Fuel 184 (2016) 481489

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Fuel
journal homepage: www.elsevier.com/locate/fuel

Review article

Influence of alternative fuels on trace element content of ordinary

portland cement
Coleman Horsley a, Marion H. Emmert b, Aaron Sakulich a,
a
Department of Civil and Environmental Engineering, Worcester Polytechnic Institute, 100 Institute Road, Worcester, MA 01609, United States
b
Department of Chemistry and Biochemistry, Worcester Polytechnic Institute, 100 Institute Road, Worcester, MA 01609, United States

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

Article history: Over the last 20 years, interest in diverting waste from landfills and recovering energy from waste mate-
Received 14 April 2016 rials has grown significantly. The cement industry in particular has adapted its production methods to
Received in revised form 1 July 2016 accommodate a wide variety of waste materials as alternative fuels in order to lower both cost and envi-
Accepted 12 July 2016
ronmental footprint. The incineration of waste products at existing cement plants is generally cheaper
Available online 18 July 2016
than building a new, dedicated incinerator as cement kilns generally meet the requirements for inciner-
ating hazardous wastes. In addition to negative perception, particularly where potentially hazardous
Keywords:
waste materials are concerned, there are a number of technical challenges in the use of alternative fuels
Alternative fuels
Waste incineration
at cement plants. This paper focuses on the incorporation of trace elements in ordinary portland cement
Trace elements through the use of alternative fuels, including the behavior of trace elements in the manufacturing pro-
Clinker chemistry cess and their effects on final products. A brief overview of the use of waste tires, solidified sewage
sludge, and meat and bone meal as alternative fuels is presented along with a discussion of challenges
and opportunities facing the field.
2016 Elsevier Ltd. All rights reserved.

Contents

1. Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 482
2. Origins of trace elements in OPC. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 482
2.1. OPC production processes. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 482
2.2. Fuel consumption in OPC plants . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 482
2.3. Types of fuel . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 483
2.4. Benefits and challenges of alternative fuel usage . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 483
2.5. Alternative fuels . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 484
2.6. Waste tires. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 484
2.7. Sewage sludge . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 484
2.8. Meat and Bone Meal (MBM). . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 485
2.9. Trace elements originating in raw materials . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 485
2.10. Trace elements originating in supplementary cementitious materials . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 485
3. Effects of trace elements in OPC products . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 486
3.1. General mechanisms of trace metal incorporation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 486
3.2. Transition metals. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 486
3.3. Main group elements . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 486
4. Discussion . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 487
5. Conclusions. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 487
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 488

Abbreviations: OPC, ordinary portland cement; C-S-H, calcium silicate hydrate; MBM, Meat and Bone Meal; BSE, bovine spongiform encephalopathy; SCM, supplementary
cementitious material.
Corresponding author.
E-mail addresses: cmhorsley@wpi.edu (C. Horsley), mhemmert@wpi.edu (M.H. Emmert), arsakulich@wpi.edu (A. Sakulich).

http://dx.doi.org/10.1016/j.fuel.2016.07.038
0016-2361/ 2016 Elsevier Ltd. All rights reserved.
482 C. Horsley et al. / Fuel 184 (2016) 481489
1. Introduction
Concrete is the most widely manufactured material in the
world, with more than one cubic meter produced annually for
every person on earth [1]. Globally, it is being produced at a rate
that has never been seen before: Between 2011 and 2013, China
alone placed more concrete than the United States produced dur-
ing the entire 20th century. A typical concrete contains roughly
70 vol.% aggregate embedded in a cementing phase of hydrated
ordinary portland cement (OPC), which, in turn, is primarily com-
posed of tri- and dicalcium silicate phases (known as alite and
belite, respectively) [2]. When exposed to water, calcium silicates
form calcium hydroxide and calcium silicate hydrate (C-S-H) gel,
a cohesive phase that is the source of compressive strength in con-
crete [3]. Minor phases rich in aluminum and/or iron (AFm, AFt,
etc.) are typically present due to impurities in the raw materials
that play important roles as fluxes during the pyroprocessing step
of OPC production, but contribute little to the mechanical proper-
ties of the final product [4].
OPC-based concrete is likely to be the dominant building mate-
rial for the foreseeable future, as previous attempts to develop
alternatives have been largely unsuccessful. For example, calcium
aluminate cements are generally less economically viable and have
a controversial history, having been banned in many building
codes after a series of early failures. These binders can also
decrease in strength under potential exposure conditions as meta-
stable reaction products begin to degrade [5]. Calcium sulfoalumi-
nate cements consume less energy and release less greenhouse gas
during manufacture than OPC, but are economically less attractive
and can undergo substantial reduction of volume during curing
[5,6]. Slag-based supersulfated cements have almost disappeared
as changes in ore refining began producing slags that are
chemically inappropriate as raw materials; furthermore, alkali-
activated slags in general suffer from logistical difficulties includ-
ing handling and the highly localized distribution of raw materials
[7,8]. Despite the fact that geopolymers, based on the alkali-
activation of fly ash or metakaolin, are the focus of significant aca-
demic research interest and have been implemented in some niche
applications, the variability of fly ash composition and uncertainty
regarding environmental impacts are significant hurdles to broader
acceptance [9]. Finally, established building codes and various legal
precedents in effect discourage the implementation of non-OPC
based building materials [10].
Due to the energy-intensive processes used to produce OPC
and legal restrictions on waste disposal in municipal incinerators,
interest in burning alternative fuels at cement plants has
increased tremendously over the last two decades [11]. These
alternative fuels are generally waste products from industrial or
agricultural applications whose incineration reduces both the
burden placed on landfills and the operating costs of a cement
plant, however, the use of such fuels can also impart trace ele-
ments on OPC. Trace elements in the form of alkali metal com-
pounds can interfere with cement plant processes or make the
final product vulnerable to deleterious processes; the presence
of phosphates and sulfates can significantly reduce the quality
of the final product; and transition metals or main group ele-
ments may leach into soils or water, eventually entering the food
chain to the possible detriment of biological organisms. This
paper reviews the pathways by which trace elements can enter
OPC through alternative fuels (with specific detail regarding
waste tires, sewage sludge, and meat and bone meal) as well as
rawmix or supplementary cementitious materials; the effects
of trace elements on the properties of OPC; and likely future
trends regarding the use of waste materials as fuel in cement
production.
2. Origins of trace elements in OPC
2.1. OPC production processes
The production of OPC is a three step process: Raw materials,
primarily limestone and clay, are acquired and ground to produce
rawmix; the rawmix is then pyroprocessed in a rotary kiln at tem-
peratures approaching 1480 C (2700 F) to form clinker; and the
clinker is finally interground with various additives and/or supple-
mentary cementitious materials (SCMs) to form OPC. Modern
cement production facilities can be configured in a number of
ways, and a variety of ancillary equipment may or may not be used
depending on the age, size, and purpose of the plant. For example,
multiple cyclone preheaters are used to recover waste heat from
the kiln exhaust and to prepare the rawmix for pyroprocessing;
precalciners (which consume additional fuel) can be used to fur-
ther prepare rawmix and improve the output of the kiln; and a
wide variety of supplemental materials can be incorporated during
the final intergrinding step. Each configuration choice has the
potential to influence the trace element content of the final pro-
duct (Fig. 1).
2.2. Fuel consumption in OPC plants
Although OPC has a low embodied energy when compared to
other infrastructure materials, the cement industry produces
roughly 5% of anthropogenic CO2, partially due to chemical
reactions occurring within the kiln and partially due to the
consumption of fuel to run the kiln. Some 30006500 MJ
(2.846.16 million BTU) of energy is consumed per ton of clinker
produced, accounting for roughly 35% of total production costs
and roughly 10% of the worlds industrial energy consumption
[1215]. Although the tremendous amount of energy consumed
by the cement industry is often cited as a motivation for the devel-
opment of alternative binder materials, it should be noted that
over the last two decades the energy efficiency of cement kilns
has been significantly improved, even during a time of rapid
market growth The average thermal energy consumption of the
companies reporting to a program of the World Business Council
for Sustainable Development decreased from 4260 MJ per ton
(3.67 million BTU per ton) of clinker in 19903580 MJ per ton
(3.07 million BTU per ton) in 2010, a 16% decrease [13].
Possible feed points for supplying fuel depends on the exact
configuration of a OPC production facility, and may include [16]:
1. The main burner at the outlet end of the kiln.
2. Mid-kiln valves or feed chutes (in long kilns only).
3. A feed chute at the inlet end of the rotary kiln.
4. Secondary burners at the riser duct, located between the rotary
kiln inlet and the precalciner or preheater system.
5. Precalciner burners.
6. Feed chutes within the precalciner or preheater systems.
The first two feed points supply energy directly to the kiln,
although in the case of mid-kiln access points the kiln must be
operated in a way that ensures temperatures and residence times
are high enough for the complete combustion of the fuel. Feed
points three to six supply energy, along with heated air from the
kiln, to the precalciner or preheater. In modern production facili-
ties equipped with both precalciner and preheater systems,
roughly 60% of the fuel energy is consumed by the precalciner
while only 40% is consumed in the main kiln burner [17]. Although
technically possible, the burning of alternative fuels to generate
power to run ancillary equipment is not considered here, as it
 C. Horsley et al. / Fuel 184 (2016) 481489
Fig. 1. The cement production process, from the quarrying of raw materials to packaging and distribution of final products. Pathways for high-boiling point trace elements,
which travel through the process along with the rawmix, and low-boiling point or volatile trace elements, which enter the exhaust gases in the kiln, are shown in solid and
dotted lines respectively.
represents a distinct process unlikely to add trace elements to final
products.
2.3. Types of fuel
Coal accounts for 67% of energy consumed in cement plants
worldwide; coke refined from either coal or petroleum accounts
for 14% of energy consumption. Liquid wastes account for only
8% of energy consumed, while other energy sources (miscellaneous
solid wastes, 4%; tires, 3%; natural gas, 3%; and fuel oil, balance)
account for only a small fraction of overall energy consumption
[18]. Alternative fuels made from a blend of sources, such as Refuse
Derived Fuel (RDF) are also available, but even less widely
employed [19].
In total, less than 15% of the energy consumed in cement plants
worldwide comes from alternative fuels, although this number
approaches 60% in some countries, such as Germany. Higher adop-
tion generally occurs in countries with more restrictive environ-
mental standards and emission reduction targets, higher energy
costs, or both [20,21]. Between 2000 and 2010, average alternative
fuel consumption in the 27 nations of the present European Union
quadrupled to roughly 20% [22]. Alternative fuels employed in OPC
production are generally classified as hazardous or non-hazardous
and further subdivided into six main categories [23]:
1. Gaseous wastes, which exist but are impractical and rarely used
in cement kilns.
2. Liquid wastes such as waste solvents, oils, and emulsions.
483
3. Lump fuels, such as whole tires, printer toner cartridges, or filter
cakes.
4. Sludges such as paint waste, petrochemicals, and sewage
sludges, which can be pumped through pipes but are otherwise
treated as lump fuels.
5. Coarse solids, defined as three-dimensional particles with a
diameter smaller than 50.8 mm (2 in.) or two-dimensional par-
ticles with a length of less than 203.2 mm (8 in.), including
waste materials such as tire chips, rice husks, and plastic fluff
(i.e. shredded postconsumer plastic waste).
6. Fine solids, defined as three-dimensional particles with a diam-
eter less than 5.08 mm (0.2 in.) or two-dimensional particles
with a length less 5.80 mm (2 in.), including meat and bone
meal, dried and ground sewage sludge, and post-consumer
carpet.
Liquids and fine solids are fed into burners using compressed
air, while coarse solids and lump fuels are generally added at feed
chutes. The precalciner system can accommodate the widest vari-
ety of fuels, being fed by both burners and feed chutes, whereas the
main kiln is fed only by a single burner at the outlet end (or,
uncommonly, a mid-kiln feed chute) [23].
2.4. Benefits and challenges of alternative fuel usage
The use of waste products as alternative fuels at cement plants
has many merits. First, it is generally cheaper to adapt a cement
kiln to waste incineration than it is to build a new, dedicated
484 C. Horsley et al. / Fuel 184 (2016) 481489
incinerator; cement kilns also generally meet the requirements of
applicable laws that specify the methods allowed for incinerating
hazardous wastes. Further advantages of using alternative fuels
include the lowering of the carbon footprint of a cement plant, a
reduction in CO2 emissions, lower production costs, and environ-
mental advantages associated with reducing the amount of wastes
that are landfilled, while providing a safe disposal option for
organic or biologically hazardous wastes.
There are also a number of challenges, including limited avail-
ability, high entry costs, potential process issues depending on
the type of fuels used, quality concerns associated with the poten-
tial heterogeneity of alternative fuels, higher transportation
demands to deliver the same caloric value of fuel to the plant,
and societal perceptions. A training document used by Holcim, a
major cement producer, states that the use of waste as alternative
fuel is perceived by the general public to contribute to environ-
mental pollution [23]. Further concerns revolve around the legality
of waste incineration and the potential abuse of the process to dis-
card unsuitable wastes. These concerns can only be addressed by
engagement with stakeholders and educating the public regarding
the safety and legality of the alternative fuel use. A technical chal-
lenge revolves around how to establish infrastructure that is neces-
sary for the efficient use of alternative fuels. In addition to what is
available in a typical OPC plant setting, receiving stations, fire sup-
pression equipment, raw material inspection and pre-processing
facilities, storage systems, transport systems to the feed points,
and additional testing mechanisms (e.g. of exhaust composition)
may be needed. Possibly the most significant challenge is associ-
ated with the lower energy content of alternative fuels, which
leads to production of significantly more ash during its incinera-
tion. These ashes require disposal, and may enter the kiln along
with exhaust gases and impart trace elements to the final product.
2.5. Alternative fuels
There are hundreds, if not thousands, of individual alternative
fuels that can be employed at a cement plant [24]. Tire waste is
by far the most broadly produced and employed fuel, while sewage
sludge and meat and bone meal are also produced on large scales
in all global markets [25]. The following sections provide more
details on these particular alternative fuels, the regions of their
use, and unique characteristics. The influence of alternative waste
trace metal content on the manufacture of OPC (e.g. why phos-
phates reduce alite content) are described in detail in Section 3.
2.6. Waste tires
The U.S., Japan, and the European Union dispose of over
5 million tonnes (5.5 million tons) of tires every year. Roughly
13% of American tires are consigned to landfills, where they pose
significant hazards. Due to their relatively low density, they often
migrate to the top layer of a landfill, where they collect standing
water and breed insects. Furthermore, occasional spontaneous tire
fires are extremely difficult to extinguish and contaminate the
environment with smoke and pyrolitic oils. Dozens of major tire
fires have occurred on U.S. soil since the massive 1983 blaze in
Winchester, Virginia, which consumed some seven million land-
filled tires over the course of six months and required nearly
22 years for site remediation [26,27]. Due to such uncontrollable,
toxic conflagrations and the relatively high estimated energy con-
tent (
31.4 MJ/kg or 13,500 BTU/lb) of waste tires, the disposal of
tires as fuel in cement kilns is potentially highly beneficial [28,29].
In addition to burning whole tires as lump fuel or shredding tires to
produce a coarse solid fuel, tires can be pyrolized in a high temper-
ature vacuum process that yields oil, char, and gas [3032]. Ko
et al. estimated that the production and use of tire-derived oil in
place of coal could lead to a 1927% return on investment
[33,34]. In addition to reduced fuel costs, the incineration of tires
requires relatively little adaptation cost and produces few solid
wastes, assuming the ashes are incorporated into the final product.
However, tire wastes as fuel also lead to increased emission of
organic volatiles [3537]. Furthermore, Acternbosch et al. reported
that used tires are the most common sources of antimony, cad-
mium, chromium, cobalt, lead, titanium, and zinc contaminations
in clinker, while Hita et al. reported zinc emissions of 2400 g/h
(5.3 lbs/h) when tires were burned as lump fuel. This value was
significantly higher than the 15 g/h (0.03 lbs/h) emissions that
have been documented for conventional fuels [35,38].
The post-combustion ashes of tires or tire-derived fuels are most
often used as an SCM. Trezza and Scian produced ashes by burning
Argentinian waste tires, in which large quantities of calcium, zinc,
and silicon oxides (47 wt.%, 33.1 wt.%, and 14.1 wt.%, respectively)
were measured. Relatively high heavy metals contents, ranging
from 2 mg/kg thallium to 185 mg/kg lead, as well as intermediary
amounts of chromium (94 mg/kg), nickel (92 mg/kg), and cadmium
(6 mg/kg) were reported. The ashes were mixed with a conven-
tional rawmix at levels of up to 30 wt.% and pyroprocessed to pro-
duce clinker. The resulting samples hydrated more quickly than
control samples and displayed relatively little drop in early age
properties, although decreases in compressive strength of up to
10% were observed at 28 days. Characterization of the OPC sug-
gested, but did not quantitatively prove, that strength reductions
were due to diminished alite content [39].
2.7. Sewage sludge
Sewage sludge is a byproduct of wastewater treatment and its
disposal has become more tightly restricted over the past 25 years.
This is due to concerns over landfill space and the accumulation of
heavy metals or pathogenic organisms in soils [40]. Husillos
Rodrguez et al. found the energy content of sewage sludge to be
8.2 MJ/kg (3.5 thousand BTU/lb), which is somewhat higher than
the energy content determined by Ruiz Garcia (6.2 MJ/kg or
2687 BTU/lb) [41]. Incineration in a cement kiln occurs at temper-
atures that are high enough for the destruction of potentially
pathogenic organisms and hazardous organic compounds and is
thus a suitable processing option for such materials.
In the United States, the use and disposal of sewage sludge was
governed by the Clean Water Act of 1972 until authority was trans-
ferred to the National Pollutant Discharge Elimination System per-
mit program in 1993. In particular, applications of sewage sludge
as fertilizer, in landfills, or for incineration are thus regulated.
Approximately one quarter of the 6.5 million tonnes (7.1 million
tons) of dried sewage sludge produced annually is incinerated,
though this occurs not only in cement plants [25]. In Europe, dis-
posal at sea was banned in 1998 and mandatory landfill reduction
targets were set in 1999 [42]. Overall, the 27 nations of the Euro-
pean Union produce an estimated 11.25 million tonnes (12.4 mil-
lion tons) of dried sludge per year, of which nearly half is used in
agricultural applications. In China, more than 2.9 million tonnes
(3.2 million tons) of dried sewage sludge are produced annually.
Most of this material is used in agricultural applications or land-
filled, while only 3% is incinerated [43]. A 2008 report by the UN
Human Settlements Programme notes that developed countries,
with more well-established water infrastructure, produce much
more sewage sludge than developing countries. Thus, the amount
of disposable material is expected to increase continuously over
time [44].
Raw sewage sludge is composed primarily of water and organic
matter in the form of fine-grained solid suspensions or colloids. To
be used as a fuel source, sewage sludge must first be dried
Husillos Rodrguez et al. reported the composition of sewage
 C. Horsley et al. / Fuel 184 (2016) 481489
sludge sampled from a Spanish wastewater treatment plant and
dried using a proprietary process to be primarily organic com-
pounds and trace elements ranging from concentrations of 6 ppm
cadmium to 1270 ppm chromium. Zinc, vanadium, cobalt, and
other metals were also observed in varying concentrations [41].
As another example, sewage sludge is received with a moisture
content of about 70% at the Vassiliko Cement Works in Southern
Cyprus. 22,000 m3 (28,774 yd3) of this material were processed
there in 2003 by mixing with petroleum coke, drying using kiln
exhaust, and burning at a replacement rate of 7.5%. Overall, it
was estimated that economic savings amounted to 7 (then
$9.40) per hour.
In addition to being used as a fuel source, sewage sludge ashes
can be used at various other stages of the OPC production process
as documented by Lynn et al.: as an alternative raw material, as a
lightweight aggregate, and as an SCM. However, several drawbacks
were noted: Strength was reduced in all samples containing sew-
age sludge ashes, either due to phosphates entering the clinker
(discussed in detail below) or due to the mechanical weakness of
ash particles used as aggregate. Furthermore, ashes contained
highly variable metal contents (up to 68,454 52,037 mg/kg Fe)
that could potentially influence the reactivity of the clinker. These
issues might be mitigated by careful screening of raw material
composition and potential phosphorous extraction treatments,
thus, the more widespread use of sewage sludge ashes in OPC
was considered to be a valuable alternative to traditional OPC pro-
duction methods and a suitable pathway for sewage sludge dis-
posal [42].
2.8. Meat and Bone Meal (MBM)
The outbreak of bovine spongiform encephalopathy (BSE),
which causes fatal neurodegenerative diseases in mammals, has
made the regulation of animal byproducts a priority for many
countries, particularly in Europe. High risk animal products (brains
and other organs, or the carcasses of infected animals) must be
burned to prevent outbreaks of infection. Low risk products, gener-
ally abattoir waste in the form of meat scraps and bones, are inter-
ground and processed to produce tallow, which is extracted for
other uses, and a waste product called Meat and Bone Meal
(MBM) [45]. MBM is rich in hydrocarbons due to the meat portion
of the raw materials; the bone portions provide calcium, phos-
phates, and a variety of trace metals [46].
Prior to the BSE crisis, most European MBM was used as animal
feed. Since 2002 animal wastes have been separated into three dif-
ferent risk groups; today, only MBM produced from Category 3
wastes (i.e. those derived from healthy animals slaughtered for
human consumption) can be used as an animal feed. MBM is sterile
and is most often either burned as a fuel (its energy content lies
between 13 and 30 MJ/kg) or landfilled [47]. Upon incineration
above 800 C, all potentially harmful species are destroyed
[46,48]. Although Ariyaratne et al. found that up to 40% of the total
fuel for a cement kiln could be replaced with MBM without signif-
icant negative effect on the clinker, the high chloride content of
MBM limits the amount that is used and has led to the construction
of dedicated incinerators, particularly in the United Kingdom. Gen-
erally speaking, no more than 15% of the energy needed by the kiln
is sourced from MBM [17]. This limit also reduces the likelihood
that MBM will contaminate the clinker with phosphates that affect
performance.
More than 3.5 million tonnes (3.8 million tons) of MCM are pro-
duced annually in the European Union, with France, Britain, Spain,
and Germany accounting for 25%, 15%, 12%, and 11% of production,
respectively [45]. Over 382,500 tonnes (421,634 tons) and
205,000 tonnes (225,973 tons) of MBM are coincinerated in French
and British cement plants each year, respectively. In addition to the
485
destruction of the waste, an advantage of burning MBM is the
resulting reduction in CO2 and NOx emissions from the plant
[25]. Ash production, however, is significantly increased: It is esti-
mated that between 317,500 and 907,000 tonnes (350,000 and
1 million tons) are produced annually in Europe alone [48]. Due
to the low aluminosilicate content of MBM ash, it does not display
pozzolanic behavior and is thus a poor SCM. A brief feasibility
study by Collins noted that fine MBM ash was a practical filler
material for concretes, but not generally reactive [49]. Cyr and Lud-
mann, however, found that MBM bottom ash (the heavier, coarser
ash that settles to the bottom of the incineration chamber) had
similar physical and mechanical characteristics as sand; the ashs
greater absorption of water, however, necessitated the use of
superplasticizer and an aggregate replacement limit of 30% [50].
No leaching of heavy metals was observed when the concrete
was exposed to aqueous environments.
2.9. Trace elements originating in raw materials
Limestone, clay, and other components of the rawmix contain
naturally-occurring trace elements. In some plants, waste materi-
als (particularly those containing lime, alumina, and silica) are
used as substitutes for natural raw materials. Trace elements with
relatively high melting points such as chromium, beryllium, and
arsenic proceed through the pyroprocessing and intergrinding
steps along with the rest of the raw materials to enter the final
product. More volatile trace metals such as mercury, selenium,
and thallium boil and enter the kiln exhaust, which condenses
downstream and may become mixed with cement kiln dust, a
general term for all materials collected and removed from the
cement production process [51]. The partitioning of volatile trace
metals between the final product and the exhaust gases depends
on the kiln processing temperature, the fineness to which the
raw materials are ground, the residence time of the raw materials
in the kiln, the effectiveness of dust removal systems, and the
potential use of kiln bypass systems. Cement kiln dust can either
be disposed of as waste or returned to the raw material feed, fur-
ther influencing the trace element content of OPC [51].
2.10. Trace elements originating in supplementary cementitious
materials
SCMs are incorporated during OPC production to alter the
physicochemical properties of the final product or to reduce unit
cost and environmental impact. These materials are generally
industrial waste materials rich in silicon, calcium, and/or alu-
minum oxides that display cementitious or pozzolanic properties.
Pozzolans are not cementitious on their own, but will react with
water and alkalis such as the calcium hydroxide in OPC to produce
secondary C-S-H. In addition to the economic benefits of consum-
ing waste materials, the most important benefit of their pozzolanic
reaction is that it can lead to a more refined pore structure, which
reduces the diffusion of corrosive media and improves service life.
Depending on the plant configuration and their nature, supple-
mental cementitious materials may be pyroprocessed along with
the rawmix or added during the final intergrinding step.
Each SCM is capable of imparting trace metals on the final
cementitious product. Fly ash and blast furnace slag are the two
most frequently used SCMs, with roughly 500 million tonnes
(454 million tons) of fly ash and 300 million tonnes (272 million
tons) of blast furnace slag produced annually worldwide [52,53].
The exact concentration of trace elements in fly ash can vary
depending on the type and origin of the coal as well as the burning
conditions [5456], leading to a wide variety of trace elements that
have been detected [5763]. This is illustrated by a recent investi-
gation of six Chinese fly ashes by Tang et al. who determined the
486 C. Horsley et al. / Fuel 184 (2016) 481489

Table 1 ples when salts of these elements had been incorporated in the
Trace metal concentrations in waste materials from six municipal boilers (mg/kg). clinker by co-pyroprocessing along with the raw materials. Chro-
Values for both fly ash (collected by electrostatic precipitation) and bottom ash
(collected from the furnace interior) were reported. Data reproduced from [64].
mium and nickel, on the other hand, were better immobilized
when added to OPC as a solution with mix water. It was proposed
Boiler # 1 2 3 4 5 6 that chromium that had been co-pyroprocessed formed highly
Fly ash mobile hexavalent chromium during hydration reactions; whereas
Arsenic 2.44 3.14 4.7 7 5.6 6.2 chromium that had entered the cement dissolved in mixing water
Boron 76.9 92.8 87 64 53.4 59.9
Cadmium 0.36 0.5 0.74 1.95 2 2.12
was in the trivalent form [70]. An earlier study by Serclrat et al.
Cobalt 37.9 42.6 40.6 60.4 44.4 50.8 concluded that trivalent chromium was strongly absorbed by AFt
Chromium 85.7 88.7 76.6 92 76.2 94 phases [71]. Sinyoung et al., however, reported that clinkers pyro-
Copper 105 146.5 122 107 124 186 processed in the presence of chromium oxide contained minerals
Manganese 50 54.2 63.6 88.2 94.6 106.8
with a variety of chromium oxidation states [72]. Alite content
Nickle 44.4 58.4 53.8 66.6 50.5 57.4
Lead 35.3 49.6 50.5 62 63 113 (and thus reactivity and early age strength) was reduced; further,
Tin 4.82 8.55 2.4 5.8 5.7 11.2 in tests following both U.S. and E.U. standards, leaching of chro-
Titanium 8245 7890 8850 7690 8290 8340 mium far exceeded regulatory limits. The authors concluded that
Vanadium 243 266 288 221 245 249 waste relatively rich in chromium should not be incinerated at
Zinc 47 52.4 43 62.8 75.3 75
cement plants.
Bottom ash Yang et al. compared clinkers produced from raw materials con-
Arsenic 1.1 2 2.02 1.7 2.7 1.37
taminated with nickel and cadmium, finding that nickel is primar-
Boron 41.4 53 46.5 38.4 36.6 29.2
Cadmium 0.3 0.29 0.71 0.6 0.65 0.83 ily incorporated as a contaminant in periclase (MgO) [73]. Other
Cobalt 32.9 33.2 29.1 34 35.8 31.5 authors have determined that the incorporation of nickel in precip-
Chromium 75.3 73 62 60.8 62 64.6 itated minerals has little effect on clinker properties [74]. The
Copper 75.6 59.9 85.4 95.3 93.9 88.2
experiments of Yang et al. showed that cadmium was more diffi-
Manganese 60.9 101 130 268 165 151.4
Nickle 41.4 28.2 34.9 39.3 41 42.3 cult to immobilize than nickel; substitution for calcium in calcium
Lead 15.3 16.8 17.2 23.5 22.2 22.5 oxide seemed to be the main immobilization mechanism. Other
Tin 3.88 3.51 2.4 3.92 2.92 2.93 observed mechanisms for cadmium immobilization included the
Titanium 8930 9170 9230 9600 9860 9380 formation of an interstitial solid solution, in which either cadmium
Vanadium 209 120 165 185 192 194
or nickel entered the ferrite phase; the replacement of calcium or
Zinc 15.23 18.6 17.5 34.9 30.2 16.3
iron in the ferrite phase; and cadmium replacing calcium in alite.
Wang et al. reported that the latter mechanism reduced the reac-
presence of 13 potentially toxic elements in widely varying quan- tivity of the alite and belite phases, resulting in a reduced average
tities (Table 1) [64]. These elements were also detected by Yu et al. chain length of C-S-H, retarded hydration, and thus lower strength
in three Japanese fly ashes, along with selenium [65]. The trace ele- [75].
ment content of slag varies depending on the production process Copper becomes concentrated primarily in the ferrite and alite
and the ores used [66,67]. phases or in copper-rich phases containing calcium oxide. Further-
more, copper encourages the decomposition of alite into belite and
3. Effects of trace elements in OPC products calcium hydroxide, thus leading to lower reactivity, and inhibits
the reaction of tricalcium aluminate with sulfur to create minor
3.1. General mechanisms of trace metal incorporation phases during hydration [38].
Zinc salts are particularly well known for retarding cement
In general, trace metals will enter clinker in one of several hydration; however, the exact mechanisms causing this behavior
forms: (1) in solid solution with the various calcium silicate and are not unambiguously established. As summarized by Gineys
calcium aluminate phases; (2) as substitutional atoms that may et al. there is significant disagreement in the literature as to
distort the crystal structure of those phases, as when cobalt whether zinc can be found primarily in silicates, the ferrite phase,
replaces aluminum in AFm; (3) physically adsorbed on the surface or a zinc-contaminated calcium aluminate phase [74,76]. Actern-
of various phases as insoluble hydroxides, sulfates, or carbonates; bosch et al. further report that existing data suggest zinc may be
and (4) or as precipitated minerals intermixed with the final prod- immobilized in the C-S-H, AFm, or AFt phases, may replace calcium
ucts, as when molybdenum forms powellite (CaMoO4) at relatively in the AFt phase, adsorb onto C-S-H as a hydroxide or carbonate, or
high molybdenum concentrations [38]. These multiple immobi- may precipitate as zinc oxide, calcium zincate, or hemimorphite
lization mechanisms make incorporation in cement a viable [38].
method for the long-term mitigation of industrial, medical, or Finally, Mllauer et al. reported that vanadium can substitute
nuclear wastes rich in heavy metals. for aluminum in the AFt phase or form calcium vanadate, while
The presence of metals in the kiln can be advantageous, as they Acternbosch et al. report phases that are enriched in various ele-
can produce intermediary phases that then react with silicon and ments after hydration, including mercury-enriched C-S-H and
oxygen to form calcium silicates, effectively reducing the necessary AFt, and cobalt-enriched AFm [38,77]. However, the exact mecha-
clinkering temperature and improving output. However, during nisms of enrichment and the behavior of these metals in clinker are
hydration, metals present in concentrations above
1 wt.%, can unclear.
form salts that precipitate on unreacted cement grains [68]. Highly
insoluble salts significantly retard cement hydration; less insoluble 3.3. Main group elements
salts result in a less significant retardation; and highly soluble salts
may act as accelerators [69]. Relatively little is known about the exact behavior of other ele-
ments in cementitious systems. Tin has been reported to preferen-
3.2. Transition metals tially contaminate the alite phase, leading to associated lowered
alite reactivity [78]. Moreover, the reaction of tin with calcium
Zhang et al. found that arsenic, cadmium, and zinc were less hydroxide has also been reported, resulting in calcium stannate
likely to leach into the environment from solidified cement sam- during hydration [22]. Rodella et al. proposed the immobilization
 C. Horsley et al. / Fuel 184 (2016) 481489 487

of arsenic due to absorption on the surface of silica particles 4. Discussion

[38,79]. Vollpracht and Brameshuber suggested that antimony is
incorporated in clinker as a calcium antimonate, which is either
incorporated in C-S-H as a hydroxide or enters solid solution with
the ferrite phase after hydration [80]. Mllauer et al. reported that
barium and strontium precipitate from the pore solution as sul-
fates [77]. (Pore solution contains the remnants of mix water along
with various dissolved species, which occupy the internal porosity
generated as part of the hydration of calcium silicates.) Nothing
appears to be known about the chemistry of thallium or selenium
incorporation in cementitious materials, other than that their rela-
tively low and high boiling points, respectively, may encourage or
discourage their entry into the exhaust gases [38].
Alkali metal salts can have a variety of effects, some of which
depend on the nature of the anion. Alkali chlorides, for example,
are more volatile than alkali sulfates and are thus more likely to
evaporate in the kiln and recondense elsewhere in the form of en-
crustations that interfere with plant operation. Chlorides are
rarely incorporated in clinker during pyroprocessing due to their
high volatility; potassium and sodium salts, including alkali metal
sulfates, however, enter the clinker primarily in solid solution with
belite and/or aluminate phases and migrate to the pore solution
after hydration [81]. While alkali metal compounds may increase
the alkalinity of a hydrating cement, accelerating hydration reac-
tions, a more likely concern is that they will eventually participate
in deleterious processes such as the alkali-silicate reaction and
cause premature failure of the cementitious system [82,83]. For
this reason many specifications place strict limits on the content
of alkali metal compounds.
On the macroscale, the incorporation of phosphates has many of
the same effects on clinker as the incorporation of sulfates. Nastac
et al. found that high levels of phosphorus interfere with the for-
mation of alite, but encourages the formation of belite. Below a
phosphorous oxide composition of 0.16 wt.%, a significant increase
in the quantity of calcium oxide in the final product at the expense
of alite was also observed, which did not occur at higher concentra-
tions of phosphorous oxides [84]. Usn et al. further reported that
phosphorous oxide leads to instability in the ferrite phase [85]. Sta-
nek and Sulovsky proposed that these effects are due to phospho-
rous oxide reacting with calcium oxide to produce calcium
phosphates, preventing the reaction of calcium oxide with belite
to produce alite. At concentrations of 0.7 wt.% P2O5 content, dimin-
ished alite content was observed. At 4.5 wt.% P2O5 content, alite
formation was completely suppressed even after clinkering for
4 h at 1450 C (2650 F) [86]. De Noirfontaine et al. concluded that
the reduction of alite was due to phosphorous stabilizing the a0 H
orthorhombic polymorph of belite [87].
An exhaustive study of the trace metal contents of commer-
cially available OPC was carried out by Construction Technology
Laboratories, Inc., in 1992 [88]. This study was primarily concerned
with the possibility of toxic trace metals leaching out of concrete
into groundwater, and did not investigate their origins (raw mate-
rials, SCMs, alternative fuels, etc.). The study did not comment on
the presence of other trace elements, such as phosphates, sulfates,
or alkali metal compounds, and investigated specimens from 89
production facilities, representing over 70% of the cement plants
operating in the U.S. and Canada at the time. Atomic absorption
spectroscopy was used to measure the concentrations of 12 trace
metals, which varied from a threshold of 0.001 mg/kg of mercury
to a high level of 25 mg/kg of chromium (Table 2). The report also
analyzed the cement kiln dusts affiliated with each facility, which
varied from a low of 0.04 mg/kg mercury content to a high of
776 mg/kg thallium. Statistical analyses were complicated by the
fact that not all trace elements were detected in all samples, for
instance, measurable levels of antimony were observed in only
two cements and nine kiln dusts. The report concluded that, gener-
ally speaking, clinker is enriched with trace elements exhibiting
high boiling points, while volatile trace elements are concentrated
in cement kiln dust. As described above, cement kiln dust may or
may not be reused in cement production (Fig. 1).
This study, the most recent major effort of its kind, concluded
that total metal concentrations were not reliable predictors of
the likelihood that metals would leach from a cementitious system
into the environment. A great deal of literature is available regard-
ing the leaching of potentially toxic heavy metals from cementi-
tious binders (e.g. [38,51,77,8992]), and a full review is beyond
the scope of the present paper. However, the general trend
described in the literature is clear: the numerous mechanisms by
which metal contaminants can be immobilized in properly propor-
tioned cementitious systems, as described above, are effective at
preventing the leaching of potentially toxic species into any but
the most extreme environments. Future challenges regarding the
use of alternative fuels in cement plants are therefore more likely
to focus on technical aspects of cement production, rather than
potential threats to public health.
5. Conclusions
Barring a sudden and radical change in the world population,
the production of both cementitious and waste materials will con-
tinue to grow for the foreseeable future. As economic pressure,

Table 2
Trace metal concentrations in cementitious materials (mg/kg). The report provides minimum, average, and maximum concentrations and the number of samples (out of 97) in
which the metal was observed, but no estimate of error. Non-detectable values are excluded; NM indicates that an average is not meaningful due to the large number of non-
detectable values. Data reproduced from [88].

Ordinary portland cement Cement kiln dust

Min. Avg. Max. n (out of 97) Min. Avg. Max. n (out of 97)
Mercury <0.001 0.014 0.039 21 0.004 0.66 25.5 68
Selenium 0.62 NM 2.23 6 2.68 28.14 307 54
Thallium 0.01 1.08 2.68 32 1.4 43.24 776 89
Cadmium 0.03 0.34 1.12 42 0.1 10.3 59.6 81
Lead 1 12 75 82 34 434 7390 95
Antimony 0.7 NM 4 2 0.3 NM 3.4 9
Silver 6.75 9.2 19.9 93 4.8 10.53 40.7 92
Arsenic 5 19 71 54 2 18 159 50
Nickel 10 31 129 85 1 22 60 65
Barium 91 280 1402 94 35 172 767 95
Beryllium 0.32 1.13 3.05 93 0.13 0.65 3.54 94
Chromium 25 76 422 94 8 41 293 95
488 C. Horsley et al. / Fuel 184 (2016) 481489
environmental concerns, and regulatory frameworks continue to
grow, it is all but certain that interest in incinerating waste mate-
rials in the cement industry will remain high. Doing so can be ben-
eficial for all parties involved, as the waste is rendered safe in
accordance with applicable laws and energy costs at the produc-
tion facility are reduced. Although cement production is, in terms
of volume, the largest single industry on earth, the technical con-
siderations limiting the amount of alternative fuels consumed at
cement plants and the mass quantities of waste available for
coincineration make it likely that the use of alternative fuels will
become much more widespread, but the cement industry will
never be able to accommodate all potential wastes.
Significant future research is needed. A better scientific under-
standing of the behavior of trace elements in cementitious systems
at the molecular level is needed, as the current understanding is
incomplete. More detailed studies regarding the potential for the
leaching of harmful elements from cementitious systems should
build on this better scientific understanding, and will require con-
tinuous updating as the more widespread use of alternative fuels
leads to a wider variety of trace elements entering cementitious
systems at higher concentrations. With a clearer understanding
of trace metal sources, incorporation, and leaching mechanisms,
the development of improved guidelines for the use of alternative
fuels can be envisioned.
Presuming that such improved guidelines accommodate higher
rates of alternative fuel use without compromising the quality of
the final product, the much more significant amount of ash pro-
duced from alternative fuels would seem to be the most pressing
challenge, and will likely require input stakeholders outside of
the cement sector. Due to the inability of the cement industry to
accommodate all wastes, these stakeholders from other industries
will also be critical in developing other technologies to recover
value from waste materials diverted from disposal sites.
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