Chemical Speciation & Bioavailability

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Assessment of heavy metal species in

decomposed municipal solid waste

Sebasthiar Esakku, Ammaiyappan Selvam, Kurian Joseph & Kandasamy

Palanivelu

To cite this article: Sebasthiar Esakku, Ammaiyappan Selvam, Kurian Joseph & Kandasamy
Palanivelu (2005) Assessment of heavy metal species in decomposed municipal solid waste,
Chemical Speciation & Bioavailability, 17:3, 95-102, DOI: 10.3184/095422905782774883

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Chemical Speciation and Bioavailability (2005), 17(3) 95

Assessment of heavy metal species in decomposed

municipal solid waste
Sebasthiar Esakku, Ammaiyappan Selvam, Kurian Joseph and Kandasamy Palanivelu*
Centre for Environmental Studies, Anna University, Chennai – 600 025, India

ABSTRACT
Heavy metal speciation studies on municipal solid waste samples collected from Kodungaiyur dumpsite
in Chennai, India, were carried out for Cu, Ni, Pb, Zn, Cr, Fe, Mn and Cd. Three samples were collected
at depths of 0 – 1 m, 1 – 2 m and 2 – 3 m, and analyzed. X-ray diffraction studies showed the presence of
montmorillonite, illite, quartz and calcium carbonate minerals. The Tessier method was used to
fractionate the metal content into exchangeable, acid extractable, reducible and oxidizable fractions.
Residual and total metal contents were determined in the aqua regia digest. Iron was the major metal
constituent (20 g kg
1) while the lowest metal concentration was found for cadmium (3 mg kg
1).
Descending order of the average total metal contents for these three depth levels was Fe, Cu, Zn, Cr,
Mn, Pb, Ni and Cd. The bioavailable fraction (exchangeable and acid extractable fractions) comprised
less than 40% of the total metal content for all the metals studied, except Cd. Most of the Fe and Cr
were found to be associated with the residual fraction, which is almost inert. Based on the average of
absolute values for the three depth levels, the bioavailability order of metals is
Zn4Mn4Pb4Ni4Cu4Fe4Cr4Cd. Recovery obtained by comparing the aqua regia extracted metal
content with the sum of sequentially extracted fractions was in the range of 91 – 110%.

Keywords: heavy metals, speciation, sequential extraction, municipal solid waste, bioavailability

INTRODUCTION ingful than the total metal content determination.

The environmental impacts of solid wastes, sewage
sludges and contaminated sediments are greatly
influenced by their heavy metal contents. There are
two types of heavy metal sources namely, natural
and man-made. Natural contamination results from
leaching of ore deposits and ordinary rocks while the
man-made sources include metal refining, industrial
effluents and solid waste disposal (Reeve, 1994); for
example, Pb and Ni comes from coal and gasoline,
Mn, Cd and Zn from discarded batteries (Brady,
1990).
Their form influences the effect of metals on the
environment. Assessment of the species of metals
enables to evaluate the bioavailability and find the
suitability of decomposed waste as compost or cover
material. In order to evaluate the pollution potential
of heavy metals, speciation studies are more mean-
*To whom correspondence should be addressed:
E-mail: kpvelu@hotmail.com
www.scilet.com
Metal speciation, in this context, is taken to mean the
fractionation of the total metal content into
exchangeable (bound to exchangeable sites of clay
minerals), acid extractable (bound as carbonates and
hydroxides), reducible (bound to FeyMn oxides),
oxidizable (bound to organic matterysulfides) and
residual (bound to clay minerals) forms. It is the
study of different chemical forms of metal ions
present in environmental samples. The chemical
form of the metal controls its bioavailability or
mobility (Norvell, 1984). The exchangeable and
acid extractable fractions are mobile fractions that
are easily bioavailable. The oxidizable and reducible
forms will be leached out only under extreme
conditions while the residual fraction is almost
inert towards bioavailability.
Different methods have been proposed for metal
speciation studies (Tessier and Campbell, 1998).
However the method developed by Tessier et al.
(1979) is the one widely used for this purpose. The
Community Bureau of Reference has developed a
96 Assessment of heavy metal species in decomposed municipal solid waste
three-stage extraction technique (Quevauviller et al.,
1993). A few researchers have carried out compar-
ison of the efficiencies of these two methods in
sequential extraction of metal ions in real samples
and reference materials (Perez-Cid et al., 1996;
Albores et al., 2000). An inter-laboratory compar-
ison in speciation of Cd, Cr, Ni, Pb and Zn in a
certified reference material CRM 601 has been
evaluated by Lopez-Sanchez et al. (1998). Selective
assessment of a sequential extraction procedure for
metal mobility characterization using model phases
has been reported by Gomez-Ariza et al. (2000).
Zufiaurre et al. (1998) studied the speciation of
metals in sewage sludge collected from a wastewater
treatment plant in order to evaluate the fertilizer
value and pollution potential of heavy metals of
sewage sludge. An assessment of metal speciation
in sewage dewatered sludge in vertical flow reed
beds using sequential extraction scheme was
reported by Staelens et al. (2000). Gumgum and
Ozturk (2001) have reported the heavy metal species
in Tigris river sediment. Goen and Liang (1998)
carried out chromium speciation studies on muni-
cipal solid waste samples.
The present study examines the fractionation of
heavy metal contents into different species and
evaluates the bioavailability of metals in municipal
solid waste samples collected from Kodungaiyur
dumpsite, one of the open dumpsites in Chennai.
EXPERIMENTAL
Site description
The dump at the study area is 10 years old. The
combustible constituents are less than 5% indicating
the stabilized status of the waste (Kurian et al.,
2003). A total of 64 samples were collected from
different depth levels of various locations. The
physico-chemical investigations on these samples
indicated the homogeneous nature of the waste. A
leachate monitoring programme of the site was also
carried out with 40 samples and the results confirm
the complete degradation of the solid waste.
Furthermore, total metal content was determined in
the aqua regia digest of 46 samples collected from
the same area. The results indicate the uniformity of
metal content throughout the study area. Therefore
we have selected a limited number (three samples
from different depth levels of a single location) of
representative samples for our sequential extraction
studies and these are presented here. However, a
detailed study of other samples from the same site as
well as from another dumpsite at Chennai is in
progress.
Sampling
Municipal solid waste samples were collected from
about 10 years old dumping area of Kodungaiyur
dumpsite (13 07’ 37.6’’ North and 80 16’ 48’’
East) near Chennai, India by drilling into the desired
depth levels (0 – 1 m, 1 – 2 m and 2 – 3 m). Mixed
together for each depth level, samples were collected
in polythene bags, air dried in the laboratory and
screened for fine fraction (51 mm). Then they were
ground with an agate mortar and pestle. The homo-
genised samples thus obtained were stored in poly-
ethylene bottles in desiccators at room temperature
before extraction.
Reagents
All reagents and acids used were of analytical grade.
Double distilled water was used for the preparation
of reagents.
Extraction
The extraction was carried with an initial mass of
1.0 g oven dried (105 C) sample. The selective
extraction was carried out in polypropylene centri-
fuge tubes of 50 mL capacity. After each successive
extraction, the supernatant liquid was removed after
centrifugation at 2500 rpm for 5 min and diluted to
volume. The residue was washed with 10 mL of
distilled water by shaking and centrifugation
without loss of solids. The extracts were stored in
polythene bottles for metal content determination.
The conventional method developed by Tessier et al.
(1979) was used for the sequential extraction, which
involves the use of HF and HClO4 extraction for
residual and total metal analysis. In the present
study, residual and total metal contents were deter-
mined in aqua regia digest (Devkota, 2001;
Shrivastava and Banerjee, 1998). The residual frac-
tions of the sequentially extracted samples and the
total metal content in fresh samples were extracted
with aqua regia using a behrotest digester block with
a TRS200 microprocessor controller. The different
extractions were carried out as follows:
(1) Exchangeables: 1 g sample was extracted at
room temperature with 8 mL of 1 M MgCl2
(pH 7) with continuous agitation for 1 h.
(2) Acid extractable: Residue from step (1) was
leached at room temperature with 8 mL of 1 M
of NaOAc (pH 5 adjusted with HOAc) with
continuous agitation for 5 h.
(3) Reducible: Residue from (2) was extracted with
20 mL of 0.04 M NH2OH.HCl in 25% (vyv)
HOAc agitated for 6 h at 96 C.
(4) Oxidizable: To the residue from (3) were added
3 mL of 0.02 M HNO3 and 5 ml of 30% H2O2
 Sebasthiar Esakku, Ammaiyappan Selvam, Kurian Joseph and Kandasamy Palanivelu
(pH 2, adjusted with HNO3); heated at 85 C for
2 h with occasional agitation. A second 3 mL
aliquot of 30% H2O2 was added and heated at
85 C for 3 h with occasional agitation. After
cooling, 5 mL of 3.2 M NH4OAc in 20% (vyv)
HNO3 was added; diluted to 20 mL; agitated for
30 min and centrifuged.
(5) Residual: Residue from (4) was digested with
8 mL of aqua regia (HCl and HNO3, 3 þ 1 vyv)
for 2 h at 120 C.
(6) Total: Fresh sample, 1 g, was digested with 8 mL
of aqua regia (HCl and HNO3, 3 þ 1 vyv) for 2 h
at 120 C. For validation, 1 g sample was
digested with a mixture of HF and HClO4
(5 þ 1) in a platinum crucible near to dryness.
Subsequently a second addition of 1 mL HClO4
and 10 mL HF was added and evaporated to
dryness. Then 1 mL HClO4 alone added and
evaporated. The residue was dissolved in 12 N
HCl and diluted to the volume.
Instruments
For X-ray diffraction, the analyses were carried on
water sedimented samples with a Philips X-ray
diffractometer (X-ray generator PW 1130, diffract-
ometer PW 1050, Microprocessor controller PW
1070). The setting of X-ray generator was 35 kV
and 25 mA. Ni filtered Cu-Ka radiation was
employed. The chart speed was 2 ymin. spread
over from 5 – 90 . A Vario-6 Atomic absorption
spectrophotometer (Analytik Jena, Germany) with
D2 background correction was used for metal content
determination. Acetylene-Air flame was used for all
elements except for Cd and Cr, for which electro-
thermal atomisation was employed with argon as
carrier gas.
Quality control
The analytical results obtained were validated with
spiked samples. The percentage recovery of metals
obtained by the summation of sequential fractions in
relation to the total metal content extracted with
aqua regia was computed. The analytical precision
was confirmed with triplicates throughout the study.
RESULTS AND DISCUSSION
The predominant clay minerals of these samples
were montmorilonite, illite, quartz and CaCO3 with
d- spacings at 16.7 – 17.7, 10.08, 4.32 and 3.3 –
3.44 A ). The particle size analysis results with
45 – 60% ( 2 mm), 10 – 20% ( 75 m) and 510%
( 2 mm).
97
Table 1 Comparison of aqua regia and HF þ HclO4 extraction
methods for total metal content in MSW
Metal Total metal content (mg kg
1)
HCl þ HNO3 HF þ HClO4
Fe 20485.0  574 20315.0  367
Cu 169.9  10.3 161.0  7.9
Zn 331.1  1.8 322.8  3.0
Cr 210.3  15.7 203.4  9.4
Mn 345.6  3.7 361.2  2.1
Pb 110.8  3.2 115.6  6.9
Ni 81.0  0.2 82.4  4.6
Cd 1.04  0.04 1.14  0.02
Values are average of 5 measurements.
Values reported are for 0 – 1 m depth level.
In the Tessier (1979) scheme, a mixture of HF and
HClO4 was used to extract the residual and total
metal content. In order to eliminate the use of HF in
extraction, in this study the use of aqua regia to
extract total metals for sample collected from 0 – 1 m
depth was evaluated. Comparison of the results
obtained in these two methods showed a deviation
of +10% (Table 1). Hence, aqua regia was used
throughout the study to extract the total and residual
metals.
The mean values of metal contents in each fraction
for Cu, Ni, Pb, Zn, Fe, Mn, Cr and Cd in samples
collected from Kodungaiyur dumpsite at different
depth levels are presented in Table 2. The sum of the
five fractions obtained in sequential extraction is
compared with the total metal content determined
by aqua regia digest method. Among all the metals
estimated, Fe was present up to 20 g kg 1 and Cd
was the lowest constituent, (53 mg kg 1). The order
for metal content in these MSW samples is
Fe4Cu4Zn4Cr4Mn4Pb4Ni4Cd. There is
a difference in absolute metal fractions of these
samples with depth variation. In general, the total
metal content increased with increasing depth level,
which may be due to downward migration of
leachates. Furthermore, the top layer is exposed to
biological processes, which produce mobilizing
metals.
Sequential extractions
The per cent contributions of exchangeable, acid
extractable, reducible, oxidizable and residual
species in total metal concentration for Cu, Ni, Zn,
Cr, Pb, Fe, Mn and Cd for the samples collected
from 0 – 1 m, 1 – 2 m and 2 – 3 m are depicted in
Figure 1.
Iron
Though iron is not a heavy metal, it was also
analyzed in the present study and the results
discussed since it is the predominant metal available
98 Assessment of heavy metal species in decomposed municipal solid waste

Table 2 Absolute metal fractions (mg kg
1) obtained in sequential extraction of MSW soil fraction from Kodungaiyur dumpsite
Fraction Fe Cu Zn Cr Mn Pb Ni Cd
(a) Depth: 0 – 1 m
1 5.15  2 2.63  0.3 6.80  0.5 BDL 19.7  0.4 9.10  0.1 19.6  0.2 0.60  0.003
2 16.0  2 6.30  0.2 52.1  1.1 0.88  0.2 92.2  3.3 16.3  1.0 11.6  0.5 1.32  0.11
3 2201.5  83 12.4  0.5 171.9  6.8 19.1  1.5 160.7  5.0 27.9  0.5 15.8  0.2 0.58  0.03
4 591.6  15 102.1  0.1 38.4  1.0 27.9  1.6 8.36  0.6 20.8  1.7 9.12  0.9 BDL
5 18502  171 50.9  4.2 67.3  3.4 172.0  0.8 82.9  2.8 45.3  4.7 31.9  0.02 1.37  0.10
S1–5 21316  69 174.3  5.3 336.5  6.0 219.9  4.0 363.8  0.9 119.4  3.6 88.0  1.3 3.80  0.45
T 20485  574 169.9  10.3 331.1  1.8 210.3  15.7 340.6  3.7 110.8  3.2 81.0  0.2 1.04  0.04
(b) Depth: 1 – 2 m
1 3.32  0.02 2.18  0.1 5.52  0.2 0.10  0.03 15.8  1.1 14.1  0.9 19.5  0.8 0.57  0.02
2 27.5  0.2 7.39  0.1 68.4  0.6 1.30  0.17 107.6  5.3 30.0  2.2 14.2  0.1 1.18  0.04
3 2393.1  58 11.8  0.2 168.6  1.6 22.6  2.18 153.3  0.2 71.5  8.9 22.9  0.2 0.57  0.12
4 615.8  4.2 142.1  0.2 35.2  0.2 43.5  0.83 10.0  0.8 40.9  3.1 13.9  0.1 BDL
5 15336  379 48.1  1.9 51.4  3.5 368.3  3.67 96.4  12.1 115.3  7.9 101.0  3.0 0.97  0.09
S1–5 18376  441 211.6  1.8 329.1  6.1 435.8  0.51 383.1  4.7 271.9  22 171.5  2.0 3.29  0.1
T 20085  671 225.3  29 352.1  1.8 437.3  15.3 363.8  2.2 253.0  8.2 160.0  1.8 1.07  0.06
(c) Depth: 2 – 3 m
1 3.22  0.3 5.30  0.03 22.5  0.6 0.90  0.5 14.8  0.4 15.0  0.4 19.0  0.8 0.53  0.01
2 22.6  2.2 84.3  1.93 263.9  2.1 1.52  0.2 104.2  1.4 38.5  0.8 17.0  0.2 1.53  0.04
3 3563  235 77.6  5.9 362.6  8.0 25.8  0.5 163.3  5.0 78.5  0.8 26.2  1.0 0.71  0.07
4 840.8  28.0 665.9  8.25 64.6  1.1 47.5  2.5 10.0  0.6 31.3  7.9 13.5  1.2 BDL
5 14282  283 145.0  3.57 57.4  2.4 410.3  14.7 79.0  0.7 87.2  7.4 135.8  4.4 0.86  0.01
S1–5 18712  78 978.1  12.5 771.0  6.6 486.0  13.0 371.3  26.9 250.5  1.8 211.5  7.6 3.63  0.12
T 20148  0 1005.2  6.0 777.9  23.3 536.5  2.5 380.8  3.5 227.0  8.1 191.5  5.8 1.30  0.04
Fraction 1, Exchangeable; 2, Acid extractable; 3, Reducible; 4, Oxidizable; 5, Residual; T, Total by aqua regea extract.
S1–5 – sum of fractions 1 – 5. Values are means of three replicates, followed by deviation.

in this MSW. Iron was the predominant metal in
these samples and 80% of the Fe is in residual form,
followed by reducible and oxidizable. If the concen-
tration of the metal is too high, the efficiency of the
fractionation may be reduced, as reported for Pb
(Staelens et al., 2000; Rauret et al., 1989). Since Fe
concentration is very high the sequential extraction
may be less effective with other fractionations.
Therefore, the higher percentage of Fe was noted
in the residual fraction. The high concentration of Fe
in the residual form may be due to the conversion of
amorphous iron oxides into more stable crystalline
iron oxides, which may be extracted in residual
fraction (Staelens et al., 2000). Otte et al. (1995)
reported that the residual fraction could be converted
to the reducible fraction by the activity of plant
roots.
1996; Zufiaurre et al., 1998). This may be due to the
higher stability constants of Cu complexes with
organic matter. Negatively charged functional
groups such as phenolate and carboxylate increase
in number during humification (Foth, 1978); hold
heavy metals by complexation (Evans, 1989) and
enhance the formation of metal complexes at high
pH (Rieuwerts et al., 1998). Although there is a
difference noticed in Cu content of various fractions
in varying depth levels, the general trend is similar
when considering percent availability. The existence
of about 10% copper in the reducible form may
result from the microbial activity in the oxidized
rhizosphere, which enhances the precipitation of
hydrous oxides of Fe and Mn (Kadlec and Knight,
1996; Mendelssohn et al., 1995). Only under strong
oxidizing conditions can Cu from these solid waste
samples be leached into the environment.

Copper
The highest fraction obtained for Cu is the organic
fraction. Based on the metal concentration, the order
of sequential fraction is oxidizable 4 residual 4
reducible 4 acid extractable 4 exchangeable. The
mobile fractions of Cu contribute less than 10%. The
availability of copper in organic fraction is about
60%. A higher Cu content in the organic fraction is
reported for sewage sludge samples (Perez-Cid et al.,
Zinc
The predominant form for Zn is the reducible
fraction, followed by acid extractable, residual,
oxidizable and exchangeable. Perez-Cid et al.,
1996 reported similar levels of Zn in the reducible
form in sewage sludge. Higher concentration of
heavy metals in the reducible fraction (bound to Fe
and Mn oxides) can be attributed to diffusion
 Sebasthiar Esakku, Ammaiyappan Selvam, Kurian Joseph and Kandasamy Palanivelu 99

Figure 1 Percentage of various species of metals in MSW fine fraction collected from KDG. (Exc, Exchangeable; AE, Acid
extractable; Red, Reducible; Oxi, Oxidizable; Res, Residual.)
100 Assessment of heavy metal species in decomposed municipal solid waste
mechanism (Backes et al., 1995). These metals can
be released into the environment under extremely
reducible conditions. The acid extractable fraction of
Zn increased with the increase in depth level of
samples. The mobile form i.e. exchangeable and
acid extractable fractions contribute about 20 –
40%. A similar study of the sewage sludge showed
40 – 50% mobile fraction of Zn (Staelens et al.,
2000). Among all the metals determined, Zn is the
one that contributes the least to the residual or inert
phase.
Chromium
The residual fraction constitutes about 80% of the
total Cr, followed by the oxidizabe and reducible
fractions. No mobile fractions of Cr are noticed in
these samples. Since remobilization of residually
bound metals is rare (Staelens et al., 2000), the
leaching of Cr to the environment from these
samples may not occur. It is also noticed that there
is no significant difference between different depth
levels. It is surprising to observe that the total Cr
content is higher than Mn at 1 – 2 m and 2 – 3 m depth
levels (Table 2). This may be due to local dumping
of Cr containing waste.
Manganese
The order of availability of Mn in different fractions
is reducible 4 acid extractable 4 residual 4
exchangeable 4 oxidizable. There is no depth-
wise variation noticed in percentage of various
species. Under reducible conditions Mn can be
released into environment. The high percentage of
the reducible fraction may be due to the precipitation
of amorphous hydrous oxides of Mn during aging
(Staelens et al., 2000) and is higher than that
obtained for hydrous oxides of Fe.
Lead
About 40% of Pb contributes to residual fraction and
decreases in the order of reducible, oxidizable, acid
extractable and exchangeable. The high residual
fraction may be due to the precipitation of Pb as
stable compounds. Some 20% of the total Pb contri-
butes to mobile form (exchangeable and acid extrac-
table fractions). Kinniburgh et al. (1976) observed
the excess lead content in the reducible fraction at
low pH.
Nickel
It is evident from Figure 1 that the residual fraction
of Ni contributes the maximum to the total Ni
content. The order of availability of Ni fraction is
residual 4 exchangeable 4 reducible 4 acid
extractable 4 oxidizable. About 20 – 40% Ni is in
the exchangeable and acid extractable forms which
can cause environmental toxicity during its mobility.
The acid extractable fraction is soluble in the low pH
condition. A constant exchangeable fraction for Ni
during MSW composting has been observed by Pare
et al. (1999). About 10 – 15% of Ni is present in
reducible form representing hydrous oxides of Fe
and Mn. Although there is no significant variation in
absolute mobile fractions (exchangeable and acid
extractable), the percentage of mobile fractions
decreased with increasing depth levels.
Cadmium
Cadmium is the least abundant metal in these MSW
samples and hence the species of Cd may not be
crucial in the environmental perspective. The
existing order in sequential extraction is acid extrac-
table 4 residual 4 reducible 4 exchangeable. No
oxidizable fraction of Cd was noticed. Since the total
metal content is very low, values obtained in sequen-
tial extraction may not sensitive enough to reveal the
real situation. Hence, the percent availability and
recovery are not presented in the tables. Similar
results for the speciation of Cd was reported by
Tessier et al. (1979) in which the total concentration
of Cd was 50:1 mg kg 1, whereas for each fraction
0.1 – 0.3 mg kg 1 were reported.
Mobile fractions
The mobile fractions of trace metals are more
available for environmental functions than other
fractions. In the ecological context, the mobile
fractions rather than the total metal content are
important. Further the chemical species play impor-
tant role in transfer of metals along the water-soil-
plant-animal-human chain (Shrivastava and
Banerjee, 1998). Comparison of the percentage of
mobile fraction (sum of exchangeable and acid
extractable fractions) to the total metal content is
shown in Table 3. In the case of Cu, the available Cu
contents in 0 – 1 m and 1 – 2 m are almost same while
the 2 – 3 m shows appreciable amount of mobile form
Table 3 Percent mobile fractions of metals in MSW fine
fraction
Depth Fe Cu Zn Cr Mn Pb Ni
(m)
0–1 0.10 5.24 17.79 0.43 32.85 22.92 38.49
1–2 0.15 4.22 20.99 0.32 33.92 17.43 21.06
2–3 0.12 8.91 36.82 0.45 31.25 23.62 18.80
Mobile fraction is the sum of exchangeable and acid extractable
fractions.
Percentage based on total content obtained in aqua regia extract.
 Sebasthiar Esakku, Ammaiyappan Selvam, Kurian Joseph and Kandasamy Palanivelu 101

of Cu due the substantial raise of total Cu at the Table 4 Percent recovery of metals in sequential extraction
with respect to aqua regia extract
bottom layer. The allowable Cu content for compost
as per Indian standard is 300 mg kg 1. For these Metal Depth (m)
solid waste samples though the total Cu content
0–1 1–2 2–3
exceeds the limit, the environmentally available
fraction is less than that of specified limit. Fe 104.06 91.49 92.75
Although there is a difference noticed in the total Cu 102.65 93.92 97.29
Ni content for these three samples, the absolute Zn 101.63 93.47 99.11
Cr 104.28 99.66 90.59
mobile fraction remains almost the same. Such a Mn 106.81 105.31 97.48
constant mobile fraction of Ni in the composting of Pb 108.32 107.47 110.19
municipal solid waste was already reported by Pare Ni 108.55 107.22 110.40
et al. (1999). For lead, the mobile fraction increases
with increasing depths (25, 44 and 53 mg kg 1 for
0 – 1 m, 1 – 2 m and 2 – 3 m, respectively) and the
total Pb content ranges between 111 to 253 mg quantities in the exchangeable and acid extractable
kg 1. Among the metals analyzed, highest concen- fractions, which are easily bioavailable. These
tration of mobile fraction was observed for Zn metals can be leached during degradation of the
(286 mg kg 1, about 40%) in the bottom layer. organic matter in solid waste and the downward
Although Fe contributes the highest quantity in movement of leachate poses threat to the ground-
total metal content (20 g kg 1), the mobile Fe water quality. In the case of Cr and Fe, the residual
fraction is only 20 – 30 mg kg 1. Manganese is the fraction contributes the maximum, which is inert
only metal having no variation in total and mobile form and hence the environmental effects may not
fractions in all the samples analyzed. About 33% of be significant. The mobile fractions of Cu are very
the total Mn is extracted with exchangeable and acid less and appreciable amounts of Cu existed in
extractable fractions. The contribution of Cr and Cd oxidizable form, which can be leached only under
in the mobile fractions is less than 2.5 mg kg 1. In extreme oxidizing conditions. Since the contribution
general, less than 40% of the metals is bioavailable of heavy metals in mobile fractions is less than 40%,
which may be attributed to the near neutral pH of the the mined material can be used as compost for non-
samples (7.0 – 8.0). Neutral pH enhances the immo- edible crops and for covering material in landfills.
bilization by complexation (Elliott et al., 1986). Remedial measures such as phytoextraction can be
employed to reduce the heavy metal concentration.
Since the solid waste in the study area is almost
Recovery
decomposed and homogeneous in nature, a limited
The recovery of added metal ions obtained with number of samples were fractionated. However, a
spiked samples was found to be 498:5%. The detailed investigation on the heavy metal speciation
percent recovery of metals computed by the summa- of MSW fines collected at dumpsites at Chennai is in
tion of sequential fractions in relation to the total progress.
metal content extracted with aqua regia is presented
in Table 4. For all metals, except Cd, recovery
ranged from 91 to 110%, which is within the ACKNOWLEDGMENTS
acceptable range. This variation may be attributed
to the differences in leaching time, reagents and the We sincerely thank Swedish International
total volume of extractant (Ciba et al., 1999). Similar Development Agency (SIDA) for financial support
ranges have already been reported in literature for and Dr N. Balasubramanian, Professor (Retired),
sequential extraction (Perez-Cid et al., 1996; Albores Department of Chemistry, IIT-Madras, Chennai for
et al., 2000). his critical review of this paper.

CONCLUSION
Among all the metals analyzed, Fe is the highest and
the Cd is the lowest in the absolute concentrations in
municipal solid waste samples from Kodungaiyur
dumping ground. Depth-wise variation is significant
in absolute metal contents but for sequential frac-
tions the percentage variation is not significant.
Nickel, Zn, Pb, Mn and Cd contribute significant
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