Environmentalist (2012) 32:383393

DOI 10.1007/s10669-012-9399-0

Fractionation of selected metals in the sediments of Cochin

estuary and Periyar River, southwest coast of India
Mahesh Mohan Toms Augustine K. K. Jayasooryan
M. S. Shylesh Chandran E. V. Ramasamy

Published online: 22 April 2012

Springer Science+Business Media, LLC 2012

Abstract Cochin estuary is one of the highly polluted

aquatic systems of the southwest coast of India. The present
study focuses on the assessment of heavy metals (Zn, Cd,
Pb, and Cu) present in the sediments of Cochin estuary and
the adjoining Periyar River. The sediments were analyzed
for total metal content and various chemically bound fractions such as exchangeable, carbonate bound, easily
reducible, organic, and residual. Total metal content of
sediment was found higher than the average values reported
from other Indian rivers. The mean concentration of Zn, Cd,
Pb, and Cu in the sediments was 1,249.44, 9.5, 221.37,
and 166.14 lg/g, respectively. The results of sequential
extraction showed that the concentration of Cd was high in
the first two weakly bound fractions (exchangeable and
carbonate bound) than the other metals, which are high in
residual and organic bound fractions. Risk-assessment code
analysis and environmental indices (enrichment factor and
pollution load index) suggest that the sediments are highly
polluted with metals, especially Cd.
Keywords

Metal  Sediment  Fractions  Bioavailability

1 Introduction
River sediments are basic components of the aquatic environment as they provide nutrients for living organisms and
serve as a sink for many deleterious chemical species.
Sediments also constitute a major source of persistent

M. Mohan (&)  T. Augustine  K. K. Jayasooryan 

M. S. Shylesh Chandran  E. V. Ramasamy
School of Environmental Sciences, Mahatma Gandhi University,
Priyadarshini Hills P.O., Kottayam 686 560, Kerala, India
e-mail: mahises@gmail.com

bioaccumulative toxic chemicals, which may pose a threat to

the ecosystem as well as human health. Many studies have
documented the level of sediment contamination as a major
criteria in ecosystem quality assessment and there are reports
on widespread incidences of sediment contamination
(Zhigang and Gao 2007; USEPA 1997). Among the various
toxic chemicals released into the environment, heavy metals
are very crucial as they cause considerable damage to the
aquatic ecosystems (Lasheen and Ammar 2008; Honglei
et al. 2008). The level of heavy metals in the environment is
increasing notably in the recent past due to human activities
(Rai 2008; El-Hassan and Jiries 2001). Accumulation of
heavy metals and other persistent environmental contaminants in the sediments (Tao et al. 2005) becomes toxic to
organisms especially at high concentrations (Young 2005).
A wide range of monitoring studies have been conducted
globally in recent years in order to estimate the degree
of heavy metal contamination in aquatic ecosystems
(Purushothaman and Chakrapani 2007) and their adverse
effects on the aquatic fauna (Luoma and Carter 1990).
According to Lasheen and Ammar (2008), the concentration and behavior of trace metals in sediment is very
critical in detecting the source, degree of pollution, and
distribution mechanisms in the aquatic environment. The
metal behavior in river systems is mainly based on the
chemical partitioning and dynamics of metals within the
sediment matrix. Additionally, geochemical information
restricted only to the determination of total element concentrations associated with bed sediments is not sufficient for
impact assessment because metals of environmental significance are distributed over the various chemical compounds
and minerals in sediments (Alomary and Belhadj 2007). The
mobility of metals in sediments depends considerably on
their distribution between different physico-chemical phases
such as organic matter, oxides of ferric and manganese,

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silicates, and carbonates (Jain et al. 2008). Most of the

researchers have now realized that the toxicity of heavy
metals has much to do with the bioavailability and not the
total concentration (Li et al. 2008).
Bioavailability, which is the amount of substance available or accessible to a living organism, is an important
characteristic of contaminant evaluation (Campbell and
Reece 1991). The bioavailability of sediment-bound trace
metals is dependent not only on the total metal concentration
but also on the strength of the association between the metal
and sediment compounds (Lacerda et al. 1992). Therefore,
the relative availability of metals in biological communities
depends on its selective distribution (Rao and Rao 2001). In
the Tessiers Standard Extraction Procedure (1979), the
bioavailability of an element decreases with the decreasing
order of the chemical phases from the exchangeable to the
residual fraction.
The heavy metals of anthropogenic origin are found
predominantly as labile, extractable fraction in sediments
because they are introduced into the environment as inorganic complexes or hydrated ions, which are easily
adsorbed on surfaces of sediment particles through relatively weak physical and chemical bonds (Jain et al. 2008).
The labile extractable fractions are adsorptive, exchangeable, and bound to carbonate fractions, which are having
weakly bonded metals that could equilibrate with the
aqueous phase and thus became more rapidly bioavailable
(Singh et al. 2005). Sequential extraction procedure is the
most widely used approach to distinguish different geochemical associations of metals and to gain a better insight
of geochemical processes occurring in sediments (Zhigang
and Gao 2007; Purushothaman and Chakrapani 2007).
Bioavailable fractions of metals in the sediments of
various Indian rivers have been well studied (Jain et al.
2008; Prasad et al. 2006; Rath et al. 2005), however, studies
are meager on the rivers of Kerala. Periyar River, one of the
major rivers of Kerala, is heavily polluted due to the
effluents discharged from the Udyogamandal industrial
area, the largest industrial manufacturing center in the
Kerala state, which is around 15 km upstream of the confluence point of the river with the Cochin estuary (Ouseph
1996; Paul 2001). The major parts of the industrial effluents
are discharged into the Periyar River without much treatment. Acids, suspended solids, free ammonia, ammoniacal
nitrogen, various dyes, metals, and radioactive materials are
some of the significant pollutants discharged into the river
through the industrial effluents (Ouseph 1996). Despite its
prominence and severe pollution, only a few fractionationbased studies have been reported on this river.
As Cochin is a major fish-landing center of India, the
studies on the accumulation of metals and other pollutants
in the biota become highly significant vis-a`-vis health risk
to humans. In this context, the present study aims to

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Environmentalist (2012) 32:383393

quantify heavy metals such as Zn, Cd, Pb, and Cu in the

sediments of Cochin estuary and lower reaches of Periyar
River. Moreover, the bioavailability of metals in the sediments were also analyzed through sequential extraction.

2 Materials and methods

2.1 Sample collection
Onboard sampling was carried out at Cochin estuary and
lower reach of Periyar River during the pre-monsoon season. Seven surface sediment (SD) samples were collected
by using a grab sampler. The sampling locations are shown
in the Fig. 1. About 250 g of sediment samples were collected in plastic bags and stored under refrigeration until
the analysis was performed.
2.2 Sample analysis
2.2.1 Physico-chemical characteristics
The \200-lm fraction of the dried and ground sediment
sample was taken for the analysis of pH and organic carbon
(Maiti 2003). Textural analysis of sediment samples were
carried out by international pipette method (Friedman and
Johnson 1982).
2.2.2 Metals
Sediment samples were analyzed for the total concentration of
metals such as zinc (Zn), cadmium (Cd), lead (Pb), iron (Fe) and
copper (Cu). An aliquot of 0.25-g powdered sediment samples
were digested with a mixture of acids (3:1 HNO3/HClO4) using
a microwave digester (MARS Xpress, CEM, USA).
The metals in the digested sediment samples were
determined using a voltammetric trace metal analyzer (797
VA Computrace, Metrohm, Switzerland) with a Hanging
Mercury Drop Electrode (HMDE). All samples were analyzed in triplicate.
2.3 Metal fractionation in sediments
The metal speciation was carried out using sequential
extraction scheme (Tessier et al. 1979; Jain et al. 2007; Rao
et al. 2008). Accordingly, the following five fractions
(F) were extracted and analyzed.
2.3.1 Fraction 1 (F1): Exchangeable cation fraction (ECF)
One gram of the \63-lm sediment sample was mixed with
15 ml 1 M magnesium chloride (MgCl2) and agitated for
2 h at 30 C.

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385

Fig. 1 Map showing study area and sampling points

2.3.2 Fraction 2 (F2): Carbonate-bound fraction (CBF)

The residual solid from fraction 1 was agitated with 15 ml
of 1 M sodium acetate (NaOAc) adjusted to pH 5.0 with
99.83 % acetic acid for 12 h at 30 C.
2.3.3 Fraction 3 (F3): Easily reducible fraction (combined
with Fe/Mn oxyhydrates; ERF)
The residue obtained from step 2 was refluxed at 96 C
with 15 ml of 0.04 M hydroxylamine hydrochloride
(NH2OH HCl) in 25 % (v/v) acetic acid for 12 h.
2.3.4 Fraction 4 (F4): Organic fractions including
sulfides (OF)
The residual solid obtained from Fe/Mn-Oxide fraction
(fraction 3) was shaken with 5 ml of hydrogen peroxide
(30 % H2O2) at 85 C in a water bath for 3 h. The pH was
maintained at 2 with 0.02 M HNO3. Then, 1 M NH4OAc
was added and kept for 24 h at room temperature. A second
3-ml aliquot of 30 % H2O2 (pH 2 with HNO3) was then
added and the sample was heated again to 85 C for 3 h.
After cooling, 5 ml of 3.2 M ammonium acetate in 20 %

(v/v) HNO3 was added. The sample was diluted to 100 ml

and agitated continuously for 30 min.

2.3.5 Fraction 5 (F5): Residual fraction (RF)

Finally, the residual solid from the organic and sulphide
fraction of metals was digested in a microwave digester
with a mixture of HNO3 and HClO4 (3:1) at 180 C for
30 min and then it was filtered and the final volume was
made up to 25 ml with ultrapure water.
In each fractionation step, the extractions were carried
out using centrifuge tubes (50-ml polypropylene tubes with
cap) in order to minimize losses of solid materials, and
centrifuged at 2,000 rpm for 30 min. The supernatant was
filtered through Whatman No. 41 filter paper, and the
residue was washed, shaken with 8 ml of deionized water
for 30 min, and centrifuged, so it was ready for the next
step. The extracted metals were detected with voltammetric
trace metal analyzer.
All the glassware and plastic containers were washed
with 15 % nitric acid solution and rinsed thoroughly with
ultrapure water. All the samples, chemical solutions, and
standards were prepared using ultrapure water. Working

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standards were prepared from 1,000-ppm standard stock

solution of metals (Merck, Germany). The result of heavy
metals in sediment is presented as lg/g dry weight. Statistical analysis was performed by Statistical Package for
Social Sciences (SPSS Version:11; SPSS Inc. 1995).
2.4 Enrichment factor
The reference element used was Fe, as it was observed
that Fe could be used as a normalization element for the
sedimentary geochemistry, which would provide a better
result and also help in universal comparison. The concentration of metals in the world surface rock average
(Martin and Meybeck 1979) was used as the base level
for metals.

Environmentalist (2012) 32:383393

Table 1 Physico-chemical characteristics of sediments
Sample

pH

OC
(%)

Sand
(%)

Silt
(%)

Clay
(%)

Textural
class

SD-1

6.89

2.11

39.95

0.62

59.43

Sandy clay

SD-2

6.87

1.58

77.89

4.85

17.26

Clayey sand

SD-3

4.96

1.46

78.19

3.27

18.54

Clayey sand

SD-4

4.98

1.00

85.52

4.66

9.82

Muddy sand

SD-5

4.93

4.21

79.94

2.30

17.76

Clayey sand

SD-6

4.99

5.12

63.71

3.96

32.33

Clayey sand

SD-7
Mean

5.17
5.54

3.22
2.67

86.78
73.14

2.65
3.19

10.57
23.67

Clayey sand

Table 2 Total metal content of sediments

Enrichment factor EF) C1 M=C1 R=C2 M=C2 R

Sample

Zn (lg/g)

where C1M = the content of the examined element in the

examined environment, C2M = the content of the examined element in the reference environment, C1R = the
content of the reference element in the examined environment, and C2R = the content of the reference element
in the reference environment.

SD-1

1,124.62

Cd (lg/g)
3.79

Pb (lg/g)

Cu (lg/g)

234.16

49.92

Fe (%)
9.53

SD-2

968.27

5.12

390.72

115.66

7.83

SD-3

2,586.44

17.64

245.86

84.45

10.30

SD-4

856.78

5.99

228.98

141.38

7.68

SD-5

1,560.46

12.76

169.06

109.7

13.02

SD-6

571.2

8.44

194.57

504.67

12.75

SD-7

1,078.34

12.76

86.24

157.22

19.50

2.5 Pollution load index (PLI)

Mean

1,249.44

9.5

221.37

166.14

11.52

Pollution load index (PLI) for a particular station (site

index) has been calculated (Tomlison et al. 1980) by taking
the nth root of the n highest contamination factors multiplied together:

carbon was 2.67 %. The sample SD-6 showed the highest

value of OC.

PLI CF1  CF2  CF3      CFn 1=n

3.2 Heavy metals

where n is the number of metals, CFx (contamination

factor) = concentration of metal x/background concentration of metal x.

The total metal concentration is shown in Table 2. The mean

concentration of Zn, Cd, Pb, and Cu in the sediment was
1,249.44, 9.5, 221.37, and 166.14 lg/g, respectively. Fe
content varied from 7.68 to 19.5 %, with a mean of 11.52 %.
Previous studies showed that Zn concentrations in the
polluted sediments were up to 4,000 lg/g (Everrarts and
Fischer 1992; Spencer and MacLeod 2002) and in unpolluted sites it ranged from 9 to 162 lg/g (Ridgway et al.
2003). The sediments of the present study fall under the
former one as the concentration of Zn ranges from 571.2 to
2,586.44 lg/g.
The Cd concentration varied between 3.79 and
17.64 lg/g. The cadmium concentration recorded in the
present study was well above the permissible limit (2 lg/g)
given by USPHS (1997). Similarly, Padmalal et al. (1997)
noticed a high concentration of Cd in some places of
central Vembanad estuary, where the Periyar River drains.
Previous studies on Cd in estuarine sediments have
reported that polluted areas had Cd concentrations in the
range of 20.5130.0 lg/g (Svete et al. 2001; Tack and
Verloo 1999), whereas the concentrations of Cd in

3 Results and discussion

3.1 Physico-chemical characteristics
Textural characteristics, pH, and percentage of OC (OC %)
are given in Table 1. The major textural classes observed
are sandy clay, clayey sand, and muddy sand. All the
sediment samples were slightly acidic in nature. Normal
values of pH at site 1 owed to the tidal influence prevailing
in this area. The maximum, minimum, and mean values of
sediment pH were 6.89 (SD-1), 4.93 (SD-5), and 5.54,
respectively. The trend shows a lower pH in the estuarine
region compared to the industrial region. The same trend
was also observed for OC. High organic carbon content
was observed at the sites downstream of industrial effluent
discharge points. On average, the percentage of organic

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387

unpolluted areas were within the range of 1.568.0 lg/g

(Santamaria-Fernandez et al. 2005; Svete et al. 2001).
Thus, the sediment samples investigated in the present
study are considered as moderately polluted by Cd.
Several studies on Pb in sediments have been reported
from several regions. High levels of Pb, 26630 lg/g, were
detected in the sediments of polluted areas (Aluoupi and
Angelidis 2001; Leivuori 1998; Everrarts and Fischer 1992).
Low levels of Pb, 0.560 lg/g, were found in the sediments
of unpolluted regions (Leivuori 1998). The Pb concentration
recorded in the current study (the mean concentration) when
compared to those reported studies revealed that the sediment samples collected were from polluted sites.
A very high concentration of Cu was noticed in all the
samples, especially SD6, compared to the standard value
(30 lg/g, USPHS 1997). It has been reported that the concentration of Cu in polluted areas ranges from 20.0 to
343.0 lg/g, while in unpolluted areas it will be between 1.0
and 13.0 lg/g (Santamaria-Fernandez et al. 2005; Spencer
and MacLeod 2002; Sulivan and Taylor 2003). In comparison
to these results, the concentrations of Cu in the samples of the
present study are high (49.92504.67 lg/g). Therefore, the
investigated samples are considered as polluted by Cu.
The results are compared to generic sediment quality
guidelines (SQGs). Threshold effect sediment quality
guidelines for metals are given in Table 3. Zn concentration was well above the severe effect level (SEL), except
for one sample (S6). In the case of Cd, four samples fell
between the probable effect level (PEL) and SEL and three
were above SEL. Only one sample showed higher Pb
concentration than SEL. Most of the samples showed Cu
concentration less than PEL, except sample no. 6. All the
sediments were under the highly polluted class of USEPA
(1992) for metals Zn, Pb, and Cu (Table 3).
The previous studies (Ouseph 1996; Tuna et al. 2007)
conducted in this region showed that the concentration of
Table 3 Sediment quality guidelines (SQG) for metals (lg/g)

MacDonald et al.
(2000)

USEPA (1992)

SQG

Zn

Cd

Pb

Cu

TEL

123

0.6

35

35.7

PEL

315

3.53

91.3

197

SEL
TEC

820
121

10
0.99

250
35.8

110
31.6

PEC

459

4.98

128

149

Non-polluted

\90

\40

\25

Moderately
polluted

2550

4060

2550

Highly
polluted

[50

[60

[50

TEL threshold effect level, PEL probable effect level, SEL severe
effect level, TEC threshold effect concentration, PEC probable effect
concentration

metals in water and sediments was higher during the premonsoon season (February to May). This behavior of trace
metals can be explained by the impact of wastewaters
along with reduced river flow that cause elevated levels of
metals during the dry season.
The correlation of heavy metals in sediments with sediment pH and organic carbon has been statistically tested
(Table 4). The present study observed a weak correlation
of OC with clay and Fe, which is supported by earlier
studies done by Balachandran et al. (2006). The results
exhibit a negative correlation between sediment pH and
heavy metals except Pb. Organic carbon (OC) was negatively correlated with Pb and Zn and positively (not significant) with Cd and Cu. In an earlier study, Nasir and
Harikumar (2011) observed a significant positive correlation between Zn and organic matter where as negative
correlation with Pb and Cu. According to them, no significant correlation was noticed between Cd and organic
matter. Various studies have shown that sediments rich in
organic materials serve as a biogeochemical sink for heavy
metals, mainly due to the high concentrations of organic
matter and sulphides under permanently reducing conditions (Nelson and Lamothe 1993). The lack of a significant
correlation of metals obtained in this study with organic
matter might be due to the high metal concentrations.
Metals have not shown any significant correlation with
sediment texture. This is well supported by Selvam et al.
(2011) who found that Zn and Cd were not controlled by
any size fraction, whereas other heavy metals were negatively correlated with sand. The same results have also
been observed by Padmalal et al. (1997). This shows that
the lithogenic component is not a controlling factor of
metals in sediments and the high concentrations were
affected by anthropogenic discharges. The present study
focused on the metal contamination of lower reach of the
Periyar River and nearby areas of Cochin barmouth, which
is contaminated by a large number of industries (Harikumar et al. 2009; Selvam et al. 2011) where as the earlier
studies analyzed the whole Cochin backwater system.
Hence, the absence of a significant correlation between
metals and any of the sediment physic-chemical parameters
might be owed to the high influx of contaminants from the
industries, which is the lower rate of formation of organic
complexes with respect to the input of metals from
anthropogenic sources as the organic matter influences the
distribution of metals by forming organic complexes
through flocculation (Zourarah et al. 2007).
The concentration of metals observed in the sediments
of the lower reaches of the Periyar River was compared to
the concentration of metals reported for other rivers/estuary
in India and elsewhere (Table 5). From Table 5, it can be
noticed that the mean values recorded for Zn and Cd in the
Periyar River are found to be higher than for the other

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Environmentalist (2012) 32:383393

Table 4 Pearsons correlation between physico-chemical characteristics and metals of sediments

Zn

Cd

Zn

Cd

0.768*

Pb

0.015

-0.438

Pb

Cu

Fe

pH

OC

Sand

Clay

1
1

Cu

-0.520

-0.057

Fe

-0.035

0.488

pH

-0.234

-0.680

0.630

-0.368

-0.410

OC

-0.301

0.176

-0.528

0.698

0.595

-0.358

0.167

0.488

-0.148

-0.053

0.252

-0.578

-0.120

Silt

-0.225

-0.058

0.438

0.357

-0.313

-0.222

-0.196

0.622

Clay

-0.138

-0.456

0.102

0.019

-0.212

0.565

0.130

Sand

Silt

-0.202
-0.834*

1
0.231

1
1
1

-0.998**

1
-0.673

** p = 0.01; * p = 0.05, significant correlation

Table 5 Comparison of sediment metal concentrations with other rivers/estuaries and average values
Zn (lg/g)

Cd (lg/g)

Pb (lg/g)

Cu (lg/g)

Fe (%)
11.52

Periyar

1,249.44

9.5

221.37

166.14

Achankovil

415

72

224

1.19

Reference
Present study
Prasad et al. (2006)

Ganga

569.91

466.32

717.09

15.27

Nile

106.38

2.42

89.61

45.58

4.68

Lasheen and Ammar (2008)

Brahmani
Nandira

21.56
48.18

1.96
2.09

11.57
20.51

13.3
17.01

2.28
3.17

Rath et al. (2005)

Rath et al. (2005)

Godavari

53

13

73

6.03

Subramanian et al. (1985)

Narmada

50

40

3.14

Cochin estuary

542.2

4.33

35.5

6.72

5.30

Balachandran et al. (2006)

Harikumar et al. (2009)

Subramanian et al. (1985)

Vembanad wetland

Purushothaman and Chakrapani (2007)

528.21

6.63

66.40

64.35

1,963.67a

26.35a

162.59a

1,723.75a

Indian average

16

11

28

2.90

World average

350

1.0

150

100

4.80

Subramanian (1987)

Surface rock

129

0.13

20

32

3.59

Martin and Meybeck (1979)

Maximum values, which were observed at the industrially polluted areas of Periyar River

rivers. The concentration of metals observed in the present

study was higher than the values given by the earlier
studies in the Cochin estuary and Vembanad wetland. The
location of sampling sites and the higher number of samples from the downstream region of an industrial area
might be the major reason for this difference. The overall
results point out that the concentration of metals recorded
in Periyar River is higher than average metal levels
reported in India (Subramanian 1987) and the rest of the
world (Martin and Meybeck 1979).

4 Sequential extraction of heavy metals in sediment

The mobility and availability of heavy metals in sediments
depend largely on how the metals are associated with the

123

components of the sediment. The selective sequential

extraction of heavy metals provides detailed insight on the
behavior of heavy metals in the sediment. In the present
study, the metals bound to the sediment through phases
such as exchangeable cation fraction (ECF: F1), carbonate
bound fraction (CBF: F2), easily reducible fraction (ERF:
F3), organic fraction (OF: F4), and residual fraction (RF:
F5) were analyzed. Exchangeable fraction is bound to the
sediments by weak adsorption onto sediment particles.
Metals bound to carbonates are sensitive to pH changes, the
lowering of pH being associated with the release of metal
cations. The exchangeable and carbonate-bound fractions
of metals are considered as anthropogenic origin. The
metals bound to reducible fraction (FeMn oxides) are able
to redissolve into water under reducing conditions while
degradation of organic matter can lead to the release of

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389

over the last few decades and this might be the reason for
the shift in the fractionation of metals in the study area, i.e.,
the fractionation behavior of metals in the Periyar River is
almost the same as that of Cochin estuary.
The sum of total fractions of each metal in various
samples is given in Table 6. The cumulative amount of
elements recovered during the five-step sequential extraction procedure was up to 86.2993.37 % of that obtained
by total metal analysis (Table 7). This supports the overall
accuracy/efficiency of the extraction procedure.
Figures 2, 3, 4, 5 illustrate the mean percentage of metal
fractions for various metals, which is in the following
order:

120
100

Pb (%)

metals bound to organic matter fraction. Mainly FeMn

oxide and organic matter act as a sink for heavy metals in
the aquatic ecosystem. The metals within the crystalline
matrix of minerals, which are naturally occurring fractions,
are known as residual fractions and are generally less bioavailable.
The results of sequential extraction in terms of percentage of each metal fraction in sediment samples are
graphically represented (Figs. 2, 3, 4, 5). Zn, Pb, and Cu
showed higher percentage in the last two fractions, especially the residual fraction (RF), where as Cd was found
(Fig. 3) in the first two fractions (ECF and CBF). A relative
increase in the organic bound (F4) and residual fraction
(F5) at the downstream was observed in the case of Cd,
which was already reported by Nair et al. (1991). More
fractions of Pb were found in the upstream sites, especially
for SD-1. The very low concentration of Pb in the F1
fractions observed in this study is comparable with the
earlier studies done by Nair et al. (1991), but the high
concentration of Pb observed in F5 in this study is contrary
to his results. Cu was absent in the EC fraction (ECF) and
showed high concentration in F5 and F4. The earlier study
(Nair et al. 1991) showed that Cu was found distributed in
F1, F2, and F3 fractions at upper reaches (near industrial
outlets) of the Periyar River and in F4 and F5 at lower
reach (estuarine part). The freshwater regions of the lower
stretches of Periyar have changed into saline water regions

80
60
40
20
0
SD1

SD2

F1

SD3

SD4

F2

F3

SD5

SD6

F4

F5

SD7

Fig. 4 Percentage of Pb in various chemical fractions of sediments

120

120

100

Cu (%)

Zn (%)

100
80
60

80
60
40

40

20
20

0
0

SD1
SD1

SD2

F1

SD3

F2

SD4

SD5

SD6

F3

F4

F5

F1

Fig. 2 Percentage of Zn in various chemical fractions of sediments

Cd (%)

SD2

SD3

SD4

SD5

SD6

F4

F5

SD7

SD7

F2

F3

Fig. 5 Percentage of Cu in various chemical fractions of sediments

120

Table 6 Sum of five fractions of metals in the sediment

100

Sample

80

Zn (lg/g)

Cd (lg/g)

Pb (lg/g)

Cu (lg/g)

SD-1

945.78

3.37

207.10

40.13

SD-2

884.19

4.81

389.95

117.35

40

SD-3

2,362.42

15.22

202.57

76.55

20

SD-4

692.08

5.97

185.47

129.14

SD-5

1,244.58

12.21

167.58

109.33

SD-6

539.86

7.61

199.70

433.61

SD-7

877.85

12.89

78.52

147.37

Mean

1,078.11

8.87

204.41

150.50

60

SD1

SD2

F1

SD3

SD4

SD5

SD6

F2

F3

F4

F5

SD7

Fig. 3 Percentage of Cd in various chemical fractions of sediments

123

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Environmentalist (2012) 32:383393

Table 7 Comparative analysis of total metal concentration and the

sum of extraction procedure
Metal
(lg/g)a

Sum of five-stage
extraction

Direct
procedure

Recovery (%)

Zn

1,078.11

1,249.44

86.29

Cd

8.87

Pb
Cu

204.41
150.5

9.5

93.37

221.37
166.14

92.34
90.59

Mean concentration of seven samples

Zn  RF [ OF [ ERF [ CBF [ ECF

Cd  CBF [ ECF [ RF [ OF [ ERF
Pb  RF [ CBF [ OF [ ECF [ ERF
Cu  RF [ OF [ ERF [ CBF [ ECF
The results indicate that Cd is distributed very
dangerously in the mobile fractions, F1 and F2 (i.e., in
ECF and CBF), indicating its high mobilization potential in
the study area. According to Muniz et al. (2004), the
changing pH and redox conditions were of primary
importance in the potential release of metals from
sediment. Therefore, a great percentage of this metal can
be mobilized from sediment to water by a decline in pH
(from carbonate fraction) or by a decrease of redox potential
(from oxide fractions), due to the input of organic matter or
the depletion of dissolved oxygen content. The chemistry of
cadmium in surface and ground waters has been reviewed
by Hem (1972), who gives calculations of equilibrium
solubilities with Cd(OH)2 or CdCO3, showing minimum
solubility at pH 9.010.0. Therefore, the acidic pH obtained
in the river water during the present study is of great
concern. Low organic and residual fractions of Cd indicate
the authigenic association with riverine sandy sediments
(Nair et al. 1991).
For Zn, Pb, and Cu, the highest concentration of metals
was found in residual fractions (57.14, 78.35, and 64.03 %,
respectively). It was found that exchangeable and carbonate fraction of Zn is much less (14.5 %) compared to Pb
(18.97 %). These indicated that both Pb and Zn are
regarded as relatively stable under normal conditions. This
finding agrees well with the data reported by others
(Lasheen and Ammar 2008; Yuan et al. 2004). The second
and third largest portion of Zn was bound with organic and
easily reducible fraction, which may be due to the scavenging effect of Mn/Fe oxides in the sediments. This
sorption of zinc with iron in the sediment may strongly
hinder their mobility in the Periyar River environment, but
an earlier study conducted by Nair and Balchand (1993)
showed a composite fractionation of Zn. The significant
portion of Zn in the carbonate-bound fraction might be due
to the complexation with calcium carbonate (Li et al.

123

2000), but the carbonate-bound fraction of Pb showed the

second highest at different sites compared to residual
fractions (Fig. 4). The high concentration of Pb in residual
fractions might be due to the incorporation of Pb in alumino-silicate minerals (Yuan et al. 2004). Ho (2000) suggested that the high affinity of organic ligands makes Cu in
river sediments more stable, leading to the suppression of
diffusion and dispersion of Cu. In addition, organic compounds under the reduced condition may be more active to
bind with Cu. The significantly high Cu concentration in
organic and sulfide fraction in the sediments of Periyar
River and Cochin estuary can be attributed to the high
stability constant of organic-Cu compounds (Lasheen and
Ammar 2008). Cu is preferentially retained on the organic
matter by complexation rather than by ion exchange (Prasad et al. 2006). Thus, the organic matter plays an important role in the immobilization of Cu, but mineralization of
the host organic material under oxidizing conditions will
release Cu into the overlying water column (Jain et al.
2007). Dredging in the study area can cause oxidation of
the organic-rich sediments. In this context, the widespread
dredging activities in the study area are of concern because
it could cause oxidation of the organic-rich sediments.
The present study analyzed the distribution of metals in
various chemical phases. Cadmium is found distributed in
easily available fractions such as CBF and ECF compared to
other metals. As per Nair et al. (1991), estuarine reactivity is
such that exchangeable species are subject to severe changes.
The low percentage of Cu in this fraction is mainly due to the
presence of other competing strongly binding phases and Zn
and Pb normally have affinity for sediment in the
exchangeable form. The selective build-up of Cd and Pb
observed in the CBF fraction compared to the other metals
and the results agree well with the observations made by Nair
et al. (1991), except in the case of Pb, who also observed that
at high saline conditions, the percentage distribution of Cd in
CBF fraction is higher. The metal concentrations associated
with ERF are of comparatively low magnitude, especially Cd
and Pb. Zn and Cu distributed more in the OF compared to
other metals. The weak distribution of metals in ERF indicates the presence of reducing conditions in the study area.
According to Jain et al. (2007), these conditions can release
metals into pore water. The anoxic condition of the system is
also confirmed by the high percentage of Cu in OF. The
distribution of metals in this phase indicated the status of the
sedimentary process. This is as important as the metal
behavior, and natural levels as well as anthropogenic stresses
are influenced by the sedimentary process. All of the metals
except for Cd have large residual fraction content in the
sediments of the study area.
The geochemical properties of the sediments critically
affect the bioavailability of metals in sediments (Wang and
Fisher 1999). The remobilization potential of metals bound

391

60

Very high risk

50
40
30
20

High risk

160

14

140

12

120

10

100

CF

ECF and CBF %

70

Medium risk

80

60

10
SD1

40

Low risk

0
SD2

SD3
Zn

SD4
Cd

Pb

SD5

SD6

SD7

20

Cu

SD1

Fig. 6 Percentage of exchangeable and carbonate-bound fraction of

metals in sediments

to various sedimentary phases is different and is based on

bond strength. Therefore, the strength values can give a clear
indication of sediment reactivity that can be used to assess
the risk related with metals to the aquatic organisms. The
Risk Assessment Code (RAC) is based on the percentage of
metal in the first two fractions (exchangeable and carbonate
bound). The major RAC classes are no risk (\1 %), low risk
(110 %), medium risk (1130 %), high risk (3150 %), and
very high risk ([50 %; Jain et al. 2007). According to this,
for any metal, sediments with 1130 % carbonate and
exchangeable fractions would be at medium risk to the
environment. Furthermore, the sedimentary metals with
these fractions at more than 50 % are considered as a very
high risk and could easily enter the food chain (Jain 2004).
The relatively high percentages of exchangeable and carbonate-bound fractions of Cd in the sediment indicated high
risk to very high risk (Fig. 6) in all the samples. Other metals
are in the range of low to medium risk.
Metals and elements exist in relative proportions to each
other in natural systems. Therefore, the ratio between
metals and conservative elements can reveal the geochemical imbalances due to anthropogenically deposited
high metal concentrations. Enrichment factor analysis
therefore can indicate anthropogenic pollution of heavy
metals. Metal accumulation in the sediments was compared
with other places of the country/world by enrichment factor
(EF) analysis (Simex and Helz 1981). The EF calculated
for the sediments is given in Table 8. For Zn, Pb, and Cu,
the factor values showed that most of the sites are
Table 8 Enrichment factor of metals in the Periyar River sediments
Sample

Zn

Cd

Pb

Cu

SD1

3.28

10.99

4.41

0.59

SD2

3.44

18.07

8.96

1.66

SD3

6.99

47.32

4.28

0.92

SD4

3.11

21.55

5.35

2.07

SD5

3.34

27.07

2.33

0.95

SD6

1.25

18.29

2.74

4.44

SD7

1.54

18.09

0.79

0.90

PLI

Environmentalist (2012) 32:383393

SD2

CFZn
CFCu

SD3

SD4

CFCd
CFFe

SD5

SD6

SD7

CFPb
PLI station

Fig. 7 Concentration factor (CF) and pollution load index (PLI) of

metals at various sites

moderately contaminated (2 \ EF \ 10). A very high EF

value was found for Cd (10.9947.32), which indicates
significant contamination of Cochin estuary and the lower
reaches of Periyar River during the study period (Alomary
and Belhadj 2007). These results confirm the observations
made by Nasir and Harikumar (2011). The concentration
factor and PLI for Periyar River sediments are given in
Fig. 7. The PLI of the sites were [1 (6.5812.04), which
showed a significant metallic pollution in this region.
Heavy metals bound to sediments can be released into
the aquatic environment when reduced sediments are
transported to the oxic environment due to natural processes such as bioturbation, tidal action, storm events, as
well as human activities such as shipping and dredging
(Tao et al. 2005). Also, the microbially mediated redox
reactions result in a reduction of some of the insoluble
Fe(III) and Mn(II) oxides and release them into pore water.
In this process, metals may also get into the overlying
water and benthic biota (Petersen et al. 1995).
The total metal concentration, metals bound to various
fractions, and analysis of environmental indices showed
that the sediment of Periyar River and Cochin estuary is
highly contaminated with metals such as Zn, Cd, Pb, and
Cu. This indicated that the present physico-chemical characteristics of this system are capable of remobilization of
metals (especially cadmium) into the water and which will
be a potential hazard to the biological system. It will be
more deleterious if there are further changes in the physicchemical characteristics such as pH, salinity, oxic/anoxic
conditions, and organic and inorganic complexing agents.

5 Conclusions
The present study explained various fractions of metals and
will help in aquatic eco-toxicity studies. The confluence
point of the Periyar River and Cochin estuary was highly
polluted with industrial effluents. The present study confirms
the significant level of heavy metal pollution in this area. The

123

392

distribution of heavy metals in the sediment was not uniform

over the whole study area. In general, the upstream regions of
the study area showed higher values compared to the
downstream regions. The average sediment metal concentrations in the study area decreases in the order
Zn [ Cu [ Pb [ Cd. It was evident from the sequential
extraction that Cd is weakly bound with sediment compared
to other metals. Hence, the bioavailability of Cd in the system is significantly higher than Pb and Cu. Also, environmental quantification shows high accumulation of metals in
the Periyar River sediment. The high concentration and
bioavailability of metals indicate that there is a need to
conduct more detailed and continuous monitoring studies in
this region and to take steps to reduce the sources of pollution. Further deterioration of geochemical parameters may
enhance the bioavailability of metals and will adversely
affect the aquatic system and health of local people, as they
are depend on the system for their livelihood.
Acknowledgments The financial support from the Ministry of Earth
Sciences (MoES), Government of India, through their project
(No.MoES/8/PC/2(3)/2007-PC-IV) is gratefully acknowledged. The
authors also wish to acknowledge the suggestions by the anonymous
referee in improving the quality of the manuscript.

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