Environ Chem Lett (2011) 9:151–166

DOI 10.1007/s10311-010-0302-2

REVIEW

Cement industry: sustainability, challenges and perspectives

F. A. Rodrigues • I. Joekes

Received: 26 April 2010 / Accepted: 6 October 2010 / Published online: 23 October 2010
Ó Springer-Verlag 2010

Abstract Cement-based materials, such as concrete and its properties are also presented. Special attention is given to
mortars, are used in extremely large amounts. For instance, the role that cement chemistry can play in terms of sus-
in 2009 concrete production was superior to 10 billion tons. tainability. The most relevant aspects are outlined, such as
Cement plays an important role in terms of economic and the use of alternative materials, new possibilities and also
social relevance since it is fundamental to build and improve the recycling of materials. It is also argued that an important
infrastructure. On the other hand, this industry is also a aspect is the role of research and development necessary to
heavy polluter. Cement production releases 5–6% of all improve cement sustainability.
carbon dioxide generated by human activities, accounting
for about 4% of global warming. It can release huge amounts Keywords Cement  Sustainability  Green chemistry 
of persistent organic pollutants, such as dioxins and heavy Carbon dioxide  Pollutants
metals and particles. Energy consumption is also consider-
able. Cement production use approximately 0.6% of all
Abbreviations
energy produced in the United States. On the other hand, the
CKD Cement kiln dust
chemistry underlying cement production and its applica-
c/s Cement to sand ratio
tions can be very helpful to overcome these environmental
ITZ Interfacial transition zone
issues. In terms of manufacture, there are many alternative
MDF Macro-defect-free cement
materials that can be used to minimize carbon dioxide
NOx Nitrogen oxides
production and reduce energy consumption, such as calcium
PCDDs Polychlorinated dibenzodioxins
sulfoaluminates and b-Ca2SiO4—rich cements. Using resi-
PCDFs Polychlorinated dibenzofurans
dues from other industrial sectors can also improve the
PCBs Polychlorinated biphenyls
sustainability of cement industry. Under adequate condi-
PAHs Polycyclic aromatic hydrocarbons
tions, waste materials such as tyres, oils, municipal solid
PCDDs Polychlorinated dibenzo-p-dioxins
waste and solvents can be used as supplementary fuel in
w/c Water to cement ratio
cement plants. Concrete can be used for encapsulation of
waste materials such as tyres, plastics and glasses. In this
review, we discuss some aspects of the cement industry Introduction
associated with environmental science. Other issues such as
economic aspects, the chemistry of cement manufacture and Construction industry is an important and dynamic sector in
the world economy. It is responsible for the creation of jobs,
the modernization of infrastructure and the improvement of
F. A. Rodrigues (&) life standards, among others. Also, this industrial sector is
Universidade de Mogi das Cruzes, Mogi da Cruzes, Brazil directly related to many other areas, such as financing,
e-mail: flavioar@umc.br
energy, mining and transportation, just to mention a few.
I. Joekes Cement, the most important component of construction,
Universidade Estadual de Campinas, Campinas, Brazil plays a fundamental role in modern world. This material is

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152 Environ Chem Lett (2011) 9:151–166

produced in almost every country and region and presents imagine a world without cement-based materials. The
many interesting aspects, such as physical, chemical and availability of basic raw-materials, the simple manufacture
mechanical stability. Cement, when compared to other process and its endless applications make cement a very
materials, can be considered inexpensive and abundant. On popular and widespread material. According to Meyer
the other hand, in many aspects, the chemistry of cements is (2009), the world production of concrete is superior to 10
not so familiar or well established. Additionally, the pro- billion tons yearly.
duction of cement is not an environmentally friendly process. A comparative analysis may be useful to introduce
It requires very high temperatures (usually above 1,500°C) cement industry. For instance, let us consider data from
and the consumption of large amounts of non-renewable world mining production in 2007. Combined, the extrac-
raw-materials. It is estimated that 5–6% of all carbon dioxide tion of aluminum, alumina and bauxite, cadmium, cobalt,
generated by human activities is derived from cement fab- cooper, garnet (industrial), gypsum, kaolin, lead, lime,
rication. Also many important pollutants are usually gener- manganese, phosphate rocks, soda ash and zinc rendered
ated, such as dioxins and heavy metals, among others. about 1,398,000 thousand metric ton. Therefore, the pro-
Numbers related to cement-based materials and construc- duction of all these materials together corresponds to
tions are very impressive. Engineers use to say that concrete is approximately half of cement production for the same year
the second component mostly used by man, just after water. (US Department of Interior 2007).
Cement, as a technological material, is very successful, as Table 1 shows the top-10 producers of cement among
everyone knows. Many characteristics can be easily cited. countries (US Department of Interior 2005–2009). There
First of all, it works very well at room temperature. It is simple are many interesting features worthy to mention. In 2007,
to use, easy to shape, and within few hours, renders an China produced about half of the cement in the world. It
‘‘artificial’’ rock, having numberless applications. Cement is reflects not only the extraordinary growth of Chinese
used to build simple houses, highways, bridges and more economy but also, in some sense, the changes occurring in
complex systems as dams or nuclear power plants. In fact, it is that country (Shen et al. 2005; Zhang and Zhao, 2000). In
almost impossible to imagine the world without cement or the last 20 years or so, China experienced many important
concrete. Despite such popularity, cement industry faces changes: the raising income of foreign investment, unem-
many challenges due to environmental concerns. As will be ployment in rural areas, reorganization of state-owned
discussed in this review, cement industry is an important facilities and business and the liberalization of private
polluter, releasing huge amounts of carbon dioxide, NOx, business. Probably, the most visible result of these modi-
dibenzo-p-dioxins (PCDD), dibenzofurans (PCDF), heavy fications was the urbanization and the growth of cities.
metals and particles, among other pollutants. Also energy Urbanization is an important issue regarding cement con-
consumption is considerable. It is estimated that about 0.6% sumption. In only 22 years (from 1978 to 2000), the urban
of the energy consumed in the United States is used to produce Chinese population changed from 170 million to 456 mil-
cement. Moreover, large amounts of non-renewable materials lion or from 17.9 to 36.1% of total population. In 2003,
are consumed in the process. Many efforts have been made to urbanization in China reached 41% while world average is
minimize the impact of these issues. Governments, industrial around 46% (Shen et al. 2005). India, the second major
sector, researches and other organizations are dealing seri-
ously to improve the sustainability of cement industry.
On the other hand, construction materials can be very Table 1 Cement production for major countries in the period
2004–2007 (thousand metric tons)
useful to minimize hazardous effects from other economic
activities. The industry is using and/or testing alternative Country 2004 2005 2006 2007
materials to generate energy in cement production, such as China 934,000 1,040,000 1,200,000 1,350,000
used tires and other solid wastes. In this review, the role of
India 125,000a 145,000a 155,000a 170,000a
cement industry in a challenging perspective is presented.
USA 99,000 101,000 99,700 96,500
Many important aspects are discussed, such as the recent
Japan 67,400 69,600 69,900 67,700
improvements in cement industry, new technologies in a
Russia 43,000 48,700 54,700 59,900
materials, new remediation methods, the recycling of waste
Korea 53,900 51,400 55,000 57,000
materials, among others.
Spain 46,800 50,300 54,000a 54,500
Turkey 38,000 42,800 47,500 49,500
Italy 38,000a 46,400 43,200 47,500
Cement and the economy
Brazil 38,000a 36,700 39,500 46,400
World 2,130,000a 2,310,000a 2,550,000a 2,770,000a
Probably, the most remarkable aspect of cement industry is
a
the large-scale numbers. It would be very difficult to Estimative

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cement producer, shows a different but similar pattern, and
urbanization is also an important driving force in cement
industry.
Cement is used to build better houses (especially in poor
countries and regions) and to improve infrastructure, such
as dams, airports, roads and sanitation. In many countries,
the consumption of cement is a consequence of the lack of
infrastructure. In countries like China and India (and cer-
tainly many others), part of population does not have
adequate housing or simple services, such as electricity and
treated water. Also they lack satisfactory roads, power
supply and jobs. To attend this demand, in most cases,
public investments are necessary to build infrastructure and
so, to consume cement. Moreover, especially in Asia, the
transition to ‘‘modern’’ societies has many implications in
terms of political and sustainable production (Rock et al.
2009). The continuous urbanization of these countries also
demands construction materials due to growth of cities and
migration of population. Furthermore, the mobility of
population requires the construction of many kinds of new
buildings (Shen et al. 2005).
It should be pointed out, though, that unlike other
materials, increasing cement consumption is not a good
parameter to measure economic growth. In countries like
USA and Japan, where population has attained excellent
life standards, the cement production has not changed very
much in recent years. It is used to maintain existing
infrastructure and, of course, to reform old facilities and
build new ones (Horvath 2004). In 1997, European Union
(15) produced and consumed about 11% of world cement,
being Italy the major producer. On the other hand, for
obvious reasons, Africa shows the lowest production and
consumption of cement among continents (Szabó et al.
2006).
In some way, the use of cement materials is a general
claim in modern societies. In the last one hundred years,
world has changed enormously in terms of life standards
and infrastructure, due in part to cement-based materials.
There is no signal that this trend will change in the forth-
coming future. At the end of XIX century, United States
and Europe accounted for approximately 91% of world
cement production (Tafunell 2007). Table 2 shows that this
situation has changed dramatically. Cement industry plays
Table 2 Major components of ordinary Portland cement type I
Component Formula Notation % (average)
Tricalcium silicate Ca3SiO5 C3S 45–60
Dicalcium silicate b-Ca2SiO4 b-C2S 15–30
Calcium aluminate Ca3Al2O6 C3A 2–15
Calcium ferroaluminate 4CaOAl2O3Fe2O3 C4AF 5–15
Gypsum CaSO41/2H2O CS 5
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a fundamental role in modern world, since it is responsible
for sustaining population growth and economic
development.
The economic importance of the construction industry is
doubtless considerable. It is indeed difficult to measure its
economic impact. Cement is a produced and consumed at
extraordinary rates and amounts. However, cement is never
used alone. For instance, in order to make an ordinary
building, many other materials and economic sectors are
involved. Before a construction starts, the planning may
involve engineers and architectural companies. Many
materials are needed such as sand, rocks, steel, aluminum,
gypsum, glasses and polymers, just to mention a few. Con-
tractors and construction firms are responsible by personnel
and services. Also other services are fundamental in building
sector: hydraulics, electricity and gas. Electric and elec-
tronic components, heating and/or air conditioning systems
are also present (Horvath 2004; Pulselli et al. 2008). Finally,
it should be mentioned that individuals are also cement
consumers, since it is very usual that people buy cement to
make small reforms or home improvements.
It is clear that cement is an important material in everyday
life; in fact, few other materials could claim to be as uni-
versal as cement. Its importance is not restricted to con-
struction and repair but is an important part of world
economy and life standard. From the historic viewpoint,
cement was studied mainly by civil engineers, interested in
the development of mechanical properties. As any other
material, there is an increasingly interest in the compre-
hension of fundamental aspects and properties of cement-
based materials, in order to improve their performance. In
this sense, the chemistry of cement is fundamental to
improve sustainability. Innovation seems to be the keyword
to face the many challenges in this sector. ‘‘Greener’’ pro-
cesses can be achieved in many different ways, and some
important issues are discussed in the following sections.
Terminology, chemical aspects and hydration
The term cement is widely used in many different areas as
dentistry (Zhao et al. 2009; Nakajo et al. 2009), medicine
(Gupta et al. 2004; Dorozhkin 2008; Boesel and Reis,
2008) and civil construction (Brandt 2008; Millard and
Kurtis 2008). It may be applied to polymeric, metallic,
ceramic and composite materials. In common, all these
cements present the capability of hardening under specific
conditions and to maintain its structural stability for an
extended period of time. In this sense, cement-based
materials can be thought as a solid, whose binder is any
kind of cement. However, in the present context, the term
binder is limited to Portland cement and related materials,
used for construction purposes.
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Historically, cementitious materials were used for a long
time. The Egyptians used gypsum and lime for the con-
struction of Pyramid of Cheops, approximately 3,000 BC.
Romans built many concrete structures, such as the Coli-
seum in Rome. In fact, the word concrete comes from the
Latin ‘‘concretus,’’ or in modern terminology ‘‘grow
together’’ (Young and Mindess 1981).
In many situations, the words cement and concrete are
used as synonymous although this is incorrect. In order to
clarify some terminological aspects, it is useful to keep in
mind some definitions. Concrete can be defined as a
composite formed by cement, water, coarse aggregates
(usually crushed rocks and stones) and fine aggregates
(mostly sand). Mortars are similar to concrete but lack
coarse aggregates (Lea 1971; Taylor 1997). To guarantee
satisfactory mechanical and durability properties, the rel-
ative proportion of each component should be within a
limited range. For instance, if we think about mortars, the
proportion between solids is expressed as cement to sand
ratio (c/s). This ratio is dependent on the kind of applica-
tion, but a ratio of 1:3 is usual. It can be observed that
‘‘aggregates concentration’’ is much higher than ‘‘cement
concentration’’. Aggregates are used to fill up higher vol-
umes in construction. ‘‘Water concentration’’ is expressed
as water to cement ratio (w/c); the w/c ratio in mortars is
typically in the range 0.3–0.6.
There are many other composites prepared with Portland
cement, besides plain concrete. Probably, the best known is
reinforced concrete, where steel is introduced to improve
stability (Belmouden and Lestuzzi 2007). In fiber-rein-
forced concrete, many materials are actually used to pre-
pare specific composites, although metals, polymers and
ceramics are more frequent (Buchan and Chen 2007;
Ahmed and Mihashi 2007). A very interesting composite
made from Portland cement is called MDF, macro-defect-
free cement (Kendall et al. 1983). MDFs combine cement
properties and water-soluble polymer, such as poly acryl-
amide or poly(vinyl) alcohol. MDFs are processed as
polymers, through calandering, pressing and machining. In
many aspects, MDF’s properties are very superior when
compared to traditional cement-based materials (Rodrigues
and Joekes 1998; Santos et al. 1999). Unfortunately, MDFs
present an important limitation; their mechanical properties
are severely damage when exposed to water. This behavior
is exactly opposed to the idea of hydraulic cements. To the
best of our knowledge, commercial use of MDF is limited
(Scrivener and Kirkpatrick 2008).
Nowadays, most of the commercial concretes or mortars
contain also admixtures. These components are usually
added to concrete to modify certain properties and to attain
specific needs and performance (Aitcin 2000; Idorn 2005).
Admixtures play an important role in cement chemistry and
sustainability, but this subject will not be treated here.
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Environ Chem Lett (2011) 9:151–166
There are many interesting papers and books available
(Malhotra 1983; Houst et al. 2008; Hale et al. 2009; Brooks
et al. 2000).
Many types of cements are available for use in civil
construction. Standard ASTM (American Society for
Testing and Materials) C150/150 M covers 10 types of
Portland cement. The distinction between these cements is
based on chemical composition and specific needs and
requirements, such as the development of mechanical
resistance or durability. The discussion presented here is
mostly based on cement type I; Table 1 displays the major
components of commercial cement.
It is common in cement chemistry to express chemical
formulas in abbreviated terms. The notation C3S means
that this component presents three molecules of CaO (=C)
and one molecule of SiO2 (=S). In terms of oxide com-
position, this compound can be described as 3CaOSiO2.
Here, we will preferentially use the familiar chemical
formulas.
It can be seen that tricalcium and dicalcium silicates are
the major components of ordinary cement. Many properties
of concrete that we recognize on a daily basis are conse-
quence of these calcium silicates. Probably, the key aspects
for cement popularity are the many interesting (and chal-
lenging) characteristics of the reactions between these sil-
icates and water (Manzano et al. 2007; Richardson 2000).
Probably, chemists and other scientists do not realize how
difficult would be to explain the ‘‘upcoming’’ events, the
hydration of cement (Hadley et al. 2000; Faure and Rodts
2008; Hartman and Berliner 2005). First of all, cement
hydration takes place at room temperature. It should be
pointed out that cement hydration is an exothermic process
(Azenha et al. 2009; Trtnik et al. 2008); after addition of
water, a ‘‘paste’’ is produced. This paste presents very
attractive rheological properties (Wallevik 2009; Nachbaur
et al. 2001) since it can be easily casted and shaped. Within
minutes, many coupled chemical reactions are occurring,
and interesting enough, far from thermodynamic equilib-
rium (Lothenbach et al. 2008). Moreover after few hours, a
solid is formed, and it is ready to support relatively high
loads without significant volume variation.
These changes, from a gray powder to a stable solid, can
be attributed mainly to the hydration kinetic of calcium
silicates, especially tricalcium silicate. This chemical
hydrates faster than dicalcium silicate (Young and Mindess
1981; Garrault and Nonat 2001). In the initial ‘‘curing’’
stage and even after months, tricalcium silicate dominates
the characteristics of concrete. After about 1 year, both
silicates show the same chemical characteristics and
hydration degree. In addition, the hydration products are
about the same for both components (Young and Mindess
1981). However due to complexity of the final product, the
hydrated phase, it is usual to denote this material as C–S–H
Environ Chem Lett (2011) 9:151–166 155

(hydrated calcium silicate). Literature reports many dif-

a b
ferent viewpoints on the structure and nanostructure of
C–S–H (Matschei et al. 2007a; Kalinichev et al. 2007;
Chen et al. 2004). Also, hydration of calcium silicates is
affected by many variables (Peterson and Juenger 2006;
Ridi et al. 2005).
Calcium aluminates are also important in cement
chemistry and concrete properties. The phase diagram for
the system calcium oxide–calcium aluminate shows that
many compounds can be formed. The presence of con- c d
taminants may influence the final chemical composition
and phase formation for this system (Dı́az et al. 2005;
Matschei et al. 2007b). The presence of iron leads to the
formation of solid solutions. Usually, this complex system
is referred as C4AF. The hydration and the products formed
during aluminate hydration are also very complex (Ghorab
et al. 1998a, b). If pure, calcium aluminates react imme-
diately with water, forming hydroaluminates (Minard et al.
2007). The presence of hydroaluminates is very undesir-
Fig. 1 Simplified version of the topochemical hydration of cement
able since it would make the paste unsuitable for casting,
due to very fast stiffening (Clark and Brown 1999, 2000).
This reaction would be faster than the corresponding for several variables. The above representation is a very simple
calcium silicates. During the cement preparation, gypsum illustration; however, it is helpful to present a chemical
is added to avoid this behavior. The hydration of calcium reaction between common solid and liquid water, rendering
aluminates in the presence of gypsum leads to the forma- a hydrated phase.
tion of a thermodynamic unstable phase called ettringite
(Ca6Al3(SO4)3(OH)1226H2O). The mechanism involved in
the delay of calcium aluminate hydration is still a matter of Cement production and the environment
discussion (Collepardi 2003; Tian and Cohen 2000).
On the other hand, since Portland cement is a material Cement can be considered an inexpensive material. In
produced worldwide, it should be clear that for each order to be competitive, manufacture plants tend to be
country or region, it will present specific characteristics. close to raw-material sources to minimize the costs of
For instance, actual chemical composition is dependent on production (Kendall et al. 2008). In fact, the costs of
many variables, such as the nature of raw-material and transportation are very important and may determine the
impurities, among others (Mechling et al. 2009; Papadakis final cement price (Newmark 1998). Figure 2 presents a
and Tsimas 2005; Sahu and Thaulow 2004; Heikal 2000). simplified diagram for the production of commercial
The use of supplementary material, intentionally added to Portland cement.
cement, will be discussed later. To prepare cement, sources of calcium and silica are
The mechanism of cement hydration can be described needed. The major raw-materials used are limestone and
as a topochemical process (Mehta and Monteiro 1993). dolomite as the sources of calcium; usually quartz, clays
Figure 1 is a simplified description of hydration. When and shale are used to provide silica. Many other minerals
water reaches anhydrous grains (a) it reacts rapidly on the can be used as bauxite, iron ore and slag, among others
surface, in an exothermic process. For tricalcium silicate, it (Türkmenoğlu and Yavuz-Işıkli 2008; Ewais et al. 2009).
takes about 15 min. As consequence, an external core is Also a large number of raw-materials are used or under
formed (b); the presence of hydrate cement particles will test (Erdem et al. 2006; Carrasco et al. 2005; Konsta-
retard internal hydration of cement grains. This is some- Gdoutos and Shah 2003). It should be considered that in the
times referred as the dormant period (Mindess and Young forthcoming future, may be experienced a shortage of raw-
1983), and it takes about 2 h. After this period, by diffu- materials in certain regions (Shih 1999; Shen et al. 2005). A
sion, water penetrates into the interior of particles, pro- more detailed and interesting analysis about materials con-
moting the set of cement (c). Finally, after many months sumption in the world, in the last 100 years, indicates the
the hydration will be almost complete (d). need of more efficient processes (Krausmann et al. 2009).
As pointed out before, however, the actual cement After mining of raw-materials and initial crushing, the
hydration is a very complex phenomenon, determined by chemical composition is adjusted using several possible

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1. Quarrying raw
-material
2. Intial processing (crushing)
3. Blending, mixing, adjusting composition
4. Initial heating
5. Secondary heating
6. Clinker cooling
7. Gypsum addition (cement)
8. Final grinding
9. Packing, distribution
Fig. 2 Major steps of commercial production of cement
mineral sources. The solid mixture is heated at very high
temperatures, usually above 1,500°C. This solid product is
called clinker. Commercial cement is obtained after addi-
tion of gypsum to clinker and final grinding.
A curious aspect is that cement productions has not
changed significantly over the last 150 years or so. It does
not mean, however, that many improvements were not
added to production. Thomas A. Edison, for example,
received 49 patents related to cement production (Thomas
Edison Papers).
The fabrication of commercial Portland cement is a
typical solid-state reaction, mostly based on the use of high
temperatures (Suresh and Ghoroi 2009). Many other cera-
mic materials are produced in a similar way (Schackelford
and Doremus 2008). Usually, the reaction between solids is
limited by the very low mobility of individual species, in
contrast to reactions in gaseous or liquid environments. The
use of elevated temperatures enhances diffusion in solids
favoring the reaction between them. The mechanism and
kinetic of solid-state reactions are also relatively more
complex (Khawam and Flanagan 2006).
An important aspect should be presented at this point.
Cement plants can be very different. New facilities tend to
be more efficient and better prepared to avoid environ-
mental risks (Huntzinger and Eatmon 2009). These dif-
ferences arise even in developed countries; however, in
underdeveloped countries it can be dramatic, due to the
lack of legislation and poverty. In many situations, working
conditions are really unsatisfactory (Mwaiselage et al.
2005).
On the other hand, from the environmental viewpoint,
perhaps it should be more appropriate to visualize cement
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Environ Chem Lett (2011) 9:151–166
Fig. 3 Environmental map for cement production: the release of
pollutants into atmosphere
production, taking into account the potential generation of
hazardous substances. This ‘‘environmental map of cement
production’’ is not definitive since there is a great vari-
ability of processes, raw-materials and plant design; how-
ever, it can be useful to better understand the impact of
cement fabrication on environmental issues.
Figure 3 shows a schematic diagram (environmental
map) describing the preparation of cement. It can be dis-
tinguished three major regions inside the rotary kiln,
according to temperature and released substances: (1)
dehydration, (2) calcination and (3) clinkering zones. Here,
we will describe three major sources of environmental
concerns: generation of particles, generation of organic
pollutants and the release of carbon dioxide.
Generation of particles
In all three stages, solid particles can be spread into
atmosphere and cause several problems (Spoo and Elsner
2001; Xiao and Cai 1995). As a matter of fact, the gener-
ation of particulate material starts with mining and may
continue until cement is used by final consumer. For
instance, the great majority of cement particles shows
diameter much inferior to 100 lm (Chindaprasirt et al.
2005) favoring their dispersion. It is well known that small
particles, presenting high surface area, can be easily
transported by air (Sun et al. 2004).
Nevertheless, here we are concerned only with particles
that are produced in cement facilities. In the three stages
presented here, the particulate material will collectively be
named cement kiln dust (CKD), as it is usual in cement
industry. CKD is also a complex solid with variable com-
position. It can be assumed that major components are
sulfates, chlorides, aluminates, oxides and salts (Duchesne
and Reardon 1998). Due to high calcium oxide concen-
tration, it is a very basic material. An interesting study
(Massicotte et al. 2004) on the effect of CKD on earthworm
Environ Chem Lett (2011) 9:151–166
(Lumbricus terrestris) suggested the inhibition of immune
system of this invertebrate, although more detailed inves-
tigation is still needed.
According to van Oss and Padovani (2002), up to 20%
of clinker mass can be lost as CKD, even though modern
plants can reduce this number significantly. Once particles
are released, their dispersion is dependent on many factors,
such as topography and atmospheric conditions (Polat et al.
2004; Abdul-Wahab 2006). Humans and animals can be
contaminated by inhalation and contact with skin and eyes.
Also these particles can be carried to large distances and
accumulate in soils, rivers, etc. More important, this dust
may have relatively high concentrations of heavy and toxic
metals (Zaki et al. 2007; Eckert and Guo 1998). For
instance, Isikli et al. (2006) showed that in vicinity of a
cement plane in rural Turkey, the concentration of cad-
mium in plants and soil was much above control sites.
A similar study (Morales et al. 1996) suggested that
atmospheric concentration of zinc and cadmium was higher
in western Venezuelan savannah than expected, also due to
emissions from a cement factory. A more dramatic situa-
tion was described in Nigeria (Abimbola et al. 2007) where
the high concentration of heavy metals was associated with
human diseases. On the other hand, negligible effect of
cement and cement dust was observed in rats (van Berlo
et al. 2009).
The emission of CKD can be reduced by the use of
modern technologies. Also, there is a continuous interest in
the utilization of CKD. It has been used in soil adjustment
(Peethamparan et al. 2008) or sewage treatment or even in
concrete manufacture (Maslehuddin et al. 2009).
Organic pollutant
The term dioxin encompasses a large number of com-
pounds. It can be applied to a class of substances related to
halogenated aromatic hydrocarbons. Basically, three clas-
ses are usually considered (Srogi 2008): polychlorinated
dibenzodioxins (PCDDs), polychlorinated dibenzofurans
(PCDFs) and the ‘‘dioxin-like’’ polychlorinated biphenyls
(PCBs). All these compounds are extremely toxic, even in
very small concentrations (Schecter et al. 2006; Jin et al.
2009). Dioxins are generated in many industrial processes
such as incineration (Reis et al. 2007; Yasuhara and
Katami 2007), paper industry (Charlestra et al. 2008),
preparation of pesticides (Götz et al. 2007) among others.
The formation of PCDDs, PCDFs and PCBs may occur
during cement fabrication, especially due to the co pro-
cessing of hazardous materials in cement kilns (van Loo
2008). Many residues can be used as supplementary fuels
in cement industry. In fact, it seems to be a very good
approach to the disposal of materials as used tyres, carpets,
oils from industrial activities etc. (Prisciandaro et al. 2003;
157
Karstensen 2008; Carrasco et al. 2002). Since cement kilns
reach very high temperatures, the initial idea is that these
residues could be used together with traditional fuels,
generate specific heat and after all, they could be com-
pletely destroyed.
Previous experience showed that PCDD/F and PCBs can
be formed during the burning of municipal solid waste
incinerators. The mechanisms involved in the formation of
these organic pollutants are sometimes very complex
(Dickson et al. 1992). It is a good assumption that engi-
neering aspects such as feeding rate and type of incinera-
tor may inhibit or minimize the formation of pollutants
(Prisciandaro et al. 2003).
On the other hand, in the second stage (calcination zone)
it was confirmed the formation of PCDD/Fs, associated
with the lower temperatures. In this case, the burning
conditions seem to be of fundamental importance on the
concentration of these pollutants (Lohman and Seigneur
2001).
In dehydration zone (roughly up to 600°C), free or
unbounded water is lost, and most of clays start to
decompose. Also depending on fuels used or available to
cement production, many organic pollutants can be gen-
erated such as dioxins, furans, polycyclic aromatic hydro-
carbons (PAHs), polychlorinated dibenzofurans (PCDFs),
polychlorinated dibenzo-p-dioxins (PCDDs) among others.
Also gases like NOx and sulfur compounds, just to mention
a few, can be expelled from industrial kilns if the process is
not well controlled (Lemieux et al. 2004; Börjesson and
Gustavsson 2000).
In the third stage of cement manufacture (clinkering
zone), the addition of liquid wastes as partial substitution
of traditional fuels leads to almost no generation of organic
pollutants (Benestad 1989).
Carbon dioxide
In the calcination zone, there is an additional source for
environmental concern: the release of carbon dioxide.
Numbers are somewhat controversial, but it is estimated
that cement production accounts for about 5–6% of all
carbon dioxide emissions caused by human activities
(Morsli et al. 2007; Gartner 2004; Pulselli et al. 2008). For
instance, as result of Kyoto Protocol, in 2003, European
Union set through the Emissions Trading Directive (ETD)
specific target for the reduction of green house gases. Some
industrial sectors were selected, such as oil refining, pulp
and paper, steel and cement (Lund 2007).
The production of CO2 in cement plants does not occur
only in the calcination zone, inside the kiln. In fact, there
are four major sources of CO2 formation during the pro-
cess: the burning of fossil fuels, chemical reactions,
transport and electricity, as presented in Fig. 4.
123
158
fossil
40%fuels
40%
5% electricity
50% 5% 5%
transport
5%
50%
chemical reactions
Fig. 4 Distribution of carbon dioxide release during cement
preparation
About 50% of carbon dioxide produced during cement
fabrication is due to thermal decomposition of calcium
carbonates (Rehan and Nehdi 2005). Although the com-
plexity of raw-materials used in the process, a simplified
equation can be used to represent the release of carbon
dioxide:
D intensive process. When the burning of fossil fuels and
CaCO3 ! CaO þ CO2
After calcium carbonate decomposition (and many other
possible carbonates), the calcium oxide will be able to react
with other components to render the silicate.
The syntheses of tricalcium and dicalcium silicates can
be presented as follows:
D produced in the country. In terms of natural resources, the
SiO2 þ 3CaO ! Ca3 SiO5
D of raw-materials (Horvath 2004).
SiO2 þ 2CaO ! Ca2 SiO4 :
Disregarding other sources of calcium, calcium silicates
will demand the release of carbon dioxide; each molecule
of Ca3SiO5 requires 3 molecules of CO2, and b-Ca2SiO4
needs two molecules of CO2. As it will be presented latter,
the preparation of cements containing higher concentration
of b-Ca2SiO4 can be an effective way to minimize the
release of carbon dioxide.
Clinkering zone is the final stage for cement manufac-
ture. Under these conditions, as pointed before, particles
can be release to atmosphere, being a potential cause of
many healthy problems.
It is clear that chemical reactions and the burning of
fossil fuels are the major contributors in the process. It
means that an efficient way to reduce CO2 release is the use
of lower temperatures. In practice, however, this is a very
ambitious task, since the preparation of Ca3SiO5 requires
huge amounts of energy.
The whole process of cement production presents many
environmental risks and may be harmful to people and
other life forms as well, if not properly conducted (Zhang
and Wong 2007; Conesa et al. 2008; Iliuta et al. 2002).
However, other aspects should be considered in terms of
123
Environ Chem Lett (2011) 9:151–166
80
CO2 released (103 tons)
75
70
65
60
55
1990 1992 1994 1996 1998 2000 2002
year
Fig. 5 Carbon dioxide released in United States of America from
cement industry
sustainability. Clearly, cement manufacture is an energy-
other energy sources are considered, the total balance is
quite impressive: 1 ton of cement generates approximately
1 ton of carbon dioxide (Worrell et al. 2001). Also it
consumes about 60–130 kg of fossil fuel and 110 kWh
(Morsli et al. 2007). Interesting enough, in United States of
America, cement industry consumes 0.6% of total energy
production of 1 ton of cement demands about 1.4–1.6 ton
Figure 5 shows the variation in carbon dioxide released
by cement industry in USA, from 1990 to 2001 (Jacott
et al. 2003). It can be seen that there is a continuous growth
in CO2 emissions since 1991. In this period, the total
variation amounted 32%.
In relation to carbon dioxide release, many other aspects
could be presented. Engineering aspects are out of the
scope of this work; briefly, for instance, industry works to
improve the efficiency of cement preparation in many
aspects; the use of chemical admixtures allows reduction in
cement dosage, saving raw-materials and limiting carbon
dioxide release; the utilization of alternative materials to
produce concrete; better designed buildings and others
(Damtoft et al. 2008; Jegatheesan et al. 2009; Gartner
2004). Recycling in cement production will be discussed
later, as a separate topic, although in many circumstances
carbon dioxide reduction is also obtained.
Considering only environmental and sustainability
aspects, it is clear that cement industry faces many chal-
lenges in forthcoming future. Moreover, some may argue
that the appearance of new technologies and materials for
construction could dismantle cement industry. However,
cement and cement-based materials have great potential
Environ Chem Lett (2011) 9:151–166
not only to overcome these challenges but, especially act-
ing as an important industrial sector, to improve environ-
mental and life quality.
Perspectives
Cement industry, researchers and academics are not
secluded from general claims to improve sustainability and
to develop cleaner processes (Chan et al. 2007; Phair 2006;
Damtoft et al. 2008; Jegatheesan et al. 2009; Chen and
Juenger 2009; Mandal and Madheswaran 2010). Many new
materials and methods are currently under development,
and it is almost impossible to cover all major aspects and
efforts toward a ‘‘greener’’ cement chemistry and
manufacture.
From the many aspects presented so far, it appears that
substitution of Portland cement would be a great
improvement to the environment. In these authors’ view-
point, however, other similar materials can be successfully
used in constructions, together with conventional Portland
cement. Instead of think about substitution, probably it is
more adequate to work with the concept of partial
replacement, complementary materials and technological
innovation. Literature reports many aspects of these
materials (Pellegrino et al. 2009; Chaipanich et al. 2007;
Chung 1997). However, this work will describe only a
limited number of options available nowadays.
Cement is so widespread and popular to simply be cir-
cumvented. In this sense, a more realistic and reasonable
approach is to use other materials in conjunction with
cement. Any candidate to partial replacement of commer-
cial cement should fulfill at least some requirements. It
should be inexpensive, available in many parts of world,
minimize or completely avoid emission of carbon dioxide
and other greenhouse gases and particles. Furthermore, this
material should present about the same characteristics of
ordinary cement, as rheological and mechanical properties,
to start with (Sabir et al. 2001; Raupp-Pereira et al. 2008;
Gartner 2004; Kacimi et al. 2006). Even if we had now this
‘‘ideal’’ candidate, it would take probably many years to
use it in large scale. Many tests should be carried out to
assure safety and long-term performance. Regulatory
codes, standard methods and many other issues should be
detailed treated to guarantee its safe use and acceptance
(Hooton 2008; Becchio et al. 2009).
As in many other areas, cement manufacture is contin-
uously looking for new and/or innovative solutions to face
the environmental concerns and economic restrictions as
well. Nowadays, industry and scientific community con-
duct many efforts in order to address these relevant ques-
tions. Here, it will be discussed only two classes of
materials that can be thought as ‘‘candidates’’ for partial
159
replacement of traditional Portland cement: b-Ca2SiO4–
rich cements and calcium sulfoaluminates cements. It
should be pointed out, however, that pozzolanic cements
are also very attractive materials. There are many paper
and reviews dealing with pozzolanic cements (Siddique
and Klaus 2009; Kani and Allahverdi 2009; Velosa and
Cachim 2009; Mertens et al. 2009; Shi and Qian, 2000),
and this subject will not be treated here.
b-Ca2SiO4 presents a great potential to reduce envi-
ronmental impact on cement industry. As pointed out
before, b-Ca2SiO4 consumes less calcium oxide (carbon-
ate) than Ca3SiO5. Energy requirements for the synthesis of
b-Ca2SiO4 are also much lower than Ca3SiO5. Standard
formation enthalpies for b-Ca2SiO4 and Ca3SiO5 are
respectively 1,810 and 1,350 kJ kg-1 (Kurdowski et al.
1997).
An interesting point is that many methods were devel-
oped for the synthesis of b-Ca2SiO4, such as hydrothermal
methods, sol–gel, ultrasonic treatment and also solid-state
chemical reaction. Ishida et al. (1994) developed a
method based on hydrothermal synthesis of hillebrandite
(Ca2(SiO3)(OH)2), an hydrated calcium silicate, having
ratio Ca/Si = 2. Quartz was used as starting material,
together with calcium oxide. Solids were treated at dif-
ferent hydrothermal conditions. For example, hillebrandite
was obtained after treatment of reactants for 10 h and
200°C. After this, thermal decomposition of hillebrandite
was performed at 600°C, forming b-Ca2SiO4.
A different approach is based on the preparation of
b-Ca2SiO4 using renewable materials. Silica (SiO2) is a
basic raw-material for preparation of b-Ca2SiO4. It is usu-
ally obtained from mineral sources. However, many organic
materials have important amounts of silica. Rice hull con-
tains about 10–30% of silica. Silica can be extracted from
rice hull by many methods (Kalapathy et al. 2000; Dahlan
et al. 2006). More interesting is the use of rice hull ash
derived from thermoelectric power plants. Rice hull is
burned to generate electricity giving a silica-rich material.
From this residue, silica can be easily extracted. Under
usual conditions, this material is simply discarded in land-
fills. A complete green cycle could be devised to generate
basic food, electricity and to produce cement to be used
locally. Rodrigues and Monteiro (1999) developed initially
the synthesis of b-Ca2SiO4, from rice hull ash, using
hydrothermal treatment. Chemicals were mixed together in
stoichiometric proportion and treated hydrothermally for
2 h and 150°C. After this, an intermediate silicate with a
ratio Ca/Si & 1.6 plus the excess of calcium hydroxide
were obtained. After drying, solids were heated at 800°C,
giving b-Ca2SiO4. It can be seen that silica derived from
rice hull ash presents a very good reactivity under these
conditions. Latter, the synthetic method was improved;
instead of using hydrothermal method, the solids were
123
160
treated in ultrasonic bath (Rodrigues 2003a, b). Once again,
after drying, a mixture of solids was obtained: the inter-
mediate silicate and calcium hydroxide. The solids were
fired at 800°C, forming b-Ca2SiO4. Ultrasonic treatment
was able to replace hydrothermal processing, making the
method much more suitable in terms of economic per-
spectives. Also since the method is highly versatile, many
modifications can be devised in order to modulate solid final
properties (Romano et al. 2006, 2007). As presented before,
kinetics hydration of b-Ca2SiO4 is slower when compared
to Ca3SiO5. The introduction of ‘‘foreign’’ atoms (doping)
may have influence on the reactivity of b-Ca2SiO4 in rela-
tion to water (Mahfouz et al. 2008). Also an important
aspect is related to chemistry of this solid. To date, very
little information of b-Ca2SiO4 chemistry is available from
scientific viewpoint. Most information is devoted to prop-
erties such as mechanical resistance and durability. How-
ever, there are many examples in material science where the
relation between chemical composition (and crystallogra-
phy) and macro properties is well established leading to
important developments.
Calcium sulfoaluminate cements are mainly composed
by tetracalcium trialuminate sulfate (4CaO3Al2O3SO3),
b-Ca2SiO4 and gypsum (Ca2SO41/2H2O), although other
phases may also be present (Péra and Ambroise 2004).
Most development of calcium sulfoaluminate cements
was conducted by China Building Materials Academy
(CBMA). Calcium sulfoaluminate cements also present
great potential to be used along with commercial cement.
Usually, the temperature needed to produce sulfoaluminate
cements is around 1,350°C. Also the production of calcium
sulfoaluminate cements limits CO2 emissions, even when
compared to b-Ca2SiO4. Table 3 (Glasser and Zhang 2001)
compares amounts of carbon dioxide released by the main
components of commercial Portland cement and tetracal-
cium trialuminate sulfate.
In contrast to Portland cement, the alkalinity of sulfoa-
luminate is very limited, and it can be used for the prep-
aration of composite materials (Živica 2000). Studies on
hydration of this material have been conducted (Janotka
et al. 2003; Luz et al. 2006).
Another important issue is that calcium sulfoaluminate
cements can be prepared using the same rotary kilns used
for Portland cement preparation, which may facilitate its
Table 3 Comparative analysis
Compound CO2 release
of carbon dioxide released by
(kg mol-1)
components of cement
Ca3SiO5 0.58
b-Ca2SiO4 0.51
Ca3Al2O6 0.28
4CaO3Al2O3SO3 0.22
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Environ Chem Lett (2011) 9:151–166
rapid implementation, in the places where raw-materials
are available.
Concrete and the recycling of waste materials
Some aspects about recycling were discussed in conjunc-
tion with Portland cement preparation. Here, we are con-
cerned about the incorporation of solid residues into the
cement matrix, during concrete preparation. All around the
world, many industrial by-products such as plastic bags and
bottles (Ambrose et al. 2002), used tyres (Ferrão et al.
2008), electric and electronic wastes (Zoeteman et al.
2009), just to mention a few, are increasingly a cause of
environmental concern. The disposal of these and other
residues can be very difficult or expensive. From the many
aspects presented so far, it appears that concrete can be an
extraordinary ‘‘storage space’’ for many types of residues.
Unfortunately, the actual situation is far more complex.
In plain concrete, there is an important interface
between large aggregates and hydrated cement matrix,
called interfacial transition zone (ITZ). This solid–solid
interface is about 50 lm thick (Mehta and Monteiro 1993);
nevertheless, it plays an important role in concrete prop-
erties. Figure 6 shows schematically the interfacial zone in
concrete.
Although many other factors are important, it is gener-
ally assumed that the interfacial zone is the weakest link
for this composite (Akçaoğlu et al. 2003; Akçaoğlu et al.
2004; Paulon et al. 2004). As a consequence, the intro-
duction of solids in concrete (for example, waste materials)
will always create new interfaces and probably compro-
mise the mechanical behavior of concrete. In other words,
addition of waste materials will probably damage concrete
Solid-solid interface: transition zone
coarse aggregate
Hydrated cement matrix
Fig. 6 Solid–solid interfaces in plain concrete: representation of
interfacial transition zone
Environ Chem Lett (2011) 9:151–166
properties. It means that thinking of concrete as ‘‘storage
space’’ for residues is tempting, but it is a far too simple
idea to be considered. Durability of concrete structure is a
key aspect in sustainability (Gaspar and Brito, 2008).
Improper design will reduce the lifetime of the structure,
demanding more cement. It may create also a new and
unwanted solid waste: debris, which means, more and more
residues.
There are a large number of studies dealing with the
insertion of solid residues in concrete (Guo et al. 2009;
Frı́as et al. 2009; Nehdi and Sumner 2003). Here, we will
discuss only tyres, plastics in general and debris.
Waste tyres represent a world environmental problem.
European Union countries dispose approximately 600,000
tons of waste tyres yearly (Aiello et al. 2009). In Spain,
80% of waste tyres are placed in dumps and about 40% in
illegal way (Merino et al. 2007). USA generates about
250,000,000 of used car tyres each year (Holst et al. 1998).
Also discarded tyres may healthy problems since they are a
potential place to grow mosquitoes, even in unexpected
places (Harding et al. 2007).
There are many works dealing with the addition of tyres
into cement matrix (Turki et al. 2009; Hernádez-Olivares
et al. 2002; Bignozzi and Sandrolini 2006; Siddique and
Naik 2004). Probably, the major problem is associated with
the reduction in compressive strength (Chou et al. 2007),
although some properties can be enhanced (Turatsinze
et al. 2007). In order to improve compatibility between
rubber and hydrated cement matrix, tyre surface can be
treated with different agents (Colom et al. 2006, 2007). The
main idea is to reinforce the adhesion between matrix and
rubber, an approach largely used in composite technology
(Atsu et al. 2006; Moya et al. 2007; Chandra et al. 2002).
However, unlike other composites, in concrete the costs of
surface treatment may difficult its wide application, at least
in the forthcoming future. On the other hand, perhaps the
use of limited waste tyres could reduce significantly envi-
ronmental problems without damaging concrete properties.
Polymers, in general, and particularly plastics are widely
used in many industrial activities, such as automobiles,
packaging, computers, housing, aerospace, aircrafts, boat-
ing just to name a few (Shah et al. 2008). Perhaps the major
concern about plastics is the long time needed for its nat-
ural degradation. The improvements in biodegradation and
photo oxidation are two technologies commercially used
that tend to minimize this issue (Siddique et al. 2008).
Thermal decomposition of polymers is also an alternative
to produce chemicals (Zassa et al. 2010).
Since there are many classes of polymers and differ-
ences among polymers of the same nature (for instance,
molecular weight, density and branching), there is not a
simple protocol for recycling (Luttropp and Johansson
2010). Perhaps, even more important is the plastic post-
161
consumer history, which may determine many physical and
chemical characteristics (Hoang et al. 2010). Usually,
recycling of plastics can be performed in many ways, such
as chemical, thermal and mechanical processing. Some
polymers as polyethylene (PE), polypropylene, polyethyl-
ene terephthalate (PET) or polystyrene (PS), used in large
amounts, are very hydrophobic and if used ‘‘in nature’’ will
render a solid–solid interface with very low adherence to
the cement matrix (Pingale and Shukla 2008; Burat et al.
2009; Phuong and Villoutreix 2008).
Polymers have lower density than concrete and if used
as aggregate, will show this effect, lower the density of the
composite. Many aspects of the inclusion of a polymer into
a cement matrix were studied (Bayasi and Zeng 1993;
Soroushian et al. 2003; Batayneh et al. 2003). In general, it
can be considered that concrete is not the best available
choice to the disposal of common plastics, although it can
be one more useful option to alleviate this problem.
Although there are many other residues that can be
incorporated into concrete (Shi et al. 2008; Tam and Tam
2006), this topic will be finished considering concrete itself
as a possible waste. Although concrete may be a very
useful matrix to ‘‘accommodate’’ many kinds of waste
materials, it should be considered that concrete will
become a waste material, when we look at long-term per-
spective. The lifetime of a common building may be esti-
mated at 50–100 years (Horvath 2004; Scrivener and
Kirkpatrick 2008). For instance, in China, it was estimated
(Shi and Xu 2006) that debris will reach about 239 million
metric tons in 2010, and in 2020 this number will be close
to 638 million metric tons.
The utilization of construction and demolition debris to
prepare new concrete structures is an excellent alternative
to its disposal to landfill; also, this practice can be eco-
nomically feasible (Limbachiya et al. 2007) and save nat-
ural resources (Poon et al. 2002). Some limitations to the
use of debris are specific gravity, durability and the pres-
ence of contaminants (Robinson et al. 2004).
The use of crushed concrete presents an inherent prob-
lem; since the material must be processed in some way
(crushed, for example), there will be the formation of
macro- and microcracking in the solid. On the other hand,
mechanical resistance may not be affected in a significant
way (Rahal 2007).
Finally, it should be pointed out that in many situations,
natural disasters will also be responsible for the production
of concrete wastes. In 2010, Haiti has suffered a strong
earthquake that almost dismantled the country. It is
impossible to determine the production of waste material
and, of course, human losses. In 2005, Hurricane Katrina
caused the partial or total destruction of 275,000 homes,
causing an estimated $100 billion in damages (Denhart
2010). The demolition or implosion of concrete structures
123
162
and even more dramatic events (Tang et al. 2004; Herdt-
Losavio et al. 2008; Hopke 2009) generates large amounts
of particles that can be spread for great areas and cause
respiratory diseases.
Conclusions
The construction business is a very important segment in
world economy. Its magnitude is somewhat neglected by
scientists, researchers and general public. This industry is a
heavy polluter and an energy-intensive consumer; nowa-
days, there is a great pressure to improve its sustainability.
For example, the production of cement accounts for about
5–6% of carbon dioxide generated by human activities; it
consumes enormous amounts of non-renewable raw-mate-
rials and generates organic and inorganic pollutants into
atmosphere.
Cement is the most important material for constructions.
It is present in every part of the world. There is no reason to
believe that cement can be substituted in the foreseen
future. The continuous growth of world population and the
urbanization in many countries will guarantee the con-
sumption of cement and cement-based materials. Also, in
many countries, the lack of infrastructure requires the
production of cement to improve life standards.
However, in terms of sustainability, cement production
needs to advance its situation. Usually, it seems that there
is little or no space to improve cement manufacture or the
utilization of cement-based materials. However, this
assumption is not adequate. Some issues can be mentioned
to improve sustainability: modernization of factories and
logistics, rationalization on the use of raw-materials,
development of new cementitious components and blended
materials, proper recycling, among others.
It is important to recognize the efforts made by manu-
facturers, researchers and other organizations. However,
there is still a long way to achieve satisfactory goals. Many
other economic activities are in similar position. In some
sense, the challenges for the transformation of such tradi-
tional industry could be used as an example to other eco-
nomic sectors. In order to accomplish all expected results, it
is important the continuous investment in research and
innovation.
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