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Impacts of opencast coal mine and mine fire on the trace elements' contentof the surrounding soil vis-à-vis human health riskReginald E. Mastoa; Lal C. Rama; Joshy Georgea; Vetrivel A. Selvia; Awadhesh K. Sinhaa; Santosh K.Vermaa; Tofan K. Routa; Priyadarshinia; Pritish Prabala

a Environmental Management Division, Central Institute of Mining and Fuel Research, DigwadihCampus (previously Central Fuel Research Institute), Dhanbad 828108, Jharkhand, India

First published on: 27 September 2010

To cite this Article Masto, Reginald E. , Ram, Lal C. , George, Joshy , Selvi, Vetrivel A. , Sinha, Awadhesh K. , Verma,Santosh K. , Rout, Tofan K. , Priyadarshini and Prabal, Pritish(2010) 'Impacts of opencast coal mine and mine fire on thetrace elements' content of the surrounding soil vis-à-vis human health risk', Toxicological & Environmental Chemistry,,First published on: 27 September 2010 (iFirst)To link to this Article: DOI: 10.1080/02772248.2010.510922URL: http://dx.doi.org/10.1080/02772248.2010.510922

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Toxicological & Environmental Chemistry2010, 1–15, iFirst

Impacts of opencast coal mine and mine fire on the trace elements’ content

of the surrounding soil vis-a-vis human health risk

Reginald E. Masto*, Lal C. Ram, Joshy George, Vetrivel A. Selvi, Awadhesh K. Sinha,Santosh K. Verma, Tofan K. Rout, Priyadarshini and Pritish Prabal

Environmental Management Division, Central Institute of Mining and Fuel Research,Digwadih Campus (previously Central Fuel Research Institute), Dhanbad 828108, Jharkhand, India

(Received 14 July 2010; final version received 22 July 2010)

Coal from its excavation, processing, and utilization creates environmentalproblems and health hazards. In these processes, the mobilization of potentialorganic and heavy metal contaminants affects the quality of soil and health of theinhabitants. Soil samples were collected from the nearby areas of an opencast coalmine (OCM) and a coal fire affected area (CFA) located in Jharia coalfield ofDhanbad, India. The control site was an abandoned land approximately 15 kmaway from the sources of contamination. These samples were analyzed for traceelements including Cr, V, Co, Ni, Cu, Zn, Ga, Rb, Zr, Ba, Th, and U. The soils ofOCM were enriched with Cr and Ni and this is attributed to the mining activitiesin view of the absence of other sources of pollutants. In case of CFA, the soilswere enriched with Cr, V, Ni, and Zn. However, the concentrations of Cr, Ni,and Zn in both the soils were well below the USEPA soil screening levels forhuman health risk assessment. The levels of Co and V exceeded the soil screeninglimits. Human exposure risks were evaluated for Co and V. The total intake ofV concentration exceeded the EPA’s reference dose, which may pose adversehealth risks.

Keywords: trace metals; coal; mine fire; exposure assessment; enrichment

Introduction

Coal mining releases materials mainly organics and heavy metals into the surroundings,which are detrimental for environment and human health. Similarly, uncontrolled coalfires create a great environmental hazard (Kuenzer et al. 2007). Hazardous effects fromcoal fires include the emission of noxious gases and particulate matter into the atmosphere,and condensation of emission products responsible for stream and soil pollution (Stracherand Taylor 2004). Many of the environmental and health problems attributed to coalmining and processing are due to mobilization of potentially toxic substances. Particularly,large volume of impurities such as tailings and solid wastes are discarded during miningand utilization of coal. Accumulation of these materials, aqueous effluents, and emissionof dust produces severe soil pollution (Masto et al. 2007). Soil is an important naturalresource that needs to be preserved and if possible, its quality and productive capacitymust be improved. The ecological equilibrium of soil may be perturbed easily byanthropogenic intervention, resulting in a consistent decrease in its natural quality.

*Corresponding author. Email: ebhinmasto@rediffmail.com

ISSN 0277–2248 print/ISSN 1029–0486 online

� 2010 Taylor & Francis

DOI: 10.1080/02772248.2010.510922

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Similar to air or water, the quality of the soil has a profound effect on the health of a givenecosystem and surroundings related to it; however, unlike air or water for which qualitystandards exist, the definition and quantification of soil quality is complicated, especiallyin view of the fact that it is not directly consumed by human and animals.

Fine soil particles, together with the adsorbed pollutants enter the human body viavarious pathways through direct ingestion and inhalation of the dust (OEM 1996) orindirectly from food from the contaminated areas (Abdullah 1995). Soil samples representa medium to monitor heavy metal pollution because anthropogenic heavy metals areusually deposited in topsoils. Sustaining soil quality has become a major concern globallysince soil is an essential natural resource (Pasqual et al. 2000) that is intrinsically linked tooverall environmental quality (Marcote et al. 2001).

Coal mining involves excavation of the earthly bound coal by removing overburdensusing mechanical devices. In the process of excavation, large quantities of mine spoil anddust are generated along with coal. Coal mine spoils are a type of metal-rich industrialsolid wastes (Jeng and Bergseth 1992; Sebestova et al. 1996). Natural weatheringconditions may produce these exposed coal mine spoils to degrade into small clay-sizedparticles. Through this process, large amounts of fine particles are then released into theenvironment within the course of a few weeks (Haigh 1992). The trace elements present incoal are of concern as some of the elements have higher enrichment factors (CFRI 2000).Bi is considered as highly enriched in coal with a factor410, whereas As, Cd, B, Sb, Mo,and Hg are less enriched (factor, 2–10). Gupta (1999) reported potential human healthrisks due to trace elements in coal in Pench Valley Coal Co. Ltd. (India). Gupta (1999)found As, Cu, Mn, and Pb in nearby surface and subsurface waters at higherconcentrations than the threshold limits which might result in gastrointestinal disorders,cardiovascular diseases, pneumoconiosis, as well as carcinogenic, teratogenic, andmutagenic effects.

Mine fire is unintentional burning of coal in its seams of abandoned coal mines or coalmines in use. Mine fire has implications for environment, resource depletion, and societalsafety concerns, as it releases volumes of polluted air and also channelizes heavy metalsinto the environment. Herein, the soil gets contaminated by deposition of dusts or bywashing of pollutants from the air through rain. Burning coal beds volatilizes someelements like As, F, Hg, and Se which are then inhaled, or adsorbed on crops and foods,taken up by livestock or bioaccumulated in birds and fish (Finkelman 2004). Elementalsulfur and sal ammoniac (ammonium salt) are the coal fire gas minerals neoformed on thesurface of piles, near burning zones (Ribeiro, da Silva, and Flores 2010).

Studies conducted on environmental problems associated with coal mining, processing,combustion, and related problems such as acid mine drainage, acid rain, smog, andgreenhouse gas emissions in India are known. In contrast, there is relatively littleinformation regarding the direct human health impacts of coal use in India. These directhealth problems may be severe (leading to death), widespread (affecting many millions ofpeople), and complex (requiring a multidisciplinary research approach). In view of theabove, this study was carried out around an opencast coal mine (OCM) and fire affectedareas to assess the status of some of the trace elements and their human exposure risks.

Materials and methods

The sampling sites selected were located in Lodna, coal fire affected area (CFA), which is alocus of underground coal fire in Jharia coalfield and where the fire has been burning for

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nearly a century. It is located at 23�430N 86�260E, with an average elevation of 180m.The other sampling site selected was in Bhowra OCM, which is an active surface coal minearea comprising many small OCMs. Bhowra is located at 23�400N 86�240E, with anaverage elevation of 153m. The control (CNT) site was Chandankiari, which is about10 km away from the coalfield, located at 23�340N 86�210E with an average elevation of174m. The CNT site was away from sources of contamination. The total surface (0–15 cm)soil samples collected include n�25 from the CNT site, 16 from the fire affected area, and19 from the OCM area. The collected samples were air dried and passed through a 2mmsieve. For determination of trace elements, soil samples were digested using acid mixture(containing 7 : 3 : 1 of HF–HNO3–HClO4) at approximately 200�C for about 1 h. Thecontent of trace elements in the digested solution was measured using an inductivelycoupled plasma–mass spectrometry (ICP–MS; Perkin Elmer). Human health riskassessment estimates the total exposure to the trace elements which are likely to occur.The potential exposure pathways identified are (1) incidental ingestion of soil particles,(2) inhalation of fugitive dusts, (3) dermal absorption, and (4) ingestion of produce thathas been contaminated via plant uptake. The receptors were infants, toddlers, children,teens, and adults. Levels of metal entry through the above-mentioned pathways wereindividually calculated as per the equations and receptor parameters given in Table 1.These equations and receptor parameters are as per USEPA (1996) and OME (2002).Data were analyzed for correlation and factor analysis using the statistical softwareSYSTAT-12.

Results and discussion

Soil trace elements

Table 2 illustrates the status of different trace elements in soils of CNT site, CFA, andOCM. Of the prominent 12 trace elements, Cr (82.77 vs. 58.90), V (92.94 vs. 79.80),Ni (67.86 vs. 32.80), Zn (161.76 vs. 83.20) and Zr (152.86 vs. 135.20) were enriched in CFAwith respect to CNT; levels of Rb (88.34 vs. 100.20) and Ba (556.94 vs. 619.40) were lowerin CFA; and the levels of Co, Cu, Ga, Th, and U were not affected. Finkelman (2004)reported that during natural coal burning, Se, As, Pb, Sn, Bi, and fluorine may condensewhen the hot gaseous emissions come in contact with ambient air and form mats ofconcentrated efflorescent minerals on the surface of the ground.

In a study of mineral formation around vents of surface and below-ground coal fires inthe Anthracite Region of Pennsylvania, Lapham et al. (1980) identified some of themineral species of Se, Pb, As, and F. Similar results were found at other coal burning sitesin the former Czechoslovakia (Rost 1937) and Russia (Chesnokov 1997). In another study,Ribeiro, da Silva, and Flores (2010) found that the levels of As, Cr, Li, Nb, Ni, Pb, Rb, Sr,and light rare earth elements were enriched in the coal burning zones. Zhao et al. (2008)studied the emissions of trace elements from spontaneous combustion of gob piles fromcoal mining in Shanxi Province, China, and found that Se (20�) and Tl (12�) weresignificantly enriched in the clinkers; whereas, F, As, Mo, Sn, Sb, Hg, Th, and U (2 – 5�)were moderately enriched. Huggins and Goodarzi (2009) conducted a detailed assessmentof emission of elements from a coal-fired power plant using Western Canadiansubbituminous coal. The total stack emission of toxic elements was 1.02 kg day�1,Cr being the highest contributor to this group 0.4 kg day�1. Vanadium is enriched in CFAsoils and may occur both with clays and organic matter in coal (Finkelman 1995;Querol et al. 1996; Goodarzi 2002). The enrichment of V content in most Turkish feed

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coals, especially in Kangal lignite and its organic association was reported by Karayigitet al. (2000).

In case of OCM, Cr (95.46 vs. 58.90) and Ni (71.27 vs. 32.80) were enriched; levels ofRb (46.59 vs. 100.2) and Ba (395.51 vs. 619.40) were lower in OCM; other elements did notshow any significant variations. Most of the trace elements except Cr and Ni were belowthe CNT values. The rate of release of Cr into the global atmosphere from coalcombustion is estimated to be in the order of a few thousands of tons per year. The meanCr content of coals is only 20mgkg�1 worldwide (Huggins et al. 2000). Ruppert et al.(1996) indicated that the occurrence of high Cr values in Serbian lignites (up to176mgkg�1) may be due to the deposition of detrital Cr-bearing minerals transported intothe palaeoswamp by rivers draining through Paleocene laterites. Chromium occurs in mostbituminous coals as Cr3þ in organic associations and Cr3þ in illite, but its occurrence inchlorite, chromite/magnetite spinel, and crocoite was also reported (Huggins and Huffman2004). The average range values for Cr and Ni in the Indian coal fly ashes was noted to be50–225 and 50–145mgkg�1, respectively, (Ram and Masto 2010). Huggins, Najik, and

Table 1. Different equations and receptor parameters used for characterization of human exposurefrom soil.

Pathways Equation

1. Soil ingestionCDI ¼

Xn

1

C � IR1...n �AT1...n

BW1...n � LTð1Þ

2. Soil dermal uptakeCDI ¼

Xn

1

C � SA1...n �DA1...n �DUC �AT1...n

BW1...n � LTð2Þ

3. Soil inhalationCDI ¼

Xn

1

C � 1PEF �AI1...n �AT1...n

BW1...n � LTð3Þ

4. Soil–plant–humanCDI ¼

Xn

1

C � BA � CR1...n �AT1...n

BW1...n � LTð4Þ

Parameter Units Infant Toddler Child Teen Adult

Averagetime, AT

Years 0.5 4.5 7.0 8.0 50.0

Bodyweight, BW

kg 8.2 16.5 32.9 59.7 70.7

Soil ingestionrate, IR

g day�1 0.035 0.1 0.1 0.02 0.02

Dermal adhesionrate, DA

mg cm�2 0.2 0.2 0.2 0.07 0.07

Surface areaexposed, SA

m2 0.203 0.344 0.586 0.908 1.03

Air intake, AI m3 day�1 2.0 5.0 12.0 21.0 50.0Vegetable

consumptionrate, CR

g day�1 11.3 12.58 18.84 25.2 23.7

Notes: CDI, chronic daily intake (mg kg�1 day); C, concentration in soil (mg kg�1); LT, lifetime(70 years); DUC, dermal uptake coefficient (0.01); BA, bioaccumulation factor (0.001); PEF,particulate emission factor (1.32� 109m3 kg�1).Source: USEPA (1996); OEM (2002).

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Table

2.Statusofsoilheavymetals(m

gkg�1).

S.No

Element

CNT

site

(n�25)

Fireaffectedarea(n�16)

OCM

(n�19)

USEPA

soil

screening

(mgkg�1)

Minim

um

Maxim

um

Median

Minim

um

Maxim

um

Median

T(psig.)

Minim

um

Maxim

um

Median

T(psig.)

1Cr

37.5

111.3

58.9

31.54

184.64

82.77

0.004

44.26

116.83

95.46

0.000

1.2�105

2V

47.7

163.2

79.8

60.57

155.80

92.94

0.024

54.39

108.71

82.01

NS

5.50

3Co

6.3

25.6

14.1

10.11

37.94

14.97

NS

5.01

19.41

13.69

NS

23.0

4Ni

17.0

98.3

32.8

23.99

158.36

67.86

0.000

50.57

103.04

71.27

0.000

1.5�103

5Cu

32.7

190.2

54.0

35.38

571.86

55.40

NS

23.69

83.33

49.60

NS

3.1�103

6Zn

49.6

254.1

83.2

63.99

438.59

161.76

0.002

35.76

140.44

75.97

NS

2.3�104

7Ga

11.3

21.7

15.5

10.05

30.52

15.64

0.042

7.57

19.07

13.01

NS

–8

Rb

21.1

185.2

100.2

55.96

180.74

88.34

NS

21.13

102.17

46.59

0.000

–9

Zr

98.7

254.9

135.2

78.94

435.59

152.86

0.037

51.77

348.88

121.91

NS

–10

Ba

282.5

1467.0

619.4

299.37

858.86

556.94

0.027

217.90

635.92

395.51

0.000

1.5�104

11

Th

7.5

36.5

13.2

9.14

31.72

15.59

NS

5.79

32.21

12.93

NS

–12

U1.5

6.4

3.6

2.34

7.48

3.84

0.000

2.51

6.37

4.08

0.000

2.3�102

Note:T(psig.),t-test

significance

withrespectto

control.

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Huffman (1999) reported a high Cr(VI) in fly ash samples from an Israeli combustionplant utilizing South African coals. The concentrations of trace and heavy metals in thecoal fly ashes are indicative of the presence of these elements in the corresponding coals,especially when the concentrations of the trace and heavy metals are 4- to 10-fold higher infly ash than feed coal (Fernandez et al. 2003). Huggins et al. (2000) reported two majorforms of Cr in the bituminous coals: Cr associated with the clay mineral illite (10–50%),and Cr associated with organic portion of coal, which is the form that occurs in majorquantities (50–90%) and is not leached by any of the reagents, except possibly HCl.Anthropogenic activity resulted in the widespread atmospheric deposition of Ni from theburning of oil and coal (McGrath 1995). There is a high level of uncertainty about theoccurrence of Ni in bituminous coals. It is thought to be associated with pyrite and theorganic matter. Ni was reported to have a mixed association with possible sourcesincluding clays and sulfides (Swaine 1990) and also organic matrix (Volkovic 1983).Ruppert et al. (1996) found that most of the Ni in Pliocene lignite was associated with thedetrital mineral phases and resistant to release. The Ni content in the soil around a coal-fired thermal power plant in Germany was found to be 5–40mgkg�1 (Bunzl, Rosner, andSchmidt 2007). In Indian coals, Mukherjee et al. (1982) noted 250 and 754mgkg�1 Ni incoal ash from Rajmahal basin and Tertiary coals of northeast India, respectively. In PenchValley coal, Ni concentrations ranged from 59 to 78mgkg�1 (Gupta 1999). The traceelements present in coal are of concern as some of the elements like As, Hg, Cd, Bi, B, andMo have a higher enrichment factor. The Indian coals have significant amounts of Mn, Cr,Cu, Co, Ni, or V in comparison to world average (Masto et al. 2007). Mandal andSengupta (2006) found that the topsoils and the soils collected from the different depthprofiles surrounding a coal-fired power plant in India, were enriched in the trace elementsMo, As, Cr, Mn, Cu, Ni, Co, Pb, Be, V, and Zn, with a maximum enrichment (2–5) in thetopsoils. Soils near a coal mining area in Bangladesh showed a significant enrichmentwith Ti, Mn, Zn, Pb, As, Fe, Sr, and Nb, indicating inputs from mining activities (Bhuiyanet al. 2010).

Even though the concentration of Cr and Ni were found to be enriched in the soils ofOCM and CFA (Table 2), their concentrations in all these soil samples were well below theUSEPA soil screening level. The median concentrations of Cr in CNT, CFA, and OCMwere 58.99, 82.77, and 95.46mgkg�1, respectively, which is below the soil screening valueof 1.2� 105mg kg�1. In case of Ni, the median concentrations were 32.8, 67.86, and71.27mg kg�1, respectively, for CNT, CFA, and OCM soils and were below the soilscreening value of 1.5� 103mg kg�1. Hence, from the point of health risk, these metalsmay not be posing any serious threat. The effects of Cr contamination might be slight inthe soil due to lower ecological toxicity of Cr (Hakanson 1980). This may be attributableto the reason that Cr is not a mobile element as it tends to occur in trivalent oxide orco-precipitates with Fe hydrous oxide that have low mobility and bioavailability in soilsand remain stable for a long time (Kumpiene, Lagerkvist, and Maurice 2008). It is alsopossible that Cr(VI) (high toxic and mobile) tends to be converted to Cr(III) (low toxic andimmobile) by soil organic matter (Kumpiene, Lagerkvist, and Maurice 2008) becausehumic acids act as electron mediators or shuttles between the microorganisms and Cr(Gu et al. 2005). However, weak alkalinity favors the presence of Cr in oxidized forms ofCr(VI) in calcareous soils (Kumpiene, Lagerkvist, and Maurice 2008). The majority of Crin coal fly ash is present in the less toxic Cr3þ form (Nelson et al. 2010). Nickel in themilled coal was mostly (80–90%) in nontoxic oxide or silicate form (Goodarzi andHuggins 2004) and no apparent evidence for carcinogenic Ni sub-sulfides was observed(Goodarzi, Huggins, and Sanei 2008). Huggins and Goodarzi (2009) reported that Ni in

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Canadian coals and ashes was in the form of nontoxic Ni2þ, predominantly incoordination with oxygen. Nickel from coal is unlikely to be a health or environmentalconcern. Moreover, Cr and Ni are considered to be in the moderate toxicity level PECH(1980).

The concentrations of V and Co in all the soil samples exceeded their respectivescreening levels given in Table 2. For V, the median soil concentrations for CNT, CFA,and OCM were 79.8, 92.94, and 82.01mgkg�1, respectively, which is higher than theUSEPA screening value of 5.50mg kg�1. In case of Co, the median soil concentrations forCNT, CFA, and OCM were 14.1, 14.97, and 13.69mgkg�1, respectively, and the soilscreening value being 23mgkg�1, shows that the values are close to the limit prescribed.Hence for this study, V and Co were considered for human exposure risk assessment.

Correlation, factor, and cluster analysis

Correlation coefficients between the different trace elements are given in Table 3. Most ofthe elements were correlated with each other except for Ba and Cu. Factor analysis wasperformed by evaluation of principal components and computing the eigenvectors. Theresults of factor analysis are given in Table 4. Three factors explained to a relatively largeextent the total variance (81%) of the 12 variables used in the analysis. Cr, V, Co, Zn, Ga,Rb, Zr, Th, and U showed a strong association with the first component (PC-1) (59%),and correlation analysis also showed significant correlations between these elements(Table 3), which indicated that they might originate from the common source. The secondfactor (PC-2), 13.4% of variance, was composed of Ni and Ba, and correlation analysisdemonstrated no correlations between Ni and Ba. For the third factor (PC-3), 8.5% ofvariance was associated with Cu. Based on PCA, three elements Ba, Ni, and Cu wereisolated and probably originated from different sources. The enrichment pattern given inTable 2 also supports this particularly for Ni and Ba. Facchinelli, Sacchi, and Mallen(2001) indicated that the variability of Cr, Co, and Ni in soils of Piemonte (Italy) wereassociated in the same factor and controlled by soil parent rocks, whereas Cu together withZn, and Pb alone were controlled by anthropic activities. To further classify the elementsas per the source of origin, cluster analysis was used on the basis of the similarities of theirchemical properties. Hierarchical cluster analysis was performed using Ward’s method,with Euclidean distances as the criterion to form clusters of trace elements. Figure 1 showsthree clusters: (1) Ga–Th–Co–U–Ni, (2) Cr–V–Rb–Zn–Cu–Zr, and (3) Ba. Co, and Ni incluster-1 might have sulfide origin (Ribeiro, da Silva, and Flores 2010); Cr, V, and Zr incluster-2 probably represent a silicate fraction. The first two clusters could be joinedtogether at a relatively high level implying the common sources. The Ba group wasremarkably different from the other elements in terms of Euclidean distances in clusteranalysis, which is in conformity with the findings of Ribeiro, da Silva, and Flores (2010).Similar studies were conducted by Qi, Hu, and Zhang (2007) who studied the distributionof elements in lignites and classified them into four groups: The first group (Ge–Moassociation) contained elements having organic affinity. The elements in the second group(Tl–Ga–Zn–Co association) showed organic affinity, but most of them were mainly relatedto mineral matter (such as sphalerite). The last two groups (Rb–Cs and W–U–Cd–Y–Pb–Cu–Hf–Zr–Th–Sn–Nb–Ta–TiO2–Sb–Ba–Sr–MnO–Be associations) contained elementsassociated mainly with mineral matter (such as anatase, manganite, zircon, and barite).Using multivariate statistics, Chen et al. (2005) concluded that Ni and Zn levels in soils ofBeijing City were controlled by parent material in the soils, whereas Cu, Pb, and Zn in

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Table

3.Correlationsbetweenthetrace

elem

ents

(Pearsoncorrelationcoefficients).

Cr

VCo

Ni

Cu

Zn

Ga

Rb

Zr

Ba

Th

U

Cr

1.000

0.872**

0.810**

0.580**

0.350**

0.631**

0.855**

0.589**

0.633**

0.221

0.683**

0.887**

V1.000

0.841**

0.505**

0.229

0.543**

0.845**

0.584**

0.616**

0.198

0.654**

0.827**

Co

1.000

0.423**

0.216

0.516**

0.822**

0.608**

0.489**

0.257*

0.618**

0.751**

Ni

1.000

0.222

0.424**

0.290*

0.050

0.295*

�0.238

0.248

0.556**

Cu

1.000

0.519**

0.245

0.173

0.274*

0.004

0.291*

0.349**

Zn

1.000

0.603**

0.506**

0.454**

0.231

0.526**

0.690**

Ga

1.000

0.802**

0.681**

0.453**

0.797**

0.863**

Rb

1.000

0.674**

0.475**

0.870**

0.703**

Zr

1.000

0.333**

0.689**

0.689**

Ba

1.000

0.377**

0.197

Th

1.000

0.844**

U1.000

Note:*and**indicate

significantcorrelationatp50.05andp50.01,respectively.

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part, were accounted for mainly by anthropogenic activities. Ribeiro, da Silva, and Flores

(2010) noted that cluster analysis could be used to separate the burned and unburned coal

samples based on chemical variations induced by the burning process.

Human exposure risk

Various aspects regarding mobilization of trace elements into the environment during coal

mining and utilization have been studied. However, it remains difficult to quantitatively

estimate the potential human health impacts that these hazardous elements have after their

Rescaled distance cluster combine

Figure 1. Hierarchical dendrogram for trace elements obtained by Ward’s hierarchical clusteringmethod.

Table 4. Principal component analysis for heavy metal data.

PC-1 PC-2 PC-3

1 Cr 0.916 0.204 �0.1132 V 0.882 0.145 �0.2583 Co 0.839 0.067 �0.2514 Ni 0.478 0.732 �0.1875 Cu 0.385 0.319 0.801

6 Zn 0.722 0.191 0.4067 Ga 0.938 �0.177 �0.1028 Rb 0.800 �0.446 0.0359 Zr 0.764 �0.154 0.05710 Ba 0.364 Z0.732 0.12911 Th 0.860 �0.239 0.05412 U 0.947 0.138 �0.041

Variance (%) 59.1 13.4 8.5Cumulative (%) 59.1 72.5 81.0

Note: The values in boldface indicates factor loadings are considered.

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release during coal utilization (Wang et al. 2010). In order to estimate the potential healtheffects associated with exposure to trace elements for the residents near the CFA andOCM, it is necessary to know the daily intakes of trace elements from the potentialexposure pathways. Estimated daily intake values for each receptor group on a per bodyweight basis is expressed as mg kg�1 day. The exposure assessment was made as per thedifferent exposure pathways and receptors given in Table 1. The mean chronic daily intake(Figure 2) of V in CNT, CFA, and OCM site soils are 0.121, 0.167, and 0.157 mg kg�1 day,respectively. Exposure to V seems to be critical irrespective of the site selected. Tocharacterize the potential health risks for the residents, the total V intake from all exposurepathways was compared with the USEPA’s reference dose (RfD) of 0.07mg kg�1 day(USEPA 2010). From Figure 2(b), among the different age groups, the vulnerability ofexposure could be arranged as toddler4infant4child4teen4adult. The daily intake for

CFA-Coal fire affected area; OCM-Opencast coal mine

(a)

(b)

0 0.07 0.14 0.21 0.28 0.35 0.42 0.49 0.56 0.63 0.7 0.77 0.84

Infant

Toddler

Child

Teen

Adult

Lifetime

Control CFA OCM

VANADIUM0.30

0.25

0.20

0.15

Chr

onic

dai

ly in

take

(ug

kg–1

day)

0.10

0.05

Vanadium intake (mgkg–1day)

Opencast mines

Fire affectedUSEPA Exposure Limit

Figure 2. Total daily intake of vanadium: (a) total lifetime intake; (b) receptor-wise intake.CFA, coal fire affected area; OCM, opencast coal mine.

10 R.E. Masto et al.

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infant and toddlers was almost 10-fold higher than the USEPA RfD (Figure 2b); 6-foldhigher for child, and 2-fold higher than lifetime intake. Thus, V has the potential toproduce toxicity as per exposure studies.

Similarly for Co, the lifetime mean total intake from all the exposure pathways was0.027, 0.053, and 0.049 for CNT, CFA, and OCM, respectively (Figure 3a). The totalchronic daily intake for people exposed to soil-containing Co in CFA or OCM (maximumCo approximately 40mgkg�1) for their entire lifetime estimates 0.05 mg kg�1 day (about16% of the USEPA RfD). Here, the calculations show that the intake value is still belowthe USEPA exposure limit of 0.3 mg kg�1 day (Figure 3b). The trend of different agegroups shows that the value is getting closer to pose threats, especially in case of toddlerand infant (0.17 and 0.15, respectively).

CFA-Coal fire affected area; OCM-Opencast coal mine

(a)

(b)

0 0.1 0.2 0.3 0.4

Infant

Toddler

Child

Teen

Adult

Lifetime

Cobalt intake (mgkg–1day)

Opencast mines

Fire affected

USEPA Exposure Limit

Control CFA OCM

0.10

0.12 COBALT

0.08

0.06

0.04

Chr

onic

dai

ly in

take

(ug

kg–1

day)

0.02

0.00

Figure 3. Total chronic daily intake of cobalt: (a) total lifetime intake; (b) receptor-wise intake.CFA, coal fire affected area; OCM, opencast coal mine.

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It appears that the surroundings of coal mines and fire affected areas are safe in mostof the trace elements, except V. Gurdal (2008) reported high V values in some of theTurkey coals. Vanadium content in Indian coals (86mgkg�1) is higher than the worldaverage of 25mgkg�1 (Masto et al. 2007). Environmental levels of V were increased andhad raised concern over the injection of V into the atmosphere from the anthropogenicsources. The anthropogenic V inputs could pose environmental hazards (Hope 1994).Levy, Hoffman, and Gottsegen (1984) in an occupational exposure study of a coal-to-oilplant reported that the common symptoms due to V exposure were productive cough, sorethroat, dyspnea on exertion, and chest pain or discomfort. In an inhalation health study offine particles from the co-combustion of coal and refuse-derived fuel, Fernandez et al.(2003) reported the presence of water-soluble vanadium along with S and Zn in inhaleddusts, and suggested that these elements increased lung permeability of the test organism(mice). Thus, the higher level of V in this study, particularly under the CFA soils, may posehuman health hazard through chronic intake.

Conclusions

Impacts of OCM and coal fire on the status of soil trace elements were studied. Among theelements studied, Cr and Ni contents were elevated both in CFA and OCM soils; V and Znwere enriched in CFA soils. However, the levels of Cr, Ni, and Zn in these soils are belowthe USEPA soil screening limits. Human exposure studies showed that content of V in soilmay lead to exposure risks as the total V intake calculated across different exposurepathways is approximately 10-fold higher than USEPA RfD.

Acknowledgments

We express our thanks to Director, Central Institute of Mining and Fuel Research, Dhanbad, India,for providing support in publishing this study. The funding for this study provided through theNetwork Project NWP-0017 (11th Five Year Plan), Council of Scientific and Industrial Research(CSIR), Ministry of Science and Technology, Government of India, is greatly acknowledged.

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