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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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10.
11.
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).
831
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832
832
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
Percentage share
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
821
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
822
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
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
Table 4
Arsenic speciation data in water-soluble extracts of y ash samples (Wadge and
Hutton, 1987).
Arsenic
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.
824
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
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.
[AS]FA
ash content of coal %
100
[AS]coal
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).
825
Fig. 2. A schematic diagram for the fate of arsenic-y ash cycling in biosphere generated by coal-based thermal power plants.
826
827
828
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)
Leachates
Land ll drainage
Arsenic
0.05
0.01
0.2
0.01
0.21.0
Table 8
Arsenic accumulation in edible crops/food of India.
Edible crops/food
State
References
Rice
Wheat
Wheat our, turmeric power, beans and green chili
West Bengal
West Bengal
West Bengal
0.74
0.0800.335
5. Analytical points
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).
830
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
831
832
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