Review of Thaumasite Sulfate Attack on

Cement Mortar and Concrete

Caijun Shi1; Dehui Wang2; and Ali Behnood3
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Abstract: Durability is one of the most important considerations regarding the design of new concrete structures in aggressive environments.
Thaumasite sulfate attack (TSA) is one durability consideration. This paper reviews the features of TSA, factors affecting TSA, thaumasite
formation mechanisms, and prevention measures. Finally, some needs for future studies are also suggested. TSA can completely destroy the
cementitious binding ability of concrete by transforming it into a mush. Many factors affect thaumasite formation and TSA. The four primary
factors affecting TSA on portland cement-based materials are low temperatures (below 15°C) and the presence of sulfates, carbonates, and
moisture. Apparently, the dissolution–precipitation mechanism can be used to explain most phenomena during TSA. A procedure for field
studies is also proposed. Both material compositions and surrounding environments should be considered for the prevention of TSA in
concrete structures. DOI: 10.1061/(ASCE)MT.1943-5533.0000530. © 2012 American Society of Civil Engineers.
CE Database subject headings: Cement; Mortars; Concrete; Sulfates; Concrete structures.
Author keywords: Thaumasite; Attack; Mechanism; Prevention.

Introduction (Hu et al. 2006) and a tunnel in Bapanxia Dam in Lanzhou

In conventional sulfate attacks, incoming sulfate ions react
with calcium aluminate phases and calcium hydroxide in
hardened cement pastes to form either ettringite (3CaO · Al2 O3 ·
3CaSO4 · 31H2 O) or gypsum (CaSO4 · 2H2 O). The consequences
include expansion and spalling of the attacked concrete or mortar
[American Concrete Institute (ACI) 2008]. The attack from mag-
nesium sulfate usually causes the decomposition and decalcifica-
tion of calcium silicate hydrates (C-S-H) (Skalny 2002; Metha
and Monteiro 1993), which does not cause any expansion. Thau-
masite has long been known as a naturally occurring mineral of the
type CaSiO · CaSO4 · CaCO3 · 15H2 O, which has been found in
metamorphosed rocks that have undergone hydrothermal changes
with time. It may be formed by the reaction of water with calcium
carbonate, calcium sulfate, and hydrated calcium silicates, which
are present in concretes and mortars. Thaumasite sulfate
attack (TSA) was first reported by Erlin and Stark (1966) in
1965. They observed the formation of thaumasite in some sewage
concrete pipes and road foundations. TSA again received consid-
erable attention in 1998, when it was observed in several motorway
bridge foundations in the United Kingdom. Since then, many cases
have been reported throughout the world. Several TSA cases have
also been identified in China, such as in Yongan Dam in Xinjiang
1
Professor, Key Laboratory of Building Safety and Energy Efficiency
(Ministry of Education), College of Civil Engineering, Hunan Univ.,
Changsha 410082, China (corresponding author). E-mail: cshi@hnu
.edu.cn
2
Ph.D. student, Key Laboratory of Building Safety and Energy Effi-
ciency (Ministry of Education), College of Civil Engineering, Hunan Univ.,
Changsha 410082, China.
3
Research Associate, Division of Civil Engineering, Univ. of Dundee,
Dundee DD1 4HN, UK.
Note. This manuscript was submitted on March 2, 2011; approved on
March 28, 2012; published online on November 15, 2012. Discussion per-
iod open until May 1, 2013; separate discussions must be submitted for
individual papers. This paper is part of the Journal of Materials in Civil
Engineering, Vol. 24, No. 12, December 1, 2012. © ASCE, ISSN 0899-
1561/2012/12-1450-1460/$25.00.
(Ma et al. 2006a). Thus far, more than 80 field cases have been
identified all over the world (Crammond 2002). Some cases are
summarized in Table 1 (Loudon 2003; Sims and Huntley 2004;
Suput et al. 2003; Freyburg and Berninger 2003; Thomas et al.
2003; Romer 2003; Hagelia et al. 2003; Eriksen 2003; Hu
et al. 2004).
Thaumasite is a pulp with no bonding capability. Thaumasite
formation (TF) is accompanied by a transformation of the cement
paste into a mushy and incohesive mass with a distinctive white
coloration, which can easily be crumbled by hand; reduction in
the binding ability of cement paste; and loss of strength of the
hardened concrete. Thus, TSA can be much more severe than other
sulfate attacks. This paper reviews the features of TSA, factors af-
fecting TSA, TSA mechanisms, and measures that can be used to
prevent TSA. Finally, some needs for future research are suggested.
Features of TSA
Thaumasite forms in the presence of abundant Ca2þ , CO2− 3 , silicate,
sulfates, and moisture, especially at low temperatures. The thauma-
site form of sulfate attack is different from the conventional form
because it is the C-S-H in the hardened portland cements that are
targeted for reaction and not the calcium aluminate hydrates. C-S-H
is the primary binding agent in most conventional cement mortars
and concretes. During the course of TF, calcium aluminate hydrate
and ettringite also disappear (Ma et al. 2004). Although the forma-
tion of ettringite during sulfate attacks can cause expansion and
cracking, ettringite still possesses binding capacity. Whether TF
can cause expansion in concrete is still not clear. Blanco-Varela
and colleagues (2006) found that TF involved expansion, regard-
less of other conditions. Some studies (Aguilera et al. 2003) con-
sidered thaumasite to be an expansive product. However, Mulenga
et al. (2003) did not observe obvious expansion from concrete with
TF. In fact, additional investigators (Macphee and Barnett 2004;
Justnes 2003) could not observe any direct relationship between
TF and expansion. The possibility is that concrete expands due
to the water absorption of formed thaumasite, not due to TF. Thus,

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J. Mater. Civ. Eng., 2012, 24(12): 1450-1460

 Table 1. Typical Examples of TF and TSA
Detection
time Locality Structure type Deterioration characteristics Possible influence factors
1984 Eastern Transvaal, Concrete brickwork Severe expansion and cracking, with Carbonaceous, sulfide-bearing
South Africa of several houses white, powdery deterioration products cummingtonite slate aggregates, no mobile
water, no direct source of carbonate,
ambient temperatures up 15°C
1987 Formazzo Valley, Tunnel lining The entire 300-mm thickness of the tunnel Sulfide-bearing and carbon-bearing
Italy lining became detached aggregates, no direct source of carbonate
indicated
1994 Arctic, Canada Structural concrete of Severe deterioration of the structural Carbonates dominated aggregate, sulfate
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columns and a slab concrete within two years of casting concentrations within the soil around the
columns were very high, ground is
permanently frozen beneath a shallow
depth (Sims and Huntley 2004)
1997 Copenhagen, Waterworks The surface material was soft and greasy, The temperature of the ground water is
Denmark whitish to brownish, and could easily be 5–8°C, air above the water contains
peeled off hydrogen sulfide (Eriksen 2003)
1997 Ontario, Canada Concrete pavement Concrete was characterized by a light- Crushed dolostone coarse aggregate of
colored mottled appearance, cracking being undergone a de-dolomitization
(Thomas et al. 2003) process, up to 15% sulfide-bearing shale
present in the fine aggregate
1998 Gloucestershire, M5 Buried columns and Concrete surface is a mushy consistency, Use of limestone aggregates, use of sulfate
motorway, UK foundations of warty appearance and expansions and sulfide bearing materials for
backfilling, groundwater movements,
leaking motorway drainage, relatively cold
conditions (Loudon 2003)
1998 Southern Slovenia Railway tunnels Mortar has swollen and flaked away from Limestone claddings, the water containing
(Semič, Peščenik) the surfaces of the stone and the mortar dissolved CO2 , Ca2þ and Mg2þ ions, the
joints, mortar has changed into a soft, tunnels are polluted by gypsum, the air
white mushy powder, there is greater temperatures are sometimes below 5°C
dampness, a light grey mud, often in (Suput et al. 2003)
kidney-shaped clumps
2000 Ekeberg, Oslo, Highway tunnel A quite friable, permeable and brittle Aggressive groundwater, alum shale
Norway concrete (Hagelia et al. 2003)
2001 Koblenz, Railway tunnels Larger pieces of shot-concrete could be Sulfur-bearing soot layer on the concrete
Switzerland detached from their support lining, leaking drainage (Romer 2003)
2002 Germany Concrete basin of a The concrete can be broken by hand Limestone aggregates, the concrete
saltwater swimming borders on gypsum, and contact with
bath sulfate-containing ground water, saltwater
containing sodium and magnesium sulfate
(Freyburg and Berninger 2003)
2004 Xinjiang, China Dam A pulpy and water-leakage concrete Frequent low temperature, sulfate bearing
ground water, carbon-bearing aggregate
(HU et al. 2004)

the expansion mechanism associated with TF requires further
study.
TF and TSA may be two different concerns (Sims and Huntley
2004; Crammond 2003). TSA refers to cases in which there is sig-
nificant damage to the matrix of a concrete or mortar as a conse-
quence of the replacement of cement hydrated by thaumasite. TF,
on the other hand, refers to incidences in which thaumasite can be
found in preexisting voids and cracks, without deterioration of the
host concrete or mortar. TF may cause no disruption to the con-
crete/mortar, whereas TSA often refers to significant damage to
the concrete/mortar. TF is a precursor to TSA, thereby indicating
a potential future problem. TSA causes the concrete to become in-
coherent and nonresistant, and is much more severe than any other
form of sulfate attack such as ettringite or gypsum formation.
The primary feature of TSA on concrete is rapid loss of its bind-
ing ability and strength. A severe TSA converts hardened concrete
from artificial rocks to artificial slurry. Gorst and Clark (2003) com-
pared the bonding between reinforcement steel and concrete before
and after TSA. They found that the bonding coefficient, the ratio of
the strength loss after TSA to the original strength before TSA,
decreased by 24% for bars at corners and 10% for bars elsewhere.
Gao et al. (2005) studied the effects of TSA on flexural and com-
pressive strength coefficients of concrete, and found that severe
TSA can reduce the strength coefficients approximately about
30%. Concrete subjected to TSA can have four obvious zones
(Crammond 2002), as described in the following.
• Zone 1: No visual evidence of attack; occasional voids are lined
with either ettringite or thaumasite.
• Zone 2: Thin cracks lined with thaumasite appear running sub-
parallel to the concrete surface. Little portlandite is observed in
the paste and calcium carbonate sometimes lines the cracks.
• Zone 3: Sub-parallel, thaumasite-filled cracks become wider
and the amount of unattacked cement paste is greatly reduced.
Haloes of pure white thaumasite are observed around aggregate
pieces. Little portlandite is observed in the paste and calcium
carbonate sometimes lines the cracks.
• Zone 4: Transformation of cement paste to thaumasite is com-
plete. All that remain are aggregate particles embedded in

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J. Mater. Civ. Eng., 2012, 24(12): 1450-1460

 extremely soft white mush. Localized anaerobic corrosion oc- • Presence of carbonate (including carbonate in concrete
curs in isolated chloride-rich areas, where the depth of attack aggregate);
penetrates through the concrete cover to the steel. • Presence of moisture; and
Thus, if TSA happens in a concrete or mortar, its cement • Low temperatures (below 15°C).
paste matrix should be transformed into a white mush composed The secondary factors include:
of thaumasite, which loosely holds the surrounding aggregate par- • Type and quantity of cement used in concrete;
ticles together. Other visual signs include sub-parallel cracks filled • Quality of the concrete;
with thaumasite and white haloes of thaumasite occurring around • Changes to ground chemistry and water regime resulting from
aggregate pieces. Concrete attacked by TSA can be crumbled with construction; and
a hammer, or even by hand in the foundations of some 30-year-old • Type, depth and geometry of buried concrete.
motorway bridges in Gloucestershire, as shown in Fig. 1(a) TSA involves many complicated physical and chemical proc-
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(Longworth 2003). Field cases showed that TSA on concrete
can cause the loss of strength, binding ability, and resistibility
of penetration (Mario 1999; Deloye et al. 1988), and the failure
of all layers of rendering mortars (Corinaldesi et al. 2003). In
extreme cases, TSA converted the matrix into a fluid (Macphee
and Barnett 2004). As shown in Fig. 1(b), the concrete of the
Ferenc Puskaas stadium in Budapest suffered from severe TSA
(Révay and Gável 2003), where Schmidt-hammer tests had been
routinely conducted since 1973, and the strength of the concrete
decreased gradually with an ever-growing deviation. Significant
restoration works took place and various safety measures, such
as limiting the number of spectators and banning high-load beat
concerts, were simultaneously implemented in the 1990s. The
stadium had to be demolished in 2000.
Factors Affecting TSA
As stated previously, thaumasite can form in portland cement con-
crete when certain requirements are met. The Thaumasite Expert
Group (TEG) (Clark 1999) suggests that TSA is affected by four
primary and four secondary factors. The four primary factors for
portland cement-based materials include:
• Presence of a sulfate, including sulfide that may decay to
sulfate;
esses and is affected by so many factors, so in some cases, it is
very difficult to say which is the most important. For instance, some
authors (Blanco-Varela et al. 2006; Crammond 2003; Floyd 2003;
Loudon 2003; Sims and Huntley 2004; Torres et al. 2006; Zhou
et al. 2006) believe that the presence of mobile water is a necessary
factor, but others disagree (Sims and Huntley 2004). In fact, it is
very important to consider all possible factors, and especially their
interactions, that can have greater effects on TSA than any single
factor. The following sections discuss these factors in detail.
Source of SO 2−
4 Ions
Sulfate ions may originate from inside or outside of concrete. The
internal sources are primarily from cement and aggregate. Cement
clinker itself may contain sulfate components that come from raw
materials and fuel combustion products. Various forms of calcium
sulfate are added to cement during finish grinding to control the
setting characteristics of the cement. Some aggregates may contain
sulfates or sulfides. A typical example of sulfide in aggregate is iron
sulfide (pyrite). In the presence of oxygen and moisture, pyrite can
be oxidized to form a sulfate solution that may contribute to sulfate
attack on concrete.
The primary sulfate sources for TSA on buried concrete were
found to be calcium, magnesium, sodium, and potassium sulfates
in soils or groundwater. Because of the complexity of TSA, the

Fig. 1. Pictures of deteriorated concrete caused by TSA: (a) a 29-year-old underground column of Tredington-Ashchurch bridge on the M5 motorway
in Gloucestershire, western England (Reprinted from Cement and Concrete Composites, Vol. 25, Issue 8. Longworth, T.I., Contribution of con-
struction activity to aggressive ground conditions causing the thaumasite form of sulfate attack to concrete in pyritic ground, 1005-1013, Copyright
2003, with permission from Elsevier); (b) Ferenc Puskaas Stadium in Budapest, Hungary (Reprinted from Cement and Concrete Composites, Vol. 25,
Issue 8. Révay, M., Gável, V. Thaumasite sulphate attack at the concrete structures of the Ferenc Puskás stadium in Budapest, 1151-1155, Copyright
2003, with permission from Elsevier)

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J. Mater. Civ. Eng., 2012, 24(12): 1450-1460

 classification of surrounding soils for TSA becomes difficult
(Crammond and Nixon 1993). In 2001, BRE Special Digest 1
[Building Research Establishment (BRE) 2001] suggested a
classification of surrounding soils, which seems correct for most
field cases. However, Floyd (2003) found that false results may
be sometimes obtained according to the normal classification sys-
tem, because the potential sulfate classification is too conservative.
The classification is also geologically confined to the formation of
Lower Lias Clay and recent alluvium. Thus, the proposed classi-
fication system needs to be modified based on more field cases.
It is also very common for some external sulfates to go into
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tunnel concrete and sewage concrete pipes during their service.
For example, the emissions from old steam and diesel locomotives
resulted in the formation of a layer of gypsum on the surface of the
Koblenz railway tunnel in Switzerland after approximately 40 years
of service.
Blanco and colleagues (2003) studied TF through the reactions
between SO2 in the atmosphere and concrete. They found that a
certain concentration of SO2 in the atmosphere may also result
in the formation of sulfates for TSA. SO2 reacts with cement hy-
dration products to first form gypsum, and then gypsum reacts with
calcium carbonate and C-S-H gel to form thaumasite. A minimum
amount of sulfate is required for TF, which is associated with the
alumina content of the cement (Gaze 1997). Recent research
showed that thaumasite precipitated only in systems where the
Al present has already been consumed to form ettringite and the
molar SO3 =Al2 O3 ratio exceeded 3. Only ettringite formed for
lower amounts of SO2 (Schmidt et al. 2008).
Source of Carbonate
Available carbonate is an essential requirement for TSA (Sims and
Huntley 2004). According to most of those identified TSA cases,
carbonates come from cements, concrete admixtures, or aggregate.
Many cement standards in the world allow the use of limestone as a
blended ingredient in cement. For example, the new European
cement standard allows the use of up to 35% limestone in
CEM II/B-L, ASTM standard C150 (ASTM 2005) allows the
use of up to 5% limestone in different types of portland cement,
and Chinese standard GB175-2008 (General Administration of
Quality Supervision, Inspection and Quarantine of the People's
Republic of China 2008) allows the use of up to 5% in many types
of cement. According to Justnes’s results (2003), a large amount of
thaumasite was detected in mortars made with cement containing
20% limestone filler. The mortars were stored in a 5% sodium sul-
fate solution saturated with gypsum for 10 months at 5°C. However,
only ettringite was detected in the mortars made with cement
containing 20% quartz filler. The results indicated that limestone
within cement could be the source of carbonate for TSA.
TEG’s report suggested that aggregate was the dominating
carbonate source for TSA on concrete (Crammond and Halliwel
1995). Crammond et al. (2003) designed some experiments to
study the effect of aggregate type on TF in concrete. In their experi-
ments, the concrete cubes made with siliceous aggregate performed
satisfactorily, whereas those made with carbonate aggregates
showed significant signs of TSA. Moreover, the de-dolomitization
of dolomite aggregate may also supply carbonate for TF (Thomas
et al. 2003); additionally, the oxidation of carbon in the form of
graphite sometimes present in aggregates and/or surrounding bed-
rock (Loudon 2003) could be the source of carbonate for TSA.
Carbonate from concrete carbonation or an external source can
also be the source for TSA (Crammond 2002; Suput et al. 2003;
Thomas et al. 2003; Macphee and Barnett 2004). The carbonation
can be attributable to the CO2 in the air (Sibbick et al. 2003a) or
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J. Mater. Civ. Eng., 2012, 24(12): 1450-1460
CO2−
3 in groundwater, surface water, seawater, or marine water
(Torres et al. 2006). Atmospheric carbon dioxide could provide
the required carbonate for TSA via the intermediate formation
of bicarbonate ions, and therefore TSA could occur in systems
without the addition of limestone filler or aggregate if exposed
to atmospheric carbon dioxide (Torres et al. 2006; Collett et al.
2004). Thus, many raw materials and processes could produce
carbonate sources for TSA on concrete.
Moisture
For thaumasite to form, all components (sulfate ions, carbonate
ions, and calcium silicate or calcium silicate hydrate) must either
be available at the reaction site or transported to the reaction site
by water. Thus, the presence of water can further increase ion
migration and increase the probability of outer attack ions invading
into concrete (Crammond 2002). This is why, in the past, the pres-
ence of water was regarded as a primary factor affecting TSA
(Crammond 2003). The force for water mobility is often a capillary
rising force (Mario 1999), which sucks water from the environment
into concrete.
Although moisture is necessary and favorable to the occurrence
of TSA in concrete, it is often neglected, because concrete contains
moisture or because concrete is often used in a moist environment.
For example, water is added to concrete during the mixing course,
and groundwater usually saturates concrete while the concrete is
buried. Even when concrete is in a relatively dry environment, rain-
water and moisture in the air can provide enough water for TSA
(Mario 1999). Water attracts less attention in laboratory studies,
because researchers usually conduct experiments in solutions in
which water is treated as a necessary condition instead of as a
study object.
Temperature
It is generally agreed that low temperature is necessary for thauma-
site to be stable. Many researchers (Blanco-Varela et al. 2006;
Loudon 2003; Sims and Huntley 2004; Zhou et al. 2006) believe
that the threshold temperature for stable thaumasite is 15°C or even
lower. Pipilikaki et al. (2008) reported 5°C as the temperature of
thaumasite formation for the mortar specimens immersed in the
sodium sulfate solution. However, evidence has been found that
TF accompanied by a severe breakdown of mortar specimens
occurred in laboratory tests at temperatures as high as 23°C (Mario
1999). On the other hand, Pauri and Collepardi (1989) found that
thaumasite in a concrete sample (taken from an historic building
where low temperatures prevailed at the site) was stable when
stored at 40°C, and thaumasite decomposed only at temperatures
as high as 60°C, particularly at low relative humidity (∼35%).
Recent laboratory studies (Blanco-Varela et al. 2006; Macphee
and Barnett 2004) also confirmed that thaumasite formed or TSA
happened in prisms immersed in solutions with a high concentra-
tion of sulfate ion at approximately 21°C. Thaumasite was also
identified in a field case in Orange County in southern California,
where average temperature is approximately 20°C (Diamond
2003). Similar findings have been reported in several other publi-
cations (Lee et al. 2008; Irassar et al. 2005). Apparently, not only
temperature, but also some other factors, affect the stability of thau-
masite (Gao and Ma 2006). It is certain that the low temperature
favors TF and TSA, because (Hu et al. 2004):
• Thaumasite is much more insoluble;
• Six coordinated SiðOHÞ6 groups are more stable;
• Solubility of CO2 in water increases; and
• Portlandite is more soluble.
 According to Knudsen (1990), the lack of formation of thauma-
site at temperatures higher than room temperature is attributable
to kinetic hindrance rather than a thermodynamic cause. Based
on the Kleber’s rule, low temperature contributes to higher degree
of coordination so that it would further the expansion to octahedral
coordination, while it can also enhance calcium solubility (Ramirez
et al. 2011; Bensted 1988).
C 3 A Content in Cement
As stated previously, limestone, sulfate, and C3 A contents in
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cement effect TF. C3 A controls the amount and rate of TF (Nobst
and Stark 2003; Barnett et al. 2003), and possibly TSA. Thaumasite
could not be observed in mortars made with cement without C3 A at
20°C (Macphee and Barnett 2004). However, Aguilera et al. (2003)
detected thaumasite in mortars by using the same experimental
conditions at a lower temperature. This means that the effect of
C3 A content in cement on TF is dependent on temperature. Hagelia
et al. (2003) did not observe an obvious relationship between TF
and the C3 A content when the C3 A content varied between 1 and
8%. From the preceding discussions, it seems that the presence of
C3 A is very important to TF. However, C3 A content has little effect
on the amount of thaumasite formed.
pH Value
Generally speaking, TSA occurs at pH above 10.5. According to
Zhou’s laboratory study (2006) regarding the role of pH in TSA,
the presence of acid does not promote TF. The higher the pH value
of the system, the more the amount of thaumasite forms (Gaze and
Crammond 2000). Decalcification of C-S-H gel during TSA tends
to reduce the pH from approximately 13 to neutral (Macphee and
Barnett 2004). RBE’s recent research (Sibbick and Crammond
2001) indicated that even with a pH less than 10.5, the deterioration
of mortar can still happen. However, the reaction product is not
thaumasite, but popcorn calcite, which was found by Iden and
Hagelia (2003) and Sibbick et al. (2003b). The popcorn calcite,
previously termed cornflake calcite, can be described as large
(up to 60 μm) tightly packed rosette-like clusters of calcite crystals
surrounded by a calcium-depleted, highly porous and otherwise fri-
able, cement paste matrix. Sulfate ions are simultaneously released
back into pore solutions in concrete, which results in new attacks
on sound concrete if the pH of the concrete is still high. Thaumasite
is very stable in highly basic conditions (pH ¼ 13.0) (Karim
et al. 2003).
Calcium Hydroxide
Hartshorn et al. (1999) found that calcium hydroxide was a reactant
rather than a reaction product during TSA. Bellmann and Stark
(2008) also investigated the role of calcium hydroxide during
TF by exposing mortar bars to moderate sulfate attack. Thaumasite
was identified by X-ray diffraction (XRD) analysis in samples con-
taining high contents of calcium hydroxide, whereas samples
containing no or minor amounts of calcium hydroxide showed
no sign of TSA after 18 months of curing under the same condi-
tions. This is why mineral admixtures such as fly, slag, silica fume,
and metakaolin can be used to prevent the formation of thaumasite,
as discussed later.
Role of Ettringite
Although TSA mechanisms are still not fully understood at
the moment, it seems that thaumasite is closely associated with
ettringite. In many field cases, thaumasite and ettringite coexist
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J. Mater. Civ. Eng., 2012, 24(12): 1450-1460
(Blanco-Varela et al. 2006; Brown et al. 2003; Wimpenny and
Slater 2003). Köhler and colleagues (2006) studied the effects
of ettringite on TF. In their experiments, all suspensions were pre-
pared with the stoichiometric composition of thaumasite, however,
in the absence of aluminate, no thaumasite formed even after one
year. Irassar et al. (2005) immersed mortar specimens containing
20% limestone filler (without C3 A) in a N2 SO4 solution (5% w/w
or 0.352 M) with controlled pH value for two years at 20
2°C,
and no thaumasite was detected in any specimens. In another study
(Blanco-Varela et al. 2006), it was found that thaumasite formed in
mortars made with low C3 A content cement, whereas mixed crys-
tals or solid solutions of thaumasite and ettringite formed in mortars
made with high C3 A content cements. Brown et al. (2004) observed
similar phenomena. They even found that thaumasite and ettringite
always coexisted in their experiments. The formation of exces-
sive ettringite might inhibit the amount of thaumasite formed
(Wimpenny and Slater 2003). Ettringite formation may lead to
TF because cracking due to ettringite formation and expansion
can provide a means for the ingress of carbon dioxide to support
TF (Hartshorn et al. 1999). Apparently, the direct formation of
thaumasite from a solution is extremely slow or even unlikely.
The presence of ettringite is the requirement for TF. However,
the optimum concentration of ettringite for TF is still not clear.
Thaumasite is a complicated sulfate-bearing mineral, which has
a structure similar to ettringite. For a long time, ettringite was
regarded as the principal mineral responsible for expansion and
deterioration occurring in concretes and mortars suffering from
sulfate attack. However, over the last 30 years, a third mineral,
thaumasite, has been increasingly found in cement-based materials
that have been exposed to sulfates (Crammond 2002). Hu et al.
(2006) found a large amount of needle-like crystals by scanning
electron microscopy (SEM) at Yongan Dam. According to the
traditional theory of sulfate attack in cementitious materials, the
needle-like crystals should be ettringite. However, when energy-
dispersive X-ray (EDX) analysis was conducted, the crystal
included Ca, S and Si, but no Al, which should be contained in
ettringite. The attacked concrete was then analyzed by XRD,
and the results showed that the concrete did contain thaumasite,
but no ettringite.
Comparisons between thaumasite and ettringite are summarized
in Table 2. Two possible mechanisms, as described later, have
been proposed by Crammond (2003) based on its chemical com-
position: topochemical conversion from ettringite to thaumasite,
and dissolution–precipitation process.
Thaumasite Formation Mechanisms
Topochemical Conversion from Ettringite to
Thaumasite
The topochemical conversion mechanism from ettringite to
thaumasite is based on the similar structures between thaumasite
and ettringite, as summarized in Table 2. When Si and [2CO2− 3 þ
2SO2− 2−
4 ] replace Al and [3SO4 þ 2H2 O] in ettringite, ettringite is
converted into thaumasite. At the same time, some Al3þ ions are
released into the solution, which results in the formation of more
ettringite. Thus, the process takes place in solid ettringite and is a
topochemical reaction process. However, Si and [2CO2− 3 þ 2SO4 ]
2−
can only replace Al and [3SO2− 4 þ 2H 2 O] at the surface layer of
ettringite structure. This theory cannot explain the rapid formation
of large amounts of thaumasite (Köhler et al. 2006).
Thaumasite and ettringite are needle crystals and have very
similar appearances, as shown in Fig. 2. Researchers used a
 Table 2. Comparisons between Thaumasite and Ettringite
Name Chemical formula/structural formula
Ettringite 3CaO · Al2 O3 · 3CaSO4 · 31H2 O Ca6 ½SiðOHÞ6 2 ·
24H2 O · ½ðSO4 Þ2 · ðCO3 Þ2 
Thaumasite CaCO3 · CaSiO3 · CaSO4 · 15H2 O Ca6 ½AlðOHÞ6 2 ·
24H2 O · ½ðSO4 Þ3 · 2H2 O3 
combination of SEM observation, XRD, and EDX analyses to
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identify thaumasite in concrete (Hu et al. 2006; Freyburg and
Berninger 2003). If thaumasite and ettringite concentrations are
low, it is very difficult to distinguish them. Selective dissolution
with Na2 CO3 solution was recommended to dissolve ettringite
completely before XRD analyses (Mario 1999). Recent research
(Freyburg and Berninger 2003; Aguilera et al. 2003) indicated that
it is possible to conduct a quantitative determination of thaumasite
and ettringite by the Rietveld method.
Fig. 2. Microstructural pictures of newly formed thaumasite: (a) Envir-
onmental Scanning Electron Microscopy image; (b) Reflection Elec-
tron Microscopy image (Reprinted from Cement and Concrete
Composites, Vol. 25, Issue 8. Freyburg, E., Berninger, A.M. Field ex-
periences in concrete deterioration by thaumasite formation: Possibili-
ties and problems in thaumasite analysis, 1105-1110, Copyright 2003,
with permission from Elsevier)
JOURNAL OF MATERIALS IN CIVIL ENGINEERING © ASCE / DECEMBER 2012 / 1455
J. Mater. Civ. Eng., 2012, 24(12): 1450-1460
Characteristics Damage
Needle crystal, characteristic peaks of EDS Expansion, cracking,
are Ca, S, Si corrosion
Needle hexahedron crystal with parallel orientation, A mushy
characteristic peaks of EDS are Ca, S, Al, non-binding
characteristic peak of Raman spectrum line is reaction product
658 cm−1 (Crammond and Nixon 1993)
Dissolution–Precipitation Mechanism
This mechanism suggests the formation of thaumasite through
reactions in solution as follows:
3Ca2þ þ SiO3− þ CO2− 2−
3 þ SO4
þ 15H2 O → 3CaO · SiO2 · CO3 · SO3 · 15H2 O ðthaumasiteÞ
When there is sufficient amount of SO2− 4 in pore solution at the
beginning of cement hydration, it will result in the formation of
ettringite. Once aluminate is used up, ettringite ceases to form.
Any further ingress of sulfate ions will react with portlandite
[CaðOHÞ2 ] to form gypsum, which causes the pH of the pore
solution to drop to 13 or lower. If carbonate or bicarbonate ions
are present, thaumasite forms. Thaumasite has very low solubility,
especially at low temperature. C-S-H is much more soluble than
thaumasite and will be dissolved into the solution to maintain equi-
librium (Crammond 2003). Therefore, once CO2− 3 and SO4 are
2−
present in the system and the pH of the pore solution is above
10.5, thaumasite will form, as demonstrated in Fig. 3.
Some researchers detected a solid solution of thaumasite and
ettringite (Blanco-Varela et al. 2006; Aguilera et al. 2003; Torres
et al. 2004; Barnett et al. 2002) or a solid woodfordite (Ma et al.
2006a; Bensted 2003), whose composition lies between ettringite
and thaumasite. Köhler and colleagues (2006) studied whether the
solid woodfordite was a middle product during the transformation
from ettringite to thaumasite. They found that thaumasite
was clearly not formed via the woodfordite route, because no trans-
formation of ettringite into woodfordite or woodfordite into thau-
masite was observed in their experiments. Apparently, ettringite
formed first. Si and [2CO2− 2−
3 þ 2SO4 ] in the solution replaced
Al and [3SO2− 4 þ 2H 2 O] in ettringite, which results in the forma-
tion of thaumasite. Then, the thaumasite crystal grows once the
replacement is completed. Barnett and colleagues (2003) found
a gap in the unit cell dimensions between thaumasite and ettringite
in the solid solution. They believed that the gap corresponded to
a change in symmetry from the thaumasite to the ettringite.
Continued examination of specimens during the immersion of
specimens in sulfate solution in a laboratory indicated that ettringite
formed first, then gypsum appeared, and thaumasite formed last
(Gaze and Crammond 2000). Decalcification leads to the decom-
position of C-S-H. The preceding course is consistent with the
dissolution–precipitation mechanism. The course was also con-
firmed by Ma et al. (2006c), whose experiments revealed that ex-
cessive sulfate was required for TF. Due to limited studies and
limitations of the testing methods, the TF and TSA mechanisms
are still not well understood and require more research.
Prevention of TF and TSA
During the investigations into M5 highways in England, guide-
lines for new construction and a strategy for existing structures
were developed by Highways Agency based on the investi-
gations on field cases and the Expert Group requirements
 External SO42-
Rapid reaction of SO42- and aluminum component
and other ions
C-S-H gel, invade
Ca(OH)2,
Compositions of
other alkali Reaction with portlandite
pore solutions
ions
change
Solid equilibrium
Presence of CO32- or carbonate
in pore solutions
breaks
pH 13 in
pore pH change
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solutions
Fig. 3. Dissolution–precipitation formation of thaumasite
(Highways Agency 2001). Before that, recommendations were
suggested by department of the environment, transport and the re-
gions (DETR) Expert Group (1999). A new standard of concrete in
aggressive ground was advanced to manage the new construction
buildings and minimize the potential TSA risk (BRE 2001). How-
ever, almost all guidelines were based on a relatively small number
of scientific investigations of structures in England. It is argued that
the screening program, on which the guidelines are based, is incom-
plete or too limited in scope (Sims and Huntley 2004). More re-
search and in-depth information are needed to establish more
comprehensive guidelines to ensure minimal risks in TSA on con-
crete structures. Some measures, which can be used to prevent the
occurrence of TSA, include (1) use of proper cement and aggregate,
(2) use of mineral admixtures, (3) improvement of impermeability
of concrete, and (4) proper initial curing. The following section
discusses how these measures prevent or eliminate TF or TSA.
Cement and Aggregate
Numerous research works (Aguilera et al. 2003; Zhou et al. 2006;
Collard-Jenkins et al. 2003) have indicated that even the reduction
in the use of cement or aggregate containing limestone can lower
the possibilities of TSA. However, limestone is widely used to pro-
duce portland limestone cement. It is well known that the presence
of a proper amount of limestone particles facilitate the grinding of
clinker, accelerates the early hydration and increase the early
strength of cement. Of course, it also reduces the cost of cement.
Schmidt et al. (2009) reported that the addition of 5 wt.% limestone
in portland cement systems led to a decrease in sulfate uptake due
to its lower initial capillary porosity, so that the sulfate-induced
deterioration was especially reduced at ambient temperatures.
Because of these reasons, most countries allow the use of lime-
stone in cement. Carbonate-based aggregates account for 70% of
all the aggregates used at present. In many cases, it is impossible to
restrict the use of carbonate aggregates. Thus, it is very difficult to
control carbonate in cement and aggregate.
The use of sulfate-resistant cement offers little help to resist
TSA or TF (Crammond and Nixon 1993; Sibbick and Crammond
1999). Studies by Ma et al. (2006b) and Gao et al. (2007) revealed
that rapid hardening sulfoaluminate cement (SAC) or a mixture of
SAC and ordinary portland cement exhibited satisfactory resistance
to TSA, whereas sulfate-resistant cement showed an opposite trend.
The good resistance of SAC to TSA could be attributed to its low
CaðOHÞ2 content. Based on the relationship between the compo-
sition of cement and TSA in concrete, the new UK guideline on
the use of concrete in aggressive environments offers an interface
with emerging European standards for cement and concrete
(Nixon et al. 2003).
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J. Mater. Civ. Eng., 2012, 24(12): 1450-1460
Ettringite
Gypsum
Thaumasite pH
unchanged Reactions
continue
pH drops to 10.5-13
Use of Mineral Admixtures
The use of mineral admixtures such as ground granulated blast
furnace slag (GGBS), fly ash, and silica fume has been proven
an effective measure for reducing or even inhibiting TSA in con-
crete (Glasser et al. 2008). According to Higgins and Crammond
(2003), concrete made with 70% GGBS and normal quality carbon-
ate aggregates performed extremely well and showed no evidence
of TSA in any of the solutions, such as magnesium sulfate (1.8% as
SO4 ), magnesium sulfate (0.42% as SO4 ), magnesium sulfate
(0.14% as SO4 ), and sodium sulfate (1.8% as SO4 ). However,
concrete made with inferior quality carbonate aggregates and
70% either normal or high-alumina GGBS did not perform well
at either 5 or 20°C. Concrete made with GGBS became more
vulnerable to conventional sulfate attack.
Mulenga et al. (2003) investigated TF in concrete and mortars
containing fly ash. The results indicated that TF could occur within
84 days of exposure to sulfate solutions. However, high volumes of
fly ash limited TF. The mixtures of portland limestone cement with
40% fly ash exhibited very limited TF, whereas the mixtures with
50% fly ash had no TF. Additionally, the effect of fly ash on TSA in
concrete was dependent upon temperature and cement type. The
concrete with a high content of fly ash performed well at high
temperatures (20°C), but was more vulnerable to conventional
sulfate attack at low temperatures (8°C). When sulfate-resistant
cement was used, the presence of 50% fly ash accelerated the
deterioration of concrete. According to Zhang and Zhang
(2002), the reason why fly ash could restrain TF was that fly
ash consumed the calcium hydroxide in concrete, which is one
of the necessary reactants for TF. However, it was also found that
an excessive volume of fly ash in concrete was unfavorable for the
prevention of TSA (Gao et al. 2007). Skaropulou et al. (2009)
reported that the incorporation of metakaoline and GGBS sub-
stantially improved the TSA resistance, whereas the use of fly
ash seemed to retard TSA and natural pozzolan was not very
effective against TSA.
Bellmann and Stark (2007) investigated the mechanism of min-
eral admixtures preventing the occurrence of TSA through thermo-
dynamic calculations. They studied the effect of the C=S ratio (the
mole ratio of CaO to SiO2 ) of C-S-H gel on TF and found that
C-S-H gel with a C=S ratio of approximately 1.1 resisted much
higher sulfate concentrations without giving way to thaumasite,
whereas C-S-H gel with a C/S ratio of approximately 1.7 trans-
formed into thaumasite at very low sulfate concentrations. Appa-
rently, the C/S ratio of C-S-H is a key factor for TF in concrete.
The addition of mineral admixtures is an effective way to lower
the C=S ratio of C-S-H. In relevant experiments, concrete made
with a sufficient amount of fly ash or GGBS, which completely
 converted portlandite into additional C-S-H phases and reduced the
C=S ratio of the C-S-H gel to 1.1, performed under excellent con-
ditions without any signs of deterioration within 4.5 years of ex-
posure to sulfate solutions. These results explained the principles of
admixtures preventing the occurrence of TSA in concrete, and also
provided a new study direction for protecting concrete from attack
by TSA.
Improved Impermeability of Concrete
A less impermeable concrete matrix improves its durability and
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demonstrates better resistance to the penetration of aggressive
chemical species into hardened concrete (ACI 2008; Skalny
2002). The use of low water/cement ratios (w=cm) can
minimize the internal transport of ions like Ca2þ , CO2− 2−
3 , SO4 ,
and water as the carrier for aggressive chemical species (Bensted
1999). Moreover, mineral admixtures can also decrease the per-
meability of concrete because of their pozzolanic and mini-
aggregate effects. If the w=cm is decreased to a value of less than
0.45, the possibility of TSA occurrence is significantly reduced
(Deng et al. 2005). Some engineers tried to use an impermeable
barrier to prevent concrete in contact with external sulfate solutions.
However, DePuy (1994) felt that impermeable barriers could
not be recommended as a long-term solution to an aggressive
sulfate solution because there is no guarantee that the barrier
would perform effectively over the required period.
Initial Curing
Higgins and Crammond (2003) investigated how the initial curing
affected the susceptibility of concrete to TSA. Twenty-four hours
after casting, concrete cubes were cured for a further 27 days, either
in water or air at 65% relative humidity at 20°C. Following the
curing, the cubes were immediately transferred to containers con-
taining sulfate solutions at 5°C. The experimental results showed
that the cubes initially cured in air appeared to be relatively immune
to both the conventional and thaumasite forms of sulfate attack. At
the 4.5-year assessment, no significant thaumasite-related attack
was observed on those cubes. Even after six years of immersion
in sulfate solutions, these cubes were still in good condition,
whereas those initially cured in water showed a significant attack
by sulfate solutions. The authors believed that air-curing could
prevent the occurrence of TSA because a carbonated layer on
the surface contained less or zero calcium hydroxide.
Many measures can be used to reduce or eliminate the occur-
rence of TF or TSA. An effective prevention strategy should be
designed according to technical, environmental, and economical
requirements.
Future Needs
During the past decade, many laboratory and field studies have
been conducted to understand different aspects regarding TF and
TSA. However, there are still gaps between laboratory studies
and field cases due to differences in raw materials and surrounding
environments. In laboratory studies, performance indexes such as
strength and dimensional deformation are often measured in com-
bination with micro-structural analyses (Yang and Buenfeld 2000).
Field study is much more complicated than laboratory study. To
produce enough information and to properly understand TF and
TSA under field conditions, a procedure is suggested, as shown
in Fig. 4. First, field investigations should be conducted. The
deterioration characteristics and environmental conditions are care-
fully recorded and samples are taken for further laboratory studies.
JOURNAL OF MATERIALS IN CIVIL ENGINEERING © ASCE / DECEMBER 2012 / 1457
J. Mater. Civ. Eng., 2012, 24(12): 1450-1460
Deterioration
cases
Field
investigations
Sampling
Experiments Characteristics
Environmental
investigations Severity
Mechanism of
deterioration
analysis
Systemic
analyses
Repair Lessons and
measures experience
Guidelines
Fig. 4. Suggested procedures for studying TSA
Second, these conductions and samples should be systematically
analyzed for the identification of the primary courses of deteriora-
tion. Third, repair is designed and conducted, and prevention
guidelines are developed.
As mentioned previously, many factors can affect TF and TSA.
In many cases, it is very difficult to determine which is more or less
important. Many controversial phenomena and conclusions have
been obtained during laboratory and field studies. Many more
studies are needed to better understand TF and TSA mechanisms
and kinetics to prevent the potential deterioration of concrete
materials and structures. Some aspects related to TF and TSA need
further investigations, including:
• Relative importance of potential source of carbonates for the
reaction;
• Precise process by which cracking forms sub-parallel to the
surface;
• Occurrence and relevance of different forms of thaumasite;
• Factors in the progress of the reaction, e.g., role of magnesium
and other ions;
• Dual effect of sulfate and chloride ions and the combined thresh-
old for steel corrosion;
• Potential expansion of thaumasite itself;
• Model of the TSA phenomenon (Santhanam et al. 2001); and
• Relationship between TSA and popcorn calcite (Crammond
2003).
It is also important to consider interactions of TF or TSA with
other forms of attack on concrete. As mentioned previously, the use
of sulfate-resistant cements may be effective to resist normal sulfate
attack, but not the thaumasite form of sulfate attack. The use of slag
can inhibit the formation of thaumasite, but is favorable to other
forms of sulfate attack under conditions when the slag contains
a certain amount of aluminum. In addition, the presence of Mg2þ
can hasten TF, while TF can also promote a magnesium sulfate
attack (Ma et al. 2007). Carbonation may be helpful to prevent
TSA due to the formation of a less porous layer on the surface
of concrete, but can be deleterious to the reinforced bars in the
concrete (Osborne 1991). In addition, the carbonation of concrete
may provide a source of carbonate for TSA (Aguilera et al. 2003;
Tsivilis et al. 2007). For example, the simultaneous occurrence of
 carbonation and TSA was found in the case of Baipanxia Dam in
western China (Ma et al. 2006a). Some researchers (Diamond
2003) indicated that the two may be independent from each other,
because it is difficult to distinguish which mechanism follows the
other. It is believed that the carbonation of concrete plays different
roles under different conditions.
Summary
TF and TSA have been identified in many parts of the world. TSA
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on mortars and concrete can be very destructive because it converts
the primary binding components in concrete into thaumasite, which
has no bonding capability and results in an incoherent and mushy
concrete.
TF and TSA are very complicated processes that are affected by
many factors. It is often very difficult to state which factor is more
or less important. However, it is definite that sulfate, carbonate, and
moisture are the controlling factors under any conditions. The pres-
ence of ettringite, which can easily form in many cases, is very
important for the formation of thaumasite, but excessive ettringite
may inhibit the amount of thaumasite formed. C3 A content in
cement, pH value of the system, and low temperature also have
effects on TSA. A minimal pH value of 10.5 is required for
thaumasite to be stable. After the pH value is above the critical
value, the higher the pH value of the system, the more the amount
of thaumasite that forms.
Among the two proposed mechanisms, the topochemical con-
version mechanism from ettringite to thaumasite has many defects,
whereas the dissolution-precipitation mechanism seems to be able
to explain the most corresponding phenomena in most cases.
Both materials and surrounding environments should be consi-
dered to prevent concrete structures from TSA. For example, a re-
duction in the use of cement or aggregate containing limestone can
obviously lower the possibilities of TSA. Proper use of mineral ad-
mixtures, such as GGBS, fly ash, and silica fume is also an effective
measure for inhibiting TSA in concrete. In practical applications, a
corresponding strategy should be developed by considering several
measures instead of a single one, according to available materials
and the surrounding conditions to prevent the occurrence of TSA.
Although many field and laboratory studies have been con-
ducted during the past decades, there are still many unsolved issues
related to TF and TSA, due to their complexity. It is also necessary
to develop or improve systematic guidelines or specifications to
identify and/or prevent the occurrence of TF and TSA in concrete.
Acknowledgments
Financial supports from Chinese National 973 Program under con-
tract No. 2009CB6231001, and National Natural Science Founda-
tion of China (under contract Nos.50978093 and 51072050) are
greatly appreciated.
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