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Resources, Conservation and Recycling 55 (2011) 819835

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Resources, Conservation and Recycling


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Review

Arsenic hazards in coal y ash and its fate in Indian scenario


Vimal Chandra Pandey a, , Jay Shankar Singh a , Rana P. Singh a , Nandita Singh b , M. Yunus a
a
b

Department of Environmental Science, Babasaheb Bhimrao Ambedkar (Central) University, Raibarelly Road, Lucknow 226025, Uttar Pradesh, India
Eco-Auditing Group, National Botanical Research Institute, Council of Scientic and Industrial Research, Rana Pratap Marg, Lucknow 226001, Uttar Pradesh, India

a r t i c l e

i n f o

Article history:
Received 1 June 2010
Received in revised form 4 April 2011
Accepted 8 April 2011
Keywords:
Arsenic hazards
Coal
Environmental problems
Fly ash pollution

a b s t r a c t
Fly ash (FA) generated as a waste produced from thermal power plants globally has started gaining as
a potentially signicant anthropogenic source of arsenic (As). In India electricity generation is predominantly dependent upon coal-based thermal power plants and are being producing huge amount of FA.
Coal contains many toxic metals, arsenic is one of those, which is signicantly toxic for aquatic and terrestrial life including human being. Coal used in Indian thermal power plants is mainly bituminous and
sub-bituminous and which on combustion generate over 40% of FA. Generated FA is being disposed to
open ash pond in thin slurry form. More than 65,000 acre of land in India is occupied for storage of this
massively generated quantity of FA. Dumping of FA in open ash pond causes serious adverse environmental impacts owing to its elevated trace element contents, in particular the As which causes ecological
problems. Although, the As problem in our country is not new, in recent years the occurrence of As contamination cases of agricultural soil, ground water as well as human health has resulted a great concern
for its mitigation. Very recently India has been charged for being a dumping hub for As. Utilization of FA
in India is still infancy (more than 38%) as compared to developed countries (more than 70%). In India FA
is used particularly in cement production, brick industry, as road base, as amendments in the restoration
ecology and forestry. This review emphasized on the concentration of As in FA, its fate and behaviour as
hazardous element on human health, environment quality and on mitigation strategies to accomplish
environmental management.
2011 Elsevier B.V. All rights reserved.

Contents
1.
2.

3.

4.

5.
6.
7.
8.
9.

Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
Indian coal . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
2.1.
Arsenic forms in coal . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
2.2.
Arsenic existing forms during coal combustion . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
Fly ash . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
3.1.
Arsenic status in y ash . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
3.2.
Residence mode of arsenic in y ash . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
3.3.
Fate of arsenic in y ash . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
3.4.
Arsenic-leaching from y ash . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
Arsenic poisoning of biosphere due to y ash disposal . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
4.1.
Atmosphere and arsenic-poisoning . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
4.2.
Agricultural soil and arsenic-poisoning . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
4.3.
Water and arsenic-poisoning . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
Analytical points . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
History and chemistry of arsenic . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
Sources of arsenic contamination . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
Arsenic toxicity due to y ash . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
Arsenic in rice agriculture . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .

Corresponding author. Tel.: +91 522 2995605; fax: +91 522 2441888; mobile: +91 9454287575.
E-mail address: vimalcpandey@gmail.com (V.C. Pandey).
0921-3449/$ see front matter 2011 Elsevier B.V. All rights reserved.
doi:10.1016/j.resconrec.2011.04.005

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Future prospective and recommendations . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .


Discussion and conclusions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
Acknowledgments . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
References. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .

1. Introduction
India ranks 6th in the world as largest energy consumer,
accounting for 3.4% of the global energy consumption. The government of India has set an ambitious target to add approximately
78,000 MW installed generation by 2012. The total demand for
electricity in India is expected to cross 950,000 MW by 2030
(http://www.livemint.com/2009). India has the 4th largest reserves
of coal and the worlds 3rd largest coal excavator in India with 292
million tonnes (Mt) in 1998, after United States (951 Mt) and China
(1243 Mt) (OECD/IEA, 1999). In India the electricity generation is
mainly dependent upon the coal-based thermal power plants and
will continue in the coming several decades due to its huge reserves.
FA generation in India was 112 Mt in 200506 and it is expected to
hike between 150 and 170 Mt per year by the end of 2012 (MoEF,
2007). In our country, most of the thermal power plants have been
situated in the vicinity of coal reserve area. Major coal elds of India
are situated in the eastern region (Bihar and West Bengal) which
are densely populated. The three major thermal power plants of
eastern India are Kolaghat, Durgapur and Bandel and consume bituminous coal (Gondwana coal) which contains low sulfur but high
ash content. The combustion of such coal in these power plants
results in generation of huge amounts of ash, which is disposed-off
in large ash ponds (dykes). The ash, after being dumped in these
open dykes is left to get dried up. These FA-ne solid particles of
ash, dust, and soot containing arsenic and other toxic elements.
It becomes a deadly source of health hazards when carried into
the atmosphere and reached to the domestic area. Therefore, the
heavy metal pollution from these FA deposited dykes can affect
the surrounding population, on prolonged exposure. Thus special
attention is to be needed to manage these toxic As emitted from FA.
The Singrauli region in the south-eastern part of Uttar Pradesh,
India is one of the highly polluted industrial areas of the Asia continent. This region has six thermal power plants (Uttar Pradesh State
Electricity Board (UPSEB), Vindhyachal, Singrauli, Rihand, Anpara
and Renusagar), situated in the transition zone of Madhya Pradesh
and Uttar Pradesh states of India. Therefore, Singrauli region has
been recognized as Energy Capital of our country. This Energy
capital generates about 10% of Indias installed generation capacity 7500 MW electricity approximately. A huge human population
have been shifted from their native homes from this region during
the establishment of these thermal power plants. Due to working
of these power plants, some environmental problems such as contamination of the surface water, groundwater, man-made Rihand
water reservoir is rife in this region. Besides these the soil, vegetation and air are also contains higher level of toxic heavy metals
than the permissible limits. Consequently, urgent corrective measures are required in this region to save the domestic population
from arsenic contamination due to FA.
Presently the power plants situated in the Singrauli
area accounts 10% of India and 0.3% of the global carbon dioxide emission, a major cause of global warming
(www.pollutedplaces.org/region/south asia/india/singrauli.shtm).
These thermal power plants are responsible for the main source of
pollution in this region, emitting 6 Mt of FA per year, making land
unt for cultivation due to toxic trace elements such as As, Hg, Pb,
Se, and Cd.
According to the reports in Indian news-papers, FA poses major
health hazard for people living in Delhi (the capital city of India).

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Driving down the Capitals Ring Road during summer is a nightmare. Strong westerly winds pick up FA from the Indraprastha
power station, and disperse it over a large area. Residents of the
surrounding areas and commuters are the worst hit. Within four
years of its commissioning in 1982, the Indraprasatha power plant
is today perceived by people living in Delhi as a serious health
hazard (http://sundaytimes.lk/060813/ft/2.1.html).
Recently, the problems of toxicity and occurrence of As have
drawn much attention in Indian scenario. The issue of release of
As from FA has risen from several thermal power plants and produces air, soil and water pollution. The heavy metal As exists in
the 3, 0, +3 and +5 oxidation states (Smedley et al., 2002). Due
to the existence of different oxidation speciation the arsenic may
be found in many different chemical states and forms. Therefore,
the health effects of As may vary widely depending on the chemical
form of the As. The burning of coal and smelting of metals are major
sources of As in the air. The most sensitive ecological indicator of
environmental pollution of arsenic, via air, was a mass eradication
of honeybee families, rst described as Tisins disease by Svoboda
in 1936, which occurred in the vicinity of agglomeration furnace
facilities. Similar situations also have found in the vicinity of different smelters and power plants that burn coal with a high As content
(Bencko, 1987). This may emphasize environmental problem by As
leaching in to soils and groundwater and re-entrance of As in to
atmosphere from y ashes dumped near the plant area. A number
of information has been available on the environmental problems
related to FA. However, this review paper will reveal As hazards in
coal FA, its fate in India scenario and future strategies to achieve
environmental concerns and sound management issues.
2. Indian coal
Coal is the principal source of commercial energy in India. It
is combustible sedimentary rock which consists organic and inorganic materials and its formation and composition depends on the
earth crust composition, climate and ora of its location (Clark and
Sloss, 1992; Finkelman, 2004; Walker, 1993). Coal quality depends
upon its rank and grade. Ascending order of coal rank on the basis
of carbon contents is lignite sub-bituminous coal bituminous
coal anthracite. Indian coal is largely of sub-bituminous rank,
followed by bituminous and lignite. Ash content in Indian coal
ranges from 35% to 50% (Bhattacharjee and Kandpal, 2002;
http://www.hvfacprojectindia.com/Summary Report.pdf). Occurrence of adventitious mineral impurities in these coals has been
found to be high in comparison to most of the foreign coals. Properties of coal from different regions vary widely. India is the third
largest coal producing country in the world after China and USA.
Some of the important coal elds in the country from which bulk
of the coal production comes are mentioned in Table 1. Indian
coal, albeit has high ash, bears many positive traits in respect of
environmental perspectives such as low sulfur content, refractory
nature of ash, low chlorine content, low toxic trace elements, high
ash fusion temperature and low iron content in ash. Arsenic has a
strong afnity to concentrate in sulde minerals and its association
with pyrite (FeS2 ) in some coals is well-documented (Yudovich and
Ketris, 2005a,b). Average As content at world level for bituminous
and lignite coals are, respectively, 9.0 and 7.4 ppm and maximum As
contents for the former and later coals are 50 and 49 ppm, respectively (Yudovich and Ketris, 2005a,b). In contrary, As content in

V.C. Pandey et al. / Resources, Conservation and Recycling 55 (2011) 819835


Table 1
Coal producing states with major coal elds in India (Banarjee, 1999).
States

Percentage share

Major coal elds

Madhya Pradesh

31.5

Bihar

26

Orissa
Andhra Pradesh
West Bengal
Maharashtra

9.6
10.2
7.7
8.3

Korba,
Mand-Raigarh,
Hasdeos-Arrand
Jharia, East and
West Bokaro, North
Karanpura
Talcher, Ib valley
Godavari Valley
Raniganj
Wardha Valley,
Kamptee

Table 2
Arsenic concentration in coal and its derivative substances (Tripodi and
Cheremissinof, 1980; Baba, 2000).
Element (ppm)

Whole
coal

Coal ash
(525 C)

Bottom
ash

Worldwide y
ash average

As

55

320

0.02168

2.31,700

Indian bituminous coal is 22.362.5 ppm. For bituminous coal FA,


the As concentration ranges from 1 to 1000 mg kg1 (EPRI, 1987).
Arsenic element in coal and its derivative substances are given in
Table 2.
2.1. Arsenic forms in coal
There are three dominant forms of As that are found in coal.
These are suldes, organic and arsenate forms but one of all forms
the most common form of occurrence in coal is suldes. Some other
forms are also possibly occur such as in clay arsenopyrite. The work
of Bayet and Slosse (1919) has been considered that pyrite is a
main carrier of As, while arsenopyrite is another probable minor
host. Arsenic enrichment is generally related to sulde mineralization, either syngenetic or epigenetic. The As-bearing suldes
are epigenetic where as syngenetic pyrites are generally very poor
in As (Yudovich and Ketris, 2005). Usually it has been considered
that As exists in coal with inorganic afnity because As is concentrated in heavy density fractions enriched in pyrite or clay. But
some researchers (Minchev and Eskenazy, 1972; Kryukova et al.,
1985; Goodarzi, 1987) proved that As is also present in organic
form in coal. Belkin et al. (1997a,b) reported arsenopyrite and Asrich pyrite in the coals. Later study showed that As is partly present
as an arsenate (Ren et al., 1999). A complex procedure (selective
leaching, SEM, X-ray and microprobe analyses) showed that 85% of
the gross As is associated with pyrite but some part is in the arsenate form as a result of an As-bearing pyrite oxidation (Finkelman
et al., 1999). From the bright, low-ash and low-sulfur coals of the
Central Appalachian (USA) Elkhorn and hazard seams, As is leached
by HCl (30%) and by HNO3 (25%). The second is accounted for as
As-bearing pyrite, but the rst may be arsenate resulting from
oxidation of pyrite containing As, was in the range from 100 to
2700 ppm (Crowley et al., 1997). The rst case of As poisoning in
the Inner Mongolia, Autonomous Region of PR China, occurred in
1990. Guizhou, China is the only known arsenicosis endemic area
caused by As contaminated coal. In eastern India coal combustion
is one of the major sources of anthropogenic As emission in the
biosphere.
There are many analytical methods that can be employed to
quantify the various As forms in coals (Abernathy et al., 2001;
Huggins et al., 2002; Dai et al., 2004; Goodarzi and Huggins,
2005; Yudovich and Ketris, 2005a,b; Zielinski et al., 2007). Arsenic
may exist in more than 200 species of minerals and its general
occurrence form is arsenopyrite (Abernathy et al., 2001). The As

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association with pyrite (FeS2 ) in few coals has been well demonstrated (Finkelman, 1993; Finkelman et al., 1999; Zielinski et al.,
2007). Zhang et al. (2002) studied the occurrence of As in major
minerals that were specially selected and found As high in calcite
and pyrite. Belkin et al. (1997a,b) examined wide forms of As in coal
samples. High As coals for their amount, distribution and forms of
As (Ding et al., 2001; Dai et al., 2005, 2006; Yang et al., 2006) showed
that As was positively correlated with the ash content and indicates
high sulde afnity.
2.2. Arsenic existing forms during coal combustion
The information related to As release during coal combustion
are very rare. The various known forms of As, released during coal
combustion usually depends on the combustion temperature. In
addition, upon coal combustion, a large amount of As elements
leave the coal matrix and is distributed between the vapor and
particulate phases in different proportions, depending on factors
such as the initial concentration in the parent coal, the design
and operating conditions of the combustion facility and the particulate control devices. In general, As is more concentrated in
particles as well as also present in volatile form. The concentration of As species in the ue gas depends on a large extent on
temperature and chemical interactions with FA have been shown
to be responsible for partial As retention in particulate phases
(Wouterlood and Bowling, 1979a,b). The elemental (As) and oxide
forms (As2 O3 ) are considered the most probable As species in the
oxidizing ue gas environment of a coal combustion process. However As is much more volatile as As2 O3 than as the elemental
As and researchers have concluded that As could only be present
in the ue gas in the form of an oxide (Dismukes, 1994; Winter
et al., 1994). In coal gasication, the most probable species is As4
with traces of arsine (AsH3 ) (Clark and Sloss, 1992; Helble et al.,
1996). On the basis of thermodynamic modeling, As partitioning
in combustion wastes at temperature lower than 925 C, up to
6.6% As must go into the slag. Arsenic escapes to the gas phase
in the form of AsO and As2 O3 during low-temperature combustion (10001200 C) but at high temperature (12001600 C), only
the As2 O3 species is released (Shpirt et al., 1990). Arsenic yield in
gaseous phase from the high-temperature zone of a furnace is controlled by the furnace construction and slag removal coefcient
(Ks ) where Ks is a ratio: slag yield/gross ash content. Eary et al.
(1990) shows that As concentrations in the combustion residues
vary widely depending on the coal quality, pH of ashes and the
ignition conditions, ranging from 2 to 240 ppm in the FA and from
0.02 to 168 ppm in bottom ash. Flue gas temperature at the collection point is also a main factor. According to Bool and Helble
(1995), equilibrium thermodynamic modeling shows that suldic
As should evaporate, presumably as As and in the temperature
range 1226.851726.85 C as As2 O3 . Condensed As species in FA
should be theoretically controlled by the chemical composition of
the FA: in acid (high-Si) FA as Fe3 [AsO4 ]2 and in alkali (high-Ca) FA
as Ca3 [AsO4 ]2 . However in realty, Fe-arsenate does not occur due to
kinetic limitations, because Fe goes into the silicate glass. Arsenic
is condensed on the silicate sphere surface as As2 O3 . Actually, it is
only physical-sorption, as indicated by strong positive linear relation between As concentration in FA and 1/d value (d is median
diameter of the FA fraction).
Zevenhoven et al. (2007) reported that combustion of fossil
fuels gives rise to As emissions into the atmosphere with the levels of 0.180 mg kg1 (dry) in coal and biomass fuels. A signicant
amount of As will end up in y ashes, but the fate of As depends on
temperature, condensationvaporization processes, the presence
of calcium, gaseous sulfur and chlorine compounds in ue gases.
Fortunately, equipment installed at power plants for the control of
emissions of FA and sulfur oxides (SOx ) effectively remove most of

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V.C. Pandey et al. / Resources, Conservation and Recycling 55 (2011) 819835

Fig. 1. A schematic diagram for y ash formation during coal combustion. [Modied from Seames (2003)].

the As from ue gases as well, devices specially designed to control the emissions of trace elements (Zevenhoven and Kilpinen,
2001). One aspect related to As oxides in ue gases is that it is
a proven poison for catalysts used in catalytic reduction equipment for nitrogen oxides (NOx ) (Mukherjee, 1994; Kema, 1997).
Especially when ring coals with low Ca/As ratio, this may cause
rapid catalyst deactivation. Zevenhoven et al. (2007) showed that at
two Finnish coal-red power plants, both feeding around 60 t h1
pulverized bituminous Polish coal indicated that 94 mass% of the
received As was captured in electrostatic precipitator (ESP) FA, 6%
in the semi-dry ue gas desulfurization (FGD) unit. Arsenic concentrations in bottom ashes and the ue gases were both below
1%. With a concentration of around 5 mg kg1 in the coal, the As
input to the plant is around 300 g h1 , of which around 1.5 g h1
(i.e. around 0.5%) is emitted into the atmosphere. Arsenic concentrations in the bottom ashes and ESP ashes and FGD residues
were around 5 and 30 mg kg1 , respectively (Aunela-Tapola et al.,
1998). FA analysis from the ring of coal shows that As is enriched
in the nest fractions, which may pass particulate emission control devices (Martinez-Tarazona and Spears, 1996). For example,
considering 63462 mg kg1 in <2.5 mm particulate matter (PM)
against 45206 mg kg1 in >2.5 mm PM (for several US coals), a
detailed X-ray absorption ne structure analysis showed that the As
resides in the ashes almost completely as As2 O5 (Shoji et al., 2002).
Sterling and Helble (2003) and Seames and Wendt (2000) reported
that As has a strong afnity for Ca, with the result that As is mainly
found in Ca-rich y ashes as Ca3 (As O4 )2 and Ca2 As2 O7 , presumably
after being absorbed from the gas phase as As2 O3 , followed by oxidation of As3+ to As5+ . During coal combustion, the partitioning of
As between the vapor and solid phases is determined by the interaction of As vapors with FA compounds under post-combustion. It
has been suggested that any calcium present in FA can react with
As vapor and capture the metal in water-insoluble forms of the less
hazardous As (V) oxidation state (Sterling and Helble, 2003).
Several researches on the retention of trace compounds from
ue gases produced by coal combustion and gasication using solid
sorbents has been published (Ghosh-Dastidav et al., 1996; Mahuli
et al., 1997). These sorbents have been mostly used in two ways:
(i) by passing the ue gases through a xed or uidized bed of sorbent and (ii) by direct injection of the sorbent as a powder (Gullett
and Ragnunathan, 1994; Ghosh-Dastidav et al., 1996; Mahuli
et al., 1997). Several solid materials, such as clay minerals, y
ashes, metal oxide mixtures and specially hydrated lime [Ca(OH)2 ]
have been tested as sorbents for retaining As and other metal

compounds in gases from coal combustion and gasication (Gullett


and Ragnunathan, 1994; Ho et al., 1996; Biswas and Wu, 1998). In
most of these studies, chemical-sorption is considered to be one
of the probable retention mechanisms. Due to the occurrence of
multiple trace elements in ue gases, recent efforts of the research
community have been directed towards developing a multifunctional sorbent capable of reducing the emission of most of the
pollutants to acceptable limits. In this direction, Lopez-Anton et al.
(2007) reported that activated carbons are able to capture As and
other element present in coal combustion and gasication ue
gases to a certain extent. Although the ash content of the activated
carbon may inuence the amount of As and other element captured, no correlation between retention and the porous texture of
the sorbents was found.
The mechanisms of trace element partition between the vapor
and particle phases during coal combustion are not well understood, but a hypothetical schematic transformation pathway of FA
formation during coal combustion is presented in Fig. 1. Partitioning of trace elements to ne particles is a very crucial phenomenon
because the concentration of many trace elements is signicantly
higher in ne particles compared to bigger particles (Seames, 2003).
So many reports have demonstrated that the distribution of As in
the atmospheric suspended particles (Senior et al., 2000; Seames
and Wendt, 2000), but measurable description about As release is
lacking during coal combustion. Combustion of two kinds of high
As coal with and without CaO additive was studied by Zhao et al.
(2008) in a bench scale drop tube furnace to understand the partition and emission of As in the process. They concluded the calcium
based sorbent is an effective additive to control As emission during
coal combustion. Further, the behaviour of As during coal burning
will be dominated by its occurrence mode, and most As will be
volatilized in high temperature, being condensed and enriched on
the surface of the particulate matter and nally released into the
atmosphere as As oxide vapor or as As particles.
3. Fly ash
The FA is a part of coal combustion residues (CCRs). CCRs include
FA, bottom ash, boiler slag, ue gas desulfurization (FGD) residue
and other solid ne particles which possess major environmental problems. Currently from all coal-based thermal power plants,
dry FA has been collected through Electro Static Precipitator (ESP)
in dry condition as well as pond ash from ash ponds in semi-wet
condition. Most of the Indian thermal power plants do not have

V.C. Pandey et al. / Resources, Conservation and Recycling 55 (2011) 819835

the facility for automatic dry ash collection system. Generally both
FA and bottom ash together are discharged as slurry form to the
ash pond/lagoon. Keeping in view of the alarming future problems
due to this massive quantity of FA to achieve environmental sound
management, it is very crucial time for condence building on FA
utilization and increase in suitability of FA based products among
the end users.
During the burning of coal, minerals undergo thermal decomposition, fusion, disintegration and agglomeration. Several elements
present in a volatile form may be vaporized. A portion of noncombustible (ash-forming) elements in the boiler enter into slag or
bottom ash and the rest of the inorganic residue present in the ue
gas as FA, left after the complete combustion of coal, containing
however also small amounts of carbon and condensed carbonaceous compounds. One of the most prominent features of FA is
the gradation effects of particle size on elemental concentration.
A number of researchers (Davison et al., 1974a,b; Klein et al., 1975;
Kaakinen et al., 1975) have observed that As, Cd, Cu, Ca, Mo, Pb, S, Sb,
Se, Ti and Zn tend to increase in concentration with decreasing FA
particle size. The mechanism of such dependence is not known with
certainty. During the combustion of pulverized coal, the melting
and agglomeration of the mineral inclusions results in break up and
making of a number of usually spherical FA particles. A considerable
portion of inorganic compounds vaporizes in the cooler parts of the
installation and condenses on FA particles during the combustion
of coal particles at high temperature. It has been hypothesized as a
result of volatilizationcondensation theory which correlated mineral concentration with the particle size (Davison et al., 1974a,b),
recognized three groups of elements: Group I elements are categorized as litho les (Al, Ca, Fe, K, Mg, Na, Ti) showing little or
no enrichment in smaller FA particles, group II elements as Chalco
les (As, Cd, Mu, Pb, Sb, Se) show increased concentration with
decreasing particle size and group III elements (Be, Cu, Ni, V, Co)
have intermediate behaviour in being enriched in smaller particles
but to a lesser extent than those of group II. These elements are pref at the particle surface
erentially enriched in a thin layer (1000 A)
(Linton et al., 1975) and are readily extractable (540%) in water.
The variation in concentration of elements depends on particle size,
combustion conditions and physical and chemical properties of the
coal.
3.1. Arsenic status in y ash
FA, a coal combustion by-product of coal based thermal power
plants, contains As at various levels (Kim and Cardone, 1997; Kim
and Kazonich, 2001). The large volume of FA produced around the
world is a potentially signicant anthropogenic source of As hazards. Arsenic in FA is present in signicant amounts in the silicate
matrix (Hulett et al., 1980; Senior et al., 2000). FA minerals in general include notably high As are pyrite (FeS2 ) and inorganic suldes.
Arsenic concentrations in FA generally range from 2 to 440 mg kg1 ,
but depending on the concentration in the original coals and the
combustion methods, however, they can be as high as 1000 mg kg1
(Eary et al., 1990). An investigation of the trace elements from the
UK revealed that coal FA contained moderately elevated concentrations of As (Wadge et al., 1986). The disposal of coal FA to land
in the UK results in an annual input of about 700 tonnes of arsenic
(Hutton and Symon, 1986). Estimates of the total quantities of toxic
As contained in the y ashes produced at the power plants can be
calculated from the total quantity of FA produced and the elemental
composition of the FA. Arsenic 9000 and 3400 kg year1 produced
in the y ashes of the Mauban and Masinloc coal red power plants
of the Philippines. These gures are only approximate as they are
based upon the composition of only one sample of FA and on ash
production data given in the Environmental Impact Statement (EIS)
reports for these two power plants. These data, however, give an

823

Table 3
Attenuation factors of arsenic in leachate of y ash calculated from laboratory test
(Wadge and Hutton, 1987).
Fly ash

Arsenic

Concentration of y ash
(a) Concentration tolerated in leachatea
(b) Concentration in rst bed volume
(c) Attenuation required to conform to guidelines (b/a)

148 (g g1 )
50 (g l1 )
541 (g l1 )
11

Drinking water guidelines from WHO (1984).

Table 4
Arsenic speciation data in water-soluble extracts of y ash samples (Wadge and
Hutton, 1987).
Arsenic

Fly asha (g g1 dry weight)

As (III)
As (V)
Total concentration
Water-soluble fraction (%)

ND
1.7 1.3
136 75.7
1.4 0.7

a
Arithmetic means and standard deviations of two sub-samples from 3 power
plants, ND: not detectable.

indication of the large quantities of As element produced in one


of the waste-streams as a result of coal burning at the Mauban
and Masinloc plants (Brigden and Santillo, 2002). Fulekar and Dave
(1985) studied on coal-red power plant of Delhi and found that
FA contains a signicant amount of As which is potentially toxic
if present in a soluble form. The average As content of FA was
0.9 g t1 of ash and a maximum of 18.8% of average metal content were leachable into double distilled water in a period of ve
days.
Arsenic and other trace elements in FA are important concern
for land disposal due to their environmental signicance. Elevated
concentrations of soluble salts and potentially toxic trace elements,
including As, are reported to be present in FA, as well (USEPA,
1980). The adsorption rate of As increases in the presence of Fe
and Al oxides (Jacobs et al., 1970). Consequently, arsenate ions are
expected to be strongly adsorbed on these oxide surfaces of FA
and/or soil. But the nal impact of each trace element will depend
upon its state in FA and mobility, toxicity and availability in the biosphere. What is essential for As element is a better understanding
of the factors which determine the environmental mobility and, in
particular, the potential for ground water contamination and tendency for bioavailability. In this view, much emphasis has been
placed on measuring the chemical species of trace elements in environmental samples, as these characteristics is considered to play a
major role in determining the behaviour of the element (Florence,
1986). Less attention has been paid to the direct measurement of
As leaching behaviour at landll disposal FA sites.
A laboratory leaching tests has been used to predict the potential mobility and the attenuation characteristics of As when these y
ashes are land lled (Wadge and Hutton, 1987). Due to the absence
of any ground water leachate standards, guidelines for drinking water can be used to investigate the dilution of the leachate
required to produce water of appropriate quality for every trace
element. Table 3 shows attenuation factors of As in leachate of FA
which was calculated from laboratory test by Wadge and Hutton
(1987). Table 4 shows speciation data for As in water-soluble
extracts of FA samples. The arsenic concentration in different
wastes is mentioned in Table 5.
Few approaches are used for contents and residence sites
of arsenic in FA. These are thermodynamic modeling (Senior
et al., 2000a,b,c,d), lab experiments modeling different combustion
regimes (Huggins et al., 2003) and direct analysis of y ashes and
their size fractions (Shpirt et al., 1998; Font et al., 2003). A scheme
was devised by Kizilstein (2002) for determining As precipitation
on the surface of FA particles. Generally two types of spherical

824

V.C. Pandey et al. / Resources, Conservation and Recycling 55 (2011) 819835

Table 5
Arsenic concentration in different wastes (source: Wright et al., 1998; Killingley et al., 2000; Mitrra et al., 2005).
Element

BA

SS

FYM

PFS

Acidic FA

Alkali FA

As (mg kg1 )

8.1

98

6.3

5.64

6.85

7.425.0

56.089.0

FA: y ash, BA: bed ash, SS: scrubber sludge, G: gypsum, FYM: farm yard manure, PFS: paper factory sludge.
Table 6
Detailed arsenic in y ash in ve zones of India during 199798 (source of data:
Mohan et al., 2001).
Zones

Fly ash produced


(million tonnes)

Estimated arsenic in y
ash (tonnes) [In this
study]

Northern
Southern
Western
Eastern
North-East
Total

19.080
18.370
28.547
11.943
00.037
77.980

7.63
8.08
12.50
5.25
0.016
34.41

Zones: Northern: Jambu and Kashmir, Himachal Pradesh, Haryana, Rajasthan, Delhi,
Uttar Pradesh; Southern: Andhra Pradesh, Karnataka, Tamil Nadu, Kerala; Western:
Gujarat, Maharashtra, Madhya Pradesh, Goa; Eastern: Bihar, West Bengal, Orissa;
North-East: Meghalaya, Manipur, Sikkim, Mizoram.

particles (average diameter near 0.17 mm) are found in FA such as


hollow (density about 0.600.65 g cm3 ) and compact with a higher
density. It was proved by Kizilstein (2002) that As concentration
in hollow spheres must be higher due to their lower density than
compact spheres, though the surface condensation lm has equal
thickness on each particle (near 24 m).
In this review, based on the other data the mean As in Indian
coal can be calculated as 42.4 g g1 . Whereas the mean values of
As in Indian FA is about 46.85 g g1 (Sharma and Tripathi, 2008).
Generally As content in FA is variable and depends on the many
other factors.
The relative enrichment (RE) factor in this study may be calculated by the following equation as given by Meij et al. (2002) may
be expressed as:
REAs =

[AS]FA
ash content of coal %

100
[AS]coal

and it was found that RE = 0.44 [As in coal = 42.4 g g1 (mean


value), As in FA = 46.85 g g1 (mean value), ash content of
coal = 40 wt%].
The estimated total amount of As in y ashes in India is presented in Table 6. Based on the model data calculation indicates
that projected FA generation will be 154 Mt in 2012 in India
(Bhattacharjee and Kandpal, 2002). Whereas, according to our predicted estimates As in coal FA in the Indian scenario will be about
67.76 tonnes in 2012.
3.2. Residence mode of arsenic in y ash
There are scare of studies on the mode of As-occurrence in
FA. The form of As residence in FA is inuenced by the composition of the parent coal and the conditions during coal combustion,
particularly during cooling. Arsenic is initially volatilized at the
temperature of coal combustion, but will partition between the
vapor phase and FA particles in the cooler portions of the ue gas
stream. Compared to other trace elements in FA, As shows particularly strong enrichment (510 times) on the nest (<10-m
diameter) size fractions of highest surface area (Natusch et al.,
1974; Smith, 1980).
The concentration of As and other trace elements in FA are
related to the S content of the coal. Generally, those feed coals
with a high S content contain higher concentrations of these elements. For the same coal-red power plants, the concentrations
of these elements are also greater for bag-house FA compared to

Electrostatic Precipitator (ESP). The S-content of FA is 0.1% for pulverized ESP FA and 7% for bag-house FA from the uidized bed,
indicating that most of the S is captured by FA in the uidized bed.
Arsenic is captured by calcium-bearing minerals and hematite,
and forms a stable complex of calcium or a transition metal of iron
hydroxy arsenate hydrate [(M2+ )2 Fe3 (AsO4 )3 (OH)4 10H2 O] in FA.
Maximum elements in FA have enrichment indices of greater than
0.7 indicating that they are more enriched in the FA than in the feed
coal, except for Hg in all ESP ashes. The bag-house FA from the uidized bed has highest content of other trace elements, indicating
that CaO, for the most part, captures them (Goodarzi, 2006). Some
phases contain structural As (arsenopyrite, crystalline) As(III) oxide
(As2 O3 ), calcium orthoarsenate, scorodite (FeAsO4 .2H2 O), substituted As [arsenian pyrite, arsenian jarosite, arsenian eltrignite], and
sorbed As(V) or As(III) ettringite, several ferric oxyhydroxide polymorphs, amorphous silica, aluminosilicate clays, and manganese
hydroxides (Zielinski et al., 2007).
The widespread occurrence of the As forces researchers to nd
its sources which may negatively impact poison the environment.
Coal is one of these sources. Perhaps, the rst quantication of As
in coal was made by Daubree (1851). He determined As in two
samples of French bituminous coals (169 and 415 ppm); in three lignite samples (37, 793, and 2090 ppm) from the German Saar basin
coal (30 ppm); and traces in British Newcastle coal (Daubree, 1851).
After this work, analyses of coal and its products for As were published more frequently. For example, As was found in coke, up to
110 ppm (Simmersbach, 1917). Especially signicant were the rst
studies on cattle diseases in England and Belgium. In these studies,
the vegetation in the vicinity of coal-red plants was As enriched.
An important conclusion was made that pyrite was the main carrier
of As in coal (Bayet and Slosse, 1919).

3.3. Fate of arsenic in y ash


There is scarcely report on As hazards in coal FA and its fate
in Indian scenario. According to thermodynamic modeling, the
main factor of the As yield to gas phase is temperature. At the
time of low-temperature ignition, As forms solid phases such as
oxides and elemental As. Maximum arsenic passes into gaseous
phase in the forms of As2 , As3 and AsS at the temperature above
than 600 C (BelKova et al., 2000). Arsenic and few of its compounds are volatile and therefore, escape in general to the gas and
aerosol phase in coal combustion. Leaching studies of 18 elements
have been made from Indian coal FA by Praharaj et al. (2002). He
found that a few trace elements leach from the ashes in excess
of world health organizations (WHO) limit values (As, Mn and
Mo) or the USEPA limit values (As, Mn and Fe). Arsenic contaminated the aquatic and terrestrial environments through leaching
and erosion of FA pond. Arsenic amount more than permissible limits have been reported in the soil, tube-well and surface water near
thermal power plants. The main sources of As of thermal power
plants in the environments are atmospheric source through ue
gas and FA. The ultimate sink for most environmental As is the
river sediment. Because of its reactivity and mobility, As can cycle
extensively throughout the abiotic and biotic components of the
aquatic and terrestrial systems and a diagram showing the fate of
FA arsenic cycling in the biosphere has been presented in Fig. 2.
It is known that As can undergo a variety of chemical transformations such as oxidation and reduction. In Indian scenario, ongoing

V.C. Pandey et al. / Resources, Conservation and Recycling 55 (2011) 819835

825

Fig. 2. A schematic diagram for the fate of arsenic-y ash cycling in biosphere generated by coal-based thermal power plants.

use of coal combustion for power production will result in future


releases of toxic and potentially toxic elements including arsenic to
the environment. Due to the very large quantities of FA produced
by coal based power plants, each power plant liberates signicant
amount of arsenic each year, contaminating the biosphere. Two
power plants at Indraprastha and Rajghat combined are estimated
to contribute annually about 56 tonnes of As to the Yamuna, in
Delhi, from ash leaching alone. The element being non-degradable,
it migrates from a remote corner of the watershed to the discharge.
Leaching of As in groundwater is also expected in the vicinity areas
of landlls containing hazardous waste FA and other waste piles
(Nriagu and Pacyna, 1988; Tripathi et al., 1997; Pandey et al., 1998;
Praharaj et al., 2002). India has about 85 coal-based thermal power
plants which jointly liberate many tonnes of As per year. So, attention must be taken for mitigation of such type of anthropogenic As
poisoning, otherwise it will create a big environmental problems
in coming year in compared to other anthropogenic As sources.
Therefore, further detailed investigation is required to analyse the
inuence on the biosphere and human health due to handling and
managing of the FA containing As.
3.4. Arsenic-leaching from y ash
Presently the leaching behaviour of As from FA is not well
understood. Although much research on laboratory leaching of
FA aimed at making a quantitative estimate of the release of
toxic elements have been reported during the last three decades
(Fulekar and Dave, 1985; Ishiguro et al., 1986; Warren and Dudas,
1988; Sandhu and Mills, 1991; Querol et al., 1996; Nham et al.,
1996; Khanra et al., 1998; Wang et al., 1999; Ram et al., 2000; Choi
et al., 2002; Praharaj et al., 2002; Iyer, 2002; Kim et al., 2003; Kim,
2006; Soco and Kalembkiewicz, 2007).
From the eco-toxicological point of view, the leached As
and other heavy metals from FA may become a hazard to the
environment because of their contribution in the formation of
toxic compounds. This process can lead to health, environmental
and land-use problems (Davison et al., 1974a,b; Kaakinen et al.,
1975; Klein et al., 1975; Campbell et al., 1978; Wangen and
Williams, 1978; Gehrs et al., 1979; Hansen and Fisher, 1980;
Hulett et al., 1980; Georgakopoulos et al., 1994; Fernandez-Turiel
et al., 1994; Laumakis et al., 1996; McMurphy et al., 1996; Baba,
2000; Kamon et al., 2000; Baba and Turkman, 2001; Gulec et al.,

2001; Georgakopoulos et al., 2002a; Georgakopoulos et al., 2002b;


Mandal and Sengupta, 2002; Baba, 2003; Baba et al., 2003; Baba and
Kaya, 2004). The extent of the As in FA depends on both the mineralogy and particle size distribution of the raw material being burnt
and the combustion temperature. Contact between ash particles
and leachant can lead to partial or complete dissolution of mineral
phases that constitute the ash particles, or establishment of partial
chemical equilibrium between the ash constituents and leachant.
These interactions are well documented by EPRI (1998), Kirby and
Rimstidt (1994) and Fleming et al. (1996), which are dependent on
factors such as pH, redox state, and leachant ionic strength.
The leachate from unlined FA disposal sites is a potential
anthropogenic source of As to the environment (Burns et al., 2006).
So, understanding the leaching process of As in FA during ash
disposal and reuse is important to developing novel strategies for
the control of As in the environment. Many researchers investigated the speciation and forms of As in FA and reported that As is
associated with iron and aluminium oxide deposits on the particles
surface of FA (Silberman and Harris, 1984; Xu et al., 2001a). Both
As (III) and As (V) were detected but the latter was present in a
much greater fraction (Silberman and Harris, 1984; Goodarzi and
Huggins, 2001; Huggins et al., 2007). To determine the total As
leaching potential from FA, various leachants, including HNO3 ,
H2 SO4 , sodium citrate, geopolymer, and EDTA have been used in
a variety of experimental congurations (Silberman and Harris,
1984; Bankowski et al., 2004; USEPA, 2006). Silberman and Harris
(1984) found that as much as 7897% of the total As could be
leached from FA with a 0.5 N H2 SO4 or a 1 M sodium citrate at pH
5. Leaching experiments conducted over a range of very acidic to
very alkaline conditions revealed that total arsenic leaching varied
among different y ashes, ranging from less than 5% in half of the
ashes tested, to more than 30% in others (USEPA, 2006). Under
typical environmental conditions, signicantly lower As leaching
is expected than under extreme acid or alkaline conditions.
Experiments from laboratory leaching test have demonstrated
that As leaching from FA is mainly dependent on the pH of the solution. However, some discrepancies result from differences among
the y ashes studied, the released As concentrations are normally
high in the alkaline or acidic pH ranges low in the neutral ranges
(Van der Hoek et al., 1994a). Nevertheless, the pH dependency
could not be modeled based on the solubility of As-bearing minerals
(Fruchter et al., 1990; Van der Hoek et al., 1994a), even though the

826

V.C. Pandey et al. / Resources, Conservation and Recycling 55 (2011) 819835

various studies showed that the leaching of other trace elements


from FA is generally controlled by mineral solubility (Mattigod
et al., 1990). It has been suggested that the sorption to iron oxides
could be the cause of the pH-dependent leaching of As from y
ashes (Van der Hoek et al., 1994a). Later, they modeled the As
behaviour based on the sorption to iron oxides. However, under
eld conditions, the leaching mechanisms of As are poorly understood because most of the previous studies have been performed on
basis of lab experiments using fresh ashes. Geochemical behaviour
of As in pore-waters of an alkaline FA disposal site has been suggested by Kim et al. (2009).
Researchers and planners for a long time are anxious about
FA leachates effects on ground water quality (Milligan and Ruane,
1980). This problem is more sensitive in India due to large dependence on ground water and huge production of FA. Eary et al. (1990)
during his experiment found that As is very leachable because it
mainly occurs as a surface precipitate in FA. Arsenic leaching from
FA was governed by their concentrations, association with the ash
particles, leaching time and pH of the leachate (most inuencing
parameter). The relative concentration of calcite and clays in the
coal is one of the most prominent factors on the behaviour of FA
leaching. Due to their high pH, y ashes that contain free lime (CaO)
have leaching properties and potential for contamination very different from those ashes where free CaO is non-existent or present
in negligible quantities. The reason for the difference is that the
leaching of most trace elements is pH dependent (Goumans et al.,
1994). Particularly, the very ne particles (<1 m) in FA play an
important role above their weight concentration because of their
large active surface area. This is signicant both for leaching and
physical properties (Nathan et al., 1999). According to Nathan et al.
(1999), some toxic elements in the leachates have concentration
approaching relatively high levels, such as As, Cr and Se. However,
it is well known that FA is a natural buffer and, even after removal
of CaO and its derivatives [Ca (OH)2 , CaCO3 ], its pH is never lower
than 7.5. So oxyanions of As are not potentially dangerous. The nal
pH of the leachate is variable depending on the CaO content of the
FA. So the nal pH of the leachate should always be part of the
results; it is necessary data for evaluation of the results. Fulekar
and Dave (1985) measured the leaching of As from FA heaps, the
ash in disposal pond and FA suspensions discharged to a river from
a coal-red thermal power plant in Delhi, India, in order to investigate the associated hazard to the environment. About 18.8% of the
total As in the FA was leachable into double distilled water in a 5
day period. The leachability of elements from FA was examined by
Ishiguro et al. (1986) in an elaborate study using an outdoor longterm weathering test plant. Both tap water and rain water were
used for leaching. They demonstrated that As, Cu, Pb and Ni were
not detected in the leachate, but a trace amount of Zn was noted.
Mechanisms of mobilization and attenuation of inorganic elements
in coal FA basins were studied by Sandhu and Mills (1991). Wang
et al. (1999) investigated the potential of surface and ground water
pollution through leaching of elements such as As, Zn, Pb, and Ni
from FA at different pH (2.06.5). Jonkowski et al. (2006) worked on
mobility of As element from selected Australian y ashes. Arsenic
element is mobile under different conditions and over different
leaching times. The concentrations of As element released in leaching solution with initial pH values of 4, 7 and 10 were used to assess
the inuence of pH conditions on element mobility from the acidic
and alkaline y ashes. Arsenic concentration increased with time
in leachate solutions from acidic and alkaline y ashes: however,
in solutions in contact with alkaline y ashes the As concentration,
after reaching a maximum, later decreased with time. The pH of
the leaching solution is the key factor affecting the mobility of As
element in these y ashes.
Dutta et al. (2009) studied on leaching of ten elements including
As from four FA samples which were collected from four different

coal-red thermal power plants in West Bengal, India. The leaching


pattern and its dependence on the pH as well as the solidliquid
ratio have been critically analysed. A much higher mobility of As
elements have been expectedly observed at a low pH. Less leaching is found at a high pH except for As. The mobilization pattern
is strongly governed by the well-known phenomenon of dissolution and re-precipitation of iron with co-precipitation of a series of
elements depending upon the pH of the medium. Extraction equilibrium was reached for Ca, Fe, Na and Zn at certain pH values. A
monotonic trend of release for the elements Mn, K, Cu, Pb, Cr and
As persisted over the long-term leaching period of 180 days. The
alkalinity or the calcium content of the FA sample greatly determines the leaching pattern if the solution pH is neutral or mildly
acidic. It appears that the risk pollution of ground water as well
as of surface water may not be avoidable if FA alone is used for
abandoned coal mine back-lling in an environment where acid
mine drainage is well-known. Nevertheless, blending with lime to
enhance the alkalinity appears to offer a practical solution to the
problem.
Arsenic-y ash interactions are complex and related to surface
and aqueous chemistry. According to American society for testing
and materials, class F type y ash typically contains more than
70% of SiO2 , Al2 O3 , and Fe2 O3 (ASTM, 1992). Class F type FA is
generated from burning of bituminous coal. Because aluminium
oxide (i.e. activated alumina) and iron hydroxide are common sorbents for As removal from water (Crittenden et al., 2005), these
two oxide minerals in FA are believed to be responsible for As
adsorption. Many factors such as pH, calcium, magnesium, reducing or oxidizing conditions, solid-to-liquid (S/L) ratio, leaching time,
temperature and anionic constituents (sulfate and phosphate) have
been shown to inuence the leaching of As from FA (Lecuyer et al.,
1996; Qafoku et al., 1999; Xu et al., 2001b; Praharaj et al., 2002).
Consequently, several mechanisms have been proposed to interpret the As leaching behaviour. Iron oxide was reported as the main
sorbent in acidic ash controlling As leaching (Van der Hoek et al.,
1994a,b). A model incorporating the electrostatic effect was used
by Van der Hoek and Comans (1996) to quantify the adsorption of
As onto FA. Modeling results were strongly dependent on the initial assumptions, namely that amorphous iron oxide was the lone
reactive site and that the calculated adsorption constant was pH
dependent. Similar models were also used to quantify As adsorption onto other solid media such as soil mineral and metal oxides
(Goldberg, 1985, 1986; Goldberg and Glaubig, 1988a,b; Hering and
Dixit, 2005). Information on how to quantify site density and how
to determine the type of reactive surface sites in eld samples
is lacking. In addition, little is known regarding applicability of
previously developed laboratory-derived adsorption constants to
eld samples and settings (Miller, 2001). Improved approaches for
analysing surfaces to rapidly and consistently evaluate site acidity constants and density for various media are needed. Since, As
acid is a weak acid, As (V) present in water as different forms are:
H3 AsO4 , H2 AsO4 , HAsO4 2 , and AsO3 4 . The different As species
are expected to have different adsorption constants with FA surface sites. Therefore, a speciation-based approach needs to be used
to properly understand and quantify the interactions between As
and FA surfaces. For this purpose, Wang et al. (2008) used batch
methods to investigate As leaching using a raw ash, and As adsorption using a clean, washed ash. Results indicated that pH had a
signicant effect on As leaching or adsorption. It has been found
that between pH 3 and 7, less As was in the dissolved phase. When
pH was less than 3 or greater than 7, increasing amounts of As
were leached or desorbed from FA. The adsorption and leaching
behaviour of As was interpreted with the speciation of FA surface
sites and As. A speciation-based model was developed to quantify the As adsorption as a function of pH and FA surface acidity
parameters.

V.C. Pandey et al. / Resources, Conservation and Recycling 55 (2011) 819835

The storage and disposal of FA can lead to the release of leached


metals into soils, surface and ground waters. The majority of these
toxic elements including As are able to build up in soils and sediment, and many are persistent and high toxic to animals, humans
and plants through air water and soil uptake. The concentrations of these hazardous metals detected in the FA samples are
not signicantly higher than those typical found in uncontaminated soils (Alloway, 1990). However, the leaching of As from
high Ca-ash wastes (produced by lignites and subbituminous coals
combustion) is far less, than from acid ones. The point is that, at
water leaching of high-Ca ash disposals, low-solubility ettringite,
Ca6 Al2 (SO4 )3 (OH)12 26H2 O, appeared, although after some time
(Yudovich and Ketris, 2005a,b). Trace element analysis reveals that
As and some toxic elements are sufciently enriched in FA pond
than their crustal abundances, and preferably in the lighter size
fractions. Chemical analysis of the water samples collected from
tube-wells near the FA ponds reveals high concentration of As and
some trace elements, whose distribution is mainly controlled by
the ash deposited in the area. Among these toxic elements, As and
some other trace elements show higher concentration in the tubewell waters near the FA pond, implying signicant input from the
FA pile. The enrichment of As and some elements (Al, Fe and Mn)
above World Health Organization (WHO) guidelines for drinking
water denotes signicant contamination of the groundwater from
the toxic elements leached from the FA pile (Mandal and Sengupta,
2005).
Elements present in FA are not fully bound to the particles, and
all the elements quantied are able to leach from FA up to different
levels (Llorens et al., 2001). Reports on the fraction of these elements that are able to leach from the FA vary between methods
employed. Studies using sequential extraction methods have been
recognized that a signicant fraction of most elements present in FA
are able to leach from the ash, including As (57%), Cr (17%), Co (8%),
Cu (7%), Ni (8%), Pb (13%) and Zn (12%) (Querol et al., 1996). Even
where pure water has been used in FA leaching studies, appreciable
fractions of As and other elements have been shown to leach from
FA (Llorens et al., 2001). It has been designed to simulate rainwater
leaching of FA (Praharaj et al., 2002), As was detected in the leachate
at concentrations up to 260 g l1 , 26 times the US Environmental
Protection Agency (EPA) limit and the WHO recommended value
for drinking water (USEPA, 2002b). The use of lime ue gas scrubbing has been demonstrated to reduce the quantity of As present
in FA leachate (Lecuyer et al., 1996).
Baba et al. (2008) showed that a decrease in pH of the leachant
favours the extraction of toxic metals from FA. A signicant increase
in the extraction of As and other metals from the FA is attributed
to the instability of the mineral phases. These heavy metals concentrations increase with respect to increasing acidic conditions
and temperature. Peak concentrations, in general, were found at
around 30 C. Sometimes, the temperature of the FA may increase
up to 40 C when the FA is in contact with water. Therefore, the concentration of some heavy metals such as As may be magnied in the
FA deposited in the ash disposal site. In other words, the mobility
of trace elements from FA depends not only on the element concentration, temperature and mode of occurrence, but also on the
chemical conditions associated with the leaching process. This in
turn depends on the ash chemistry (acid or alkaline ash) as well as
the pH of the leaching solutions used.
However, if precautions will not be taken, contaminants may
well spread into the groundwater, bio-diversity and soil resources
from FA disposal sites. Therefore, groundwater and soil monitoring
need to be carried out periodically in the FA affected region. Such
monitoring activities should provide better management practices for the sake of environmental quality. In fact, the leaching
behaviour of As from the FA needs a separate review for understanding the related problems very well.

827

4. Arsenic poisoning of biosphere due to y ash disposal


Fly ash (FA) is one of the noxious environmental pollutants and
surely with this is associated the major concern in relation to draw
the environmental health strategists. It is a complex mixture with
a high degree of leaching potential in aqueous media. It contains
more than a dozen heavy metals but this review emphasized only
Arsenic. In the present time scenario much of As of the atmosphere
comes from high-temperature process such as coal combustion,
largely from thermal power plants. The As is released into the atmosphere primarily as As trioxide where it adheres readily onto the
particle surface. The mode of As occurrence in FA strongly inuences the rate of As-release to the environment and As-related
health risks associated with FA disposal. Arsenic is ubiquitous in
nature and exists in both inorganic and organic compounds. Some
of its compounds are highly toxic and because it can be dispersed
in the environment (in air, soil and water) as reported by Faust
and Aly (1981). It has been reported that the As released from
thermal power plants is of a complex nature. Arsenic is not subject to decomposing process like organic substances (Bencko and
Slamova, 2007). Biological oxidation of As contaminated sites has
recently gained increased importance and application due to the
existence of certain advantages, over the conventional physicochemical treatment (Zouboulis and Katsoyiannis, 2005). Therefore,
its efcient removal by bioremediation process from natural contaminated sites intended is considered of great importance.
4.1. Atmosphere and arsenic-poisoning
Coal is naturally contaminated with As, and when it is burned
to generate electricity, As is released into the air through the
smokestacks and coal combustion by-products (y ash). FA containing toxic elements as a result of coal burning, some toxic
elements are also emitted to the atmosphere in gaseous form. During the pulverized coal combustion of thermal power plants, main
part of initial As evaporates to gaseous phase. Most of the organic
As, pyritic As and some shielded As-bearing micro-mineral phases
escape in a gaseous phase and only a minor part of arsenic clay
remains in bottom ash. Maximum escaping arsenic is captured by
FA. Because of 9799% FA is collected by ESP, the atmospheric
emission of As (solid-phase and gaseous) is rather minor (except
some coals with extremely high As-concentrations). However, As
atmospheric emission data are contradictory: up to 3040% on the
Russian and Bulgarian data and far less on the some USA data.
It seems that such difference is caused by the different combustion regimes and different ash-hoppers systems (cool-side versus
hot-side ESP, for example). Besides, the presence of FGD-devices
(wet scrubbers, etc.) may greatly effect As emission rate. The fraction of certain elements that are emitted in ue gases compared
to the amounts in all waste-streams have been projected; these
include Hg (up to 95%), Pb (up to 40%) and As (up to 30%) (Llorens
et al., 2001). During the 1990s, As emissions in the European Union
(EU-15 states) were estimated to be 575 tonnes, of which 15 wt%
(86 tonnes) were contributed by fossil fuel-red stationary combustion plants. Atmospheric emission of As due to fuel combustion
is 186 tonnes per year in Europe during 1995 (Pacyna and Pacyna,
2001). The use of ue gas scrubbing with lime (calcium oxide) can
signicantly reduce the fraction of gaseous As released to the atmosphere through sorption to lime particles (Senior et al., 2000a).
Certain elements are vaporized to varying degrees during coal
combustion and upon cooling of the combustion gases are fully
or partially sorbed onto FA particles. This process results in their
concentrations being higher in those particles less than 10 m
(0.01 mm) in diameter. This may be due to the high surface area of
these very ne particles. Elements for which this sorption enrichment has been observed include As, Cd, Cr, Co, Pb, Hg and Zn

828

V.C. Pandey et al. / Resources, Conservation and Recycling 55 (2011) 819835

(Wadge et al., 1986) The higher concentrations of these elements


in the very ne particles of the FA have implications for the failure
of pollution control devices to capture ultrane particles, and the
threat posed by such particles upon inhalation and thus may have
greater impacts on biological systems in the vicinity of coal-red
power plants (Klein et al., 1975). When inhaled, particles <1 m in
diameter may be deposited in the pulmonary tissue of the respiratory tract and gain entry into the blood stream (Davison et al.,
1974a,b; Natusch et al., 1974). ESP, bag-house, and other devices
capture more than 99% of most elements emitted during the combustion of pulverized coal (Goodarzi, 2006). Due to the considerable
quantities of FA produced, however, particulate emissions to the
atmosphere can still be considerable. Emitted FA particles can be
deposited at distance several to hundreds of kilometers from the
emission point, depending on factors including chimney height. The
collection efciencies of pollution control devices are still insignificant for particles less than 10 m in diameter, with the greatest
penetration for ultra-ne particles of 0.11 m diameter (Senior
et al., 2000b). Particulates in the emission plume can be enriched
with elements including As and Zn by 1.53.0 times compared with
stack particles. Estimate on the quantities of toxic elements emitted
to atmosphere based on the percentage of FA retained may underestimate the total quantities due to such enrichment of elements
in the very ne particles (Llorens et al., 2001; Senior et al., 2000b).
The other results show that use of one ton of FA in concrete will
avoid 2 tonnes of CO2 emitted from cement production and reduces
green-house effect and global warming (Krishnamoorthy, 2000).

4.2. Agricultural soil and arsenic-poisoning


Generally low levels of As are naturally present in the soil. The
background levels are around 5 mg kg1 worldwide with substantial variation depending on the origin of the soil. Arsenic behaviour
is distinctly different under ooded (anaerobic) and non-ooded
(aerobic) soil conditions, with ooded conditions being likely the
most hazardous in terms of uptake by plants and toxicity. Arsenic
could be the biggest environmental toxic contaminant in most of
the agricultural soil where FA is applied. It has been observed that
due to non mobility of arsenic, it is strongly adsorbed on to the
soil particles. However, in gypsum and phosphorus amended soils
As may be much more mobile. As (III) and As (V) are taken up
by different mechanisms from soils by the plants. Arsenic (V) is
taken up via the high afnity phosphate uptake system in plants
(Meharg, 2004). Phosphate (PO4 ) applications have therefore been
suggested to reduce uptake because of competition between PO4
and As (V) for uptake. Speciation of inorganic As in the soil is largely
controlled by reduction and oxidation processes (redox). Under
anaerobic (reducing) conditions As (III) predominates, whereas As
(V) predominates under aerobic (oxidizing) conditions.
The relationships between soil As and growth of plants depend
on the form and availability of the As. The toxicity of As varies
with its form and valence, its toxic order being AsH3 > As (III) > As
(V) > organic As. In general, As availability to plants is highest in
coarse-textured soils having little colloidal material and little ion
exchange capacity and lowest in ne-textured soils high in clay,
organic material, iron, calcium and phosphate. The average As concentration naturally occurring in the soil worldwide is 10 mg kg1 .
The food hygiene concentration limit for As is 1.0 mg kg1 (Das et al.,
2004). In general, ordinary crops do not accumulate enough As to
be toxic to man from nonpolluted agricultural elds. However, in
As contaminated soil, the uptake of As by the plant tissue is signicantly elevated, particularly in vegetables and edible crops (Larsen
et al., 1992). So, there is concern regarding accumulation of As in
agricultural crops and vegetables grown in the As affected area due
to FA.

4.3. Water and arsenic-poisoning


Water is the major source of transporting As under natural conditions. In oxygenated water As occurs in a pentavalent form, but
under reducing condition the trivalent form predominates. Kim
et al. (2009) showed geochemical characteristics of As in porewaters of an alkaline coal FA disposal area using multilevel samples.
When the disposal area was covered with soil, As levels in the porewaters were very low (average of 10 g l1 ) due to co-precipitation
with siderite. The soil cover has capacity for the creation of anoxic
conditions, which raised the Fe concentration by the reductive dissolution of Fe hydroxides. Due to high alkalinity generated from
the alkaline coal FA, still a small increase in the Fe concentration
could cause siderite precipitation (Kim et al., 2009). After removing
soil cover, however, an oxidizing condition was created and triggered the precipitation of dissolved Fe as hydroxides. According
to result, the dissolution of previously predicated As-rich siderite
caused higher As concentration in the pore-waters (Kim et al.,
2009). Therefore, the As concentrations in pore-water of coal FA
disposal area can be regulated and managed by siderite precipitation and dissolution as well as could be effectively immobilized
in the presence of soil cover by forming reducing conditions that
would precipitate dissolved As in cooperation with siderite (Kim
et al., 2009). In this view, covering a disposal area with lowpermeability soils is a required management idea. Though, the
As that co-precipitates with siderite can also be simply mobilized
again when the disposal area is disturbed, because carbonate minerals are very sensitive to changes in the geochemical condition of
water chemistry. Arsenic immobilization based on siderite may not
be applicable to the disposal area where pore-water pH is acidic
because carbonate precipitation is mostly suppressed under this
condition (Kim et al., 2009).
The river, containing waste water from ash deposits of a power
plant, which was burning As-rich coal, reached an As concentration
up to 0.21 mg l1 . Of the micro-organisms occurring in this river
only diatomaceous survived. Fish can easily survive on this concentration. In an experiment trout perished at a concentration of
2025 mg As l1 and carp at a concentration of 25-30 mg As l1 . Particularly sensitive are the pike perch and roach. The eel is supposed
to be more resistant (Bencko and Slamova, 2007). The absence
of sh on a long stretch of the polluted river which received the
above-mentioned As-contamination waste water from ash deposit
was probably due to the destruction of their natural food chain
(Bencko and Slamova, 2007). Ground water As contamination
has exceeded 2000 g l1 in some areas of India and Bangladesh
(Hossain, 2006). Table 7 shows that maximum permissible limit
of As in drinking water, industrial efuent, leachates and land ll
drainage.
The release of FA pond decants into the local water bodies
increases turbidity, decreases primary productivity, affects shes
and other aquatic biota. Many studies have been exposed impacts
on amphibians inhabiting locations contaminated with FA. For
example, both adult southern toads (Bufo terrestris) and freshwater
grassshrimp (Palaemonetes paludosus) have been shown to accumulate trace elements from FA polluted areas, including arsenic
and cadmium (Hopkins et al., 1999; Rowe, 1998). Larval southern
toads (B. terrestris) and larval bullfrogs (Rana catesbeiana) inhabiting similar sites have been shown to suffer elevated incidences of
survival threatening physiological impacts (Hopkins et al., 2000).
Such effects are believed to result from the complex mixtures of
pollutants in y ashes, including teratogenic elements such as selenium, chromium, cadmium and copper (Hopkins et al., 2000). Since,
arsenic is considered as a primary pollutant in drinking water due to
its high toxicity (Zouboulis and Katsoyiannis, 2005). So, its efcient
removal from natural contaminated water resources intended for
drinking water is considered of great importance (Tables 7 and 8).

V.C. Pandey et al. / Resources, Conservation and Recycling 55 (2011) 819835

829

Table 7
Maximum permissible limit of arsenic in drinking water and industrial efuent/leachates/land ll drainage (IS, 1983, 1974; Robinson et al., 2003; DWT, 2001; CEC, 1991).
Metal (mg/l)

Drinking water (IS = 10,500)

Drinking Water (WHO)

Industrial efuents (IS = 2,490)

Leachates

Land ll drainage

Arsenic

0.05

0.01

0.2

0.01

0.21.0

All the standards are meant for eld conditions.

Table 8
Arsenic accumulation in edible crops/food of India.
Edible crops/food

State

Total As (mg kg1 dw)

References

Rice
Wheat
Wheat our, turmeric power, beans and green chili

West Bengal
West Bengal
West Bengal

0.74
0.0800.335

Roychowdhury et al. (2002)


Norra et al. (2005)
Roychowdhury et al. (2002)

5. Analytical points

6. History and chemistry of arsenic

Limit of detection (LOD) for As in Atomic Absorption Spectrophotometer (AAS) is <0.001 mg l1 . Arsenic detection limit
by atomic emission spectroscopy (Huggins, 2002) has been
generally satisfactory for determination of the near-Clarke concentration of As. Though, As can be partly depleted from
coal by high-temperature ashing, especially from high-sulfur
coals. In the boiler deposits, boron arsenate has been found,
because of evaporation of B and As (Swaine and Taylor,
1970).
Formation of gaseous As compounds can depends on the presence of chlorine in coal. On the basis of experimental data and
calculation, arsenic escapes to the gas phase in the form of AsO
and As2 O3 during low-temperature combustion (10001200 C),
but at high temperature (12001600 C), only the As2 O3 species
is released (Shpirt et al., 1990). Arsenic yield in gaseous phase from
high-temperature zone of a furnace is controlled by the furnace
construction at slage-removal coefcient (Ks ) where Ks is a ratio:
slag yield/grass ash content. In contrast, presence of illite orCaCO3
supports capturing of As because of the formation some refractory arsenates KAsO4 and Ca3 (AsO4 )2 with melting temperatures
of 1310 and 1455 C, respectively. On the basis of assumption, the
extent of the As volatility from coal is controlled by mineralogical residence of As. Therefore, by the stepped ignition of the coals
(South Siberia) at temperatures in the range 400800 C, As was
fully evaporated from low-sulfur coals containing the organic form
of As in the dominant form. From medium-sulfur coals (where
both organic form of As and pyritic form of As (arsenopyrite) are
present), 67% As was evaporated, and from coaly argillite only 31%
(Kryukova et al., 1985). The sorption of As in the FA is controlled by
the combustion rate. If particulate coal is very rapidly red, kinetics limitations on the As sorption exist, and As capture appears as
physical-sorption, with strong relation to particulate size (the ner
the FA particles, the higher the As concentration). If the coal res
more slowly, the equilibrium thermodynamics shows a chemicalsorption process (and there is no strong relation of As content in FA
to the fraction size).
Direct observation of As enrichment on surfaces of FA particles is analytically challenging due to the usually low 10100 ppm
concentration of As and the small particle size. For the subbituminous coals, up to 77% of the original As was volatilized
during semicoking. During ashing, the lower the As and S contents, the more As was evaporated. It is important that in
coaly argillite with 17 ppm As and more strongly bound: only
32.1% As is evaporated at 800 C. These data indicates that an
organic form of As is easily volatilized and probably pyritic
form of As is more difcult to evaporate (Khankhareev et al.,
2002).

Arsenic, rst isolated by Albert Magnus in Europe in the year


1250, is a metalloid and a member of the nitrogen family. Arsenic
has a long history of use in human medicine (Ferguson and Gavis,
1972) and over the last 100 years, its use has been documented
in animal feed (to promote growth). Arsenic falls into the periodic table of the elements in Group 15 (V) along with nitrogen
and phosphorous. It is considered a metalloid and as such has both
metallic and non-metallic properties. It is a brittle, grey metal in
its pure form, but in nature is most often found with other metals, such as iron, copper, silver and nickel and in combination with
oxygen and sulfur. Its atomic number is 33 and its atomic weight
is 74.9, placing it as heavier than iron, nickel and manganese but
lighter than silver, lead or gold. It has four common redox states,
3, 0, +3 and +5, but the most inorganic forms are the +3 and
+5 state when in combination with oxygen as an arsenite or an
arsenate. Arsenic is the 20th most common element in the Earths
crust, 14th in the sea and 12th in the human body. Arsenic is
found naturally in over 150 minerals, one of which is arsenopyrite, which includes both iron and sulfur; another is realgar
(AsS).

7. Sources of arsenic contamination


There are several ways of As contamination in the biosphere. Geochemical weathering of rocks, As-bearing minerals
and geothermic sources (e.g. volcanic emissions) and this largely
depends upon microbial induced reduction, oxidation and methylation, which contribute to As mobilization in the biosphere (Islam
et al., 2004).
In addition anthropogenic activities that result in the local contamination of nearby air, soil, sediment and aquatic systems with
As include FA disposal, long-term mining and the associated smelting of the sulde ores, coal combustion, runoff from mine tailings,
pigment production for paints, hide tanning waste, agricultural
pesticides (as As2 O3 ) and herbicides application and poultry feedlot supplements (Smedley and Kinniburgh, 2002). Moreover, As
is used in the production of semi-conductors, lead-acid batteries, the glass industry and the copper rening industry and in
the hardening of metal alloys (Hathaway et al., 1991). While the
use of arsenic-containing products such as pesticides and herbicides has decreased signicantly in the last few decades, their use
for wood preservation is still common (Nico et al., 2004). Arsenic,
potentially toxic heavy metal, is widely distributed in nature and
commonly occurs in a variety of natural metal-bearing suldes
(Nriagu, 2002).

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V.C. Pandey et al. / Resources, Conservation and Recycling 55 (2011) 819835

8. Arsenic toxicity due to y ash

9. Arsenic in rice agriculture

Currently, the toxic effects of As have become a great critical


issue in both developed and developing countries. Arsenic toxicity
has become an Indian concern owing to the ever-increasing contamination of water, soil and crops in many regions of the India. It
was reported in Purulia district of West Bangal, India that a large
number of people in the area are victims of lung infections and
skin disease, caused by FA contamination of air and water. The
effect of the ash was found on local animals and vegetation, too.
The cattle feeding on contaminated vegetation are victims of skin
diseases and dental disorders. The population of birds and water
animals is also decreasing. Love et al. (2009) showed that higher
foliar levels (28 fold) of As is present in Cassia occidentalis plants
which was grown on the weathered FA and also reported that elevated levels of DNA damage in leaf tissues of C. occidentalis growing
wild on FA basin compared to growing to soil. Arsenic is highly
toxic to all forms of its life. Arsenic exists naturally in both organic
and inorganic forms in the environment. The two major forms of
inorganic arsenic are the reduced form, arsenite (As3+ ) and the
oxidized form, arsenate (As5+ ). It occurs predominantly in inorganic forms. Arsenite (As3+ ) is known to be more toxic and 2560
times more mobile than arsenate (As5+ ) (Dutre and Vanecasteele,
1995; Pantsar-Kallio and Manninen, 1997). Monomethylarsenic
acid (MMA) and dimethylarsenic acid (DMA) are the most common organic species in the soil, but their natural presence is low
compared to inorganic As. So, Arsenic speciation in the environment is of signicant importance because organic and inorganic
compounds differ mainly in their toxicity. Arsenic toxicity is also
related to the rate that it is metabolized from the body and the
degree to which it accumulates in the tissues. Generally As toxicity pattern is AsH3 > As3+ > As5+ > RAs-X. Hence, according to rule,
inorganic arsenicals are more toxic than organic arsenicals and
the trivalent oxidation state is more toxic than the pentavalent
oxidation state. Water supplies and soils contaminated with As
are the major sources of drinking water and food-chain contamination in numerous countries. Especially As2 O3 are highly
toxic components of coal, As is both a carcinogen and mutagen
and leads to dangerous dermatological, respiratory and digestive system diseases. In spite of these, Chronic As poisoning can
cause serious health effects including cancers, melanosis (hyperpigmentation or dark spots and hypopigmentation or white spots),
hyperkeratosis (hardened skin), restrictive lung disease, peripheral
vascular disease (blackfoot disease), gangrene, diabetes mellitus, hypertension, and ischaemic heart disease (Guha-Mazumder
et al., 2000; Morales et al., 2000; Rahman, 2002; Srivastava et al.,
2001).
USPHS (2000) reported that most As compounds can readily dissolve in water, and so As can enter water bodies such as rivers,
lakes, pond and by surface runoff. Arsenic is toxic to many plants,
animals and humans, though lethal doses in animals are somewhat
higher than the estimated lethal dose in humans (Kaise et al., 1985;
USPHS, 2000). Arsenic exposure may not only affect and disable
organs of human bodies, especially the skin, but may also interfere
with proper functioning of the immune system (Duker et al., 2005).
Inorganic As has been reported as lethal consequences in most
of the cases. Its long term exposures even in low concentrations
may cause damage to the blood circulatory systems and may cause
injury to the nervous system and other vital organs (USPHS, 2000).
Its great risk is concerned with carcinogenicity due to consumption for a long duration. The US Department of Health and Human
Services in its 9th Report on Carcinogens lists arsenic compounds
as known to be human carcinogens. Skin cancer is the prevalent
form resulting from exposure, though there is also evidence for an
increased risk of internal cancers, including liver cancer (USPHS,
2001; USEPA, 2002b).

About 23% of the countrys total irrigated area being used for
rice production. Rice is the major crop in the irrigated areas of
India. Nearly 42% of the total food grain production is rice in India.
West Bengal is one of the major rice producing states in India and
covers 5,900,000 ha. The Residents of many arsenic-contaminated
rural villages of west Bengal depend mainly on rice for their caloric
intake, about 70% of total (Bae et al., 2002; Meharg, 2004). The substantial varietals differences are found with respect to As uptake,
accumulation and speciation in rice plants. According to market
survey (Williams et al., 2005), Indian basmati rice possessed the
lowest mean As level (0.05 g g1 ) in grains, the American longgrain rice had the highest concentration (0.26 g g1 ), whereas the
Bangladeshi and European cultivars showed intermediate values
(0.13 g g1 and 0.18 g g1 , respectively). American long-grain
rice contained As mainly in the organic form, whereas inorganic
As formed the higher proportion in all other cultivars. The differences in As accumulation also depended on the growing season
and agronomic practices (Abedin et al., 2002). Arsenic concentration in that rice which is cultivated in arsenic contaminated soils
under anaerobic conditions (at which arsenic is highly available for
plants uptake) and irrigated with arsenic contaminated water, is
supposed to be high compared to other crops and regions (Meharg,
2004; Abedin et al., 2002). Due to high As-concentration in paddy
rice, it has been considered as an important source of As intake. At
the time of rice cooking, it can also be increased if As polluted water
is being used. Arsenic amount in cooked rice could be increased by
chelation to the rice starch and/or bran (Bae et al., 2002). Abedin
et al. (2002) also reported that high As concentration in straw may
have the potential for adverse health effects on the cattle and an
increase of As exposure in humans via the plant-animal-human
pathway. According to World Health Organization (WHO), the permissible limit for rice and foodstuff is 1.0 mg kg1 and 2 mg kg1 ,
respectively (Rohman et al., 2007). It is reported that 40% of arsenic
in human body comes from food chain (BIAM, 2002).
A study was carried out to evaluate the growth performance,
elemental composition (Fe, Si, Zn, Mn, Cu, Ni, Cd and As) and yield
of the rice plants (Oryza sativa L. cv. Saryu-52) cultivated under
different doses of FA mixed with garden soil (GS) in combination
with nitrogen fertilizer (NF) and blue green algae biofertilizer (BGA)
(Tripathi et al., 2008). Signicant enhancement of growth was
observed in the plants growing on amended soils as compared to
GS and best response was obtained in amendment of FA + NF + BGA.
Accumulation of Si, Fe, Zn and Mn was higher than Cu, Cd, As and Ni.
Arsenic accumulation was detected only in FA and various amendments. Inoculation of BGA caused slight reduction in Cd, Ni and
As content of plants as compared to NF amendment. The high levels of stress inducible non-protein thiols (NP-SH) and cysteine in
FA were decreased by application of NF and BGA indicating stress
amelioration. This study demonstrated that the integrated use of
FA, BGA and NF for improved growth, yield and mineral composition of the rice plants besides reducing the high demand of nitrogen
fertilizers.
Dwivedi et al. (2007) demonstrated that the three rice cultivars viz., Saryu-52, Sabha-5204, and Pant-4 cultivated in garden
soil (GS, control) and amendments (10100%) of FA for a period of
90 days. They observed the effect of above treatments on growth
and productivity of plants as well as metal accumulation. The toxicity effect of FA at higher concentration (50%) was reected by
the reduction in various parameters such as protein, growth and
photosynthetic pigments. Arsenic accumulation was found only
in foliar parts and was not detected in seeds and below ground
parts. The order of metal accumulation in selected rice varieties
was Fe > Si > Mn > Zn > Ni > Cu > Cd > As. Further, they demonstrated
that the rice cultivars Saryu-52 and Sabha-5204 were more tolerant

V.C. Pandey et al. / Resources, Conservation and Recycling 55 (2011) 819835

and showed enhanced growth and yield in lower FA application


doses as compared to Pant-4. Table 8 shows the concentration of
As accumulation in various edible crops/foods of India.
10. Future prospective and recommendations
In Indian scenario, coal is the major natural resources available in abundance and hence coal based electricity generation
obviously will increase in the present and future to meet the
demand due to the growing industrialization and urbanization.
Consequently, there is a production of enormous quantity of FA followed by emission of green house gases and intrude signicantly
for global warming as well as toxic metal pollution. Bhattacharjee
and Kandpal (2002) presented model estimations for projected FA
consumption for 200910 mainly in three areas: cement production, road embankments and brick making. Agricultural utilization
may offer a partial solution to disposal problems, but the benets
and risks associated with using these materials must be assessed
(Pandey et al., 2009a). But in future forestry will attract more FA
utilization for growing economically and socio-ecologically important trees due to the presence of macro- and micro-nutrients in
FA and having ability to improve physico-chemical and biological
properties of the problem soils (Pandey and Singh, 2010). So, using
FA for biomass production (Pandey et al., 2009b) will be one of the
important strategies to protect environmental degradation as well
as economical importance.
11. Discussion and conclusions
There is not much study about the fate of As hazards in coal FA
and this review is the rst attempt on mapping As ows in environment due to FA. In recent years, there is debate about increased As
emissions from point sources and diffuse emission of As is alarming
in India. Coal combustion by-products mainly FA is an undesirable
waste whose interaction with air, soil and water has created effects
on human health, agriculture and natural ecosystems. Hence FA
safe disposal and utilization is an important concern to safeguard
the cleaner environment. In current years about 38.4% of Indian FA
was put to use mainly in civil construction, building materials and
some in agro-forestry, the presence of toxic metals mostly As in FA
has become a subject of much concern (contamination of soil, surface and ground water bodies), inhibiting more complete utilization
on a sustainable basis (Ram et al., 2007).
Many pilot projects were undertaken in recent years to demonstrate the bulk utilization of FA specically for Indian perspectives.
Also, it has been successfully demonstrated that FA can be utilized
in major construction projects such as dams, ash dyke, landlls,
roads and pavements, soil stabilization and for other purposes such
as brick manufacture, cement industry, tiles and paint industry.
Realizing huge amount of FA generation and its very low utilization,
the Indian Government set up the FA mission under the Department of Science and Technology, New Delhi for coordinating all
such efforts. Regulatory law has been enacted in 1999, which spells
100% utilization of FA within a stipulated period and making it
mandatory to use FA for the purpose of road construction, bricks,
etc. within a radius of 50 km from coal-based thermal power plants.
There are several reasons for low FA utilization in Indian scenario
such as easy availability of topsoil and which is cheaper than FA for
manufacturing bricks, lack of FA promotion, higher costs, dry FA
is not available always, communication gap between FA users and
the management of power plants.
The Indian agencies which have also contributed signicantly
towards adoption of new technologies for safe disposal and gainful utilization of FA include National Thermal Power Corporation;
Ahmadabad; State electricity Boards (TNEB, PSEB, RSEB, MSEB,

831

APSEB, etc.); Ministry of Environment and Forests; Ministry of


Power; Ministry of Laboratories; IITs and Engineering Institute, etc.
Instead of these, Public Work Departments (PWDs), local development and housing authorities as well as National Highway
Authority of India is also directed to prescribe use of FA and FA
based products in their respective schedules of specications and
codes of practice, etc.
India is a developing country and stands 2nd position in the
worlds population and for which it needs more and more energy for
industrialization and urbanization. So, huge FA production in thermal power plants is a result of coal combustion for more energy
requirements. It is a challenging issue for Indian people to generate low cost-based energy while promoting the biosphere by
minimizing the FA production and also increasing its utilization.
Cost-effective technologies should be applied for FA utilization in
Indian scenario also.
In India, one of main problems related to FA disposal is probably due to the presence of heavy metals in the residue. After
the coal burnings the toxic pollutants mainly As is released into
the atmosphere, which consequently leach out and contaminate
soils, as well as surface water and groundwater (Baba et al., 2010).
The As chemistry in the contaminate soils is complex and its
toxicological effects depend on its chemical forms, exposure and
bioavailability (Turpeinen et al., 2003). Arsenic can enter the body
through the lungs by inhalation, though the skin by direct contact,
and through contaminated foods. Ingestion is the most common
non-occupational exposure. The health effects of As vary usually
depending on the chemical form of the arsenic, the concentration,
the route of exposure, and the duration of exposure. Some As compounds present in soil leachate are highly toxic to various organisms (Langdon et al., 2001), including humans (Datta and Sarkar,
2005). It has been reported that elevated DNA damage are expected
in workers involved in dealing with the FA (Chen et al., 2010).
Industrial exposure may appear to be affect the persons working
in industries related to coal consumption are at increased risk of
As exposure due to FA. Contaminated drinking water resources by
As can increases the risk of various health problems. People living
in the areas with high As content (e.g., emissions from industrial
plants) are also at increased risk of As exposure. Therefore, when
the soil toxicity due to FA is characterised, the remediation of As
contaminated sites is needed to minimize the As labile pool in
excess, its transfer through the food chain and subsequent risk(s)
to plants, animals and humans (Coeurdassier et al., 2010).
The present study shows many potential environmental hazards
related to FA generation of coal combustion. Hence, proper measures should be taken to check the release of As and other toxic
metals from the FA pond and subsequent mixing with the groundwater. Using good quality coal and temperature control during coal
combustion is a key factor for controlling arsenic release in the
environment. Underground lining in the FA ponds to prevent direct
contact of the ash pile with the top soil and the local drainage bodies is a probable remedy. Green technology should also be adopted
for minimizing As and other toxic heavy metals pollution due to
the FA disposal around thermal power plants. Re-vegetation of FA
dykes, basins, lagoons and landlls serves a variety of function like
stabilizing the ash against wind and transforming the area into
aesthetically pleasing landscapes. Use of lime (calcium oxide) as
a ue gas scrubbing agent due to its high sorption capacity for As
and other toxic elements vaporized during coal combustion should
be applied in coal-based thermal power plants. For the removal
of As from ue gases, activated carbon was shown to be effective (trapping As2 O3 ) at temperatures around 200 C (Wouterlood
and Bowling, 1979a,b; Lopez-Anton et al., 2007). Using lime (CaO)
for this purpose was found to be most effective at 500600 C,
with little inuence of acidic gases such as HCl and SO2 (Jadhav
and Fan, 2001). Technology up-gradation is very necessary for

832

V.C. Pandey et al. / Resources, Conservation and Recycling 55 (2011) 819835

decreasing power plants pollution such as clean coal technology


and refurbishment of existing thermal power plants. An integrated, i.e. Organic/Biotechnological/Phyto remediative approach
for As pollution due to FA need to be applied and application of
these tools should be made mandatory to conserve or reclaim the
environment. Further, arsenic risk related to FA can be minimize
by creating awareness among the susceptible populations due to
the involvement of governmental and non-governmental organizations (NGOs), related industries and others relevant corrective
measures. In future, this can be avoided through the termination
of coal combustion and the implementation of non-polluting technologies such as solar, wind and atomic power generation.
Acknowledgments
Vimal Chandra Pandey is thankful to University Grants Commission (UGC), Govt. of India for providing UGC-Dr. D.S. Kothari
Post Doctoral fellowship. Authors are thankful to Vice Chancellor,
Babasaheb Bhimrao Ambedkar University (Central) for providing
facilities.
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