag (GGBS) as a binder
with cement has been proved to increase the durability and resistant to alkali attack,
chloride and sulphate resistance with time. Also, partial replacement of lime with
GGBS increases the characteristics of lime–gypsum treated soils. The addition of
GGBS and lime successfully controls the material plasticity and expansion potential in
lime treated soils (Wild et al., 1998). Proper control should be taken to ensure that the
amount of lime added is sufficient to stabilize the soil, and no excess lime should be
available. Substitution of lime with an industrial by-product, GGBS reduces the
swelling potential of soils containing gypsum.
† Raja (1990) reported the successful use of barium chloride to reduce the swelling
characteristics of lime treated calcium bentonite. The addition of barium compounds
prior to lime treatment was reported by Ferris et al. (1991). The use of barium
hydroxide in lime–kaolinite–sulphate mixture eliminates the ettringite formation as
reported by Tsatsos and Dermatas (1998).
† Addition of lithium salts with lime and application of double lime method are some of
the protective measures proposed by earlier researchers (Mitchell and Dermatas, 1992;
Petry and Little, 1992; McCallister and Tidwell, 1997). In the case of double lime
application method, first lime and soil will be mixed with water, stockpiled for one
month (for the completion of ettringite formation) and then proceed with usual
stabilization method such as placement, compaction and curing. Thus, the depletion of
sulphate and alumina, which results in the earlier formation of ettringite in lime or
cement treated soils and prevent the heaving conditions after placing at site.
† Ettringite formation can be prevented by providing good surface drainage and utility
trenches with impermeable synthetic liners along the slope and construction joints and
adequately sealing the stabilizing the stabilized base.

Table 4 listed the important remedial measures to be adopted for controlling or

prevention of sulphate attack in lime and cement treated soils. A detailed study has to be
1154 G. Rajasekaran / Ocean Engineering 32 (2005) 1133–1159

Table 4
Recommendations/remedial measures proposed to control heave in sulphate attacked soils

Reference Details of method(s) suggested

Hawkins and Pinches (1987a) Provide sufficient drainage, consider temperature influ-
ence in the design, and use suspended floor slabs
Hunter (1988) Avoid ponding of soils and provide good surface
drainage, use utility trenches with impermeable synthetic
liners along the slopes and construction joints
Ferris et al. (1991) Add barium chloride before lime application to soil
Ferris et al. (1991) Add barium compounds before lime application to soil
Mitchell and Dermatas (1992), Petry and Little Add lithium salts with lime, and double lime application
(1992), and McCallister and Tidwell (1997) method
DePuy (1994) Use ground cement blast furnace slag or fly ash with
cement
Tsatsos and Dermatas (1998) Apply barium hydroxide with lime
Wild et al. (1998) Add ground cement blast furnace slag with cement
Rollings et al. (1999) Use sulphate resistance cement
Apply lime first to remove sulphate and alumina from the
soil during curing period, and then apply the treated soil in
field
Use suitable pozzolans and ground granulated blast
furnace slags for portland cement concrete
Hawkins and Pinches (1997) Avoid construction on pyrite deposited deposits
Avoid sub-floor heating and/or insulate the ground floor
Maintain or raise the existing ground water level
Extend the foundations quite deep so that ettringite
growth is unlikely
Use suspended floor slabs or install flexible slabs/joints
Use raft foundations for the total unit construction
Provide sufficient lateral drainage to remove any
oxidation products or keep high pH environment

carried out to propose a suitable method based on the field conditions and the nature of
sulphates present in the marine clays.

11. Conclusions

In this paper, the various mechanisms involved in ettringite formation of lime and
cement stabilized soils have been reviewed. Also, ettringite induced effects in stabilized
soils and its stability with time have been discussed. Based on the above, the following
conclusions can be drawn.

1. It is suggested that lime or cement stabilization technique for soils should be carefully
approached in sulphate enriched environment. Also, appropriate precautionary or
remedial measures should be taken to avoid swelling or deterioration of stabilized
materials with time.
 G. Rajasekaran / Ocean Engineering 32 (2005) 1133–1159 1155

2. The presence of acid dissolved sulphates, carbonates and pyrites in soils, and their
stability with the environmental changes should be considered before the application of
lime or cement stabilization techniques in the field.
3. The ettringite induced effects is same in marine clays when compared with land soils.
However the effects are not significant in case of submerged condition of marine clays
under sea water.
4. The ettringite induced swelling not only depends on the type of metal cations present in
the soil, but also on the concentration of sulphates.
5. The adverse effects produced in monovalent sulphates enriched soils are severe
especially in sodium sulphate system, whereas divalent and higher valent sulphates
enriched soil systems do not produce any adverse effects.

Acknowledgements

The author wish to express his sincere thanks to several researchers for reporting their
results appeared in various publications. Also acknowledgement is made to Indian
Institute of technology, Madras, India for publishing the author’s research findings in this
paper.

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