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Evaluation of total trace metal (TTMs)

enrichment from estuarine sediments of
Uppanar, southeast coast of India

Article in Arabian Journal of Geosciences · December 2016

DOI: 10.1007/s12517-015-2048-4

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Arab J Geosci43:9 )6102(
DOI 10.1007/s12517-015-2048-4
ORIGINAL PAPER
Evaluation of total trace metal (TTMs) enrichment from estuarine
sediments of Uppanar, southeast coast of India
G. Kalpana 1 & A. Shanmugasundharam 1 & S. Nethaji 1 & Arya Viswam 1 & R. Kalaivanan 1 &
V. Gopal 1 & M. Jayaprakash 1
Received: 31 March 2015 / Accepted: 10 September 2015
# Saudi Society for Geosciences 2015
Abstract The present study was carried out to investigate the
impact of anthropogenic influences on Uppanar estuary situ-
ated at Cuddalore with regard to trace metal concentration in
sediment samples of the study area. The Uppanar River runs
similar to the coast south of Cuddalore town and a number of
small streams of domestic, treated and unprocessed effluents
from industries join the coast through the river. Average con-
centration of Cr, Cu and Ni (106, 87 and 137.1 ppm) is above
the continental value indicating that increase in the concentra-
tion may be due to metal industries, and surface runoff of the
fertilizer remains increases the concentration of the metal in
the sediments. There is moderate level of pollution related to
anthropogenic activities. The trace metals showed association
with Fe and Mn indicating their adsorption on Fe–Mn
oxyhydroxides. Correlation coefficient between pairs of
metals concentration show that all metals and organic carbon
significantly correlate with trace metal except sand and calci-
um carbonate. Geoaccumulation index and enrichment fac-
tors, the sediment is classified as unpolluted to moderately
polluted with Fe, and Cu and moderate to considerable with
Pb and Co. From the study, it can be revealed the anthropo-
genic activities are the prime source for the biodegradable
toxic metal in the sediment of Uppanar estuary in the
Cuddalore coastal zone.
Keywords Estuary . Trace metals . Contamination factor .
Enrichment factor and Igeo
* G. Kalpana
gkalpana1@gmail.com
1
Department of Applied Geology, Global and Environmental Change
Research Group, University of Madras, Guindy Campus, Tamil
Nadu, India
Introduction
In aquatic ecosystem, sediments are the main sink and source of
heavy metals, serving as a significant role in the transportation
and storage of potential noxious metals (Kim et al. 2010; Sun et
al. 2012, Duran et al. 2012, Alonso Castillo et al. 2013;
Superville et al. 2014). Estuaries are recognized as some of
the most productive environments on the planet, supporting
many different ecosystem goods and services (Savage et al.
2012). The trace element content in the estuarine sediments
reflects the range of chemical, oceanographic and geological
controls on their distribution. Such controls include the compo-
sition of the sedimentary detritus, the partition of the trace ele-
ments between the solid and solution and the post depositional
conditions in bottom sediments (Calvert and Pedersen 1993).
Toxic metal pollution in sediment has been proved to be an
increasingly global problem (Fernandes et al. 2008; Kucuksezgin
et al. 2008) and is considered to pose a serious threat to the
aquatic environment result from their toxicity, non biodegradable
and persistent nature, and bio enrichment ability in food chain
(Gopinath et al. 2009; Nobi et al. 2010). Heavy metals in aquatic
system are increasingly identified as important intermediate
sources for subsequent occurrence of pollution in aquatic ecosys-
tems, even public health, due to rapid urbanization and industri-
alization (Alonso Castillo et al. 2013). Besides, high variation
loads in heavy metal occur among impervious surfaces along
with different urban land uses (Zhao et al. 2010). These elements
are deposited onto sediment surfaces and immobilized through
adsorption, coagulation or flocculation and incorporation into the
lattice structure of minerals (e.g. Fe–Mn oxides) and precipitation
by forming insoluble fractionation (such as metal sulfides) (Du
Laing et al. 2009; Lin et al. 2013). Only a small portion of free
metal ions, however, stay dissolved in water (Hou et al. 2013).
and in comparable, more than 90 % of heavy metals load in
aquatic systems have been found to be related to suspended
particles and sediments (Zahra et al. 2013). Thus, the distribution
34 Page 2 of 14
of trace metals in sediment adjacent to populated areas can give
us the evidence of anthropogenic influence on aquatic system
and convenience in assessing the potential risks associated with
human waste discharge.
More than 90 % of the heavy metal load in aquatic systems is
bound to suspended particulate matter and sediments (Calmano
et al. 1993). Therefore, sediments serve as a pool of metals that
could be released to the overlying water from natural and anthro-
pogenic processes such as bioturbation and dredging, resulting in
potential adverse health effects (Long et al. 1995; Argese et al.
1997). Indeed, estuaries are among the most productive marine
ecosystems in the world, serving as feeding, migration routes and
nursery grounds of many organisms, and it is important that
sediment contamination by trace metals be evaluated and that
natural versus anthropogenic contribution be distinguished for
effective remedial actions against metal pollution (Chapman
and Wang 2001). In recent years, increasing attention was given
in the level of heavy metals in the sediment bed (Carral et al.
1992, 1995; Carballeira et al. 1997; Harikumar et al. 2009;
Ratheesh Kumar et al. 2010; Paneer Selvam et al. 2012).
Given the importance of aquatic environment, numerous stud-
ies have been focused on heavy metal pollution (Atkinson et al.
2007; Luoma and Rainbow 2005; Saeedi et al. 2013; Simpson
2005) and the metal geochemical nature association in sediments
(Lee et al. 2000; Simpson et al. 2012). Also, trace metal concen-
tration in sediment can be used to reveal the history and intensity
of local and regional pollution (Sekabira et al. 2010, Nyangababo
et al. 2005). The aim of the present study is an attempt to assess
the influence of anthropogenic activities with specific reference
Fig. 1 Study area map with
sample locations-Uppanar estuary
Arab J Geosci43:9 )6102(
to the concentrations of trace metals and spatial distribution of
trace metal in Uppanar estuary, Cuddalore coastal zone, SE coast
of India.
Study area
The Uppanar estuary is situated at Cuddalore (latitude between
11° 41′ 0″ and 11° 43′ 0″ N, longitude 79° 44′ 01″ and 79° 49′
01″ E) and is at an average height of about 1 m above sea level
(Fig. 1). It is transient through the industrial coastal town of
Cuddalore on the southeast coast of India. The Uppanar River
runs similar to the coast south of Cuddalore town, and a number
of small streams of domestic, treated and unprocessed effluents
from industries join the coast through the river. SIPCOT indus-
trial park (State Industries Promotion Council of Tamil Nadu) is
located on the northern bank of Uppanar estuary covering an area
of about 520 acres with 44 industries, which include chemicals,
petrochemicals, pharmaceutics, pesticides, fertilizers and metal
processing industries. The major industries along the western
bank of Uppanar River contain chemicals, beverage industrial-
ized, tanneries, oil, soap, paint production, paper and metal pro-
cessing plants; all industries are located along its western bank.
Material and methods
The sampling design includes collection of surface sediment
at a total of 16 sites of Uppanar estuary in Cuddalore district
using grab sampler. The stations were selected considering
Arab J Geosci43:9 )6102(
possible heavy metal concentrations in sediments of the estu-
ary from the nearby industries and sewage outlet. All samples
were collected during the month of October 2013, and collect-
ed samples were air dried and homogenized. Textural studies
of sand, silt and clay were performed out following the pro-
cedure of Ingram (1970). Carbonate content was measured
using the method described by Loring and Rantala (1992).
Organic matter was estimated in the form of organic carbon
based on the procedure suggested by Gaudette et al. (1974) to
assess the role played by organic carbon in the retention of
trace metals. For total metal analysis, a known quantity of
sediment was digested with an acid mixture of HClO4 and
HF, and the final residue was leached with HCl and made up
to the required quantity (Tessier et al. 1979).
Trace metal concentrations (Fe, Mn, Cr, Cu, Ni, Co, Pb and
Zn) were measured using flame AAS (Perkin-Elmer AA700)
equipped with a deuterium background corrector. Suitable in-
ternal chemical standards (Merck Chemicals, Germany) were
used to calibrate the instrument. All the reagents used were of
analytical grade and high purity. The accuracy of the analyti-
cal procedures in the present study was assessed using the
certified reference material MESS-1 (Sundarajan and
Srinivasalu 2010) from the National Research Council of
Canada.
Index of geoaccumulation
The index of geoaccumulation (Igeo) was computed using the
equation (Muller 1981, Selvaraj et al. 2004, Loska et al. 2004,
Magesh et al. 2011).
Igeo ¼ log2 Cn =1:5Bn
Where Cn is the measured concentration of the element in
the politic sediment fraction and Bn is the geochemical back-
ground value (average shale) in the earth’s crust Wedepohl
(1995). The constant 1.5 allows for natural fluctuations in
the content of a given substance in the environment and very
small anthropogenic influences.
Six classes of the geochemical index (Muller 1981) has
been distinguished
Class Value Sediment quality
0 Igeo 0 Practically uncontaminated
1 0 Igeo 1 Uncontaminated to moderately contaminated
2 1 Igeo 2 Moderately contaminated
3 2 Igeo 3 Moderately to heavily contaminated
4 3 Igeo 4 Heavily contaminated
5 4 Igeo 5 Heavily to extremely contaminated
6 5 Igeo Extremely contaminated
Page 3 of 14 34
Enrichment factor
The enrichment factor (EF) was based on the standardization
of a tested element against a reference. A reference element is
the one characterized by low occurrence variability. In the
present study, Fe was used as the reference doing EF (Szefer
et al. 1998) permits to calculate the heavy metal contamina-
tion, and it was calculated according to the following formula:
E F ¼ ðY=XÞsample =ðY=XÞreference
Ysample —trace element concentration in the sample;
XReference —trace element concentration in the continen-
tal crust (Wedepohl 1995);
Ysample —Fe content in the sample;
X Reference —Fe content in the continental crust
(Wedepohl 1995)
Five contamination categories are recognized on the basis
of the enrichment factor (Acevedo-Figueroa et al. 2006):
EF 2 Deficiency to minimal enrichment
EF=2–5 Moderate enrichment
EF=5–20 Significant enrichment
EF=20–40 Very high enrichment
EF>40 Extremely high enrichment
Contamination factor and pollution load index
The pollution level in trace metal was calculated by the meth-
od based on pollution load index (Tomlinson et al. 1980). This
is a simple method based on pollution load Index to assess the
extent of pollution by metals in estuarine sediments.
C F ¼pffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffi
C metal = C background ffi
PLI ¼ n ðC F1xC F2xC F3X:::::::::::::::::C FnÞ
CF indicates the contamination factor, n is the number of
metals, C metal is the metal contamination in polluted sediment,
and C background value is the background value of that metal.
Four categories of contamination factor have been
distinguished:
C f 1 1 Low contamination factor indication low
contamination
1 Cfi 3 Moderate contamination factor
3 Cfi 6 Considerable contamination factor
6 CfI Very high contamination factor
Pearson correlation coefficient (r) was employed to find the
relationship between physicochemical characteristics and
heavy metal concentration. Multivariate statistical methods
including principle component analysis (PCA) and cluster
analysis (CA) were used to identify the pollution status and
probable sources of heavy metal pollutants in the study area
(Prasanna et al. 2012). The statistical methods such as
34 Page 4 of 14 Arab J Geosci43:9 )6102(

principle component analysis, cluster analysis and Pearson
correlation were analysed using the using SPSS program ver-
sion 10.0 for Windows.
Results and discussion
Sediment texture (sand and mud)
The sediment distribution in estuaries and near shore region to
a large extent depends on the source and texture of sediments
supplied and topographic features of the concerned area
(Sesamal et al. 1986). The relative abundance of sand and
mud (silt+clay) contents of the samples are presented in
Table 1. The sand ranges from 50 to 98.2 %. Stations 2, 3,
4, 5, 12, 13, 14, 15 and 16 near the estuarine mouth region
show dominance of sand. The upstream station silt is domi-
nant i.e. stations 8, 9, 10, 14, 15 and 16. Sediments from
majority of the stations exhibited significant fluctuation in
textural characteristic indicating the discharge dependency in
riverine and estuarine zones. Most of the samples fall in the
field of sandy silt. Depending on the competency of flow, finer
material gets entrained in the runoff, thus leaving being the
coarser sediments as lag deposits. This has resulted in the
coarser sandy nature in the lower reaches.
The organic matter values ranges from 0.1 to 0.94 %
with a mean of 0.7 % and higher values observed in the
middle part of the estuary (Fig. 2). The OM concentration
is found to be high in the regions of mangroves (i.e. sta-
tions 5 and 6) in the study area, and it could be explained
by several factors, such as decrease in the estuarine OC
input, a change in the kind of input (marine vs. continental)
and increase in the sedimentation rate. Variation in organic
carbon content has been attributed to changes in either
productivity of preservation or both. The distribution of
CaCO3 in the study area ranges from 0.5 to 4.5 % with a
mean of 2.52 % which demonstrates gradual variation in
CaCO3 concentrations in middle part of the study area i.e.
stations 4, 5 and 6 (Fig. 2). The higher content of CaCO3
in the station 3 may be due to turbidity current/gravity flow
or from the influx of calcareous biogenic material whereas,
the lower content in the middle and northern part should
have been due to the emplacement of siliceous sand under
gravity flow activity (Achyuthan et al. 2002; Jonathan et al.
2004; Jayaprakash et al. 2013).
The middle transect OM contents are high whereas
CaCO3 contents are lower and the dominance of mud
also indicates that they are attached to finer particles
(Jonathan et al. 2004). The high inputs of terrigenous
material from the adjacent land mass and industrial ef-
fluents nearby have increased the CaCO3 values in the
middle and Northern part; the clayey silt and sandy silt
sediments in these areas also support the deposition of
organic debris (Rajamanickam and Setty 1973). The ob-
servations correlate well with those of the present study
(Mahalakshmi et al. 2011).

Table 1 Details of sediment type and sedimentological and trace metal data for Uppanar estuary sediments

Sample no Sand % Mud % Sediment type CaCO3 % OM % Fe (ppm) Mn (ppm) Cr (ppm) Cu (ppm) Pb (ppm) Ni (ppm) Co (ppm)

1 69.0 31.0 Silty sand 2.0 0.8 32,600 508 173.8 94.2 90.4 196.4 136.50
2 82.0 18.0 Sand 3.0 0.3 19,600 280 43.6 68.2 80.5 69.8 49.20
3 98.2 1.8 Sand 4.5 0.5 22,800 294 121.8 77.8 75.1 132.6 93.40
4 97.2 2.8 Sand 3.5 0.2 15,824 282 78.5 69.2 58.4 38.9 76.30
5 73.0 27.0 Silty sand 2.5 0.5 28,500 332 112.8 80.3 71.2 113.2 123.80
6 55.4 44.6 Silty sand 1.5 0.8 33,600 457 121.5 93.7 96.5 170.1 152.70
7 75.6 24.4 Silty sand 2.5 0.4 33,600 358 99.6 91.2 82.6 109.4 136.50
8 76.0 24.0 Silty sand 2.0 0.4 29,200 278 58.8 80.4 87.6 156.5 107.60
9 80.2 19.8 Sand 3.0 0.4 30,100 329 70.3 89.2 59.2 135.8 54.80
10 66.0 34.0 Silty sand 1.5 0.6 35,200 403 146.1 82.2 72.4 189.8 95.90
11 50.0 50.0 Silty sand 1.0 0.9 43,860 611 186.3 105.8 104.7 220.2 182.30
12 97.6 2.4 Sand 4.0 0.3 24,700 414 63.2 84.7 64.4 54.7 62.10
13 76.0 24.0 Silty sand 2.0 0.8 31,300 451 118.7 90.4 93.2 160.6 120.50
14 97.0 3.0 Sand 3.5 0.2 26,300 380 94.1 80.5 76.7 130.8 85.80
15 97.2 2.8 Sand 3.5 0.5 25,600 422 86.8 78.9 69.6 101.4 80.70
16 84.6 15.4 Sand 0.5 0.6 29,000 436 107.0 96.2 81.1 131.5 100.20
Max 98.2 50.0 4.5 0.9 43,860 611 186.3 105.8 104.7 220.2 182.30
Min 50.0 1.8 0.5 0.2 15,824 278 43.6 68.2 58.4 38.9 49.20
Avg 79.1 20.9 2.5 0.5 28,970 395 106.3 85.4 79.3 131.7 104.99
Arab J Geosci43:9 )6102( Page 5 of 14 34

Fig. 2 Spatial distribution of sand, mud, calcium carbonate and organic matter in Uppanar estuary
34 Page 6 of 14 Arab J Geosci43:9 )6102(

Fig. 3 Spatial distribution of trace metals in Uppanar estuary sediments

Arab J Geosci43:9 )6102( Page 7 of 14 34

Fig. 3 (continued)
34 Page 8 of 14
Total trace metal distribution (TTMs)
In sediment, total metal concentration can indirectly reflect
both logical mineralogy and even the beginning or nature of
sediments (Alagarsamy 2006; Gopinath et al. 2009; Nobi et al.
2010). In general, metal accumulation in aquatic biota has a
significantly correlation with total metal concentrations in the
sediment, which appear to be the most important variable
parameter in environment. The distribution patterns of trace
metals (Fe, Mn, Cr, Cu, Pb, Ni and Co) were depicted through
the interpolation of metal concentrations in Fig. 3. As it is
shown, metal concentrations increase towards the southern
part of the study area. This could be due to the high concen-
trations of industrial and urban wastes from Uppanar indus-
tries. The increasing order in concentrations of the metals is
observed at the estuarine region. Metals concentrations are
found to be higher in the southern part of the study area com-
pared to the northern part. Increasing heavy metals in these
sediments is particularly due to the enhanced OC content,
abundance of fine particles with greater surface area (Ray et
al. 2006).
The concentrations of metals are varied i.e. Mn (278–611),
Cr (43.6–186.3), Cu (68.2–105.8), Ni (38.9–220.2), Co
(49.2–182.3) and Pb (58.4–104.7). The distribution of Fe
and Mn in the sediments depends primarily on the rate of flux
of particulate and dissolved Fe and Mn, sedimentation rate,
biological contribution, the migration of Fe and Mn which in
turn controlled by Eh conditions. Mineralogical control and
oxide coatings over solid particles would also play a signifi-
cant role. Fe and Mn also act as major carriers for many trace
metals in sediments. Total Fe and Mn were low in stations 2, 3
and 4 of the study area, which is dominated by high CaCO3
and sand content near the mouth region, where as the estuarine
region i.e. station 11 indicates high values of total Fe and Mn.
Large amounts of Fe accumulate in the residual phase proba-
bly because it is basically of natural origin (it is the most
common element in the earth’s crust) and can exist as crystal-
line iron peroxides (goethite, limonite, magnetite, etc.). The
major part of the remaining Fe is associated with the reducible
phase. It seems likely that the Fe enrichment results in the
reduction of Fe in the sediment during the oxidation of organic
matter (Francois 1988). The iron and manganese can be con-
verted to complex hydroxy compounds that may eventually
precipitate (Riley and Chester 1971).
Manganese can occur in sediments as discrete oxide parti-
cles, coatings on particles and as manganese (11) adsorbed on
organic materials (Graham et al. 1976; Feely et al. 1980). In
estuaries, organic matter accumulation may lead to the disso-
lution of manganese from sediments (Luoma 1990). Since
manganese can apparently be complexed by dissolved organic
materials and can be retained in solution by the control of
redox potential through oxidation of the more labile dissolved
organics, the amount and kind of organic material present
Arab J Geosci43:9 )6102(
would determine the proportion of manganese exported from
the estuary (Wangersky 1986). It is well established that iron
and manganese oxides are excellent scavengers for trace
metals (Tessier et al. 1979). This would lead the co-
precipitation of other metals in the water column and so in-
crease the concentration of many metals in sediments. Total
trace metal average concentrations of Cu in sediment are
85.4 ppm which indicates that it is above the average conti-
nental crust value. Results indicate that Cu in sediments would
have been originated due to non-geogenic activities mainly
due to anthropogenic activities.
Total trace metal average concentration of Cr in sediment is
106 ppm, and it is found higher than the average continental
crustal values. The results indicate that Cr in sediments would
have originated from both natural and as well as by anthropo-
genic activities. The mean chromium concentration 105 ppm
was higher than the background level, which explained input
of toxic Cr to the study area. Cu shows an average value of
85.4 ppm which shows high values than the average continen-
tal crustal values. Results indicate that Cu in sediments would
have originated from both geogenic and as well as by non-
geogenic activities i.e. anthropogenic activities. Average con-
centration of Ni in sediment samples is 137.1 ppm, which
shows higher values than the average continental crustal
values. Results indicate that Ni in sediments would have orig-
inated from both geogenic as well as by non-geogenic activ-
ities i.e. industrial processes and waste disposal. Cr, Cu and Ni
display quite a similar pattern of distribution, and high con-
centration is observed in stations 5, 6, 7 and 8; these elements
are used as markers of metal industries, and surface runoff of
the fertilizer remains to increase the concentration of the metal
in the sediments (Kumar et al. 2001; Loska et al. 2004). It has
been observed from this study that in station 1 and 11, the
trace metal concentrations are higher compared to other sta-
tions which can be due to the anthropogenic inputs from the
industries and boating activities in station 1 (Krishna and
Govil 2008).
Statistical analysis
In sediments, trace metal concentrations are considered to
vary with sediment properties such as % of OC, grain size
and Fe–Mn oxyhydroxide content (Adriano 2001). In order
to identify any co-variation of trace elements among them-
selves or within sediment properties, Pearson linear correla-
tion matrix was generated. Results of correlation matrix are
presented in Table 2 indicating that significant fraction of trace
metals are found co-precipitated with or adsorbed on to Fe and
Mn geochemical phases controlling the trace metals in sedi-
ments. These characters are due to the large area, extensive
cation exchange capacity and wide spread availability (Szefer
et al. 1995).
Arab J Geosci43:9 )6102( Page 9 of 14 34

Table 2 Correlation matrix for

textural and trace element Sand Mud CaCO3 OM Fe Mn Cr Cu Pb Ni Co
parameters in Uppanar River
estuary Sand 1.00
Mud −1.00 1.00
CaCO3 0.78* −0.78* 1.00
OM −0.78* 0.78* −0.71* 1.00
Fe −0.83* 0.83* −0.71* 0.78 1.00
Mn −0.56* 0.56 −0.56 0.82* 0.75 1.00
Cr −0.61* 0.61 −0.50 0.81 0.71 0.76 1.00
Cu −0.64 0.64 −0.67 0.78 0.86* 0.83* 0.66 1.00
Pb −0.72* 0.72 −0.64 0.78* 0.67 0.62 0.57 0.63 1.00
Ni −0.75* 0.75 −0.65 0.79 0.85 0.64 0.79* 0.70 0.71 1.00
Co −0.76* 0.76 −0.62 0.79 0.77 0.67 0.78 0.72 0.80* 0.70* 1.00

*Correlation significant at 0.5 level

Correlation coefficient between pairs of metal concentra-
tions shows that all metals and OCs significantly correlate with
other parameters except sand and CaCO3. Fe has very strong
correlation with other oxides which have a higher affinity with
most elements, especially for trace elements (Stumm and
Morgan 1996). and that the organic matter contents are impor-
tant for controlling factors in the abundance of trace metals
(Rubio et al. 2000). As a consequence, the geochemistry of
Fe and organic matter could affect the geochemical behaviour
of trace metals in the aquatic environment. One of the evi-
dences is that concentrations of Fe and OC often correlate with
concentrations of other metals in marine environment
(Zwolsman et al. 1996; Basaham and El-Sayed 1998). The
strong negative effect with other trace metals (r=−0.65 to
−0.87) indicates that the latter is associated with finer clay
minerals revealing feeble relationship in the sediments.
The cluster analysis based on linear pair of coefficient of
correlation between the concentrations of trace elements and
geochemical parameters indicates two different clusters. We
investigated the relationship between metals and organic car-
bon through cluster analysis. Metals Mn, Ni, Cu, Cd and Zn
form cluster A with organic carbon (OC) join each other at a
very high similarity coefficient (0.8) (Fig. 4). It seems that the
complexation of trace metals is governed by Fe-Mn
oxyhydroxide content and OM content. Fe and Mn form the
separate clusters or major cluster indicating that the major
trace elements Fe and Mn recorded a relatively higher
favourable deposition along with organic matter and organic
matter with trace metal form the prominent second cluster.
This is in agreement with the observation of a relatively higher
concentration of organic carbon, which has been attributed to
the predominant upwelling and land runoff respectively in the
study region. Biologically available fractions (water extract-
able) of Fe and Mn levels increased in the estuary. Relatively
higher level of Fe and Mn content in estuary sediment may be
due to input of nearby land mass through detrital clay minerals
and their association with organic matter (Hanter 1983).
Significant positive correlation of Mn and Fe with organic
carbon also tends to supports this view. A part of Fe and Mn
may also be fixed up as Fe and Mn oxide coating in the
sediments. All other trace metals Cu, Ni, Zn, Cd, and Pb are
also showing significant positive correlation between organic
carbons indicating their association with organic matter. Cr,
Cu, Pb, and Ni are well correlated among themselves, clearly
supporting the hypothesis of an anthropogenic origin
(Jayaprakash et al. 2012).
Geoaccumulation index
The geoaccumulation index (Igeo), introduced by Muller
(1981). has been used to quantitatively measure metal
pollution in aquatic sediments (Muthu Raj and
Jayaprakash 2008) based on a pollution intensity classi-
fication (Igeo Class). The negative Igeo for Mn and Fe
as shown in Fig. 5 reveals relatively low levels of con-
tamination of Mn and Fe in the study area (Uppanar).
Contamination with regard to the study area (Uppanar),
Co, Ni and Cu fall under moderate to heavily. These
high levels of the enrichment factors might be related
to the anthropogenic effect from several sources (Nasr
et al. 2006).
Fig. 4 Dendrogram for the various parameters obtained for Uppanar
estuary sediments
34 Page 10 of 14
Fig. 5 Geoaccumulation index
for Uppanar estuary sediments
Enrichment factors
Anthropogenic disturbances can be evaluated without any
complexity by comparing the sediment trace metal content
of the study area with the world averages and the
values of nearby areas. In general, the degree of enrich-
ment or depletion of a trace element in a sample is
evaluated relative to its concentration in a reference that
is commonly the average crustal rocks or average shale
Fig. 6 Enrichment factor for
Uppanar estuary sediments
Arab J Geosci43:9 )6102(
(Taylor and McLennan 1985; Wedepohl 1995). This
method has been widely used to assess the enrichment
or depletion specific elements in riverine, estuarine, and
coastal environments (Selvaraj et al. 2004; Zhang and
Liu 2002). In the present study, the results are com-
pared with that of mean crust values to identify the
present level of enrichment in all stations of Uppanar.
Iron has been chosen as normalization element because
of its origin being exclusively lithospheric (Bloundi et
Arab J Geosci43:9 )6102(
Fig. 7 Contamination factor for
Uppanar estuary sediments
al. 2009). EF values were interpreted according to
Acevedo-Figueroa et al. (2006). If we consider EF>10
in the present study, Cu, Pb, Ni and Co are enriched in
these sediments (Fig. 6), which are mainly derived from
major industries and shipping activities, atmospheric de-
position of finer particles, domestic effluent discharges
and the extensive use of paints (Jayaprakash and
Ravichandran 2011).
Contamination factor and pollution load index
Sediments have been widely used as environmental indica-
tors, and this ability to trace contamination sources and mon-
itor contaminants is also well recognized. Thus, the accumu-
lation of metals in the sediments is strongly controlled by the
nature of the substrate as well as the physicochemical
Fig. 8 Pollution indices vs trace metals in Uppanar estuary sediments
Page 11 of 14 34
conditions controlling dissolution and precipitation. The accu-
mulation of trace metals in sediments gives rise to two types of
impacts on overlying water and both in a marine environment.
The trace metals themselves may have a synergistic or antag-
onistic effect on the environment. The level of contamination
expressed by the contamination factor (CF) by Pekey et al.
2004 and Savvides et al. 1995.
Cobalt and Nickel concentrations are extremely high in the
study area, the CF greater than 6 in all stations except the
station 2 and 12 which indicates that overall, the study area
is contaminated by cobalt and nickel (Fig. 7). The geochem-
ical fractionation results from the present study are consistent
with the high affinity of metals for amorphous oxide minerals.
This phase accumulates metals from the aqueous system by
the mechanism of adsorption and co-precipitation (Bordas and
Bourg 2001). The relatively higher concentrations of metals
such as Ni, Cu, Co and others associated with this fraction are
caused by the adsorption of these metals by the Fe–Mn col-
loids (Purushothaman and Chakrapani 2007) (Fig. 8).
Industrial discharge may be one of the factors for the increased
concentrations of metals in sediments of the Uppanar estuary.
Based on the pollution load index, the Uppanar estuary falls
under pollution i.e. values are >2 for trace metals in all the
stations which should be taken into consideration and prompt
management actions need to be taken.
Conclusion
The Uppanar estuary sediments is subjected to varying de-
grees of pollution caused by the input of numerous untreated
34 Page 12 of 14
or partially treated wastewaters from industrial and domestic
activities. The impact of anthropogenic heavy metal pollution
in the Uppanar sediments was evaluated using enrichment
factor (EF) and contamination factor (CF). It was found from
the results that all stations except stations 2 and 12 have high
pollution load of Ni and Co. Further, it has been found from
this study that the enrichment factor for Cu, Pb, Ni and Co is
high which is attributed due to industries and shipping activ-
ities near the study area. The abundance of metals follows the
decreasing order: Fe > Mn > Cr > Pb > Ni > Cu > Co. Results
confirmed that the estuary has seriously been polluted with
Ni and Cu. The result demonstrated that trace elements have
originated from various pollutant sources; however, the main
anthropogenic sources were industrial wastes, municipal
wastes and runoff from agricultural fields. Overall, the data
signifies the need for a regular approach towards monitoring
on enrichment of trace metals, and the present study is part of
a larger regular monitoring program in the aquatic environ-
ments of southeast coast of India.
Acknowledgments The study forms a part of the University Grants
Commission DST-FIST and SAP (Phase II), awarded to the Department
of Applied Geology and Geology, University of Madras. The critical
comments by reviewers are highly appreciated. The author (Dr. M.
Jayaprakash) is grateful to the Department of Science and Technology,
Govt. of India for the award of BOYSCAST, FASTRACK and UGC-
CPEPA programme.
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