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Assessment of trace elements in Yercaud Lake

sediments, southern India

Article in Environmental Earth Sciences · January 2017

DOI: 10.1007/s12665-017-6390-6

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Environ Earth Sci (2017)76:63
DOI 10.1007/s12665-017-6390-6

ORIGINAL ARTICLE

Assessment of trace elements in Yercaud Lake sediments,

southern India
V. Gopal1 • Hema Achyuthan1 • M. Jayaprakash2

Received: 3 November 2016 / Accepted: 2 January 2017

Ó Springer-Verlag Berlin Heidelberg 2017

Abstract Lake sediments are major sink for carbon and confirms that the concentration of Cr, Cu, Fe and Mn was
trace elements. Lake water and sediments need to be mainly derived from the natural weathering and non-point
monitored continuously for environmental and geochemi- agricultural sources. Pb and Zn arise due to the confluence
cal explorations. In the present study, sediment character- of sewage effluents, traffic and boat activities. These ele-
istics, source and distribution of trace metals (Fe, Mn, Cr, ments need to be further evaluated for pollution control and
Cu, Ni, Co, Pb and Zn) of Yercaud fresh water lake sedi- prohibiting further deterioration in the Yercaud Lake.
ments, South India, situated at an elevation of 1515 m asl is
presented. Twenty-five surface sediments were collected Keywords Lake sediments  Geochemistry  Trace metals 
covering the entire expanse of the lake in a gridded pattern. Principal component analysis  Yercaud Lake
Detailed chemical analyses reveal the following decreasing
order of elements: Fe [ Cu [ Cr [ Mn [ Zn [ Ni [
Co [ Pb. Geoaccumulation index, enrichment factor, Introduction
contamination factor and pollution load index were cal-
culated to evaluate the ecological impacts of these trace Lakes are major sinks for carbon and trace metals, and
metals in the sediments. The index calculation indicates lake floor sediments are often enriched in trace metals.
that all the trace elements were derived from natural pro- Trace metals adhere to the fine fractions of the sediments.
cess, but there are indications of anthropogenic activities. Concentrations of trace metals in sediments are affected
The study area was found to be highly contaminated with by both the geogenic and anthropogenic aspects (Lalah
Cu, moderately contaminated with Cr and Co, considerably et al. 2008). Natural influences include benthic agitation,
contaminated with Pb, Zn and Ni, and uncontaminated with flow changes, rock weathering and natural erosion, while
Mn. The spatial distribution of the trace elements supports anthropogenic aspects include sewage discharge, indus-
the strong association of sediment fine fraction and organic trial wastewater discharge, atmospheric deposition, agri-
matter. The statistical principal component analysis also cultural runoff and fertilizer leaching (Romic and Romic
2003; Tang et al. 2010; Choi et al. 2012; Rodriguez-
Martin et al. 2013; Su et al. 2013; Islam et al. 2014a, b;
& Hema Achyuthan Hasrizal et al. 2015; Iqbal et al. 2016). Geochemistry of
[email protected]
lake sediments is often influenced by both natural and
V. Gopal anthropogenic processes, and trace metal assemblages can
[email protected]
be used to investigate the contributions of different
M. Jayaprakash forcing mechanisms to the changes in the lake sedimen-
[email protected]
tary environments (Koinig et al. 2003; Routh et al. 2004;
1
Department of Geology, Anna University, Lalah et al. 2008; Li et al. 2013a, b; Ma et al. 2016). It is
Chennai 600025, India important to monitor and explore the lake floor sediments
2
Department of Applied Geology, University of Madras, for trace metal toxicity, sources and health of the lake
Chennai 600025, India water.

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63 Page 2 of 16 Environ Earth Sci (2017)76:63

Trace metal pollution in aquatic ecosystems (lakes, geochemical analyses till date have been carried out on the
rivers, estuaries and Marine) has significant reflexion due lake floor sediments that reflect the source area and plau-
to their toxicity, tenacity and biogeochemical buildup sible causes for the contamination.
(Magesh et al. 2011; Varol 2011; Jiang et al. 2012; Gu Yercaud fresh water lake is a popular hill resort in the
et al. 2012, 2014a, b; Li et al. 2013a, b; Magesh et al. 2013; Shevaroys range of hills in the Eastern Ghat region of
Krishnakumar et al. 2015; Iqbal et al. 2016; Gopal et al. southern India. It is also one of the major tourist attractions
2016a, b; Krishakumar et al. 2016). Hence, it is important in the state of Tami Nadu, India, which has been strongly
to understand how climatic variations and anthropogenic affected due to urban development. The lake receives toxic
activities influence the concentrations of geochemical metals and organic and inorganic pollutants from different
constituents, especially trace metals. High-altitude lakes sources such as rock weathering, illegal construction
are commonly considered to be pristine because they are activities, automobile exhausts and painting of boat in
small and sensitive ecosystems that experience rapid tourist season every year (Purushothaman et al. 2011). It is
flushing rates and also of limited human activity in their serving as important venues for recreational activities. As
catchments (Katrina 1994; Vreĉa and Muri 2006). How- increasing numbers of tourists visit to escape the summer
ever, human activities have faster cycling of geochemical heat in the plains and enjoy the peaceful mountain setting,
elements that result in elevated metal deliveries to water it stresses the limited resources in Yercaud town, with
bodies for the past several decades (Zahra et al. 2014; Zeng respect to housing, transportation, food and drinking water
et al. 2014). Lacustrine sediments provide archives of supply. This is evident from increasing levels of environ-
natural evolution and anthropogenic influences on lakes mental pollutants in the sediments and surface water in this
and their catchments (Leorri et al. 2014; Guo et al. 2015). region (Chakrapani 2002; Das 2005).
An assemblage of sediment organic matter (OM) in these Even though several studies have been carried out to
lakes is generally high (Vreĉa and Muri 2006; Choudhary evaluate the quality and chemistry of sediments in some
et al. 2009a, b) because of multiple processes, including important freshwater lake locations in India, only a few
high productivity, rapid sedimentation and anoxic condi- studies are pertinent to the freshwater lake sediments of the
tions on the lake bottom (Meyers 2003). As a result, these entire Indian region. Therefore, the present study assesses
organic-rich lacustrine sediments retain their original the trace metal contamination (Fe, Mn, Cr, Cu, Ni, Co, Pb
source signatures (e.g., C/N ratio, specific biomarkers) and and Zn) and sediment provenance in the Lake floor sedi-
thus reflects environmental conditions at the time of ment samples from Yercaud Lake. The main objectives of
deposition. Based on studies on investigative environ- this study were to: (1) assess the concentration and spatial
mental recent changes in lacustrine environments, natural distributions of selected trace metals (Fe, Mn, Cr, Cu, Ni,
processes affect the transportation of geochemical elements Co, Pb and Zn) in surface sediments from Yercaud Lake,
from watersheds to lakes (Braun et al. 2013; Kylander et al. South India, (2) determine the potential environmental risk
2013). using multi-pollution indices such as enrichment factor
A review of recent geochemical work carried out on (EF), geoaccumulation index (Igeo), contamination factor
lake sediments reveal that the fine fractions are positively (CF) and pollution load index (PLI) and (3) identify the
correlated with organic matter (OM) and total organic nature and/or anthropogenic sources of these metals. It is
carbon (TOC) (Vijayraj and Achyuthan 2016). Moreover, further predicted that this study would provide geochemi-
C/N ratio suggests that OM was largely produced by the cal data related to the spatial distribution and contamina-
lake algae in the Kukkal Lake, while there is a mixed tion of the metals in the freshwater lakes, which would
resource of OM in the Berijam Lake (Vijayaraj and provide essential information to support lacustrine envi-
Achyuthan 2016). Trace metal analysis of the Kodaikanal ronmental control actions for the anthropogenic pollutants
Lake sediments indicated that the natural environment in the natural ecosystem. In the present study, we also
surrounding the Kodaikanal Lake is severely contaminated compare the trace metal contamination of Yercaud Lake
by heavy metals (Cd, Pb, Zn and Cu), and multivariate with other high-altitude lakes in the Indian and other
statistics (discriminant analysis) revealed that the plots fall regions (Table 5).
scattered in the turbidite and eolian environment (Bala-
murugan et al. 2015). Further, the mercury contamination
status of the Vembanad Lake was classified as less con- Materials and methods
taminated when compared to other mercury-polluted areas
around the world (Mohan et al. 2014). However, the sur- Regional setting
face sediments have the high concentration due to the
anthropogenic sources like agricultural runoff, small-scale Yercaud is located (11°130 1500 N and 77°280 0700 E) in the
industries and fuel burning. Further, no systematic Servarayan range (anglicized as ‘‘Shevaroys’’) of hills in

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Environ Earth Sci (2017)76:63 Page 3 of 16 63

the Eastern Ghats near Salem, Tamil Nadu. It is located at Sample collection and storage
an altitude of 1515 m from the above mean sea level
(Fig. 1) (Sakthivel et al. 2015). The town gets its name Twenty-five surface sediment (0–15 cm, top layer) samples
from the lake located at its center: in Tamil ‘‘Yeri’’ means were collected from Yercaud Lake, South India during
‘‘lake’’ and ‘‘Kaadu’’ means ‘‘forest.’’ The lake is ‘‘horse- December 2015. The sediment samples were collected in
shoe’’ shaped and has an effective area of 20.0 acres (8 ha). pre-cleaned zip-locked polythene bags by using a sedi-
The lake is also known as emerald lake, and it is the only ments snapper (Ø5 cm). The collected samples were placed
natural lake among all the hill stations in the southern part in an ice cooler and transported to the laboratory imme-
of India. It is also called as the Jewel of the South and diately. Then, the samples were dried, ground, homoge-
‘‘Poor man’s Ooty’’ (Rajkumar et al. 2006). The geological nized and sieved through ASTM 230-lm nylon mesh for
formation in this area comprises both basic and acid types further processing.
of charnockite bedrock of the Archaean age, weathered into
the rugged masses of hills. The Shevaroy range is exten- Analyses and quality control
sively covered with green grass and has no dense forest
cover. The area is under the influence of both the southwest Particle size (sand and mud) was determined with a particle
and northeast monsoons, but the northeast monsoon chiefly size analyzer (Malvern Mastersizer 2000) with a mea-
contributes to the rainfall in the district (1500–2000 mm/a). surement range of 0.02–2000 lm. The Mastersizer 2000
The climate of Yercaud is the moderate one with the automatically determines size fractions with a measure-
maximum temperature of 34 °C during summer (March to ment precision\1%, and the repeated measurement error is
May), and the minimum is 16 °C during the winter; it has a less than 2%. Moment measures were calculated using
maximum depth of 5.1 m and a minimum depth of 1.5 m GRADISTAT version 4 based on Folk (1974) nomencla-
(Venkatachalapathy et al. 2014). ture. Carbonates in the collected sediments were measured

Fig. 1 Location map of the Yercaud Lake

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63 Page 4 of 16 Environ Earth Sci (2017)76:63

Table 1 Published and obtained analytical results of MESS-1 Indices of sediment pollution
Elements MESS-1 Present study Recovery %
Detecting the sources of trace metals is of particular
Fe 3.1 ± 0.38 2.95 95.16 importance in environmental investigation. Pollution indi-
Mn 513 ± 25 472 92.00 ces were used for the environmental assessment of Yercaud
Cr 71 ± 1.1 69.8 98.30 Lake sediment. The geoaccumulation index (Müller 1981),
Cu 25.11 ± 3.88 22.9 91.19 enrichment factors which were interpreted as suggested by
Ni 29.5 ± 2.7 28.3 95.93 Bloundi et al. (2009), contamination factor and contami-
Co 10.8 ± 1.9 9.9 91.66 nation degree (Hakanson 1980) are used to assess heavy
Pb 34 ± 6.1 31.8 93.73 metal contamination in sediment. Igeo, EF and CF are the
Zn 191 ± 17 173.3 90.73 top most common tactics to assess the ecological risk by an
individual element, whereas PLI appraises the environ-
mental risk posed by mixed elements (Caeiro et al. 2005;
following the method of Loring and Rantala (1992). Li et al. 2012; Zhao et al. 2012; Cheng et al. 2013; Hou
Organic matter (OM) was estimated following the titration et al. 2013; Wang et al. 2014a, b; Iqbal et al. 2016).
method by Gaudette et al. (1974). For TTMs analysis, the
sediments were air-dried and disaggregated in an agate Index of geoaccumulation (Igeo)
mortar, before chemical treatment. For each sample, a
known quantity (1 g of sediment) was digested with a The outstanding reciprocal technique for estimating the
concentrated solution of HClO4 (2 ml) and HF (10 ml) to enrichment of metal concentration above background is the
near dryness. Subsequently, a second addition of HClO4 geoaccumulation index (Igeo). This index was introduced
(1 ml) and HF (10 ml) was prepared, and the mixture was by Müller (1981) in order to determine and define metal
evaporated to near dryness. Finally, HClO4 alone was contamination in sediments by comparing current concen-
added, and the sample was dried until white fumes trations with pre-industrial levels. The geoaccumulation
appeared. The residue was dissolved in concentrated HCl index (Igeo) was used by most of the researchers for trace
and diluted to 25 ml (Tessier et al. 1979). The acid solution element studies in sediments (Jumbe and Nandini 2009;
was subsequently filtered using grade A filters, and anal- Bing et al. 2011; Magesh et al. 2011; Hasan et al. 2013;
yses of metals (Mn, Cr, Cu, Ni, Co, Pb, and Zn) were Hou et al. 2013; Zahra et al. 2014; Arunachalam et al.
performed by graphite furnace atomic absorption spec- 2014; Kalpana et al. 2016; Gopal et al. 2016a, b).
troscopy (GFAAS) PerkinElmer AA-700. The accuracy of
Igeo ¼ log2 Cn =1:5Bn
the analytical procedures in the present study was assessed
using the certified reference material MESS-1 (Table 1) where Cn is the measured concentration of examined ele-
from the National Research Council of Canada (Sun- ment in the sediment sample and Bn is the geochemical
dararajan and Srinivasalu 2010; Kalpana et al. 2016; Gopal background for the element which is either directly mea-
et al. 2016a, b). sured in pre-civilization (pre-industrial) reference sedi-
ments of the area or taken from the literature (average shale
Normalization of trace metal concentration value described by Taylor (1964). The factor 1.5 is intro-
duced to include possible variation of the background
The trace element enrichment in the lacustrine sediments values that are due to lithogenic variations (Chakravarty
was normalized to eliminate the influence of grain size and and Patgiri 2009; Goher et al. 2014), as well as very small
mineral composition. Some types of extraordinarily unaf- anthropogenic influences (Qingjie and Jun 2008).
fected metals such as Al, Fe, Mg, Ti, Sc, Li and Cs have
been used to normalize the grain size effect for metal
Six classes of the geoaccumulation index was proposed Müller (1981)
concentrations in sediments (Schropp et al. 1990; Loring
1990; Herut et al. 1993; Grousset et al. 1995; Aloupi and Igeo value Igeo class Designation of sediment quality
Angelidis 2001; Soto Jiménez et al. 2001; Wu et al. 2007;
[5 6 Extremely contaminated
Amin et al. 2009; Mil-Homens et al. 2009; Kim et al. 2010;
4–5 5 Strongly to extremely contaminated
Bing et al. 2011; Gopal et al. 2016a, b). In the present
3–4 4 Strongly contaminated
study, the results are compared with that of mean crust
2–3 3 Moderately to strongly contaminated
values to identify the present level of enrichment in all
1–2 2 Moderately contaminated
stations of Yercaud Lake. Iron has been chosen as nor-
0–1 1 Uncontaminated to moderately contaminated
malization element because of its origin being exclusively
0\ 0 Uncontaminated
lithospheric (Bloundi et al. 2009; Kalpana et al. 2016).

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Environ Earth Sci (2017)76:63 Page 5 of 16 63

Enrichment factor (EF) calculated following the method planned by Tomlinson

et al. (1980) as follows:
Enrichment factors (EFs) were measured to estimate the
PLI ¼ ðCF1  CF2  CF3      CFn Þ1=n
abundance of trace metals in sediment. The enrichment
factor (EF) was based on the standardization of a tested where n is the number of metals and CF is the contami-
element against a reference elements (Müller 1981). The nation factor.
reference elements may be Al (Chatterjee et al. 2007), Fe The PLI value of [1 is polluted, whereas \1 indicates
and Ti (Zhang et al. 2007), Mn (Liu et al. 2005) or Li, Sc no pollution (Harikumar et al. 2009). The world average
and Zr (Blaser et al. 2000). Iron was chosen as a reference concentration of Mn (950 lg/g), Cr (100 lg/g), Cu (55 lg/
element because of natural sources (1.5% vastly dominate g), Ni (75 lg/g), Co (25 lg/g), Pb (12.5 lg/g) and Zn
its input (Tippie 1984). Many authors used iron to nor- (70 lg/g) reported for crustal average (Taylor 1964) was
malize heavy metal contaminants (Szefer et al. 1998; considered as the background value.
Schiff and Weisberg 1999; Baptista Neto et al. 2000;
Mucha et al. 2003; Goher et al. 2014; Kalpana et al. 2016). Statistical analyses
It was calculated according to the following formula:
ðM=FeÞ sample Descriptive statistical analysis was carried out to know the
EF ¼ mean, maximum and minimum values. Additionally,
ðM=FeÞ background
principal component analysis (PCA) is the most common
where EF is the enrichment factor, (M/Fe) sample is the multivariate statistical method used in environmental
ratio of metal to Fe concentration of the sample, and (M/ studies and is employed to extract a small number of latent
Fe) background is the ratio of metals to Fe concentration of factors for analyzing relationships among the observed
a background. The EF values close to unity indicate crusted variables (Caeiro et al. 2005). Pearson correlation analysis
origin; those less than 1.0 suggest a possible mobilization and PCA were used to find the association among metals
or depletion of metals, whereas EF [ 1.0 indicates that the and the sources of the metals, respectively, in the surface
element is of anthropogenic origin (Zsefer et al. 1996). sediments of the study area. The PCA was carried out on
Five contamination categories are recognized and inter- the metal data of all surface sediments for source identifi-
preted as suggested by Birth (2003). EF \ 1 indicates no cation using statistical package for social science (SPSS)
enrichment, EF \ 3 is minor enrichment, EF = 3–5 is version 20. The factor analysis was also performed to
moderate enrichment, EF = 5–10 is moderately severe understand the variability among the different parameters
enrichment, EF = 10–25 is severe enrichment, using varimax normalized values.
EF = 25–50 is very severe enrichment, and EF [ 50 is
extremely severe enrichment, as shown in Fig. 5.
Results and discussion
Contamination factor (CF)
The textural parameter (sand and mud), organic matter and
The level of contamination of lake sediment or a sub-basin carbonate contents and TTM (Fe, Mn, Cr, Cu, Ni, Co, Pb
by giving toxic substance (metals) suggested by Hakanson and Zn) concentrations are given in Table 2.
(1980) is often expressed in terms of a contamination factor
and is calculated as follows. Sediment characteristics
CF ¼ C metal=C background value
Sand content varied from 66.14 to 9.58% with an overall
where C metal sample is the concentration of a given metal average of 32.97%. Likewise, the mud (silt ? clay) in the
in lake sediment and Cm background is the value of the sediments varied from 90.42 to 33.86% with an average of
metal equal to the world surface rock average given by 67.03%. Particle size distribution of lake sediments indi-
Taylor (1964). cates that Yercaud Lake is rich in (silt ? clay) mud. Clo-
sely, all sand content is deposited in the shallow regions
Pollution load index parallel to the shorelines that are characterized by the high
sand content and also showing gradational difference lat-
Pollution load index (PLI) was used to evaluate the extent erally from coarse fractions near the margin to finer frac-
of pollution by heavy metals in the environment. The range tions more toward the deeper part of the lake. Most of the
and class are same as Igeo. PLI for a particular site has been clay and silt has been transported to the deepest parts of the

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63 Page 6 of 16 Environ Earth Sci (2017)76:63

Table 2 Sediment characteristics, organic matter, calcium carbonate, C/N ratio and trace element of surface sediments from Yercaud Lake
S. Sand% Mud% OM% CaCO3% C/N Fe (lg/ Mn (lg/ Cr (lg/ Cu (lg/ Pb (lg/ Zn (lg/ Co (lg/ Ni (lg/ PLI
no. ratio g-1) g-1) g-1) g-1) g-1) g-1) g-1) g-1)

1 33.45 66.55 6.6 2.7 10.5 117,056 390 322.0 575.3 37.4 178.3 113.7 146.8 2.66
2 22.72 77.28 7.7 1.9 9.1 115,273 406 377.5 560.0 35.4 204.5 123.0 146.9 2.79
3 20.02 79.98 8.7 1.8 10.6 109,836 356 386.0 676.0 48.0 258.4 120.6 147.2 3.04
4 23.89 76.11 8.5 2.1 10.3 107,964 379 388.0 552.0 44.9 214.6 119.4 146.8 2.87
5 15.43 84.57 8.6 1.5 8.8 114,400 374 415.0 531.3 36.9 182.3 115.0 146.9 2.72
6 34.68 65.32 5.0 2.8 9.6 109,300 374 351.0 542.0 29.0 128.0 108.8 146.7 2.42
7 12.89 87.11 6.9 1.4 8.8 119,824 396 397.0 640.0 37.9 192.3 114.1 147.0 2.82
8 36.09 63.91 4.7 3.2 10.4 105,500 386 409.0 531.0 20.7 101.4 100.0 146.9 2.26
9 14.58 85.42 6.7 1.1 7.6 111,174 403 393.0 555.0 27.5 183.9 110.9 146.9 2.62
10 14.31 85.69 6.6 0.9 8.7 119,472 413 393.0 658.0 39.3 155.9 111.2 147.2 2.77
11 24.65 75.35 5.9 1.7 8.5 113,200 389 441.2 663.1 31.6 145.7 113.2 147.2 2.69
12 29.35 70.65 7.8 1.9 7.5 105,500 351 397.0 576.6 25.9 177.5 98.7 147.1 2.51
13 57.79 42.21 5.1 5.8 7.4 88,000 350 376.0 520.0 24.2 157.0 102.7 146.9 2.40
14 62.49 37.51 3.7 7.1 8.2 92,700 334 364.0 500.0 15.5 150.5 96.0 146.7 2.18
15 31.28 68.72 6.9 2.9 7.2 106,800 342 379.4 626.0 38.0 175.9 120.0 147.2 2.73
16 9.58 90.42 7.7 0.5 7.1 120,987 423 404.0 614.0 29.4 197.6 102.7 147.1 2.71
17 18.66 81.34 7.6 1.6 7.3 112,500 366 440.0 687.0 39.1 205.3 110.1 147.2 2.89
18 46.12 53.88 5.8 3.9 7.2 96,500 365 367.5 516.0 19.9 169.0 91.1 146.6 2.32
19 36.81 63.19 6.5 2.5 10.4 116,000 398 379.7 480.0 20.5 200.0 130.7 147.1 2.53
20 49.79 50.21 5.5 4.2 10.5 97,100 334 380.0 523.0 27.5 178.0 108.0 146.7 2.49
21 66.14 33.86 3.0 8.1 8.9 97,362 337 352.0 489.0 21.8 109.5 92.7 146.7 2.16
22 17.54 82.46 7.3 1.4 10.2 107,925 369 403.0 619.7 28.0 195.3 116.8 147.2 2.69
23 49.39 50.61 4.0 4.2 10.4 102,897 340 360.0 604.0 25.8 106.8 101.6 146.8 2.31
24 64.83 35.17 3.2 7.3 8.2 84,400 327 336.0 537.0 23.8 101.4 88.0 146.7 2.15
25 31.81 68.19 6.7 2.8 10.2 113,200 389 409.0 594.0 22.5 152.9 100.0 147.2 2.47
Min 9.58 33.86 3.0 0.5 7.1 84,400 327 322.0 480.0 15.5 101.4 88.0 146.6 2.15
Max 66.14 90.42 8.7 8.1 10.6 120,987 423 441.2 687.0 48.0 258.4 130.7 147.2 3.03
Avg 32.97 67.03 6.3 3.0 8.9 107,395 372 384.8 574.8 30.0 168.9 108.4 146.9 2.57

lake. The textural classification of the Yercaud Lake sur-

face sediments shows a predominant occurrence of sandy
silt and silty sand following Shepard’s (1954) trilinear
diagram (Fig. 2). The spatial diagram shows decreasing
sand (feldspar ? quartz) content from the margins and is
negatively correlated with the increasing clay fraction at
the deeper part of the lake (Fig. 3).
The OM content varied from 8.7 to 3.0% with an
average of 6.3%. The concentrations of organic matter in
the fine-grained fraction of the sediments were often higher
than that in the sand-sized fractions (Tam and Wong 2000).
This indicates that the lake sediments receive high organic
matter from soil erosion and tourist activities (Pu-
rushothaman et al. 2011). The C/N ratio is an indicator of
changes in the source of organic matter. In general, the C/N
ratios from aquatic plants (freshwater phytoplankton) are
\10. A higher C/N ratio (10–20) indicates a mixture of
Fig. 2 Ternary plot showing relative percentage of sand, silt and clay
fractions of the Yercaud Lake surface sediments
aquatic and terrestrial organic material (Mackie et al. 2005;

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Environ Earth Sci (2017)76:63 Page 7 of 16 63

Fig. 3 Spatial distributions of a sand, b mud (silt ? clay), c organic matter (OM), d calcium carbonate, e C/N ratio in the surface sediments
from the Yercaud Lake

Zong et al. 2006; Vijayaraj and Achyuthan 2015). C/N production (Meyers and Ishiwatari 1993; Wang et al.
ratio of the Yercaud Lake sediments range from 10.6 to 7.1 2014a). However, some samples show values higher than
with an average of 8.9. Most of the C/N values are \10, 10, suggesting mixed sources of OM (Meyers 1994;
indicating that the organic matter is from the in-lake algal Hedges 2002; Sollins et al. 1984). Carbonate content is low

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63 Page 8 of 16 Environ Earth Sci (2017)76:63

(0.5–8.1%) with an average of 3.0% and is related to the indicating that these metals might be included by anthro-
phytoplankton blooms associated with annual lake water pogenic inputs in the lake sediments (Iqbal et al. 2016). The
mixing and nutrient availability (Lamb et al. 2002a, b). main sources of Cu, Cr and Co in the study area is owing to
the discharge of industrial and municipal wastewaters,
agrochemicals, landfill leachates and geogenic material. In
Metal concentrations in the surface sediments
contrast, mafic rock erosion is the dominant Cr source of lake
sediments (DVWK 1998; Wantzen et al. 2008).
The overall concentration ranges and mean values of the
The EF values of all studied metals were calculated to
selected metals in the surface sediments were found as
evaluate anthropogenic influences on trace metals in the
follows: Fe, 84,400–120,987 (107,395); Mn, 327–423
surface sediments of the study area. The EF reflecting
(372); Cr, 322–441.2 (384.8); Cu, 480–687 (574); Pb,
metal accumulation for surface sediments is shown in
15.5–48.0 (30.0); Zn 101.4–258.4 (168.9); Co, 88–130.7
Fig. 3. The enrichment values \1 indicate that the metal is
(108.4); and Ni, 146.6–147.2 (146.9) lg/g-1. The metal
completely derived from geological origin, but EF values
concentrations in the surface sediments were ranked in
[1 propose that the metal is possibly sourced through
decreasing order as follows: Fe [ Cu [ Cr [
anthropogenic activities. In the present prediction, the
Mn [ Zn [ Ni [ Co [ Pb (sediments on the surface have
enrichment factor values of the high-altitude Yercaud Lake
significantly high Cu, Cr and Ni concentrations) (Fig. 4a–
indicated that Fe indicates \1, showing no enrichment; Cr,
h). In the present study, nickel and chromium was observed
Pb, Zn, Co and Ni were between 1 and 3, indicating a
to be abnormally rich, probably leached from the adjoining
minor enrichment, and Cu was between 5 and 10, revealing
rock exposures containing large amounts of olivine,
moderately severe to severe enrichment at all locations. Cr,
pyroxenes, chromite, spinels, etc. All these minerals con-
Pb, Zn, Co and Ni revealed some enrichment at all sites,
tain Ni and Cr in appreciable amounts. Also in the case of
but they were considered to be contributed by mixed
very strongly and deeply weathered soils of the tropical
sources. No enrichment of Mn occurred at all sites, in spite
areas with a humid climate, many elements are lixiviated
of good water circulation and aeration of bottom lake
(e.g., Mg, Ca, Si), but others accumulate in situ (e.g., Cr,
waters during five months of the year. This is the case, for
Ni, Cu, Mn) and combine with the diverse iron oxide forms
example, no enrichment of Fe and Mn occurs in the Lake
(e.g., Nalovic and Quantin 1972; Anand and Gilkes 1987;
Valencia sediments (Bifano and Mogollbn 1995).
Becquer et al. 1995; Trolard et al. 1995). Similar obser-
Another method used to determine contamination levels
vations were made on the basalts and basanites of the
was the contamination factor (CF), which is the ratio of
French Massif Central (Soubrand-Colin et al. 2007) or of
metal concentration to the background metal concentration
the Réunion Island (Doelsch et al. 2006) and the serpen-
of a given metal, which could be classified into four sets for
tinites in the Swiss Alps (Gasser et al. 1995).
monitoring the pollution of one single metal over a period
of time (Turekian and Wedepohl 1961; Kükrer et al. 2015;
Ecological risk assessment Han et al. 2015). It refers to the low degree (CF \ 1),
moderate degree (1 B CF \ 3), considerable degree
The Igeo value \0 indicates uncontaminated, while the Igeo (3 B CF \ 6) and very high degree (CF C 6). On this
value[5 represents the upper limit of the contamination. The basis, the high-altitude Yercaud Lake has very high Cf
highest class 6 (very strong contamination) reflects 100-fold values for Cu; considerable Cf for Cr, Co; and moderate Cf
enrichment of the metals relative to their background values for Fe, Pb, Zn and Ni except Mn, which is found to be low
(Harikumar and Jisha 2010; Goher et al. 2014). The calcu- contaminated. Calculation of the average contamination
lated index of geoaccumulation (Igeo) of the investigated factor (Cu) indicates humid substances have high affinity
trace metals in the sediments of the Yercaud Lake and its with copper, resulting in the formation of stable complexes
corresponding contamination intensity is illustrated in (Dahrazma and Mulligan 2007). To determine the envi-
Fig. 5. In the present study, Igeo values for Mn were found ronmental quality of the sediments, pollution load index
lower than 0, indicating almost unpolluted; Fe, Pb and Zn (PLI) was used (Suresh et al. 2011; Kükrer et al. 2015). The
indicated unpolluted to moderately polluted; Cr and Co PLI value 1 represents the baseline for sediment, and val-
indicated moderately polluted; and Cu indicated moderately ues greater than 1 indicate higher contamination. In this
to strongly polluted sediment quality. Fe and Ni are indi- respect, as is clear from the PLI values in Table 1, the PLI
cating unpolluted to moderately pollution at all sites; Pb is levels ranged from 2.15 to 3.03 with an average of 2.56.
moderately polluted at site S-1, 3, 4, 7, 10, 15 and 17; and Cu The PLI value was found higher for all sites. It is possible
exposed heavy pollution at site S-3, 10, 11 and 17. Overall, to state that in all stations, the contamination appears to be
the studied sediments were polluted by Cu, Cr and Co, higher in the surface sediments of the lake.

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Environ Earth Sci (2017)76:63 Page 9 of 16 63

Fig. 4 Spatial distributions of a Fe, b Mn, c Cr, d Cu, e Pb, f Zn, g Co and h Ni in the floor sediments of the Yercaud Lake

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63 Page 10 of 16 Environ Earth Sci (2017)76:63

the geoenvironment (Usha et al. 2014; Gopal et al.

2016a, b). Correlation matrix was suitable to confirm some
new associations between heavy metals. It was generated in
the present study using SPSS. In order to evaluate the
relationship between textural and chemical parameters
(TTMs), correlation matrix analysis was carried out for the
entire data set (Table 3). The correlation of the surface
sediments shows that all the trace metals are negatively
correlated with sand and CaCO3. Moreover, trace metals
have a high positive correlation with OM and mud frac-
tions. The inter-element relationship between elements
specifies a clear comparison with mud vs OM (r2 = 0.84),
Fe (r2 = 0.86), Mn (r2 = 0.74), Cr (r2 = 0.61), Cu
(r2 = 0.64), Pb (r2 = 0.64), Zn (r2 = 0.62), Co
(r2 = 0.61) and Ni (r2 = 0.65). Positive correlation of OM
vs Fe (r2 = 0.77), Mn (r2 = 0.50), Cr (r2 = 0.51), Pb
(r2 = 0.70), Zn (r2 = 0.86), Co (r2 = 0.66) and Ni
(r2 = 0.58) is also observed in the sediments. Fe exhibit-
s high positive correlation with Mn (r2=0.83), whereas
moderate correlation is found with other trace elements
such as Cu, Pb, Co and Ni (r2 = 0.51, 0.52, 0.64 and 0.58).
Cr is positively correlated with Cu and Ni and Cu–Pb, Ni
and Zn with Co.
Organic matter was positively correlated with trace
metals which reveals that they are attached to the organic-
rich clay particles in the sediments and has high fluvic/
humic acids which have a high metal-adsorbing capacity
(Mester et al. 1998; Hlavay et al. 2004; Kargar et al.
2013). Fe has a very strong correlation with other oxides
which have a higher affinity with most elements, espe-
cially for trace elements (Stumm and Morgan 1996), and
that the organic matter contents are important for con-
trolling factors in the abundance of trace metals (Rubio
et al. 2000; kalpana et al. 2016). The strong negative
values of carbonates with other TTMs suggest that they
act as diluents of the metals in the sediments and are also
recent in origin (Aloupi and Angelidis 2001). The
table presented that high positive correlation happens
between Fe and Mn (r2 = 0.83), Co (r2 = 0.96) and
Ni (r2 = 0.58). It means that these metals tend to accu-
mulate together. The significant positive correlation with
Fe indicates that the metals were derived from similar
sources and also moving together (Bhuiyan et al. 2009).
Though strong positive correlations among Fe and Mn
Fig. 5 Box and whisker diagrams of a Igeo, b EF and c CF values of indicate that these two metals are the constituent of sed-
the Yercaud Lake floor sediments
iments, and they originate mostly from geogenic origin
and not from anthropogenic process (Guo et al. 1983), Mn
Statistical analysis does not show any significant correlation with other trace
metals, indicating its independent variables in the sedi-
Correlation matrix ments (Selvam et al. 2012). In addition, significant cor-
relation between Cu and Ni and the close association of
The Pearson correlation coefficients of inter-element rela- this element confirm their common sink in the sediments
tionships provide valuable information on the sources in (Fianko et al. 2013).

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Environ Earth Sci (2017)76:63 Page 11 of 16 63

Table 3 Pearson (r) correlation coefficients for sediment texture and trace elemental analyses from Yercaud Lake surface sediments
Parameters Sand Mud OM CaCO3 Fe Mn Cr Cu Pb Zn Co Ni

Sand 1
Mud -1.0** 1
OM -.84** .84** 1
CaCO3 .96** -.96** -.84** 1
Fe -.86** .86** .67** -.85** 1
Mn -.74** .74** .50** -.74** .83** 1
Cr -.61** .61** .51** -.59** .43* .37 1
Cu -.64** .64** .47* -.60** .51** .26 .50* 1
Pb -.64** .64** .70** -.58** .52** .26 .21 .65** 1
Zn -.62** .62** .86** -.61** .47* .32 .31 .35 .62** 1
Co -.61** .61** .66** -.63** .64** .44* .25 .29 .62** .67** 1
Ni -.65** .65** .58** -.63** .58** .39 .67** .73** .39* .43* .48* 1
Bold numbers mark the high positive correlation
* Correlation is significant at the 0.05 level (2-tailed)
** Correlation is significant at the 0.01 level (2-tailed)

Table 4 Principal component analysis loadings for selected metals

Parameters PC1 PC2 PC3

Sand -.69 -.49 -.49

Mud .69 .49 .49
OM .44 .74 .34
CaCO3 -.72 -.47 -.45
Fe .80 .37 .30
Mn .94 .12 .11
Cr .35 .02 .78
Cu .08 .35 .83
Pb .09 .83 .31
Fig. 6 Rotated loadings showing correlation among trace metals Zn .22 .85 .15
Co .39 .75 .07
Source apportionment Ni .27 .26 .80
Eigenvalue % 3.62 3.56 2.97
PCA was also applied to identify sources of the metals in Variance % 30.15 29.70 24.73
sediments. The relationships among the metals analyzed Cumulative % 30.15 59.86 84.58
based on the three principal components were illustrated in
three-dimensional (3D) space (Fig. 6; Table 4). Three Bold numbers mark the high correlation coefficients
principal components (PC) were obtained with eigenvalue
greater than 1, explaining more than 84% of total variance. sediments is often transformed by different biochemical
Speciously, the result of PCA resembles well with the processes (Lepane et al. 2007), and PC3 grouped metals
correlation coefficients. PC1 explains the 30.15% of the such as Cr, Cu and Ni reveal 24.73% of the total variance.
total variance and reveals high loading values for the mud Cr and Cu in PC3 originated from the natural sources such
(silt ? clay), Fe and Mn (0.69, 0.80 and 0.94, respec- as the catchment bed rock weathering (Lv et al. 2014). Ni
tively), which are predominantly contributed by the geo- and Cr belong to the siderophile elements and are main
genic processes, transportation activities, untreated urban rock-forming elements, which are derived from terrigenous
wastes and agricultural runoff. PC2 (29.7% of total vari- detritus material transported by surface runoff (Krishna
ance) is the strong loading of Pb, Zn and Co with organic et al. 2011). All three PCA explains 84.58% of the total
matter, confirming that metals form organic complexes variance, indicating that the lithogenic factor dominates the
with humic substances in surface sediments ((Lepane et al. distribution of most part of the considered metals in the
2007). Those complexes or organic matter in surface study. Further, it is observed that Pb and Zn arise due to a

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63 Page 12 of 16 Environ Earth Sci (2017)76:63

Table 5 Comparison of the investigated trace metals levels (lg/g-1) with other international and national studies
S. no. Lake name Fe Mn Cr Cu Pb Zn Co Ni References

1 Mangla Lake, Pakistan 4959 411 25.0 22.6 30.7 127.3 41.2 70.8 Saleem et al. (2015)
2 Lake Taihu China – – 77.4 31.1 33.1 87.3 22.5 29.8 Wei and Wen (2012)
3 Lake Dianchi China – – 115.2 90.1 65.8 154.0 33.4 46.0 Wei and Wen (2012)
4 Kodaikanal Lake, India 105,229 48 451.8 54.5 44.7 112.5 1402.3 115.3 Balamurugan et al. (2015)
5 Rewalsar Lake 19,374 387 75.0 42.0 39.4 353.0 44.0 Brijraj and Birgit (2003)
6 Lake Vegoritis, Greece – – 266.0 36.6 25.8 88.1 25.5 215.8 Skoulikidis et al. (2008)
8 Vembanad Lake in India 54,000 461 107.5 30.9 32.6 184.5 18.6 48.7 Selvam et al. (2012)
9 Lake Nasser, Egypt 12,418 280 30.8 21.8 10.9 35.4 – 27.6 Goher et al. (2014)
10 Maharlu Lake, SW Iran 19,477 554 40.2 38.1 160.3 67.4 145.6 207.0 Moore et al. (2009)
11 Lake Laguna, Philippines – – 16.9 103.0 20.0 13.5 – 13.0 Hallare et al. (2005)
12 Geochemical background Value 56,300 950 100.0 55.0 125.0 70.0 25.0 75.0 Taylor (1964)
13 Yercaud high-altitude Lake 107,395 372 384.8 574.8 30.0 168.9 108.4 146.9 This study

confluence of sewage effluents, traffic and boat activities. pollution was found relatively higher at all the sites, which
Probably these elements originated from agricultural receive anthropogenic inputs from the nearby areas such as
activities, sewage sludge, untreated domestic solid wastes, villages, picnic points and other catchments. These findings
traffic pollution and boating activities (Table 5). provide useful information about sediment quality in the
lake. Therefore, the remedial measures are to develop
strategies of contamination control and management with
Conclusions the inclusive consideration of the entire area, which is
required for aquatic system/human health protection and
In this study, spatial distribution of eight selected trace future restoration of the lake.
metals (Fe, Mn, Cr, Cu, Ni, Co, Pb and Zn) in surface
sediments from the higher elevation Yercaud Lake, South Acknowledgements Gopal V is grateful to the UGC, New Delhi, for
the Dr. D.S.Kothari Postdoctoral Fellowship (No. F.4-2/2006 (BSR)/
India, was examined. Then, potential ecological risk caused ES/14-15/0020) for the financial support. The authors thank the Tamil
by these metals was evaluated by calculating index of Nadu Tourism Department, Yercaud, for granting permission to work
geoaccumulation, enrichment factor, contamination factor and collect lake sediment samples. The authors thank the anonymous
and pollution load index. Sources were identified with the reviewers for their constructive comments that helped in the presen-
tation of the work and the manuscript.
aid of multivariate statistical analyses such as principal
component analysis (PCA). The geogenic and anthro-
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