Geoscience Frontiers 9 (2018) 1577e1590

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China University of Geosciences (Beijing)

Geoscience Frontiers
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Research Paper

Geochemical contamination in the mine affected soil of Raniganj

Coalfield e A river basin scale assessment
Abhijit Manna*, Ramkrishna Maiti
Department of Geography and Environment Management, Vidyasagar University, Midnapore 721102, West Bengal, India

articleinfo abstract

Article history: The study aimed to assess the heavy metals (K, Ca, Ti, Cr, Mn, Fe, Ni, Cu, Zn, As, Pb, Sr, Zr) contamination
Received 2 December 2016 in the soil of mine affected Singaran river basin and to analyse spatial variation in the contamination
Received in revised form level considering 32 soil samples. Elemental analysis of soil samples has been performed through Energy
12 June 2017
Dispersive X-ray Analysis (EDX) to quantify the elemental concentration (mg kg —1). Heavy metal con-
Accepted 5 October 2017
centrations have been assessed through geo-accumulation index (Igeo) and enrichment factor (EF).
Available online 11 November 2017
Handling Editor: Sohini Ganguly
Indices showed soils have moderate accumulation of most of the metals with moderate enrichment of Sr,
Zr, Zn, Cu and Ni. Soil contamination level assessment has been carried out using indices like Contam -
ination Factor (CF), degree of contamination (Cdeg), modified degree of contamination (mCdeg) and
Keywords:
Heavy metals Pollution Load Index (PLI). CF shows moderate to considerable contamination by Sr, Zr, Ca, Cu, Mn, Zn and
Soil contamination Ni. Mean indices values (mCdeg and PLI for the entire basin are 3.38 and 2.23 respectively) show low to
Pollution indices moderate level of soil contamination. These indices result have been mapped and analysed in GIS
Pollution load platform to get spatial variation of pollution level. Opencast mines dominate middle catchment area and
Ecological risk so is comparatively contaminated. Sample sites 11, 18 and 25 evidenced high values of all indices of
Singaran basin pollution load. From the ecological standpoint Ecological Risk Factor ( Er) and Potential Ecological Risk
Index (RI) have been estimated to assess regional threat to native soil environment and it shows low
ecological risk potential. Analysis shows that mine dominated soil of the entire Singaran basin is less
contaminated in all respect but tends to the moderate contamination level at the mid-catchment area,
especially by Sr, Zr, Zn, Cu and Ni.
© 2017, China University of Geosciences (Beijing) and Peking University. Production and hosting by
Elsevier B.V. This is an open access article under the CC BY-NC-ND license (http://creativecommons.org/
licenses/by-nc-nd/4.0/).

1. Introduction times more ecological burden than underground mine. Opencast

Raniganj Coalfield (RCF) is one of the important mining regions
in India by its history as well as in term of production. In RCF most
of coals (76.07%) are produced by opencast mining method and rest
(23.93%) is from underground method (Eastern Coalfield Limited,
2010e2011). Mining, especially coal mining invites the debate be-
tween resource exploitation and environmental protection. Un-
derground coal mining is prone to land subsidence and coal fire
whereas opencast mine generates more ecological burden on soil,
air and surface water environment. Daozhong et al. (2011) aptly
compared the ecological rucksack between underground and open-
pit Coal Mine and showed opencast mine produces 4.31 to 11.36
* Corresponding author.
E-mail address: rge_abhijit@mail.vidyasagar.ac.in (A. Manna).
Peer-review under responsibility of China University of Geosciences (Beijing).
quarry involves excavation and removal of overburden rock and
surface soil layers and results in loss of productive soil and soil
biomass that ultimately affects agricultural lands leading to bare
unproductive land and ecological deterioration (De and Mitra,
2002). In RCF opencast mining is being increased extensively af-
ter nationalization of Indian coal mines in 1972e1973. Mine spoil
characteristics of the dump area and deterioration in soil properties
of Raniganj coalfield have been studied by Sadhu et al. (2012a).
Quarrying disrupted many tributaries, choked the ephemeral
drainage channels and the outwash from the overburden causes
drainage congestion and leads mobility of toxic metals in the RCF
(Manna and Maiti, 2016). Physical weathering helps to breakdown
the sulfides to release heavy metals from the spoil dump but metal
mobilization occurs at slow rate by the physical weathering pro-
cesses and majority remains in the residual dump spoils (Dang
et al., 2002). Masto et al. (2015) stated coal dust comprises Fe, Cu,
Zn, Mn, Pb, Cd, Cr, Ni, Co, Ti, Br, Zr, metals and organic pollutants. So,

https://doi.org/10.1016/j.gsf.2017.10.011
1674-9871/© 2017, China University of Geosciences (Beijing) and Peking University. Production and hosting by Elsevier B.V. This is an ope n access article under the CC BY-NC-
ND license (http://creativecommons.org/licenses/by-nc-nd/4.0/).
1578 A. Manna, R. Maiti / Geoscience Frontiers 9 (2018) 1577e1590
Figure 1. Location of the study area. (a) India, RCF in West Bengal and Jharkhand; (b) RCF in blocks of West Bengal and Jharkhand; (c) mine area of RCF; (d) geologic structure of
RCF (Geological Survey of India).
coal mining leads to land degradation through mine pit, quarries,
spoil dumps, coal dumps, coal washeries and other mine allied
works.
Earlier studies emphasised on the heavy metals contamination
in the coal mining region of different countries and showed these
mining features and allied activities affect the native soil by
releasing toxic heavy metals. Sahoo et al. (2016) reported world-
wide scenario of average trace metal concentration in the coal mine
affected soils through various indices using global reference.
Bhuiyan et al. (2010) made a complete evaluation of the pollution
level in the coal mine affected agricultural soils of Barapukuria coal
mine region in Bangladesh. They have shown that the average
concentrations of Ti, Mn, Zn, Pb, As, Fe, Rb, Sr, Nb and Zr exceeded
the world normal averages and in some cases Mn, Zn, As and Pb
exceeded the toxic limit and the entire area has high magnitude of
contamination level. Yu et al. (2002) assessed spatio-temporal
variation of heavy metal concentration in reclaimed soil of
Fushun coal mine of China. Distribution of heavy metals in the soil
and their environmental impact has been evaluated near the
Morupule colliery of Palapye region (only coal mine area) in
Botswana by Zhai et al. (2009). Ameh (2013) concluded that soil
near Okaba coal mine of Nigeria is remarkably contaminated by Pb,
Ni, and Cu. Chen et al. (2015) explained the characteristics of metal
pollution in the soil-river-vegetation environment and showed
Kaili coal mine affected the upper catchment of the Chongan river
basin in Guizhou Province of China.
Study of soil contamination in RCF has been attempted by
Tiwary and Dhar (1994). They tried to assess the environmental
impact of coal mine in Raniganj as well as entire Damodar river
basin. De and Mitra (2004) showed mobilization of heavy metals in
the Raniganj mine area and concluded leaching is the most effective
factor followed by surface runoff from the spoil dumps. Das and
Chakrapani (2011) assessed the soil quality through 6 selected
trace metals in the Raniganj Coalfield. They also tried to estimate
the potential toxicity of soil and showed Cr, Cu, Ni and Zn con-
centrations exceed the maximum allowable concentration. Masto
et al. (2015) assessed soil quality of Sonepur bazari mine area
which is one of the neighbouring basins of the present basin under
study and stated that most of the metals have significant content in
opencast mine than underground areas.
Many other authors tried to assess the various aspects of soil
contamination in the coal mine areas from different parts of the
world (Gangreung coalfield of Korea, Kim and Chon, 2001; Huainan
mining area of China, Yao et al., 2010; mine soil near Surat in India,
Ladwani et al., 2012; Oltu coal mine district of Turkey, Tozsin, 2014).
Still there is a lack of intensive study and application of all kind of
 A. Manna, R. Maiti / Geoscience Frontiers 9 (2018) 1577e1590
indices for a single mine affected river basin, especially in the 240
years old Raniganj coal field, present authors have attempted so by
assessing 13 trace metals among 32 samples over a completely
mine affected small river basin.
Among all the heavy metals, present study considered 13 heavy
metals (K, Ca, Ti, Cr, Mn, Fe, Ni, Cu, Zn, As, Pb, Sr, Zr) of environ-
mental interest which were frequently observed in most of the
earlier studies (along with consideration of all metals mentioned in
the literatures related to RCF). Among them Ca, Mn, K, Ti, Zn, Zr and
Fe have low toxicity which result mild health hazard. Whereas Cr,
Ni, Sr, Cu, Pb and As pose high toxicity and potentiality to severe
health hazard. Few among them also have radioactive isotope. In
the present study an attempt has been made to measure level of
contamination of heavy metals in the regional soil of coal mine
affected area along with the spatial distribution of contamination
level and pollution load. The study also tried to assess the basin
level potential ecological risk created by metal pollution.
2. Study area
In Raniganj Coalfield (RCF), mining operation commenced in
1774 AD and is going through a full-fledged operation. The Raniganj
Coalfield (Fig. 1) spreads in the state of West Bengal and Jharkhand.
In West Bengal, the coalfield covers part of Bardhaman district with
fringe area falling in the districts of Birbhum, Bankura and Purulia.
In Jharkhand, part of the coalfield located in Dhanbad and Santal
Pargana districts. Raniganj Coalfield is being mined by Eastern
Coalfield Limited (ECL), a subsidiary of Coal India Limited (CIL) and
only a small area by Bharat Coking Coal Limited (BCCL, also a sub-
sidiary of CIL) and Indian Iron and Steel Company (IISCO). Geology
of Raniganj Coalfield mainly consists of six rock formations of Up-
per Gondwana and Lower Gondwana period i.e., Talchir, Barakar,
Barren measure, Raniganj, Panchet and Supra-panchet formations
(Dutta and Dutta, 2003). Coal seams are located in the Raniganj and
Barakar rock formations of geologic segment in the RCF (Fig. 1d).
Figure 2. (a) Tributary catchment basins of Damodar River, derived from DEM image; (b) small basins superimposed on mine area; (c) sele cted Singaran river basin.
1579
Most of the coal deposited tracts of RCF are sandwiched between
the Ajay and the Damodar River. Present study concentrated on this
interfluve region. To conduct an intensive and scientific study au-
thors have selected Singaran river basin, a tributary basin of
Damodar river (Fig. 2a).
2.1. Rational for selection of the Singaran basin
The Singaran river basin is situated on the northern bank of
Damodar river covering the area 155 km2 in the center of Raniganj
Coal mine area. 60% of its basin area associated to agricultural land,
along with underground and opencast mine works. Compare to
other tributary basins of Damodar river, entire Singaran basin is
affected by the mine works mainly by the opencast mine works
(Fig. 2b). Daozhong et al. (2011) showed ecological stresses by non-
biological metals created by opencast mines which are 1.24e4.40
times more than the underground mining. Seepage of water and
mining effluents from overburden dumps, exposed overburden and
coal processing, contain heavy metals (Wong, 2003). Tiwary and
Dhar (1994) reported mining as environmental pollution source in
the RCF. They noticed 50% of mine water discharge directed to-
wards Damodar river and ECL discharges about 385 million litres
per day. This seepage and discharge cause serious exposure of
metals to humans is mainly through soilecropefood pathway
(Equeenuddin et al., 2010; Sahoo et al., 2012; Chuncai et al., 2014;
Halim et al., 2014) and can impact on crop growth and food
safety (Wuana and Okieimen, 2011; Zhang et al., 2013; Rashid et al.,
2014). Das and Chakrapani (2011) noticed the soil and water of
Singaran basin are moderate and less contaminated respectively.
So, Singaran basin is selected as it has large numbers of active and
abandoned opencast quarries (along with underground mines for
the deeper coal strata), overburden spoil dumps, abandoned mines,
coal dumps etc. compared to the basin lying in the immediate west
(having almost same areal coverage of mine works) of Singaran
basin (Fig. 2c).
1580 A. Manna, R. Maiti / Geoscience Frontiers 9 (2018) 1577e1590
3. Methods and techniques
3.1. Selection of Singaran basin
Singaran basin had been demarcated following few stages in GIS
platform. At first, micro-scale channels were extracted (by calcu-
lating flow accumulation) from a digital elevation image (Cartosat-
DEM, 2008) using Arc-Hydro Tool, an extension of ArcGIS Software.
Then small catchment polygons (basin boundaries) were processed
(Fig. 2a).
3.2. Sample collection
Plotting 10 × 10 grid (using ArcGIS Fishnet tool) over the Singaran
basin, 32 Sample sites selected and samples were collected at depth
of 10 cm from surface soil (Fig. 3a and b). All samples were from
native soil with representation of agricultural soils, soil at the
proximity of quarries; spoil dumps (mine overburden), river cour-
ses, river banks, ephemeral channels, interfluve areas and waste
land. Samples were collected in polyethylene bags by stainless
corer. Global Positioning System (GPS) reading have been collected
to confirm corresponding locations in GIS platform during data
Figure 3. (a) Sample sites over Singaran basin; (b) sample collection from 10 cm depth of surface soil; (c) dust sample (<40 mm) solution for drop cast; (d) gold coated sample ready
for EDX measurement; (e) measuring elements through EDX.
processing. Following Bhuiyan et al. (2010) one sample from mine
unaffected soil with shale as parent material (beyond the Singaran
basin area) has been collected to determine regional background
value of metal content in the soil.
3.3. Sample preparation
Samples were dried, mixed and powdered by mortar and pestle.
After sieving, dust forms (<40 mm) of samples have been collected
from the bottom pan. Then 2 mg/mL water solution drop casted on
glass slide and finally brought to zero moisture level at the desic-
cator (Fig. 3c). Following Thin-Film Method (Gullayanon, 2011),
samples were made so thin that absorption effects substantially
disappeared (during EDX instrumentation) and the solution drop
casts were smoothen (that unknown elements be near the surface)
to get suitable calibration results. Gold coating of samples was done
to remove any deflection due to conductive effect (Fig. 3d).
3.4. Elemental analysis through EDX
In this study elemental analysis has been performed through
Energy Dispersive X-ray Analysis (EDX) at chemical laboratory of S.
 A. Manna, R. Maiti / Geoscience Frontiers 9 (2018) 1577e1590
N. Bose National Centre for Basic Sciences, Saltlake, Kolkata
(Fig. 3e). EDX is able to determine both qualitative and quantitative
chemical compositions by measuring the characteristic radiations
(Gullayanon, 2011). EDX is advantageous as it allows analysis of
solid materials without digestion as in the Atomic Absorption
Spectroscopy (AAS) or Inductively Coupled Plasma Optical Emission
Spectroscopy (ICP-OES) methods (Sitko et al., 2004). The emission
of the characteristic radiation for every element is completely in-
dependent of any type of chemical bonds which enables accurate
measurements of elements existing in a given sample (Gullayanon,
2011). EDX shows the characteristic peak for each element from a
sample with atomic level precision that can directly be translated to
the chemical concentration at mg kg —1 level. Data sheets have been
generated through EDX ZAF Quantification. Final data have been
derived from mean of three different points for a single sample. In
this way 32 samples have been analysed. In case of background
sample, minimum values (among the three points) of metals con-
tent have been accepted during elemental analysis. Some of the
background metal counts have been verified with the regional
background data given by Das and Chakrapani (2011).
3.5. Quantification of soil contamination through indices
3.5.1. Geo-accumulation index (Igeo)
To estimate metal accumulation in soil and sediment, geo-
accumulation index (Igeo) is the very common approach which was
proposed by Muller (1969) as given in equation below
" #
Cmetal ðsampleÞ
I ¼ log2 1:5 × C
geo metal background
ð Þ
where, Cmetal is concentration of individual metal in sample and
Cmetal (background) is the geochemical background value of that metal.
Multiplying factor 1.5 is background matrix correction factor
intended to minimize variability of background values due to
lithological variations (Stoffers et al., 1986; Ruiz, 2001). For back-
ground value world average shale’s content (Rubio et al., 2000) and
average earth crust content (Loska et al., 2004) have been used
widely. But Rubio et al. (2000) recommended regional background
instead of constant value (world average, which produces varied
contamination levels with time and places). Especially background
values of Na, Mg, Al, K, Ca, Ba Sc, Ti, Fe, and Br vary among different
soil types (Jiang et al., 1996). Depending on parent material most of
trace metal concentration in soil easily vary over 2e3 orders of
magnitude (Blaser et al., 2000). Following these recommendations
background value of metals under present study is taken from
neighbouring uncontaminated soil sample. Muller (1981) and Ruiz
(2001) classified Igeo values in seven classes. Class 0 (Igeo ≤ 0):
practically uncontaminated; Class 1 (Igeo ¼ 0e1): uncontaminated
to moderately contaminated; Class 2 (Igeo ¼ 1e2): moderately
contaminated; Class 3 (Igeo ¼ 2e3) moderately to heavily contam-
inated; Class 4 (Igeo ¼ 3e4): heavily contaminated; Class 5
(Igeo ¼ 4e5): heavily to extremely contaminated; Class 6 (Igeo > 5):
extremely contaminated. Class 6 is an open class having all Igeo
values higher than Class 5 and metal concentrations may be hun-
dredfold greater than the geochemical background value (Bhuiyan
et al., 2010).
3.5.2. Enrichment factor (EF)
Covelli and Fontolan (1997) and many other authors preferred
enrichment factor (EF) over Igeo to estimate contaminants. It is an
improved method which normalizes the heavy metal content in
comparison to the reference (normalizer) metal (Ravichandran
1581
et al., 1995). Enrichment factor indicates the magnitude of con-
centration of any contaminant in the environment (Zahran et al.,
2015). It is frequently used to estimate heavy metal in topsoil due
to anthropogenic impact (Jiao et al., 2015). The normalized EF value
can be derived through two staged rationing in which the metal
and reference metal content ratio in sample is divided by the same
ratio of uncontaminated background levels (Rubio et al., 2000). The
equation is as below:
ðCi=CFeÞsample
EF ¼
ðCi=CFeÞbackground
where, Ci is the concentration of metal and CFe is the concentration
of iron (reference metal). Fe or Al often comes to use as reference
(normalizer) metal to determine EF. Use of Fe is more feasible as
geochemical nature of Iron is more similar to many heavy metals of
environmental interest both in oxic or anoxic environment (Rubio
et al., 2000). Its natural concentration also tends to be uniform
(Daskalakis and O’Connor, 1995). In this regard present study used
Fe as normalizer and background values are as same as for Igeo.
When EF < 2 it seems to be crustal origin and >2 indicates sources
likely to be the anthropogenic (Liaghati et al., 2003). EF values
greater than 10 are considered purely anthropogenic origin
(Bhuiyan et al., 2010). Multi-order categorization is done by many
authors (e.g. Sadhu et al., 2012b; Zahran et al., 2015) as follows:
EF < 2 (deficiencies to minimal enrichment); 2e5 (moderate
enrichment); 5e20 (significant enrichment); 20e40 (high to very
high enrichment) and >40 (strongly high enrichment).
3.5.3. Contamination factor (CF)
CF is the single pollution index (Muller, 1969; Halim et al., 2014)
which assesses the contamination level directly by individual
element in the soil of particular site. It is the ratio derived by
measured concentration of each metal in the soil by the regional
background concentration value (Cabrera et al., 1999) expressed in
following equation:
Cmetal ðsampleÞ
CFi ¼
Cmetal ðbackgroundÞ
Present study classified contamination level (CF values) into four
categories following Likuku et al. (2013) and Sadhu et al. (2012b).
When, CF < 1 refers to low contamination; 1≤ CF < 3 means
moderate contamination; 3 ≤CF < 6 means considerable
contamination; and CF > 6 indicates very high (100 times more
than uncontaminated crust) contamination (Muller, 1969; Bhuiyan
et al., 2010).
3.5.4. Degree of contamination (Cdeg)
Hakanson (1980) proposed Cdeg, (overall indicator of contami-
nation) taking CF values of all individual metals together for any
sample site. Loska et al. (2004) used Cdeg to analyse the contami-
nation level in farming soil. Ahdy and Khaled (2009) assessed the
contamination of Mediterranean sediments using Cdeg. Halim et al.
(2014) named same index as Overall Pollution Score (OPS). It
evaluates extent of multi-metal pollution by the numeric sum of
specific CF values of metals under study and was calculated using
following formula:
nX
¼ 13
Cdeg ¼ CFi
i¼1
where, n is the number of contaminants under study and CF is the
contamination factor. Present study summed up CF values of 13
Table 1

1582
Concentration of heavy elements, their geo-accumulation (Igeo) and enrichment factor (EF) values in the basin soils (concentration in mg kg— 1, median is used for EF).

Sample K Ca Ti Cr Mn Fe Ni
Concentration Igeo EF Concentration Igeo EF Concentration Igeo EF Concentration Igeo EF Concentration Igeo EF Concentration Igeo EF Concentration Igeo EF
1 5400 —0.38 0.87 11,100 1.46 3.12 3900 —0.08 1.08 250 0.40 1.50 290 0.09 1.20 3440 —0.18 1.00 230 0.77 1.93
2 5800 —0.28 3.65 6500 0.69 7.14 500 —3.04 0.54 34 —2.47 0.80 50 —2.45 0.81 880 —2.15 1.00 245 0.86 8.05
3 8100 0.20 0.86 6000 0.57 1.12 2900 —0.50 0.53 27 —2.81 0.11 400 0.55 1.10 5200 0.42 1.00 45 —1.58 0.25
4 5400 —0.38 1.13 18,300 2.18 6.67 3200 —0.36 1.15 250 0.40 1.95 320 0.23 1.73 2650 —0.56 1.00 265 0.97 2.89
5 7600 0.11 1.03 19,600 2.28 4.63 5500 0.42 1.28 620 1.71 3.13 520 0.93 1.82 4090 0.07 1.00 840 2.64 5.94
6 1400 —2.33 0.26 68,800 4.09 22.70 3300 —0.32 1.07 830 2.13 5.85 610 1.16 2.97 2930 —0.41 1.00 860 2.67 8.48
7 9400 0.42 1.56 34,700 3.10 10.04 7900 0.94 2.24 730 1.95 4.51 620 1.18 2.65 3340 —0.22 1.00 760 2.49 6.58
8 3100 —1.19 0.77 14,700 1.87 6.40 5700 0.47 2.44 360 0.93 3.35 260 —0.07 1.67 2220 —0.81 1.00 800 2.57 10.42
9 12,300 0.80 0.75 11,700 1.54 1.25 9000 1.13 0.94 190 0.01 0.43 490 0.84 0.77 9060 1.22 1.00 210 0.64 0.67
10 2400 —1.55 1.10 1400 —1.53 1.12 4500 0.13 3.53 100 —0.92 1.71 190 —0.52 2.24 1210 —1.69 1.00 180 0.42 4.30
11 17,600 1.32 1.72 8300 1.04 1.42 7300 0.83 1.23 460 1.28 1.68 840 1.62 2.12 5650 0.53 1.00 610 2.18 3.12
12 17,400 1.30 2.12 31,100 2.95 6.64 8000 0.96 1.68 700 1.89 3.19 490 0.84 1.55 4530 0.22 1.00 690 2.35 4.40
13 2700 —1.38 0.89 2600 —0.63 1.50 3700 —0.15 2.10 200 0.08 2.47 150 —0.86 1.28 1670 —1.22 1.00 160 0.25 2.77
14 3300 —1.10 0.82 52,900 3.71 23.03 4200 0.03 1.80 410 1.12 3.81 2090 2.94 13.45 2220 —0.81 1.00 310 1.20 4.04
15 4200 —0.75 1.08 1100 —1.88 0.49 17000 2.05 7.47 100 —0.92 0.96 2800 3.36 18.52 2160 —0.85 1.00 140 0.05 1.87

A. Manna, R. Maiti / Geoscience Frontiers 9 (2018) 1577e1590

16 4600 —0.62 0.78 3300 —0.29 0.98 3900 —0.08 1.14 180 —0.07 1.14 3340 3.61 14.68 3250 —0.26 1.00 205 0.60 1.82
17 16,800 1.25 1.04 14,000 1.79 1.52 9400 1.19 1.00 440 1.22 1.02 700 1.36 1.12 8900 1.19 1.00 390 1.53 1.27
18 6200 —0.19 0.38 12,200 1.60 1.30 3700 —0.15 0.39 350 0.89 0.79 3090 3.50 4.85 9100 1.22 1.00 525 1.96 1.67
19 5300 —0.41 1.19 3200 —0.33 1.26 7100 0.79 2.74 210 0.15 1.76 210 —0.38 1.22 2460 —0.66 1.00 225 0.74 2.64
20 9000 0.35 0.57 8400 1.06 0.93 7700 0.91 0.84 370 0.97 0.88 560 1.04 0.92 8700 1.16 1.00 535 1.99 1.78
21 39,400 2.48 25.95 1800 —1.16 2.07 2800 —0.55 3.16 140 —0.43 3.44 180 —0.60 3.06 840 —2.22 1.00 150 0.15 5.16
22 10,100 0.52 1.64 5200 0.37 1.48 5400 0.39 1.51 350 0.89 2.12 280 0.04 1.18 3400 —0.20 1.00 190 0.49 1.62
23 3400 —1.05 1.57 3700 —0.13 2.98 3700 —0.15 2.93 270 0.51 4.64 190 —0.52 2.26 1200 —1.70 1.00 165 0.29 3.97
24 56,700 3.01 7.11 11,700 1.54 2.56 8900 1.11 1.92 340 0.85 1.59 350 0.36 1.13 4410 0.18 1.00 555 2.04 3.64
25 19,900 1.50 1.37 5100 0.34 0.61 5500 0.42 0.65 500 1.40 1.29 360 0.40 0.64 8020 1.04 1.00 460 1.77 1.66
26 4800 —0.55 0.92 6100 0.60 2.04 4600 0.16 1.51 180 —0.07 1.29 440 0.69 2.17 2890 —0.43 1.00 250 0.89 2.50
27 5600 —0.33 1.08 3800 —0.09 1.28 2300 —0.84 0.76 40 —2.24 0.29 130 —1.07 0.65 2860 —0.45 1.00 140 0.05 1.41
28 4300 —0.71 0.49 2200 —0.88 0.44 3300 —0.32 0.64 200 0.08 0.85 200 —0.45 0.59 4860 0.32 1.00 140 0.05 0.83
29 48,000 2.77 18.19 2400 —0.75 1.59 4700 0.19 3.05 290 0.62 4.10 230 —0.25 2.25 1460 —1.42 1.00 290 1.10 5.74
30 2500 —1.50 0.71 2100 —0.94 1.05 2800 —0.55 1.37 170 —0.15 1.81 260 —0.07 1.91 1940 —1.01 1.00 135 0.00 2.01
31 31,900 2.18 2.36 3100 —0.38 0.40 23500 2.52 2.98 150 —0.33 0.41 420 0.62 0.80 7490 0.94 1.00 210 0.64 0.81
32 8600 0.29 1.28 4700 0.22 1.22 4300 0.07 1.09 360 0.93 1.99 3170 3.54 12.14 3730 —0.06 1.00 205 0.60 1.59
Max 56,700 3.01 25.95 68,800 4.09 23.03 23500 2.52 7.47 830 2.13 5.85 3340 3.61 18.52 9100 1.22 1.00 860 2.67 10.42
Min 1400 —2.33 0.26 1100 —1.88 0.40 500 —3.04 0.39 27 —2.81 0.11 50 —2.45 0.59 840 —2.22 1.00 45 —1.58 0.25
Mean/median 11,975 0.12 1.08 11,931.25 0.75 1.49 5943.75 0.24 1.32 306.28 0.31 1.69 757.1875 0.68 1.70 3961.25 —0.27 1 347.34 1.04 2.57
Background 4700 2690 2740 126 182 2600 90
value
World normal 15,000 24,000 2900 70.9 571 3800 23

Sample Cu Zn As Pb Sr Zr

Concentration Igeo EF Concentration Igeo EF Concentration Igeo EF Concentration Igeo EF Concentration Igeo EF Concentration Igeo EF
1 410 2.24 5.34 470 1.82 3.99 1 —3.75 0.08 73 0.21 1.31 347 2.00 4.52 860 2.22 5.29
2 220 1.34 11.21 120 —0.15 3.99 28 1.05 9.09 9 —2.81 0.63 125 0.52 6.37 399 1.11 9.59
3 40 —1.12 0.34 30 —2.15 0.17 9 —0.58 0.49 69 0.13 0.82 670 2.95 5.78 717 1.96 2.92
4 300 1.79 5.08 260 0.96 2.87 1 —3.75 0.11 151 1.26 3.52 310 1.83 5.25 666 1.85 5.31
5 580 2.74 6.36 840 2.65 6.01 1 —3.75 0.07 172 1.45 2.60 32 —1.44 0.35 28 —2.72 0.14
6 508 2.55 7.77 800 2.58 7.98 7 —0.95 0.68 125 0.99 2.63 46 —0.92 0.70 46 —2.00 0.33
7 480 2.46 6.44 640 2.26 5.60 25 0.89 2.14 207 1.72 3.83 83 —0.07 1.11 16 —3.53 0.10
8 503 2.53 10.16 650 2.28 8.56 16 0.25 2.06 190 1.59 5.28 196 1.17 3.96 11 —4.07 0.10
9 290 1.74 1.44 430 1.69 1.39 35 1.37 1.10 12 —2.39 0.08 412 2.24 2.04 1480 3.00 3.45
10 170 0.97 6.30 90 —0.57 2.17 25 0.89 5.90 77 0.29 3.93 222 1.35 8.23 882 2.26 15.41
11 460 2.40 3.65 790 2.57 4.09 27 1.00 1.37 158 1.33 1.73 262 1.59 2.08 239 0.37 0.89
12 500 2.52 4.95 450 1.75 2.90 1 —3.75 0.06 167 1.41 2.28 185 1.09 1.83 38 —2.28 0.18
13 70 —0.31 1.88 40 —1.74 0.70 24 0.83 4.11 21 —1.58 0.78 368 2.08 9.88 930 2.33 11.77
 A. Manna, R. Maiti / Geoscience Frontiers 9 (2018) 1577e1590 1583

12.20

36.57

26.89

23.53

36.57
1.00
0.57
0.58
0.83
0.31

0.58

5.38

0.43
0.62
8.95
8.59
7.27

7.02
3.21
0.31

0.10
3.07
—0.81
—1.67
—1.05

—0.47

—1.05

—1.75

—4.07
0.92

2.94
0.37
2.98
2.23
3.05

0.36
2.73
2.65
3.18
3.14
1.80
2.63

3.18

0.71
637.2813
1420

1453

1526

1224
1162
1671
1625

1139

1671
105

348
133

238

866

236

644

123
307
58
89

89

55

11
13.45
10.02

17.62

13.42

17.62
9.15

1.67
3.65
4.12
0.58

4.13

0.66
0.62
7.00
4.83
3.99
8.08
5.52
1.83
1.55

0.35
4.12
—0.42

—1.44
2.38
2.90
3.06
1.93
3.09
1.38
0.38
1.92
1.85
2.04

0.34
2.37
1.82
2.31
1.60
1.46
1.81
0.57
3.09

1.47
Figure 4. Mean geo-accumulation (Igeo) values of each metal.

306.2813
elements to calculate Cdeg for each (32) sample site. Contamination
classes by Cdeg depend upon number of contaminants. Zahran et al.
453
648
726
332
741
226
113
330
313
359

110
451
308
432
263
239
305
129
741

200
65

32

58

(2015) categorized as followings: Cdeg values < n indicate low de-

gree of contamination; n ≤ Cdeg < 2n, moderate degree of
2.84
1.34
1.20
1.21
1.16
2.03
1.04
1.10
0.02
2.11
1.72
0.66
0.17
1.32
0.64
7.23
0.22
0.01
0.70
7.23
0.01
1.26

contamination; 2n ≤ Cdeg < 4n, considerable degree of contami-

—0.42

—2.07
—5.98
—0.62

—2.98
—0.05
—0.33

—3.17
—5.98
—0.58

—5.98
—0.33

nation; and Cdeg > 4n indicate very high degree of contamination.

0.00
1.47
1.44
0.36
1.22

0.97
0.45

1.44

1.72
0.70

3.5.5. Modified degree of contamination (mCdeg)

Abrahim (2005) and Machender et al. (2011) divided Cdeg by the
88.1875

number of contaminants that produced a generalized approach to

estimate the mean degree of contamination as follows:
28.4
102

174
171

147

123

171

207
47
63

81

15

41

86

61
50

42

42
1

7
1

.
1.80
1.98
1.05
0.03
0.31
1.05
0.39
3.06
3.03
1.90
0.06
1.32
1.78
2.40
1.06
3.72
1.18
1.03
1.15
9.09
0.03
1.16

mCdeg ¼ Cdeg n
—0.17
—3.75
—0.43
—0.58
—0.17
—0.58

—0.75
—3.75

—0.75

—3.75
—0.46

where, Cdeg is the degree of contamination and n is the number of

0.05
0.15

1.42

1.45
0.42
0.83
0.42
0.49

1.00
0.15
1.45

considered pollutants. Rahman et al. (2012) noticed that, it requires

at least 3 samples to modify Cdeg into mCdeg. Present study gone
through 32 samples. The categorization of mCdeg is given in
15.40625

Supplementary Table 1 (Abrahim and Parker, 2008).

11.4
14
15
12

10

12

36

37
18
24
18
19

27
15
37
1

8
1

3.5.6. Pollution load index (PLI)

2.88671

Tomlinson et al. (1980) proposed index of pollution load. PLI

3.42
3.65
3.06
1.02
2.76
4.28
1.75
2.09
1.03
7.31
3.65
2.73
3.64
1.84
0.42
2.80
2.26
0.78
3.14
8.56
0.17

assesses magnitude of pollution load by all metal at different sites.

Angulo (1996) successfully applied Tomlinson’s method to assess
1.009336

coastal pollution and noticed that the PLI is necessary tool to

—1.15
—0.15

—0.93

—2.15

generate action plan. It is a simple geometric mean of contamina-

0.96
1.02
1.35
1.22
2.69
1.43
1.96

1.17
2.04
2.49
1.43
0.43

0.07
0.17
0.58
1.58
2.69

tion factor (CF) and can be expressed as:

PLI ¼ ðCF1 × CF2 × CF3 × / × CFn Þ1=n

369.0625

Present study considered 13 (n) metal pollutants of environ-

67.8
260
270
340
310
860
360
520

120
300
550
750
360
180

140
150
200
400
860
60

70

30

89

mental interest. Tomlinson et al. (1980) recommended that PLI ≤ 1

represent background levels of pollutants are present and PLI > 1
2.695196

would indicate deterioration of soil quality (i.e. the pollution load).

11.21
6.26
1.66
2.21
1.86
2.22
2.01
0.62
9.08
0.66
7.10
2.75
2.24
2.95
1.25
0.55
5.84
2.31
0.96
2.64

0.34

3.5.7. Ecological risk factor (Er)

1.213437

Hakanson (1980) assessed Ecological Risk Factor (Er) for any

—0.12

—0.80

—0.12
—0.54

—1.12
1.83

0.88
2.09
2.37
0.34
0.46
0.97

1.13
1.63
2.20
1.13

1.13
0.20
0.88
1.34
2.74

single contaminant according to toxicity response of its own. This is

calculated as:

ERi ¼ Tr × CFi
256.5938

where, Tr is the toxic response of a heavy metal, and CF is the

28.2
310

160
370
450
110
120
170

190
270
400
190

190
100
160
220
580
80

50

80
60

40

58

contamination factor of that metal. Present study considered 7

heavy metals (Ti, Zn, Cr, Ni, Cu, Pb and As) of ecological importance
Background value

according to availability of toxic factors and assigned toxic response

Mean/median

World normal

of concerned metal (Ti ¼Zn ¼ 1; Cr ¼2; Ni ¼Cu ¼ Pb ¼ 5; and

As ¼10) following Hakanson (1980) and Xu et al. (2008). Same
Max

responses have been estimated in contaminated coastal environ-

Min
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
32

ment by Mugosa et al. (2016). Sahoo et al. (2016) reviewed

1584 A. Manna, R. Maiti / Geoscience Frontiers 9 (2018) 1577e1590
ecological risk factor for the worldwide mine areas. The categories
to describe the risk factors are given in Supplementary Table 2.
3.5.8. Potential Ecological Risk Index (RI)
Potential Ecological Risk Index (RI) is also modified form of Er
and is able to evaluate degree of environmental sensitivity caused
by toxic metals to the soil environment comprehensively
(Aktaruzzaman et al., 2013; Jiao et al., 2015; Sahoo et al., 2016). RI is
the sum of all risk factors for considered metals in soils and can be
expressed following Hakanson (1980) as:
nX
¼7
RI ¼ ERi
i¼1
ERi is the ecological risk factor for individual metal. RI has been
calculated for 7 (n) metals. Jiao et al. (2015) categorized RI values as
RI < 150 (low ecological risk potential); 150 ≤ RI < 300 (Moderate
Figure 5. Distribution of enrichment factor (EF) values of metals.
potential ecological risk); 300 ≤RI < 600 (Considerable high po-
tential ecological risk); and RI > 600 (Significantly high potential
ecological risk).
3.6. Statistical analysis
Pearson’s correlation method has been adopted for the under-
standing of interdependency (r value) among the metals in regards
to the contamination factor values (CF values). It varies between —1
and þ1. When value near to þ1 it is positively correlated and value
near to —1 then negatively correlated.
3.7. GIS operations
The basin for study has been selected through GIS application
(Manna and Maiti, 2016) discussed in Section 3.1. All calibrated data
of elemental concentration and indices results have been assigned
 A. Manna, R. Maiti / Geoscience Frontiers 9 (2018) 1577e1590 1585

to the concern sample site in the GIS platform using ArcGIS soft-
ware. Distribution of metal concentration, contamination level,
pollution load and ecological risk all have been shown in maps
through interpolation techniques in GIS platform following Rubio
et al. (2000).
4. Result and discussion
4.1. Absolute metal concentration and soil quality
K and Ca show high amount absolute concentration and have
mean concentration of 11,975 and 11,931 mg kg —1 respectively. As
and Pb have lowest mean concentration of 15.41 and 88.19 mg kg —1
respectively. The rest elements Ti, Fe, Mn, Zr, Zn, Ni, Cr, Sr and Cu
have mean concentration of 5944, 3961, 757.2, 637.3, 369.1, 347.3,
306.3, 306.3, and 256.6 mg kg—1 respectively (Table 1). Average
concentration of each element is more than the regional back-
ground level but average concentration of K, and Ca shows lower
than world average concentration, Fe and As have mean concen-
trations slightly greater than world average and the rest Ti, Cr, Mn,
Fe, Ni, Cu, Zn, Pb, Sr, Zr have mean concentration more than world
average (Table 1). Distribution shows Fe has uniform distribution
over the basin. As shows isolated distribution of minimal concen-
tration among the sample sites. K, Ti and Zr show maximum con-
centration at lower reaches of the basin and the rests show
maximum concentration at middle catchment in the vicinity of
opencast mines (Supplementary Fig. 1).
4.2. Accumulation and enrichment of trace metals in surface soil
Igeo values of Pb and Zr have highest range from —5.98 to 1.72
and —4.07 to 3.18 respectively. Other metals show range of Igeo
values in descending order as Mn (—2.45 to 3.61), Ca (—1.88 to
4.09), Ti (—3.04 to 2.52), As (—3.75 to 1.45), K (—2.33 to 3.01), Cr
(—2.81 to 2.13), Zn (—2.05 to 2.69), Sr (—1.44 to 3.09), Ni (—1.58 to
2.67), Cu (—1.12 to 2.74), and Fe (—2.22 to 1.22) (Table 1). Mean Igeo
values of As, Pb and Fe are —0.46, —0.33, and —0.28 respectively
that indicate practically no contamination (Class 0, Igeo ≤ 0), K, Ti,
Cr, Mn, Zr, and Ca have mean Igeo values 0.12, 0.24, 0.31, 0.68, 0.71
and 0.75 respectively indicating uncontaminated to moderately
contaminated state (Class 1, Igeo ¼ 0e1), Sr, Cu, Ni and Zn have mean
Igeo values 1.47, 1.21, 1.04 and 1.01 respectively that indicate mod-
erate contamination (Class 2, Igeo ¼ 1e2) (Fig. 4). Sample sites 11, 12,
17, 20 and 25 have positive Igeo values for almost all metal. Whereas
sample sites 2, 13, 15, 21, 23, 27, 28 and 30 have negative Igeo values
for most of the metals.
Taking Fe as normalizing element, EF of all metals has been
analysed. The result shows average (median has been considered as
average to reduce the error generally made by mean due to single
or two high values in the distribution) EF values of metals in order
as Sr (4.12) > Zr (3.07) > Zn (2.89) > Cu (2.70) > Ni (2.57) > Mn
(1.70) > Cr (1.69) > Ca (1.49) > Ti (1.32) > Pb (1.26) > As (1.16) > K
(1.08) (Table 1). Categorization of average EF values show Sr, Zr, Zn,
Cu, Ni are moderately enriched (EF values between 2 and 5, Zahran
et al., 2015) in the surface soils which indicates anthropogenic
origin (EF value > 2, Liaghati et al., 2003). Whereas rest of the

Table 2
Contamination factors (CF), degree of contamination (Cdeg), modified degree of contamination (mCdeg ) and pollution load indices (PLI) values of trace metals in basin soils.

Sample CF Cdeg mCdeg PLI

K Ca Ti Cr Mn Fe Ni Cu Zn As Pb Sr Zr
1 1.15 4.13 1.42 1.98 1.59 1.32 2.56 7.07 5.28 0.11 1.74 5.98 6.99 41.33 3.18 2.15
2 1.23 2.42 0.18 0.27 0.27 0.34 2.72 3.79 1.35 3.11 0.21 2.16 3.24 21.30 1.64 0.99
3 1.72 2.23 1.06 0.21 2.20 2.00 0.50 0.69 0.34 1.00 1.64 11.55 5.83 30.97 2.38 1.34
4 1.15 6.80 1.17 1.98 1.76 1.02 2.94 5.17 2.92 0.11 3.60 5.34 5.41 39.39 3.03 2.11
5 1.62 7.29 2.01 4.92 2.86 1.57 9.33 10.00 9.44 0.11 4.10 0.55 0.23 54.02 4.15 2.18
6 0.30 25.58 1.20 6.59 3.35 1.13 9.56 8.76 8.99 0.78 2.98 0.79 0.37 70.37 5.41 2.45
7 2.00 12.90 2.88 5.79 3.41 1.28 8.44 8.28 7.19 2.78 4.93 1.43 0.13 61.45 4.73 3.09
8 0.66 5.46 2.08 2.86 1.43 0.85 8.89 8.67 7.30 1.78 4.52 3.38 0.09 47.98 3.69 2.24
9 2.62 4.35 3.28 1.51 2.69 3.48 2.33 5.00 4.83 3.89 0.29 7.10 12.03 53.41 4.11 3.13
10 0.51 0.52 1.64 0.79 1.04 0.47 2.00 2.93 1.01 2.78 1.83 3.83 7.17 26.53 2.04 1.46
11 3.74 3.09 2.66 3.65 4.62 2.17 6.78 7.93 8.88 3.00 3.76 4.52 1.94 56.74 4.36 3.92
12 3.70 11.56 2.92 5.56 2.69 1.74 7.67 8.62 5.06 0.11 3.98 3.19 0.31 57.10 4.39 2.73
13 0.57 0.97 1.35 1.59 0.82 0.64 1.78 1.21 0.45 2.67 0.50 6.34 7.56 26.45 2.03 1.32
14 0.70 19.67 1.53 3.25 11.48 0.85 3.44 5.34 2.92 1.56 2.43 7.81 0.85 61.85 4.76 2.87
15 0.89 0.41 6.20 0.79 15.38 0.83 1.56 1.38 3.03 1.67 1.12 11.17 0.47 44.91 3.45 1.75
16 0.98 1.23 1.42 1.43 18.35 1.25 2.28 2.76 3.82 1.33 1.50 12.52 0.72 49.59 3.81 2.17
17 3.57 5.20 3.43 3.49 3.85 3.42 4.33 6.38 3.48 0.11 4.14 5.72 2.83 49.97 3.84 2.96
18 1.32 4.54 1.35 2.78 16.98 3.50 5.83 7.76 9.66 1.11 4.07 12.78 1.08 72.76 5.60 3.81
19 1.13 1.19 2.59 1.67 1.15 0.95 2.50 1.90 4.04 1.00 1.93 3.90 11.54 35.49 2.73 2.03
20 1.91 3.12 2.81 2.94 3.08 3.35 5.94 2.07 5.84 1.33 3.50 1.95 1.93 39.78 3.06 2.79
21 8.38 0.67 1.02 1.11 0.99 0.32 1.67 2.93 0.67 1.00 0.36 5.69 11.81 36.63 2.82 1.47
22 2.15 1.93 1.97 2.78 1.54 1.31 2.11 0.86 1.35 4.00 0.02 5.40 7.04 32.46 2.50 1.58
23 0.72 1.38 1.35 2.14 1.04 0.46 1.83 3.28 3.37 0.89 0.98 6.19 12.41 36.04 2.77 1.78
24 12.06 4.35 3.25 2.70 1.92 1.70 6.17 4.66 6.18 0.11 2.93 1.12 0.72 47.86 3.68 2.35
25 4.23 1.90 2.01 3.97 1.98 3.08 5.11 6.90 8.43 4.11 2.05 1.90 1.92 47.58 3.66 3.29
26 1.02 2.27 1.68 1.43 2.42 1.11 2.78 3.28 4.04 2.00 0.19 7.78 9.95 39.94 3.07 2.10
27 1.19 1.41 0.84 0.32 0.71 1.10 1.56 1.38 2.02 2.67 1.45 5.31 9.45 29.41 2.26 1.54
28 0.91 0.82 1.20 1.59 1.10 1.87 1.56 1.03 0.79 2.00 1.19 7.45 13.59 35.09 2.70 1.68
29 10.21 0.89 1.72 2.30 1.26 0.56 3.22 3.28 1.57 2.11 4.07 4.53 13.21 48.95 3.77 2.57
30 0.53 0.78 1.02 1.35 1.43 0.75 1.50 1.72 1.69 0.89 0.17 4.12 5.24 21.18 1.63 1.17
31 6.79 1.15 8.58 1.19 2.31 2.88 2.33 2.76 2.25 3.00 0.02 5.26 9.26 47.78 3.68 2.19
32 1.83 1.75 1.57 2.86 17.42 1.43 2.28 3.79 4.49 1.67 1.00 2.22 0.45 42.76 3.29 2.16
Max 12.06 25.58 8.58 6.59 18.35 3.50 9.56 10.00 9.66 4.11 4.93 12.78 13.59 72.76 5.60 3.92
Min 0.30 0.41 0.18 0.21 0.27 0.32 0.50 0.69 0.34 0.11 0.02 0.55 0.09 21.18 1.63 0.99
Mean 2.55 4.44 2.17 2.43 4.16 1.52 3.86 4.42 4.15 1.71 2.10 5.28 5.18 43.97 3.38 2.23
1586 A. Manna, R. Maiti / Geoscience Frontiers 9 (2018) 1577e1590

Figure 6. Distribution of contamination factor (CF) values over the Singaran basin.
 A. Manna, R. Maiti / Geoscience Frontiers 9 (2018) 1577e1590 1587

metals have minimal enrichment (EF values between < 2), that may
have crustal origin. Sample sites 14, 21, 23 and 29 evidenced
moderate to significant enrichment for almost all the metals and
sample sites 3, 9, 17, 20, 25 and 31 show less or minimal enrichment
of all the metals (Fig. 5). Most of the metals having their significant
(EF ¼5e20) to high (EF ¼ 20e40) enrichment at the sample sites
located in the mine occupied middle catchment area (Fig. 5).
4.3. Soil contamination level
reach, Cr at upper catchment and Sr, Zr, Ca, Cu, Mn, Zn, Ni at middle
catchment somewhere spreading over upper or lower reach. Fe, As
and Pb have less contamination all over the basin with few
comparatively high CF values at isolated pockets.
Pearson’s correlation matrix (Table 3) shows there is a less
relationship (i.e. independency) among the CF values of the metals.
To some extent Ca, Cr, Ni and Cu show positive relationship with
other metals’ contamination values. Whereas, As and Zr show
negative relation with other metals’ contamination values.

Deployed contamination factor analysis shows contamination
level above background normal concentration. The result shows
that mean contamination levels (CF values) are in orders of Sr
(5.28) > Zr (5.18) > Ca (4.44) > Cu (4.42) > Mn (4.16) Zn (4.15) > Ni
(3.86) > K (2.55) > Cr (2.43) > Ti (2.17) > Pb (2.10) > As (1.71) > Fe
(1.52) (Table 2). Based on categorization of Likuku et al. (2013) these
CF values indicate moderate to considerable high contamination
level of each metal. Specifically Sr, Zr, Ca, Cu, Mn, Zn and Ni have
considerable contamination (3 CF ≤ < 6) whereas K, Cr, Ti, Pb As
and Fe have moderate to less level of contamination (1≤ CF < 3).
Site wise distribution of contamination level of each metal shown
in Fig. 6, indicates high contamination values of K and Ti at lower
Table 3
Pearson’s correlation matrix of observed heavy metals contamination (on CF values).
4.4. Overall pollution level in the basin soils
Degree of contamination (Cdeg) simplified the site wise
contamination factor by summation of CF values of each element.
Most of the sample sites show Cdeg values 2e4 times of the sample
number (n) that indicates considerable degree of contamination
(Table 2). Few sites like 5, 6, 7, 9, 11, 12, 14 and 18 evidenced high
degree of contamination (Cdeg values greater than four times of n).
Cdeg is modified in mCdeg which gives a comprehensive result. In the
same way, the classification of mCdeg (Abrahim and Parker, 2008)
resulted high degree of contamination at sites 5, 6, 7, 9, 11, 12, 14 and
18 (4 ≤ mCdeg < 8). Most of others have evidenced considerable

K Ca Ti Cr Mn Fe Ni Cu Zn As Pb Sr Zr
K 1
Ca —0.16 1
Ti 0.31 —0.08 1
Cr 0.03 0.73 0.03 1
Mn —0.18 0.07 0.12 0.04 1
Fe 0.13 —0.01 0.38 0.22 0.15 1
Ni 0.07 0.62 0.06 0.85 —0.02 0.22 1
Cu 0.01 0.60 —0.01 0.77 0.06 0.23 0.85 1
Zn —0.02 0.43 0.08 0.72 0.23 0.42 0.83 0.82 1
As —0.03 —0.25 0.12 —0.19 —0.11 0.10 —0.20 —0.23 —0.13 1
Pb 0.12 0.44 —0.01 0.65 0.06 0.22 0.77 0.70 0.61 —0.37 1
Sr —0.23 —0.26 0.02 —0.50 0.50 0.10 —0.52 —0.37 —0.30 —0.02 —0.26 1
Zr 0.14 —0.46 —0.07 —0.54 —0.50 —0.17 —0.63 —0.56 —0.60 0.21 —0.51 0.18 1

Figure 7. (a) Distribution of modified degree of contamination (mCdeg values); (b) pollution load (PLI values) over the catchment area.
1588 A. Manna, R. Maiti / Geoscience Frontiers 9 (2018) 1577e1590

Table 4 degree of contamination (2≤mCdeg < 4) (Fig. 7a) with a value 3.38
Ecological risk (Er) and potential ecological risk factor (RI) of trace elements in basin for the entire basin (Table 2).
soils.
PLI index performed best to analyse the pollution load on a
Sample Er RI sample site by calculating geometric tendency. Present analysis
Ti Cr Ni Cu Zn As Pb shows there is a moderate pollution load over the entire sample
1 1.42 3.97 12.78 35.34 5.28 1.11 8.69 68.60 sites with average PLI value 2.23 (Table 2). Sample sites having
2 0.18 0.54 13.61 18.97 1.35 31.11 1.07 66.83 highest PLI values are 11 (3.98), 18 (3.81) and 25 (3.29) demonstrate
3 1.06 0.43 2.50 3.45 0.34 10.00 8.21 25.99 deteriorated soil (i.e. the pollution overload). All three sites are
4 1.17 3.97 14.72 25.86 2.92 1.11 17.98 67.73
located at the middle catchment area with a well-founded prox-
5 2.01 9.84 46.67 50.00 9.44 1.11 20.48 139.54
6 1.20 13.17 47.78 43.79 8.99 7.78 14.88 137.60
imity to the opencast mine subjugated area, notably sample site 18
7 2.88 11.59 42.22 41.38 7.19 27.78 24.64 157.68 is situated at the center (Fig. 7b). Sites located far from the middle
8 2.08 5.71 44.44 43.36 7.30 17.78 22.62 143.30 catchment opencast mine dominated area, show moderate to less
9 3.28 3.02 11.67 25.00 4.83 38.89 1.43 88.12 pollution load.
10 1.64 1.59 10.00 14.66 1.01 27.78 9.17 65.84
11 2.66 7.30 33.89 39.66 8.88 30.00 18.81 141.20
12 2.92 11.11 38.33 43.10 5.06 1.11 19.88 121.52 4.5. Ecological risk of the trace metal contamination
13 1.35 3.17 8.89 6.03 0.45 26.67 2.50 49.06
14 1.53 6.51 17.22 26.72 2.92 15.56 12.14 82.61 Ecological risk (Er) for 7 elements has been analysed. The result
15 6.20 1.59 7.78 6.90 3.03 16.67 5.60 47.76
shows that Er of individual metal varied significantly as Ti ranges
16 1.42 2.86 11.39 13.79 3.82 13.33 7.50 54.12
17 3.43 6.98 21.67 31.90 3.48 1.11 20.71 89.29
from 0.18 to 10.77, Cr from 0.43 to 13.27, Ni from 2.50 to 47.78, Cu
18 1.35 5.56 29.17 38.79 9.66 11.11 20.36 116.00 from 3.45 to 50, Zn from 0.34 to 9.66, As from 1.11 to 46.67 and Pb
19 2.59 3.33 12.50 9.48 4.04 10.00 9.64 51.60 from 0.12 to 25.83 (Table 3). Ti, Zn and Cr having less toxic response
20 2.81 5.87 29.72 10.34 5.84 13.33 17.50 85.43 show less average ecological risk where Ni, Cu, Pb and As with high
21 1.02 2.22 8.33 14.66 0.67 10.00 1.79 38.69
toxic response show comparatively high mean ecological risk to the
22 1.97 5.56 10.56 4.31 1.35 40.00 0.12 63.86
23 1.35 4.29 9.17 16.38 3.37 8.89 4.88 48.32 soil. Average values of Er in descending order are as follows: Cu
24 3.25 5.40 30.83 23.28 6.18 1.11 14.64 84.69 (22.12) > Ni (19.30) > As (17.12) > Pb (10.50) > Cr (4.86) > Zn
25 2.01 7.94 25.56 34.48 8.43 41.11 10.24 129.76 (4.15) > Ti (2.24). Average Er values of all metals fall in the low
26 1.68 2.86 13.89 16.38 4.04 20.00 0.95 59.80
ecological risk group (Er≤ 40) according to classification standard
27 0.84 0.63 7.78 6.90 2.02 26.67 7.26 52.10
28 1.20 3.17 7.78 5.17 0.79 20.00 5.95 44.07
in Supplementary Table 2.
29 1.72 4.60 16.11 16.38 1.57 21.11 20.36 81.85 Sensitivity of biologic environment to the toxic substances has
30 1.02 2.70 7.50 8.62 1.69 8.89 0.83 31.25 been assessed by potential ecological risk (RI) for each sample site.
31 10.77 2.38 11.67 13.79 2.25 30.00 0.12 70.97 The result is summarized in Table 4 and shows mean RI value 80.28
32 1.57 5.71 11.39 18.97 4.49 16.67 5.00 63.80
which indicates low ecological risk potential over the entire river
Max 10.77 13.17 47.78 50.00 9.66 41.11 24.64 157.68
Min 0.18 0.43 2.50 3.45 0.34 1.11 0.12 25.98 basin area. Analysing RI values for 32 sample sites, it is found that
Mean 2.24 4.86 19.30 22.12 4.15 17.12 10.50 80.28 few sample sites (5, 6, 7, 8, 11, 12, 18 and 25) have tend to moderate
Toxic response 1.00 2.00 5.00 5.00 1.00 10.00 5.00 risk potential but not crossed the lower limit of moderate potential
category (Re-categorization with lower values has been done in
Fig. 8 as the basin shows low risk potential) and the rest (24 sites)
falls under very low risk potential category (Table 4).

5. Conclusions

Figure 8. Distribution potential ecological risk (RI) in the basin area.
Among the metals analysed, all pose more or less toxic effect on
soil environment as well as biotic environment. Their unnecessary
presence in the soil environment is the matter of concern because
of bio-magnification through the food chain from soil to plants and
impact on crop growth and food safety. Cumulative impacts create
a threat to humans and the aquatic and terrestrial ecosystem
health through direct contact with contaminated soils. Present
analysis shows that average concentrations for all the metals are
more than regional reference level. Analysis through indices
revealed that all metals have minor to moderate accumulation
except As, Pb and Fe (as par Igeo), enrichment factor (EF) analysis
shows present basin soil is moderately enriched by Sr, Zr, Zn, Cu
and Ni. According to CF analysis, soil of the study area contains
moderate to considerable contamination level by all metals
(especially by Sr, Zr, Ca, Cu, Mn, Zn and Ni). Ecological risk index
(Er) shows low grade risk by representative metals. Other indices
like modified degree of contamination (mCdeg), pollution load in-
dex (PLI) and potential ecological risk (RI) show significant varia-
tion in the spatial distribution of contamination level over the
basin. Sample site 7, 11, 18 and 25 commonly show highest values
for all these three indices and all are situated at the mine domi-
nated middle catchment area which also indicate there may be the
less mobilization over local contamination. Overall (mean) values
of mCdeg and PLI for the entire basin are 3.38 and 2.23 respectively,
 A. Manna, R. Maiti / Geoscience Frontiers 9 (2018) 1577e1590
that indicate low to moderate level of soil contamination, whereas
overall RI value (80.28) for the entire basin specify low ecological
risk potential.
Despite the low ecological risk potential, further study is needed
to monitor the changes in concentration or contamination level.
Another approach for further study is to assess the bio-
magnification rate, human exposure to the risk and to develop
the measures and methods for the remediation to make coal mine
area environmentally viable.
Acknowledgements
The authors thank the Council of Scientific and Industrial
Research (CSIR), India for financial assistance (Research Fellow-
ship). They also thank the laboratory of S.N. Bose National Centre
for basic Sciences, Salt Lake, Kolkata, for elemental analysis. Last,
but not least, assistance of their laboratory colleagues during
sample collection and preparation is highly appreciated.
Appendix A. Supplementary data
Supplementary data related to this article can be found at
https://doi.org/10.1016/j.gsf.2017.10.011.
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