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Soil and Sediment Contamination: An

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Chemical Speciation and Mobility of

Some Trace Elements in Vermicomposted
Fly Ash
a

Debopriya Bhattacharyya , S. Balachandran & Shibani Chaudhury

a

Department of Environmental Studies, Siksha-Bhavana, VisvaBharati, Santiniketan, India

Accepted author version posted online: 18 Mar 2014.Published
online: 27 May 2014.

To cite this article: Debopriya Bhattacharyya, S. Balachandran & Shibani Chaudhury (2014) Chemical
Speciation and Mobility of Some Trace Elements in Vermicomposted Fly Ash, Soil and Sediment
Contamination: An International Journal, 23:8, 917-931, DOI: 10.1080/15320383.2014.892915
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Soil and Sediment Contamination, 23:917931, 2014

Copyright Taylor & Francis Group, LLC
ISSN: 1532-0383 print / 1549-7887 online
DOI: 10.1080/15320383.2014.892915

Chemical Speciation and Mobility of Some Trace

Elements in Vermicomposted Fly Ash
DEBOPRIYA BHATTACHARYYA, S. BALACHANDRAN,
AND SHIBANI CHAUDHURY

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Department of Environmental Studies, Siksha-Bhavana, Visva-Bharati,

Santiniketan, India
Fly ash, a by-product of power plants, is currently being used extensively in India for
soil amendment. However, the toxic elements sorbed in the fly ash might pose a serious
threat to the environment, causing soil and water contamination. Vermicomposting of
fly ash is expected to reduce the contamination of toxic trace metal and could improve
the mobility of essential trace element. The current study is focused on characterizing
different species of trace metals and their bio-availability in the vermicomposted fly ash
(VCFA)-treated lateritic soil. As a fertilizer, different doses (10%, 20%, 30%, 40%, and
50%) of VCFA were applied to the soil and sequential extraction was carried out to
analyze trace elements. In the different fractions, Cr < Mn < Pb < Fe were found to be
sorbed more to Fe-Mn oxide-bound fractions, whereas Cd, Cu, and Zn were bound more
to organic-matter-bound fractions; Cr and Ni were mostly bound to residual fraction.
The Fe-Mn oxides and organic-matter-bound fractions may be bio-available with the
appropriate environmental condition, whereas chromium and nickel mostly associated
with residual fraction are very difficult to release into the environment. The mobility
factor index showed the midlevel substitution (i.e., 10% to 30% of VCFA to lateritic
soil) to be beneficial as these doses increased the bio-availability of some essential trace
elements and restricted the availability toxic trace metals in the soil. At higher doses,
the toxic trace metals were found to be released in the bio-available form, which could
be hazardous to the environment.
Keywords Trace elements, chemical speciation, vermicomposted fly ash, bioavailability

Introduction
The pollution of the environment by various anthropogenic activities is increasing day
by day. Among all of the pollutants, coal fly ash from coal-fired power plants is of great
concern. In India, almost 60-75% of electricity production is dependent upon coal, which
produces a huge quantity of fly ash that poses a serious problem to the environment in terms
of its disposal and management. The magnitude of this problem is evident from the fact that
presently about 118 Mt/year of coal fly ash is generated in India from more than 80 thermal
power plants (Patra et al., 2012) and it is predicted to increase to 440 Mt/ year by 2030
(Ram et al., 2008). One method of disposal of fly ash is its utilization in agriculture due to

Address correspondence to Shibani Chaudhury, Department of Environmental Studies, SikshaBhavana, Visva-Bharati, Santiniketan 731235, India. E-mail: shibani.chaudhury@visva-bharati.ac.in

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D. Bhattacharyya et al.

the presence of some useful nutrients like B, Mg, P, S, Ca, Mn, Fe, Cu, and Zn found in fly
ash, which are beneficial for plant growth (Sharma and Kalra, 2006; Yunusa et al., 2006;
Basu et al., 2009; Roy and Joy, 2011). Moreover, it increases the fertility (Ram et al., 2006;
Kishore et al., 2010, Mitra et al., 2005), physical, chemical, and biological properties of
the soil (Malik and Thapliyal, 2009). It was observed by Chattopadhyay and Bhattacharyya
(2010) that the bio-availability of most nutrients is low in fly ash, despite their high content
in the total amount. One of the serious environmental problems related to application of
fly ash in agriculture is the high amount of toxic heavy metals which might accumulate in
crops and are unsafe for human and animal consumption (Yunusa et al., 2012).
Chemical fractionation is one of the most suitable methods to determine the bioavailability and mobility of trace elements. The bio-availabilities of some trace elements
are beneficial at low concentration but are harmful to plants as well as to the whole
ecosystem at higher concentrations. Movement or mobilization of elements from soil or
sediment to the environment is evaluated through chemical speciation (Sushil and Batra,
2006; OECD, 1997; ACAA, 2007). The five-step sequential extraction procedure (i.e., (1)
exchangeable fraction; (2) bound to carbonate (acid soluble); (3) bound to Fe-Mn oxides
(reducible); (4) bound to organic matter (oxidizable); (5) residual fractions), proposed by
Tessier et al. (1979), is one of the most popular methods for chemical fractionation of metal
speciation. Fytianos and Tsanklidi (1998) and Ricou et al. (1999) characterized various
metals by the above method while working with coal fly ash.
Earthworms accumulate heavy metals in their bodies from the soil and make a complex
form with other compounds and reduce toxicity (Jain and Singh, 2004). Epigeic earthworms
are soil-surface dwellers and feed on organic debris that gets mixed with the microbes and
enzymes in their gut. The excreted cast can be utilized as vermicompost, which helps to
increase the mobility and bio-availability of heavy metals in the soil (Bhattacharyya and
Chattopadhyay, 2001; Wen et al., 2004; Gupta et al., 2005). In the presence of organic
waste, vermicomposting of fly ash was found to increase the considerable occurrence of
microorganisms, which helped to encourage the degradation of fly ash and promote the
release of nutrients in available forms (Roy et al., 2009).
A detailed understanding of the mobility and bio-availability of potentially hazardous
toxic elements, especially from vermicomposted fly ash, is required, which is very useful
for its disposal and utilization. Thus, the objectives of the present study were to find out
the various forms of trace elements, and their mobility and bio-availability in the lateritic
soil treated with various doses of vermicomposted fly ash. Additionally, the research was
further carried out to determine the proper dosage of vermicomposted fly ash in lateritic
soil for better availability of essential trace elements and to restrict the toxic trace metals
uptake by plants and organisms.

Materials and Methods

Preparation of Vermicomposted Fly Ash (VCFA)
The fly ash was collected from the Bakreswar Thermal Power Plant, West Bengal, India, and
the cow dung was collected from a nearby village. The vermicomposted fly ash (VCFA) was
prepared in laboratory condition. Cow dung was mixed with the fly ash in 1:1 ratio and kept
under moist condition for 15 days. This was inoculated with 20 epigeic and phytophagous
Eisenia fetida (Savigony) for vermicomposting of 300 gm of the mixture. Prior to their
introduction in the composting site, the earthworms were starved on moist filter paper
for two days to eliminate the organic and inorganic content from their alimentary canals.

Chemical Speciation of Vermicomposted Fly Ash

919

Then, the earthworms were reared in the fly ash and cow dung mixture for composting.
To maintain the aerobic condition of the compost, the matter was turned frequently. The
temperature was maintained at 2735 C for 50 days to optimize the microbial degradation
(Chattopadhyay et al., 2010). The earthworm cast was then air-dried and sieved. The
earthworms were taken out and reused for the next set of vermicompost preparation.

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The Vermicomposted Fly Ash (VCFA) Soil Mixture

The vermicomposted fly ash in the ratio of 10%, 20%, 30%, 40%, and 50% was thoroughly
mixed with 1 kg lateritic soil (pH 6.6) in different culture pots (diameter 20 cm x depth
30 cm) in triplicate. After the addition of VCFA to the soil, pH varied from 6.97.2. A
control set was also prepared by using the lateritic soil alone without VCFA. All of these
treatments in triplicates (n = 3) were incubated for 15 days with regular sprinkling of Milli
Q water (50 ml) to maintain moisture condition for microbial activities.

Metal Estimation
The VCFA-soil mixtures were collected from the culture pots by coning and quartering
method. Mixtures were air-dried and 1 g of soil was taken as an initial weight to perform
the sequential extraction progressively (Table 1), as was proposed by Tessier et al. (1979).
The residue after each extraction was used in the next step for extraction of next fraction.
The extractant and operationally defined chemical fractions were as follows.
For total metal analysis, a 1 g (dry weight) sample was first digested in a bomb
digester with 5:l mixture of hydrofluoric (HF) (10mL) and perchloric acids (HClO4 ) (2mL);
subsequently, a second addition of HClO4 (1 mL) and HF (10 mL) was made and the mixture
was evaporated to near dryness. Finally, HC1O4 (1 mL) alone was added and the sample

Table 1
Five step sequential extraction procedure for chemical speciation, proposed by Tessier et al.
(1979).
Fractions
F1 Exchangeable
F2 Bound to Carbonate
F3 Bound to Fe-Mn
oxides
F4 Bound to organic
matter

F5 Residual

Extracting chemicals for 1gm

of soil
8 ml 1 M MgCl2 at pH 7
8 ml 1 M NaOAc, pH 5.0
using HOAc.
20 ml 0.04 M NH2 OHHCl in
25% (v/v) HOAc
3 ml 0.02M HNO3 + 5 ml
30% H2 O2
3 ml 30% H2 O2
5 ml 3.2 M NH4 OAc in
20% (v/v) HNO3
4 ml HNO3 , 1 ml HClO4 and
10 ml HF.
1 ml HClO4 and 5 ml HF

Temperature and Mixing

Time
1 hr at 2530 C
5 hrs at 2530 C
6 hrs at 96 3 C
2 hrs at 85 2 C
2 hrs at 85 2 C
30 mins at 2530 C
8 hrs at 100 C
6 hrs at 190 C

920

D. Bhattacharyya et al.

was evaporated until the appearance of white fumes. The residue was dissolved and diluted
to 25 mL with 12 N HC1 (Tessier et al., 1979).

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Instrumentation
All glassware used in the extraction procedures were initially cleaned with soap, and washed
thoroughly with tap water and distilled water. To remove contamination by trace metals,
all of the glasses were soaked overnight in 14% of HNO3 and washed thoroughly with
deionized water just before use.
The analysis of trace metals (Pb, Cd, Cu, Cr, Fe, Ni, Zn, and Mn) was done by Perkin
Elmer ICP-OES Model: Optima 2100 DV. Operational conditions were adjusted in accordance with the manufacturers guidelines to yield optimal determination. Quantification of
metals was based upon calibration curves of standard solutions of the respective metals.
These calibration curves were determined several times during the period of analysis. The
precision of the metal analysis was controlled by including triplicate samples of analytical
batches and blanks.
All of the chemicals used for the sequential extraction of soil were of analytical grade,
purchased from Sigma Aldrich (USA), Sisco Research Laboratories (India), and E. Merck
(India). Milli Q water was used throughout the extraction and analysis.

Results and Discussion

Chemical Speciation of Trace Metals
A sequential extraction procedure was used to characterize the various forms of trace
metals present in the VCFA- soil mixture. Essential elements like Zn, Cu, Ni, Mn, and
Fe are required for normal plant metabolism and growth, but higher concentrations of
these elements can be toxic for plant and living organisms (Kabata-Pendias and Mukherjee,
2007). Since Cr, Pb, and Cd do not perform any known physiological function for the plants,
they are not essential for plant growth. These trace elements may be harmful for plants and
soil microbes, even in very small quantities. Moreover, toxicity of these metals depends on
easily available fractions. The partitioning percentages of trace elements in VCFA for the
five fractions are shown in Figures 18.
Cadmium (Cd): The result in Figure 1 shows that the amount of Cd in exchangeable
fraction increases with increasing dose of VCFA (1050%) when applied to the soil. The
exchangeable fraction has special importance due to the high mobility of toxic trace metals
into the environment and biomass; thereby it has the potential to contaminate the ecosystem.
When the pH of the soil condition changes (acidic; i.e., nearly 56 pH), Cd found in the
carbonate-bound fraction becomes more mobile than in the exchangeable fractions and
is released into the environment. This result is in agreement with reports by Wang et al.
(2006) and Huang et al. (2007a; 2007b) for Cd speciation in marine and soil sediment as
well as in a fly ash sample (Yuan et al., 2004a; 2004b). In all of the VCFA doses, most
of the cadmium is associated with bound organic matter and residual fractions; i.e., about
3547% and 4360%, respectively. It was also found that 40% and 50% of VCFA-treated
soil had the highest amount of Cd bound to the organic matter fraction. In the oxidizing
condition, the trace elements can be leached out into the environment by destroying organic
materials. Cd is one of the most deleterious trace metals both for plants and animals; it has
high soil-plant mobility, thereby accumulating in plant tissues.

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Chemical Speciation of Vermicomposted Fly Ash

921

Figure 1. Distribution patterns (percentage concentration) of Cd in each fraction of VCFA treated

soil.

Lead (Pb): From Figure 2, it is clear that the Pb in the VCFA-treated soil is firmly
associated with the Fe-Mn oxides fraction, which accounts for more than 50% of the
total Pb in each treatment. Fe-Mn oxides are excellent scavengers of Pb. This metal is
predominantly adsorbed on the hydrous oxides of Fe/Mn and can be mobilized from soil if
there is any change in the oxidation state of Fe and Mn, which could be a long-term source
of contamination. The second-most-abundant fraction was the residual fraction, in which

Figure 2. Distribution patterns (percentage concentration) of Pb in each fraction of VCFA treated

soil.

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922

D. Bhattacharyya et al.

Figure 3. Distribution patterns (percentage concentration) of Zn in each fraction of VCFA treated

soil.

Pb distribution varied between 2441%. Pb is bound to the organic matter fraction only in
the doses of 4050% VCFA and is absent in 1030% of VCFA, which suggests that Pb does
not form complex ligands at mid-level substitution; i.e., 1030% of VCFA to soil. This pHsensitive fraction releases the metals from the soil and VCFA mixture into the surrounding
environment through its dissolution at a lower pH. Similarly, in 1030% of VCFA, Pb
was not found to be associated with an exchangeable fraction, whereas it is considerably
high in the 40% and 50% dose of VCFA. In the controlled lateritic soil, partitioning of Pb
was in the order of residual > organic matter bound > Fe-Mn oxide bound > carbonate
bound > exchangeable; i.e., Pb in residual and non-residual fractions was 41% and 59%,
respectively. These results are in agreement with other studies by Harrison et al. (1981) and
Li et al. (2001), who reported chemical association and heavy metal contamination in urban
soil and street dust. The present study suggested that it is better to avoid the application
of a higher dose of VCFA (4050%) to soil as the availability of Pb is increased. Pb is
considered a heavy metal and the higher bio-availability is harmful to the environment.
Among the non-residual fractions, the easily bio-available fractions are exchangeable and
the carbonate bound phase, while any change in pH or redox might release the Fe/Mnbound metal. Since in 1030% of VCFA Pb was absent in the exchangeable and carbonate
fractions hence these doses may be recommended. However, a caution should be taken as
1030% VCFA also has a high amount of Pb in the Fe/Mn-bound fraction.
Zinc (Zn): Zinc is considered to be a micronutrient and is needed by plants in small
quantities. It is used as a catalyst in many biological processes. Excessive quantities of
Zn can be hazardous to human health and plant and animal life, as stated by McGrath
and Cunliffe (1985) and Gupta and Gupta (1998). In the control soil, the partitioning of
Zn was residual > organic matter bound > Fe-Mn oxide bound > carbonate bound >
exchangeable and its percentage in residual and non-residual fractions was 55.5% and
44.5%, respectively. Zn was found to be strongly associated with the residual (5865.5%)
fraction in the VCFA-treated soil. This agrees with some of the earlier works on chemical

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Chemical Speciation of Vermicomposted Fly Ash

923

Figure 4. Distribution patterns (percentage concentration) of Cr in each fraction of VCFA treated

soil.

partitioning in soil of Pb smelting and mining areas by Hickey and Kittrick (1984). Similar
results were also observed by Han and Banin (1999), where Zn was mainly transferred
to residual and organic matter bound in a saturated moisture regime. In all of the other
doses, Zn was associated with the organic-matter-bound fraction (2533%), followed by
the residual fraction. Zn is an essential element and it should be more in the non-residual
fraction. In the VCFA-treated soil, carbonate-bound and Fe/Mn oxides had higher affinities
for Zn when compared to the control soil. However, in the organic bound and exchangeable
fraction, Zn affinity was observed to be lower than in the control. In VCFA-treated soil
under favorable conditions like anoxic and/or acidic, the Zn may be leached out as a bioavailable form which can be taken up by plants. Thus, utilization of mid-level substitution
(1030%) of VCFA is recommended for the lateritic soil.
Chromium (Cr): The percentage distribution of Cr in the five extraction phases is
demonstrated in Figure 4. In the control soil, the partitioning of Cr was residual > FeMn oxide bound > carbonate bound, while exchangeable and organic-bound matter were
absent. The partition percentage of Cr in residual and non-residual fractions was 80 and
20%, respectively. Moreover, in 1040% of VCFA-treated soil, exchangeable and organicbound fractions were absent. This might be because Cr is not retained by weak forces in
the outer sphere complexes for exchangeable fractions and does not form organic complex
ligands. In all of the treated soils, almost 5866% of Cr was observed in the residual fraction,
indicting their affinity for crystal lattices where they are fixed. The second highest amount
of Cr was bound to the Fe-Mn oxide due to the preferential incorporation of chromium
into the silicate lattices, indicating that the fraction will be thermodynamically unstable
under anoxic conditions, which agrees with the earlier work on leaching characteristics of
metals in fly ash from a coal-based thermal power plant (Yuan, 2009). An increment of the
Cr concentration with increasing dose (1050%) of VCFA to soil was found in the Fe-Mn
oxide and carbonate-bound fractions. In all of the treatments, the carbonate-bound fraction
of Cr varied within 22.7%. It seems that, at the higher dose of treatment (50%), Cr can

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924

D. Bhattacharyya et al.

Figure 5. Distribution patterns (percentage concentration) of Cu in each fraction of VCFA treated

soil.

be leached out by acidity, ionic exchange, or organic matter break-up as, in this dose, Cr
was found to be present in all of the available fractions. The present study reveals that Cr is
poorly available in control soil as 80% was found in the residual fraction. A similar result
was reported by Kabata-Pendias and Pendias (2001). Application of VCFA increases the Cr
concentration in available form. The highest dose of VCFA to soil (50%) showed that the
maximum availability of Cr might be due to its capacity to form organic complexes. Thus,
they are highly susceptible to a oxidation-reduction process that governs the mobility of Cr
in soil. This metal is considered to be a trace element and, with higher bio-availability, is
harmful to the environment. Thus, to manage the bio-availability, a mid-level substitution
of VCFA is required for the soil.
Copper (Cu): Copper distribution in five fractions is demonstrated in Figure 5. This
figure demonstrates that higher amounts of copper are strongly associated with the organicmatter-bound fraction among the non-residual fractions. This observation tallies with the
result of McBride (1994), and hence may be due to the formation of stable organic Cu
complexes in soil. Similar results were found in urban soil and street dust analysis, as
reported by Li and Thornton (2001), Hickey and Kittrick (1984), and Jaradat (2002). The
chemical partitioning of Cu in controlled soil was organic matter > residual > Fe- Mn oxides
> exchangeable > carbonate. Its residual and non-residual partition percentages were 33%
and 67%, respectively. In other treatments, a higher amount of Cu was found in the residual
part (>44%), followed by organic-matter-bound fraction (25%). The chemical partition
of Cu in treated soils (1040%) was residual fraction > organic-matter-bound fraction
>Fe-Mn oxide-bound fraction >carbonate-bound >exchangeable fraction. When 1030%
of VCFA was compared to the control soils, the most easily bio-available form of Cu
(exchangeable and carbonates) was slightly higher; i.e., 2.65.3% and 3.6% for VCFA and
control soil, respectively. From the above observation, it can be noted that the mid-level
dose of VCFA (1030%) to the soil has the possibility of supplying the required amount of
Cu as an effective trace element or micronutrient. Trace elements are needed in restricted

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Chemical Speciation of Vermicomposted Fly Ash

925

Figure 6. Distribution patterns (percentage concentration) of Fe in each fraction of VCFA treated

soil.

amount for the regular activity of living organisms. In contrast, the present study showed
that the higher dose of VCFA (4050%) application increases the Cu bio-availability. Thus,
it can be recommended that 1030% doses of VCFA can be effective for the availability of
Cu in lateritic soil.
Iron (Fe): The lateritic soil used in the present study contains a high amount of
Fe in its matrix. The chemical fractionation pattern of Fe is described in Figure 6. The
order of association of Fe in controlled lateritic soil was residual >Fe-Mn oxide-bound>
organic-matter-bound>carbonate-bound >exchangeable and the residual and non-residual
percentages of Fe were 9% and 91%, respectively. In the non-residual fraction of the control
soil, the association of Fe was mostly bound to Fe-Mn oxide fractions (84%). Similarly, in
the treated soils, a high amount of Fe was attached to the Fe-Mn oxide-bound fraction, but it
decreased from 89% in 10% VCFA to 70% in 50% of VCFA, which means that it is mobile
although unstable in an anoxic condition in lower doses of VCFA. The most bio-available
form of Fe, which is bound to exchangeable and carbonates, was much lower in 1030% of
VCFA (0.40.6%) and also in the control (0.5%). With the increasing dose of VCFA to the
soil, the amount of Fe in the exchangeable fraction increased (0.41.8%). Similar results
were also observed by Bhattacharyya and Chattopadhyay (2006). A gradual increase of Fe
was also observed in the organic-matter-bound fraction with the increasing dose of VCFA
to the soil (926%). The probability of Fe mobility by various fractions with a favorable
condition is higher in the mid-level doses of VCFA; i.e., 1030% VCFA to soil. With the
application of VCFA, the most easily available (i.e., exchangeable) fraction was observed
to increase in the higher dose of VCFA. By the mid-level dose of VCFA, the excess amount
of available Fe (which is also a micronutrient) can be restricted.
Manganese (Mn): The chemical speciation of Mn is illustrated in Figure 7. For Mn,
the chemical partitioning in controlled soil was in the order of Fe-Mn oxide-bound >
organic-matter-bound > residual > exchangeable > carbonate-bound, while the residual

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926

D. Bhattacharyya et al.

Figure 7. Distribution patterns (percentage concentration) of Mn in each fraction of VCFA treated

soil

and non-residual percentages were 20 and 80%, respectively. The Mn content was found
to be highest in the Fe-Mn oxide-bound fraction in all of the VCFA (4053%), followed
by residual fractions (2348%). While considering the first four fractions (i.e., the nonresidual fraction in the VCFA), the percentage of Mn decreased in the higher doses when
compared to the controlled soil. Mn in the easily bio-available fraction (exchangeable and
carbonates) and reducible fraction was always higher in VCFA-treated soil when compared
to the control soil. In the organic-matter-bound fraction, the percentage of Mn gradually
decreased from 20% to 8% in 1050% of VCFA. Carbonate-bound fractions showed a
higher amount of Mn content in all of the doses than in the exchangeable fraction, and
both of them varied within 12%. These results are in agreement with the observations
of Li and Thronton (2001). In 1030% doses of VCFA to soil, a high amount of Mn was
found in the carbonate and Fe-Mn oxide-bound fractions than the higher doses of VCFA,
which can be easily available with the changes of pH and redox potential. As the Mn acts
as a micronutrient, it is required in trace amounts by plants and living organisms. From the
present study, it is observed that the concentration of Mn increased in easily bio-available
and reducible fractions at doses of 1030%, while with the higher doses of VCFA the Mn
concentration became low in these fractions. Thus, the application of VCFA up to 30% can
be effective to increase the availability of required Mn in the manganese-deficient soil.
Nickel (Ni): Figure 8 show the distribution fraction of Ni in the control soil and
different doses of VCFA-treated soil. The controlled soil contained the highest amount of
available Ni, which was found to be restricted by the VCFA application to the soil. For Ni,
the chemical partitioning in the controlled soil was in the order of organic-matter-bound
> residual > exchangeable > carbonate-bound> Fe-Mn oxide-bound. Organic matter
exhibits a strong ability to absorb Ni and affects its mobility. Ni may be quite mobile in
soils with high complexation ability and it is inversely proportional to the soil pH (KabataPendias and Mukherjee, 2007). The residual and non-residual percentages of Ni were 30 and

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Chemical Speciation of Vermicomposted Fly Ash

927

Figure 8. Distribution patterns (percentage concentration) of Ni in each fraction of VCFA treated

soil.

70%, respectively, in the control soil. Among all of the fractions, the residual one retained
the highest amount of Ni (8193%) in mid-level doses (1030%), indicating that they
are strongly bound to minerals and resistant components of the solid matrix, followed by
Fe-Mn oxide-bound fraction (214%) and carbonate-bound fraction (<3.2%). In 1030%
of VCFA-treated soil, exchangeable and organic-bound fractions were absent, indicating
that Ni is not retained by weak forces in the outer sphere complexes for exchangeable
fractions and does not form an organic complex ligand. Only at 40% and 50% VCFA, Ni
content was found to be higher in exchangeable and organic-matter-bound fractions along
with carbonate and Fe-Mn oxide-bound fractions; i.e., bio-available or conditionally bioavailable fractions. It was observed that, in the mid-level doses, 1030% of the maximum
amount of Ni was attached to the residual fraction, which is immobile, whereas in the 40%
and 50% of VCFA the total amount of Ni in the first three fractions was high, leading to
high Ni mobility and contamination of the soil. The bio-availability of the Ni increased at
the 4050% VCFA doses. From the present study, it can be concluded that the application
of VCFA up to 30% can be effective to lateritic soil to immobilize Ni.

Mobility and Bio-Availability

It has been suggested by Tessier et al. (1979) that the mobility and bio-availability of
metals decrease approximately in the order of the extraction sequence. The exchangeable
and carbonate fractions are the fractions in which the metals are easily available for plant
uptake. Metals bound to Fe-Mn oxides and organic matter can also be available if oxidation
and organic matter destruction occur. The Fe-Mn oxides are excellent scavengers of trace
elements and become unstable under the anoxic condition. On the other hand, the metals in
organic-bound fractions act as a sink and reservoir of metal pollution, but under an oxidizing
condition they may become active. Thus, these two fractions may also be considered as

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928

D. Bhattacharyya et al.

Figure 9. Average Mobility Factor (MF) of trace elements in soil treated with vermicomposted fly
ash (VCFA).

available form of metals under particular environmental conditions. The metals retained in
the residual fraction are expected to be immobile in soil.
Mobility factor (MF) was calculated (Figure 9) to assess the potential mobility of
metals on the basis of the ratio of exchangeable, carbonate-bound, and reducible fractions
to the sum of all fractions. The mobility of trace metals in soils may be evaluated on the
basis of the absolute and relative content of fractions weakly bound to soil components.
The MF in percentage is computed on the basis of the equation (Lu et al., 2007; Yusuf,
2007):
MF = (F 1+F 2+F 3) 100/F
where F represents the sum for all of the fractions.
If MF is high, it indicates that the metal is in a state of high mobility and, consequently,
its availability to the biological systems will be high (Huang et al., 2007b).
It was observed from Figure 9 that the metal mobility varied with the different doses
of VCFA applications to the soil. At higher doses of VCFA application, trace elements
(i.e., Cd, Pb, Cr) mobility was found to be increased. Essential trace elements like Fe, Zn,
Cu, and Mn are required in small amounts by plants and organisms. In the higher doses of
VCFA to soil, the mobility of Fe and Cu increased, which could have some adverse effect
on the environment. Mn and Zn have higher availability in the mid-level doses of VCFA to
the soil (1030%), which is beneficial for the living organisms. The bio-availability of the
trace metals in VCFA-treated soil decreases in the following order Fe > Pb> Mn> Cr>
Cu> Zn> Ni> Cd.
Recovery Rate
To evaluate the accuracy of the sequential extraction procedure and to make sure that there
was no loss of analytes during the procedure, the mass balance was conducted and the

Chemical Speciation of Vermicomposted Fly Ash

929

recovery rate was calculated. The recovery rate was calculated by the sum of the metal
concentration in five fractions and the independent total concentration of each metal (
F/total metal concentration) in each of the doses (Jaradat et al., 2006), where  F = sum for
all five fractions. The recovery rates from the sequential extraction procedure were 95.5%,
91.75%, 97.3%, 96.27%, 98.5%, 97.73%, 98.14%, and 98.18% for Cd, Pb, Zn, Cr, Cu, Fe,
Mn, and Ni, respectively, which agrees with the accuracy of the extraction procedure.

Conclusion

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From the present study, the following can be concluded:

Addition of mid-level substitution (i.e., 10% to 30%) of VCFA to the lateritic soil was
found to be beneficial for the bio-availability of some essential trace elements, and
at higher doses of VCFA (> 30%) the toxic heavy metals are found to be released,
mostly in the bioavailable forms, which could be hazardous to the environment.
In the different fractions, Cr < Mn < Pb < Fe were found to be attached more to
Fe-Mn oxide-bound fractions, whereas Cd, Cu, and Zn are bound more to organicmatter-bound fractions, and Cr and Ni are mostly bound to the residual fraction.
The MF index in the present study showed that the vermicomposted fly ash plays an
effective role by increasing the availability of essential trace elements at mid-level
doses, and at higher doses restricting the toxic trace metals availability in the soil.

Funding
One of the authors Miss Debopriya Bhattacharyya is thankful to University Grants Commission, New Delhi, India for financial support [UGC Major Project -136/2011(SR)]. Tejpur
Central University is duly acknowledged for the instrumental (ICP-OES) support.

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