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Contamination of arsenic and heavy metals in coal exploitation area

Authors:
  • Ministry of Environment & Forests (MoEF&CC)
Environmental Arsenic in a Changing World
Zhu, Guo, Bhattacharya, Ahmad, Bundschuh & Naidu (Eds)
ISBN 978-1-138-48609-6
Contamination of arsenic and heavy metals in coal
exploitation area
R. Sharma1, A. Yadav1, S. Ramteke1, S. Chakradhari1, K.S. Patel1,
L. Lata2, H. Milosh2,P.Li
3, J. Allen3& W. Corns3
1School of Studies in Chemistry/Environmental Science,
Pt. Ravishankar Shukla University, Raipur, India
2Department of Soil Science/Geology, Maria Curie-Skłodowska University,
Lublin, Poland
3PS Analytical Ltd,Arthur House, Orpington, Kent, UK
ABSTRACT: The coal is a dirty fuel, containing As and other heavy metals (HMs) at the trace levels. Several
millions tons of coals are exploited in the Korba basin, CG, India to generate electricity. In this work, distribution
of As and other HMs i.e. Cr, Mn, Fe, Ni, Cu, Zn, Cd, Pb and Hg in the surface soil and sediment are described.Three
metals i.e. Mn, Fe and Ni occurred at higher concentrations, ranging (n =30) from 2.3–6.4, 0.08–0.22 and 0.04–
0.16% with mean value (p =0.05) of 4.3 ±0.4, 0.14 ±0.02 and 0.08 ±0.01%, respectively. The concentration
of elements i.e. As, Cr, Cu, Zn, Cd, Pb and Hg in the soil was ranged (n =30) from 49–164, 30–78, 44–131,
87–220, 0.11–0.56, 72–194 and 0.11–0.39 mg kg1with mean value (p =0.05) of (p =0.05) 106 ±11, 51 ±5,
86 ±8, 156 ±10, 0.33 ±0.04, 130 ±10 and 0.22 ±0.03 mg kg1, respectively. The concentration of theAs in the
sediments (n =26) was ranged from 36–154 mg kg1with mean value of 93 ±12 mg kg1.The toxic inorganic
As(III) and As(V) species are found to exist in the soil and sediment. The concentration variations, pollution
indices and sources of the contaminants in the geomedia are discussed.
1 INTRODUCTION
Pollution of urban geomedia is of a great public health
interest due to receiving of large amounts of pollutants
from multiple sources including industrial wastes,
vehicle emissions, coal and biomass burnings, etc. (Li
et al., 2012; Obaidy et al., 2013; Plyaskina & Ladonin,
2009). India is the third-largest producer of coal in the
world. Coal is a naturally occurring combustible mate-
rial contains elemental carbon, sulfur, hydrocarbons,
trace metals, etc. (Chou, 2012). Several environmen-
tal issues i.e. acid mine drainage, deposition of toxic
compounds, environmental pollution, halting of acid
rain, health hazards, storage of solid waste, etc. were
observed due to coal burnings (Agrawal et al., 2010;
Bhuiyan et al., 2010; Guttikunda et al., 2014; Pandey
et al., 2011; Sengupta et al., 2010; Sheoran et al., 2011;
Singh et al., 2010).
Several millions tons of coal is mined out and burnt
in the Korba basin for generation of electricity by
pouring the effluents into the environment.The whole
environment is covered by the fly ash and black car-
bon (BC). The rain and groundwater are acidic with
high content of metals and fluoride Patel et al., 2001;
2016). The HMs contamination of the Korba basin has
not been carried out so far. Hence, in this work, the con-
tamination of surface soil and sediment of the Korba
basin with elements i.e. BC, As, Fe, Cr, Mn, Ni, Cu,
Zn, Cd, Pb and Hg is described. The concentration
variations, enrichments and sources of the metals in
the soil and sediment are discussed.
2 METHODS AND EXPERIMENTAL
2.1 Study area and sampling
Korba coalfield (22.35N and 82.68E) is located
in the Chhattisgarh state, India in the basin of the
Hasdeo river, extending over 530 km2. The popula-
tion of Korba area is 1.0 million. Several coal mines
are in operation with annual production of 3BT
coal annually since year 1960. A huge amount of coal
(20 MT yr1) is consumed by various units of ther-
mal power plants to produce 6000MW electricity with
emission of 6 MT ash into the environment.The Asia
biggest aluminum plant (3.2 ×105TPY Aluminum
smelter) is also in the operation in the Korba area.
The soil and sediment samples were collected from
30 and 26 locations of Korba area lie over 500 km2
areas (Fig. 1). One kilogram of sample from each site
(0–10 cm) was collected in a clean polyethylene con-
tainer during January, 2011–2017 as prescribed in the
literature (Tan, 2005). For depth profile studies, the
soil samples were collected at depth of 0–10, 11–20
and 21–30 cm.
381
Figure 1. Representation of sampling locations in Korba
basin.
2.2 Analysis
The soil samples were dried, milled and particles of
1 mm were sieved out. A 10g sample with 20 mL
deionized water in a 100-mL conical flask was agitated
in an ultrasonic bath for 6 h. The pH values of the
extract were measured by the Hanna pH meter type-
HI991300.
The weighed amount of soil sample (0.25g) was
digested with acids (3 mL HCl and 1 mL HNO3)in
closed system with P/T MARS CEM (Varian Com-
pany) microwave oven. The acid extract was used for
monitoring of the elements.
The CHNSO–IRMS Analyzer, SV Instruments
Analytica Pvt. Ltd. was used for analysis of the black
or elemental carbon (BC or EC). The total carbon (TC)
in the soil sample was oxidized at 1020C with O2into
CO2with constant helium flow.
The analytical techniques i.e. Varian ICP-OES-700-
ES, GF-AAS SpectrAA 220 and CV-AAS SpectrAA
55B were used for monitoring of metals i.e. Cr, Mn,
Fe, Ni, Cu, Zn and Pb; As and Cd; and Hg in the soil
extract, respectively. The standard soil sample (NCS
DC 73382 CRM) was used for the quality control.
A 0.2 g of sediment sample was taken into a 10-mL
Teflon centrifuge tube by subsequent addition of 5 mL
of 0.5 M H3PO4and kept overnight. A 2mL of filtered
solution was diluted to 10 mL with sodium phosphate
to use as HPLC mobile phase. The As-species (i.e.
As(III), As(V), MMA and DMA) were quantif ied by
using the technique i.e. HPLC-AFS
The pollution indices i.e. enrichment factor (EF),
contamination factor (CF) and pollution load index
(PLI) are used to determine element contents in the soil
samples with respect to the base line concentration.
These relate the concentration of an element, X, to a
crustal element (e.g. Al) in the soil sample, and this
ratio is then normalized to the ratio of those elements
in the earth’s crust. The following equations were used
for the calculation of the pollution indices (Sinex &
Helz, 1981; Tomlinson et al., 1980):
EF ={[Xs]/[Als]}/{[Xe]/[Ale]}
CF ={[Xs]/[Xe]}
PLI =(CF1×CF2×CF3×CF4.........CFn)l/n
where, symbols: Xs,X
e,Al
sand Aledenote concen-
tration of metal and Al in the soil and earth crust,
respectively.
The IBM SPSS Statistics 23 software was used for
the preparation of the dendrogram.
3 RESULTS AND DISCUSSION
3.1 pH of extract
The soil and sediment were colored, ranging from
brown to blackish. The pH values of the soil and sed-
iment extracts (n =30) ranged from 5.4–7.5 and from
5.4–8.1 with mean value (p =0.05) of 6.6 ±0.2 and
6.6 ±0.3, respectively. The extracts were observed to
be slightly acidic, may be due to high chloride and
sulfate contents. The lowest pH value was seen in
the Korba city, may be due to the high anthropogenic
activities.
3.2 Distribution of black carbon
The BC concentration in the soil and sediment was
ranged from 3.4–7.9 and 3.6–14.0% with mean value
(p =0.05) of 5.6 ±0.4 and 9.2 ±1.0%, respectively.
The higher loading of the BC in the sediment samples
was observed, may be due to its transport by the runoff
water.The BC content in the geomedia of the studied
area was found to be higher than reported in other
regions, probably due to huge coal burning (Han et al.,
2009; He & Zhang, 2009; Muri et al., 2002).
3.3 Distribution of elements
The metals i.e. Mn, Fe and Ni occurred in
the soil of Korba basin at high levels, ranging
(n =30) from 2.3–6.4, 0.08–0.22 and 0.04–0.16 %
with mean value (p =0.05) of 4.3 ±0.4, 0.14 ±0.02
and 0.08 ±0.01%, respectively. The concentration
382
Table 1. Distribution of major metals in soil, mg kg1.
S. No. Location As Cd Pb Hg
1 Niharica 146 0.47 163 0.21
2 Kuan Bhatta 80 0.26 119 0.18
3 Railway Station 78 0.11 95 0.11
4 Sitamani 140 0.43 126 0.23
5 Rajgamar 164 0.56 189 0.39
6 Rumgara 60 0.21 126 0.24
7 Darri dam 96 0.27 116 0.19
8 Chaildren Garden 61 0.35 116 0.20
9 Dipka-I 61 0.27 117 0.14
10 Dipika-II 49 0.21 137 0.23
11 Gevera Chowk 102 0.31 114 0.22
12 Kusmunda-I 96 0.17 127 0.21
13 Kusmunda-II 106 0.29 126 0.25
14 Kusmunada-III 130 0.41 154 0.25
15 Korba 145 0.54 190 0.37
16 Banki mongra 120 0.21 110 0.26
17 Balgi 111 0.38 88 0.25
18 Kuchaina 97 0.25 72 0.13
19 Balco 134 0.44 168 0.22
20 bhadrapara 86 0.33 106 0.11
21 Risdi Chowk 83 0.34 102 0.13
22 Manikpur 79 0.30 96 0.15
23 Dadar 94 0.39 138 0.24
24 SECL 98 0.41 140 0.21
25 Mudapar 105 0.38 119 0.24
26 Rampur, PWD 101 0.32 125 0.22
27 SECL Hospital 149 0.49 160 0.31
28 Belakachar 131 0.29 149 0.30
29 Urga 134 0.21 129 0.26
30 Patadi 163 0.48 194 0.38
Figure 2. Distribution ofAs in surface soil.
of elements i.e. As, Cr, Cu, Zn, Cd, Pb and Hg
ranged (n =30) from 49–164, 30–78, 44–131, 87–220,
0.11–0.56, 72–194 and 0.11–0.39 mgkg1with mean
value (p =0.05) of 106 ±11, 51 ±5, 86 ±8, 156 ±10,
0.33 ±0.04, 130 ±10 and 0.22 ±0.03 mg kg1,
respectively (Table 1).
The concentration of elements i.e. As, Cr, Cu,
Zn, Cd, Pb and Hg in the sediments ranged from
36–154, 29–7, 18–92, 42–294, 0.14–1.19, 26–127
and 0.12–0.82 mg kg1with mean value of 93 ±12,
49 ±5, 49 ±8, 142 ±28, 0.59 ±0.11, 72 ±13 and
0.44 ±0.08 mg kg1, respectively(Table 2).The lower
concentration of the elements (except Cd and Hg) in
the sediment than the soil was observed.
Table 2. Distribution of heavy metals in sediments.
S. No. Location As Cd Pb Hg
1 Shakti Nagar 63 0.14 33 0.16
2 Gevra, Dipka 96 0.24 37 0.17
3 PN, Dipka 98 0.27 49 0.23
4 Banki, Dipka 36 0.52 47 0.25
5 Delwadih 100 0.63 81 0.31
6 Shingali 82 0.36 78 0.28
7 Kusmunda 92 0.50 92 0.36
8 Rajgamar-3 65 0.45 74 0.26
9 Mudapar 114 0.65 35 0.21
10 PN, Darri 138 0.82 106 0.61
11 Darri west 127 0.95 127 0.77
12 Jamnipali 154 1.19 82 0.63
13 Gopalpur 149 1.18 120 0.82
14 HTPP, Darri 111 0.84 112 0.74
15 Manuikpur-1 127 0.77 107 0.63
16 Manikpur-2 51 0.39 31 0.30
17 Dader-1 79 0.66 54 0.54
18 Dader-2 99 0.72 87 0.65
19 Kudarikhar 43 0.42 37 0.33
20 Naktikhar 93 0.64 75 0.53
21 Danras-1 98 0.62 53 0.46
22 Danras-2 41 0.20 26 0.12
23 SN-Balco 47 0.22 48 0.32
24 Pathadi 79 0.96 125 0.71
25 Dhendheni 69 0.62 108 0.61
26 Sukhri 30 0.35 35 0.31
They occurred in the following increasing order:
Hg <Cd <Cr <Cu <As <Pb <Zn <Ni <Mn <Fe
in the soil. The highest concentration of As was seen
near the point sources i.e. thermal power plant, coal
mine, urban area, etc. as shown in Figure 2. The con-
centration of As in the geomedia of studied area was
several folds (>10) higher than permissible limit of
5mgkg
1. The concentration of the As and heavy
metals in the soil and sediment of the Korba basin was
higher than values reported in other region of the coun-
try and world, probably due to huge coal mining and
burning (Dahal et al., 2008; Ilwon et al., 2003; Kwon
et al., 2017; Muller, 1969; Sheela et al., 2012; Rud-
nick & Gao, 2003; Shrivastava et al., 2014; Whitmore
et al., 2008).
3.4 Vertical distribution of elements
The concentration of elements (i.e. As, Cr, Ni, Cu,
Zn, Cd and Hg) was increased as the depth profile
was increased up to 30 cm unlikely to Mn, Fe and
Pb, may be due to their less binding with the organic
compounds (Fig. 3).
3.5 Temporal variation of elements
The increased temporal variation of As over periods:
2011–2015 was observed due to continuous mining
and burning of the coals (Fig. 4). The rate of temporal
increase in the As concentration was 6% in the geo-
media due to continuous coal burning. At least 15%
higher concentration of the As in the soil with respect
383
Figure 3. Verticle distribution of As and other metals in soil,
x=0–10, 2x =10–20, 3x =20–30 cm.
Figure 4. Temporal variation of As in soil and sediment.
Table 3. Speciation of arsenic in sediments, mg kg1.
S. No. As(III) DMA MMA As(V) AsT EE, %
S1 1.08 14.0 15.08 27.1
S2 9.08 9.08 110.7
SE1 0.1 2.10 2.20 73.3
SE2 0.15 6.0 6.15 130.8
SD3 2.40 2.4 75
EE =Extraction efficiency (100%).
the sediment was observed due to its washout by the
aqueous media.
3.6 Speciation of arsenic
The As(III), As(V), MMA and DMA were quantified
in the soil and sediment extracts by using technique i.e.
HPLC-AFS (Table 3). The organic species i.e. MMA
and DMA were not detected in the soil and sediment
extracts. The whole As in soil and sediment samples
of studied area was found in the toxic inorganic forms.
3.7 Sources
The correlation coefficient matrix for BC and nine
metals in the soil is presented in Table 4. A fair cor-
relation (r = 0.58–0.82) of the metals with BC was
observed, may be due to deposition by multiple sources
Table 4. Correlation coefficient matrix of elements.
BC Fe Ni Cr Cu Zn Pb Hg Cd As
BC 1.00
Fe 0.58 1.00
Ni 0.59 0.41 1.00
Cr 0.70 0.55 0.39 1.00
Cu 0.74 0.60 0.56 0.73 1.00
Zn 0.74 0.64 0.45 0.56 0.75 1.00
Pb 0.81 0.77 0.59 0.59 0.72 0.72 1.00
Hg 0.76 0.55 0.52 0.52 0.65 0.67 0.80 1.00
Cd 0.82 0.68 0.57 0.57 0.58 0.67 0.69 0.59 1.00
As 0.78 0.42 0.49 0.49 0.61 0.64 0.67 0.72 0.68 1.00
Figure 5. Dendrogram for group linkage of chemical char-
acteristics of locations.
i.e. coal burning, fly ash, alumina roasting, etc. Simi-
larly, fair correlation coefficient (0.39–0.80) among
the metals was marked, showing deposition by the
multiple sources.
A dendrogram to know linkage between similar
groups is plotted, using sum of total concentration of
three metals i.e. As, Zn and Pb as discriminating fac-
tor.The dendrogram was categorized into two groups:
group-I and -II with inclusion of 20 and10 locations
as shown in Figure 5. The higher concentration of
theAs+Zn+Pb (>400 mg kg1) was seen in group-II,
may be due to loading of point sources (i.e. coal mines,
aluminum plant and thermal power plant) effluents.
384
3.8 Enrichment
The background concentration of Al, Fe, Mn, Cr,
Zn, Ni, Cu, Pb, As, Cd and Hg reported was
8.2%, 3.9%, 775 mg kg1, 92mgkg
1, 67mgkg
1,
47 mg kg1, 28mgkg
1, 17mgkg
1, 4.8 mg kg1,
0.09 mg kg1and 0.05 mg kg1, respectively. The ele-
ments i.e. Ni and As; P, Cd, Pb and Hg; and S,
Cl, Mn, Cu and Zn were highly (20EF <40), sig-
nificantly (5 EF <20) and moderately (2 EF <5)
were enriched in the soil, respectively. Similarly, the
soil was highly (CF6), considerably (3 CF <6)
and moderately (1 CF <3) contaminated with As,
Ni and Pb; S, Cl, P, Cu, Cd and Hg and Mn, Fe and
Zn, respectively. The PLI value for heavy metals i.e.
As, Ni, Pb, Cd and Hg was found to be 8.6 indicating
their high contamination in the soil.
4 CONCLUSIONS
The enormous coal burning tends to increase the con-
centration of elements i.e. As, Zn, Cd, Pb and Hg in
the geomedia of the Korba basin.The highest pollution
indices for elements i.e. As, Ni and Pb were recorded.
The vertical transport of elements i.e. As, Cr, Cu, Ni,
Zn, Cd and Hg via the soil media was enhanced with
increasing soil depth profile, may be due to less bind-
ing with the organic compounds. The whole As exists
in the toxic inorganic forms i.e. As(III) and As(V) in
the geomedia.
ACKNOWLEDGEMENTS
We are thankful to the UGC, New Delhi for awarding
BSR grant to KSP.
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... Consequently, the environmental landscape of Korba bears a heavy burden of pollution attributed to coal-related activities, resulting in elevated levels of substances such as F, As, Pb, Hg, Se, and Cd, among others Sharma et al., 2019a). Recent investigations have highlighted the contamination of groundwater resources in the Korba basin (Chandrawanshi et al., 1997;Dheeraj et al., 2023;JSSG, 2012;Patel et al., 2016;Sharma et al., 2017Sharma et al., , 2019aSharma et al., , 2019bSingh et al., 2017aSingh et al., , 2017bSingha et al., 2017), impacting water supply safety in Korba city (Chourasia, 2018;Dewanagan et al., 2020). ...
... Consequently, the environmental landscape of Korba bears a heavy burden of pollution attributed to coal-related activities, resulting in elevated levels of substances such as F, As, Pb, Hg, Se, and Cd, among others Sharma et al., 2019a). Recent investigations have highlighted the contamination of groundwater resources in the Korba basin (Chandrawanshi et al., 1997;Dheeraj et al., 2023;JSSG, 2012;Patel et al., 2016;Sharma et al., 2017Sharma et al., , 2019aSharma et al., , 2019bSingh et al., 2017aSingh et al., , 2017bSingha et al., 2017), impacting water supply safety in Korba city (Chourasia, 2018;Dewanagan et al., 2020). ...
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... Chhattisgarh state, well-known as one of the primary rice producers in India, has recently encountered a hindrance to the growth of its rice crop in highly industrialized regions such as Korba, Durg-bhilai, and Raigarh. These areas of Chhattisgarh state have suffered from extensive contamination of agricultural land and water resources of various potential toxic heavy metals (PTHMs) such as Iron (Fe), Chromium (Cr), copper (Cu), cadmium (Cd), etc (Sharma et al., 2019). The contamination may be attributed to the modern industrial activities including the establishment of refractory steel factories, coal and bauxite mining, coal based thermal power plants, and discharge of untreated or partially treated industrial solid or liquid waste (Bhaskar et al., 2020). ...
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