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Trace elements concentration and distributions in coal and coal mining

wastes and their environmental and health impacts in Shaanxi, China

Article in Environmental Science and Pollution Research · July 2018

DOI: 10.1007/s11356-018-2148-2

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Environmental Science and Pollution Research
https://doi.org/10.1007/s11356-018-2148-2

RESEARCH ARTICLE

Trace elements concentration and distributions in coal and coal mining

wastes and their environmental and health impacts in Shaanxi, China
Rahib Hussain 1,2 & Kunli Luo 1,2 & Zhao Chao 1,2 & Zhao Xiaofeng 1,2

Received: 11 September 2017 / Accepted: 26 April 2018

# Springer-Verlag GmbH Germany, part of Springer Nature 2018

Abstract
This study probe the probable impacts of coal mining pollution and its impacts on human’s health and environment. A total of
144 samples including coal and coal wastes, soil, plants, foods, and water were collected from the Hancheng county and
countryside of Shaanxi, China. All the samples were analyzed for trace elements using ICP-MS, OES, and AFS. Results showed
that the concentration of Se, As, Cr, Cu, Pb, Cd, Co, Ni, Mo, U, Th (mgKg−1), Fe, Mn, Al, Ti (%) etc., in coal and coal wastes
were 7.5, 12.1, 275, 55, 54.2, 0.8, 14.8, 94.5, 8.9, 4.9, 17.2, 3.5, 0.02, 19, 0.7, respectively. While in soil 0.6, 12, 194, 27.5, 7.4,
0.6, 11.3, 83.4, 0.7, 1.7, 9.9, 3.1, 0.04, 10.5, and 0.4 for the above elements, respectively. In Hancheng foods, the average
concentration of Se-0.09, As-0.15, Cr-1.8, Cu-3.2, Pb-0.4, Cd-0.02, Co-0.09, Ni-0.4, Mo-0.64, U-0.01, Th-0.03, Fe-129, Mn-
15.6, Al-234, and Ti-5.2 in mgKg−1, respectively, which are comparably higher than the countryside. The elemental concentra-
tion in groundwater of both areas was below the WHO-2004 standard. In Hancheng, the average daily intake (mgKg−1bw/d) of
Se 0.004–0.0038, As 0.004–0.13, Cr 0.055–0.06, Cd 0.001–0.004, Ni 0.018–13.91, Pb 0.05–0.001 adult-children, respectively.
The toxic trace elements such as Cr, Cu, Mn, Pb, Ti, Cd, Co, Th, Fe, Al, and Mo caused non-carcinogenic risk with high
morbidity in children than adults. By assessing environmental risks, coal and coal wastes caused high risk, food and plants faced
moderate to high risk, while mountain and agriculture soil are prone to low to considerable risk. The pollution in Hancheng
County is extreme as compared to the countryside. The study concluded that the contamination is geogenic in both the areas but
coal mining enhance the metals contamination and has extensive impacts on the living community and environment of Hancheng
areas.

Keywords Coal . Coal mining wastes . Environmental risk . Geochemical characters . Health risk assessment . Pollution

Introduction 2007). According to World Energy Council (WEC 2013),

China is the second major coal producer and consumer coun-
try counted about 75% of all energy resources. Among them,
70% is directly used as a fuel and the remaining 5% is used for
household and other purposes (Luo et al. 2004; Wei et al.
Responsible editor: Philippe Garrigues
Electronic supplementary material The online version of this article
(https://doi.org/10.1007/s11356-018-2148-2) contains supplementary
material, which is available to authorized users.
* Kunli Luo
luokl@igsnrr.ac.cn
1
Institute of Geographic Sciences and Natural Resource Research,
Beijing 100101, China
2
University of Chinese Academy of Sciences, Beijing 10080, China
China counted for 114.5 Bt (Billion tons) of recoverable re-
serve coal equivalent to 14% of the world total coal reserves,
and 3.4 Bt of coal production counted for 35% recoverable
ratio. Besides the energy uses, almost 60% of chemical ele-
ments are derived from coal in China. However, some of the
portions are reluctantly released to the environment (Dai et al.
2012).
The geospatial distribution of coal resource in China is
uneven coal started in the western provinces are counted about
5115 Bt (91.83%) of the total Chinese coal resources. Among
them, abundant resources are located in Shanxi, Shaanxi,
Inner Mongolia, Sinkiang, Gansu, Guizhou and Ningxia prov-
inces (Luo et al. 2004; Zeng 2001). On the basis of regional
distribution, Shaanxi province is on the top to produce 505
Mt. (million ton) of coal in 2004 and accounted for more than
1/4 of total Chinese coal (Wang 2006; Zhao et al. 2008). The
extensive growth coal mining plays a significant role in

energy sectors, but it also contributes a huge of wastes to the
environment without utilizing. This activity not only distribute
and occupies much place but also create environmental and
social problems including air pollution, acid mine drainage,
waste gobs, forest and land degradation, land sliding, infra-
structure damages, source of toxic trace elements (TTE), de-
teriorate the physical and chemical property of soil, plants,
food and water bodies (Di et al. 2015; Siddiqui and Shah
2007). Besides the wastes, Li (2006) pointed out that the coal
industry spawned 256 Mt. tailing, 107 Mt. smelting slag, 103
Mt. gangue, which results to degraded 3.2 Mha (million hect-
ares) land of China. Zhao et al. (2008) reported that almost
1500 coal waste gobs are active in China. Among them, 40%
were found in Shaanxi province (43 coal-waste gobs pile),
which are actively undergo spontaneous combustion and
emitted SO2 0.84-Kg/ton, H2S 0.61-Kg/ton, NOx 0.03-Kg/
ton, COx 99.7-Kg/ton and smoke 0.45-Kg/ton, annually.
Contamination in the environment is a seriously con-
cerned because of potential toxicity to living biota and
disturbing the natural ecosystem. Trace elements in the
environment interact with each other and sediment
through a various natural mechanism including dissolu-
tion, complexation, absorption, and desorption, which af-
fect the plant’s growth, disrupt soil quality and contami-
nate the food chain (He et al. 2005a; Sahuquillo et al.
2003). The higher consumption of the toxic element ele-
ments may cause various health problems (Min et al.
2015; Rinklebe and Shaheen 2014; Thyssen et al. 2007).
During spontaneous combustion, coal extraction and
processing, largest amounts of toxic and radioactive ele-
ments are released to the environment, which could cause
harmful impacts on the human and surrounding environ-
ment. For this purposes, the study aimed to quantify the
TTE in coal and coal wastes, rocks, soils, water bodies,
plants and food crops and their comparison with the ele-
ment in the upper continental crust according to
JeffersonLab (2007); (Kennish 2000) and (McLennan
2001). While soil and food samples will be compared
with Chinese standard, and water quality will be com-
pared with WHO standard (WHO 2004). Literature re-
vealed that there is a lack of comprehensive research to
probe the magnitude of contamination and its associated
enviro-health risks in Hancheng. To assess the compara-
tive influence, the study chooses to explore Liaoyuan
coalmine of Hancheng, Shaanxi province, the typical
China coalmine in the north China Plate that comprised
on 4 coal beds of 2#, 3#, 5#, 11# of Pennsylvanian
(Taiyuan Formation C2) and Early Permian (Shaanxi
Formation P1). For this purpose, the study aimed, to find
out effects and impacts of coal mining pollution on
human’s health and environment. All samples were trans-
ferred to state key laboratory of Institute of Geographic
Sciences and Natural Resource Research, University of
Environ Sci Pollut Res
Chinese Academy of Sciences, China for further
processing.
Materials and methods
Geological setting
Hancheng city is situated at Northeast of Shaanxi province
nearby the Yellow River at the southeast of the Ordos basin,
while Liaoyuan coal mining area is located at the eastern edge
of the Ordos basin. The study area is located to the northwest
boundary of Weihe graben system, Lvliang fold belt located to
east connected through NE-NNE (North-northeast) Fenhe riv-
er graben system, while in the west it is connected with a
thrust-fold belt located at the west edge of the Ordos basin
(Xue et al. 2012).
Liaoyuan coal mining area is situated at a distance of 10 km
to Northeast of Hancheng city and is an important area of
Shaanxi province. The study area is located between longitude
110° 26′ 30″–110° 31′ 30″ E and latitude 35 ° 35′–35° 38′ 30″
N, with an altitude of 650 m from sea level (Fig. 1). The key
features of the area are the coal bed gas exploration, middle
and high-grade coal belonging to Late Carboniferous-early
Permian. The most visible strata’s in the area are Pleistocene
(Qh), Pliocene (Qp), Early-middle-late Triassic (T1-T2-T3),
Permian, Carboniferous, Late-Middle Ordovician (O),
Cambrian (Є1) and as well as Sangan System (Ar) of
Precambrian granite are exposed in this area. The
Carboniferous-Permian coal strata are exposed to valley side
and dumped under the Quaternary strata (Wang et al. 2011).
Shaanxi province is located in the middle reaches of Yellow
River and is plain fertile land spread over 200,000 Km2. The
average annual temperature is 13.8 °C and average annual
rainfall is 549.4 mm concentrated in June to September
(Wang et al. 2011).
Field visit and sampling
The field visit was carried out at Hancheng counties, Liaoyuan
coalmines (contaminated area) and countryside (Huanglong
and other connected areas) connected areas under qualified
experts to study coalmines affected and impacted areas either
through coal exploration or through the accumulation of
wastes debris. While the countryside areas were selected to
compare acute health and ecological impacts of coal explora-
tion in surrounding regions. A number of the miners and local
people were also visited to find out the environmental and
health-related problems. The sampling plan was designed ac-
cording to the distribution of coal and coal gangue explored
rocks, affected soil, unaffected soil, and plants in the surround-
ing areas of Hancheng and countryside of Shaanxi Province.
While the groundwater and food samples (local grown) were
Environ Sci Pollut Res
Fig. 1 Regional geological and location map of Hancheng county and countryside of Shaanxi province representing samples locations
collected from the homes in Hancheng and countryside areas.
In April 2016, a number of representative samples were col-
lected including 34 coal and gangue, 35 soil, 34 plants and
food and 18 water samples and noted each sample GPS data.
All the samples were transferred to geochemistry laboratory of
Institute of Geographic Sciences and Natural Resource
Research (IGSNRR), University of Chinese Academy of
Sciences (UCAS), China for further processing.
Experimental procedures
Before the acid digestion, a dry raw coal, coal gangue, coal
slime and soil samples were pulverized through vibrating cup
mill and passed through a sieve of −200-mesh size. The
plant’s samples were dried at 60 °C in the oven and grounded
to 80-mesh size. The chemical digestion of soil, coal and coal
wastes for As and Se; a portion of 0.05 g were treated with 5:1
solution of HNO3 and HClO4, while for the plant digestion;
0.5 g samples were treated with 9:1 HNO3 and HClO4. In 2nd
step, the samples were treated with 3 mL of HCl (1:1 diluted),
and then 1 mL pure HCl in a sequence. The final solution for
Se was run through Hydride Generation Atomic Fluorescence
Spectrometry (AFS-9780 BJHG and detection limit BDL^ of
the instrument is 0.01 μgL−1). For arsenic determination, the
above final solutions (Se solution) were further treated with
1 mL thiourea-ascorbic acid reagent (2.5:2.5 g per 100 mL
Water) and 1 mL HCl (Kunli et al. 2004).
Similarly, for the chemical analysis of trace elements, a
portion of 0.05 g of soil, coal, coal slime, coal ash, coal gangue
as well as certified reference geological standard of
GBW07403 and GBW07406 were treated through a series
of HNO 3 , HF and HClO 4 of 5:5:1 (Liu et al. 2014).
However, for the plants and food digestion, 0.5 g samples
were treated through a solution of concentrated HNO3 and
HClO4 of 5:1 with the constant heat of 180–220 °C until all
the elements comes to ionic form. In order to verify analysis, a
certified reference geological standard of GBW10010,
GBW10012 were also treated by the same methods. All the
trace elements were determined through Inductively Coupled
Mass Spectroscopy (ICP-MS) (instrument DL = 0.001 μgL−1)
and Inductive Coupled Optical Emission Spectroscopy (ICP-
OES) (DL = 0.001 mgL−1) (Luo 2011; NSPRC-China 2007)
at the chemical and physical laboratory of Institute of
Geographic Science and Natural Resource Research,
Chinese Academy of Sciences.
For the quality control and assurance, duplicate sam-
ples, blank reagents and geological grade reference stan-
dard for coal, soil, rock (GBW07401, GBW07403,
GBW07406), plants and food (GBW10010, GBW10012,
GBW10016) (followed by National Research Centre for
Standard in China) were used in each samples batch to
verify the accuracy and precision of the digestion methods
and subsequently analysis (Wang et al. 2016). The preci-
sion and reproducibility of the instrument were found
within the confidence limit of 98%.
Environmental and health risk analysis
Geo-accumulation index
Geo-accumulation index (GAI) is a geo-statistical tech-
nique use to quantify the degree of elemental

contamination and was determined by equation 1 (Eq. 1)
(Shen et al. 2017).
 
Cn
GAI ¼ Log2 ð1Þ
Bn  1:5
Where Cn (mgKg−1) is the elemental concentration of
current study and Bn (mgKg−1) are the reference value
(for soil the reference values (CSS)) (Table 1), for coal
and coal waste followed China threshold values suggested
by Ren et al. (2006); Tang and Huang (2004), while 1.5 is
the possible anthropogenic existence in the reference
areas. By evaluating toxicity, a six grades were recog-
nized as; G-0 (0 < GAI ≤ 1) unpolluted, G-1 (1 < GAI ≤
2) slightly polluted, G-2 (2 < GAI ≤ 3) moderate polluted,
G-3 (3 < GAI ≤ 4) moderate sever polluted, G-4 (4 <
GAI ≤ 5) sever polluted and G-5 (GAI > 5) revealed ex-
treme polluted (Hussain et al. 2015).
Contamination factor
Contamination factor (Cf) is used to quantify the elemental
risk to the environment and human health and was determined
by Eq. 2.
Cn
Cf ¼ ð2Þ
Bn
Where Cn and Bn are the respective elemental concen-
tration of current study and a reference value, respectively
(See Eq. 1). By evaluating and applying Cf on the current
study, the following classes are considered to assess the
risk level. The class C-1: Cf < 1 low contamination, C-2:
1 ≤ Cf < 3 moderate contamination, C-3: 3 ≤ Cf < 6 consid-
erable contamination and C-4: Cf ≥ 6 very high contami-
nation (Yang et al. 2011).
Groundwater risk assessment
Groundwater risk assessment (GRA) model was used to eval-
uate the toxicity in groundwater and its risk to humans and
was calculated through Eq. (3).
Cw
GRA ¼ ð3Þ
GTV
Where Cw (μgL−1) is the elemental concentration in
groundwater, while GTV (μgL−1) is the international standard
groundwater threshold value. By evaluating integrated risk,
GRA is categorized as; G1: GRA ≤ 1 revealed low priority
pollutants, G2: 1 < GRA ≤ 10 medium priority pollutants and
if G3: 10 < GR high-level pollutants (Odukoya and Abimbola
2010).
Environ Sci Pollut Res
Health risk assessment
To assess the average daily intake of TTE through food and
water by adult and children and their relation to non-cancer
(HQ) and cancer risk were determined through Eqs. 4, 5 and 6
(Pepper et al. 2006; US-EPA 2002).
½ðCx  FiÞ þ ðCw  WiÞ  EMF
ADI ¼ ð4Þ
Bw
ADI
HQ ¼ ð5Þ
RfD
Cancer Risk ¼ ADI  slope factor ð6Þ
Where Cx and Cw are the elemental concentration in food
and water (mgKg−1), Fi and Wi are the intake of food (Kg/
day) and water (liter/d), respectively. Bw is body weight of
receptor (Kg), EMF is exposure modifying factor (default val-
ue is 1.0 unitless), RfD is the corresponding reference dose
values for elemental ingestion (supplementary file (SF)), and
HQ is hazard quotient. If the HQ < 1 indicates no substantial
risk if HQ > 1 indicate the potential of non-carcinogenic risk
(Miguel et al. 2007; Pepper et al. 2006; Siyue and Zhang
2010; US-EPA 2002).
Carbon sequestration
The soil organic carbon (SOC) in agriculture and mountain
soil were determined through Walkley-Black chromic acid
wet oxidation method using Eqs. 7 and 8. Where BBD^ rep-
resent the Bulk Density and BCtotal^ represent the total carbon
potential (mg/cm2) in the soil. Oxidizable matter in the soil
was oxidized by the 1 N K2Cr2O7 solution. The heat generated
when two volumes of H2SO4 were mixed with one volume of
the dichromate assists the reaction. The process further
followed by H3PO4 and NaF, and finally titrated with ferrous
sulfate (Burghardt and Schneider 2018; Oje et al. 2015).
mass ðKgÞ
BD ¼ ð7Þ
volume ðcm3 Þ
Ctotal ¼ BD  Depth of sample ðcmÞ  C ðmg=KgÞ ð8Þ
The contents of SiO2 and loss of ignition (LOI) in the soil,
coal, and coal waste were calculated through Eq. 9 and Eq. 10,
respectively, as suggested by Kaminskas and Kubiliute (2010).
For calculation of LOI, samples were weighed and kept in the
oven for 1 h at 104 °C to remove the moisture contents and finally
kept in the flame furnace (CTJZH-1200 °C) for 1 h at 900 °C.
SiO2 % ¼ 100%
−ðAl2 O3 þ MnO þ P2 O5 þ TiO2 þ K 2 O þ Na2 O þ Fe2 O3 þ MgO þ CaO þ LOI Þ
ð9Þ
LOI% ¼ ½ðm1 þ m2 Þ–m3 =m2  100 ð10Þ
Environ Sci Pollut Res

Table 1 Geochemical composition and comparison of trace elements in Hancheng county with countryside and other studies (average mgKg−1)

Elements Coal USA China Soil CSS ECA

Coal gangue Coal slime Raw coal Coal ash Coal Coal Mountain soil Agri. soil

Al2O3% 19.75 20.47 14.83 20.957 2.8 12.26 10.53 6.62 15.55
CaO % 3.477 2.642 4.042 3.160 0.64 11.61 5.713 1.54 5.807
Fe2O3% 3.922 3.059 3.491 3.627 1.9 3.375 3.062 2.94 7.243
K2O % 3.307 2.021 2.769 2.006 0.22 3.205 1.840 1.86 2.518
MgO % 0.753 0.503 0.836 0.538 0.18 1.913 1.317 0.78 3.86
Na2O % 5.474 3.070 5.497 2.250 0.11 6.086 2.538 1.02 31.813
MnO % 0.037 0.011 0.030 0.023 0.006 0.0117 0.046 0.044 0.073 0.1227
P2O5% 0.000 0.000 0.011 0.074 0.098 0.003 0.090 0.241
TiO2% 0.747 0.750 0.544 0.791 0.13 0.469 0.461 0.38 0.9341
SiO2% 36.45 28.73 25.3 41.493 5.8 41.46 59.10 60.32
Moisture % 0.362 3.304 0.586 0.516 1.186 1.311
LOI % 26.17 37.66 43.79 25.284 21.17 15.79
Se 3.539 5.803 10.93 9.558 2.8 2.78 1.014 0.662 0.29 0.05
As 10.31 12.89 10.1 14.601 24 3.8 9.287 12.07 11.2 1.8
Ba 524.7 437.87 371.1 703.31 170 429.6 349.3 469 425
Cr 326.8 244.3 384.3 145.8 15 16.12 216.2 194.8 61 102
Cu 41.78 77.49 49.46 51.44 16 18.39 23.91 27.57 22.6 60
La 46.52 44.25 34.78 48.41 12 26.9 24.88 28.78 39.7 39
Li 143.9 262.5 182.6 260.79 16 36.14 74.93 32.5 20
Mo 3.268 17.99 7.369 7.199 3.3 3.72 0.724 0.696 2.0 1.2
Ni 102.6 96.09 93.89 85.74 14 14.04 92.71 83.42 26.9 84
Pb 60.89 56.80 56.07 42.99 11 15.55 21.71 7.441 26 14
Sc 8.679 11.96 8.786 11.08 4.2 6.813 6.566 11.1 22
Sr 162.37 152.2 147.1 453.57 130 232.03 148.5 167 370
V 96.14 127.05 90.68 122.45 22 35.05 66.84 60.16 82.4 120
Zn 8484.1 5419 7652 3824 53 42.16 6599.3 3056 74.2 70
Cd 1.017 0.841 0.613 0.821 0.47 0.25 0.800 0.634 0.097 0.15
Co 20.04 13.72 11.95 13.33 6.1 6.88 10.81 11.32 12.7 25
Tl 0.828 0.452 0.400 0.919 1.2 0.49 0.507 0.441 0.62 0.850
Cs 8.533 6.284 4.202 6.277 1.1 7.129 5.777 8.24 3
Ga 46.15 44.50 35.86 56.23 5.7 6.52 33.38 32.11 17.5 19
In 0.135 0.566 0.181 0.184 0.3 0.075 0.067 0.068 0.250
Rb 149.9 97.12 57.89 102.01 21 133.5 115.5 111 90
U 3.573 5.477 4.954 5.744 2.1 2.41 1.789 1.659 3.03 2.7
Bi 0.868 0.802 0.730 1.080 1.0 0.350 0.447 0.37 0.0085
Be 3.953 4.394 3.406 5.421 2.2 2.13 1.800 1.988 1.95 2.8
Y 21.56 22.58 18.63 26.73 8.5 15.75 18.08 22.9 33
Ce 79.63 75.92 60.19 81.11 21 50.1 47.63 57.30 68.4 66.5
Pr 9.070 8.560 6.711 9.455 2.4 5.574 6.896 7.17 9.2
Nd 35.12 33.09 26.02 36.97 9.5 26.14 22.135 27.92 26.4 41.5
Sm 6.563 6.339 5.307 7.204 1.7 4.56 4.411 5.480 5.22 7.05
Eu 1.322 1.249 1.006 1.418 0.40 0.73 0.954 1.022 1.03 2
Gd 6.020 5.915 5.161 6.719 1.8 4.160 5.080 4.6 6.2
Tb 0.726 0.755 0.667 0.870 0.30 0.59 0.515 0.608 0.63 1.2
Dy 3.697 3.945 3.434 4.691 1.9 2.661 3.027 4.13 5.2
Ho 0.728 0.775 0.672 0.938 0.35 0.526 0.590 0.87 1.3
Er 2.175 2.256 1.919 2.763 1.0 1.557 1.703 2.54 3.5
 Environ Sci Pollut Res

Table 1 (continued)

Elements Coal USA China Soil CSS ECA

Coal gangue Coal slime Raw coal Coal ash Coal Coal Mountain soil Agri. soil

Tm 0.301 0.310 0.270 0.392 0.15 0.218 0.235 0.37 0.52

Yb 2.016 2.083 1.771 2.569 0.95 1.78 1.469 1.517 2.44 3.2
Lu 0.304 0.300 0.262 0.383 0.14 0.53 0.220 0.230 0.36 0.5
Th 14.60 17.22 17.74 19.28 3.2 5.8 8.109 9.939 13.75 9.6
pH 7.332 7.580
Cond. mS/cm 27.76 14.43
SOC ton/ha 14.99 25.03

USA coal; (Finkelman 1993)

China Coal; (Ren et al. 2006; Tang and Huang 2004)
ECA (earth crust abundance) = (JeffersonLab 2007; Kennish 2000)
CSS (China Soil Standard) = SEPAC 1995

Where m1 is the weight of porcelain crucible, m2 is the
powdered sample (before heating) and m3 is the combined
weight of sample + crucible after heating.
Results
Distribution of trace elements
The current study determined major and trace elements in the
different type of samples collected from Liaoyuan coalmine
(typical China coal) of Hancheng counties and countryside of
Shaanxi province, North China Plate. The elemental concen-
tration (average) in coal gangue, raw coal, coal slime, coal ash,
soil, plants, in a different type of foods (mgKg−1) and water
(μgL−1) were listed in Tables 1 and 2. While the respective
results and distribution of each sample and elements were
listed in the supplementary file (SF) and Fig. 2. Among the
trace elements, the average concentration of Se in coal gangue
was 3.54 mgKg −1 , coal slime 5.8 mgKg −1 , raw coal
10.9 mgKg−1 and in coal ash 9.5 mgKg−1. By compare with
Chinese coal (Ren et al. 2006) and USA coals (Finkelman
1993), the concentration of Se in the Hancheng counties was
much higher than China and USA (Table 1). The average
concentration of Se in the agricultural soil and mountain soil
(collected from Hancheng mining area) were 0.66 mgKg−1
and 1.01 mgKg−1. Similarly, the Se concentration in the min-
ing area grass, ornamental plants, corn flour, wheat flour, and
foodstuff were 0.8, 2.4, 0.09, 0.10, and 0.087 in mgKg−1 re-
spectively. However, the Se contents in the grass of back-
ground area (at a distance of 1 Km from mining) was 0.3
mgKg−1, while in countryside wheat and corn flour were
0.11 mgKg−1 and 0.05 mgKg−1. The Se contents in the
groundwater of Hancheng mining area was 0.203 and in coun-
tryside 0.23 in μgL−1, respectively (Table 2), which were
below the (WHO 2004) drinking water permissible level
(10 μg/L). The Se distribution in the Hancheng (Weibei coal-
field) were observed very low in food, plants, and water as
compared to coal. However, the Permo-Carboniferous and
igneous rock of north Shaanxi had an extremely low concen-
tration of selenium as also reported by He et al. (2002).
The average arsenic (As) contents in the Liaoyuan
c o a l m i n e c o a l g a n gu e 1 0 . 3 m g K g − 1 , c o a l s l i m e
12.9 mgKg −1 , raw coal 10.1 mgKg −1 , and coal ash
14.6 mgKg−1. By comparing with the previous study of
USA (Finkelman 1993) and China (Ren et al. 2006; Tang
and Huang 2004), their average results were 0.024 mgKg−1
and 3.84 mgKg−1, respectively, which is lower than the current
study. Arsenic content in the coal and rocks is mostly associ-
ated with sulfide and pyrite rocks (Finkelman et al. 2018).
Arsenic contents in agriculture mountain soil of the mining
areas were 9.3 and 12.1 mgKg−1, respectively, which is almost
equivalent to China soil standard (CSS) of 11.2 mgKg−1
(Table 1). The average As concentration in the grass, orna-
mental plants, corn flour, wheat flour and other foodstuff of
the Liaoyuan coal mining areas were 1.3, 0.5, 0.05, 0.093, and
0.03 mgKg−1, respectively. While As contents in the grass,
wheat flour and corn flour in the countryside were 0.96,
0.073, and 0.045 mgKg−1, respectively. It is important to
know, that the As concentration in Garlic, Brassica, Pepper,
and rice (foodstuff) in mining area were 0.6, 0.2, 0.21, and
0.14 mgKg−1, respectively. The As concentration (average) in
the groundwater of mining and countryside areas were 0.55
and 1.14 μgL−1, which was lowered than the WHO (2004)
permissible standard (10 μgL−1) (Table 2 and SF).
The average concentration of Cr, Cd, Pb, and Ni in coal
gangue were 326, 1.017, 60.8, 102.6, coal slime 244.3, 0.8,
56.8, 96.1, raw coal 384, 0.613, 56.1, 93.9, and in coal ash
145.8, 0.82, 42.9 and 85.7 in mgKg−1, respectively (Table 1
and Fig. 2). The average concentrations of Cr, Cd, Pb, and Ni
Environ Sci Pollut Res

Table 2 Geochemical composition and comparison of trace elements in plants, food, and groundwater of Hancheng county with countryside (average
mgKg−1)

Liaoyuan mining area Country side Water

Elements (Hancheng) (Hancheng) (μgL−1)

Grass Ornamental Corn flour Wheat flour Other food Grass (1 Km Wheat flour Corn flour
1 plants 3 4 5 Average from mining Hancheng Countryside
2 of area)
3, 4, 5

Se 0.851 2.418 0.105 0.090 0.087 0.094 0.301 0.111 0.055 0.203 0.245
As 1.308 0.450 0.053 0.093 0.301 0.149 0.967 0.073 0.045 0.548 1.141
Ba 41.394 17.51 1.807 2.175 11.41 5.130 35.55 3.951 0.813 106.81 71.329
Cr 19.809 6.274 0.512 1.256 3.767 1.845 12.14 0.974 0.695 9.677 11.646
Cu 18.513 7.510 1.969 3.521 4.251 3.247 6.754 4.385 1.616 0.662 0.530
La 2.377 0.248 0.011 0.022 0.290 0.108 0.582 0.019 0.009 0.0001 0.000
Li 8.727 5.338 0.063 0.069 1.362 0.498 1.854 0.076 0.101 12.568 5.950
Mn 68.359 18.80 6.419 19.215 21.39 15.675 43.45 38.294 4.556 0.677 0.977
Mo 1.286 0.485 0.579 0.807 0.547 0.644 0.615 0.723 0.491 1.503 1.861
Ni 6.638 2.079 0.255 0.332 0.716 0.434 3.558 0.251 0.511 1.771 1.966
P 2023.6 3145.4 2023. 1917.5 3423.8 2454.7 2921.1 3065.4 2080.0 0.000 0.775
Pb 21.448 1.833 0.047 0.057 1.001 0.368 7.807 0.196 0.125 0.109 0.020
Cs 0.476 0.053 0.010 0.010 0.060 0.027 0.556 0.011 0.023 0.016 0.004
Sr 79.070 89.02 0.953 1.508 36.79 13.085 62.375 2.599 0.513 646.85 14,224.
Ti 90.160 10.51 0.869 0.637 14.27 5.260 28.835 1.042 0.629 0.297 1.166
V 4.924 0.123 0.331 0.000 0.286 0.206 1.346 0.000 0.000 1.517 2.129
Zn 86.441 30.52 21.32 23.905 26.68 23.97 43.935 31.56 20.38 28.878 118.6
Cd 0.594 0.045 0.011 0.017 0.036 0.021 0.518 0.028 0.011 0.050 0.134
Co 1.628 0.232 0.021 0.039 0.212 0.090 0.712 0.037 0.019 0.210 0.631
Tl 0.082 0.011 0.001 0.001 0.083 0.028 0.063 0.001 0.000 0.006 0.000
Ga 3.546 1.558 0.931 1.175 1.789 1.298 2.256 1.063 0.628 4.946 3.361
In 0.019 0.003 0.000 0.000 0.001 0.001 0.006 0.000 0.000 0.001 0.001
Rb 8.721 8.230 1.716 3.154 2.819 2.563 35.07 3.058 3.694 0.752 1.383
U 0.161 0.017 0.002 0.003 0.021 0.009 0.083 0.003 0.003 3.543 2.890
Bi 0.585 0.071 0.002 0.003 0.030 0.011 0.155 0.003 0.001 0.001 0.000
Be 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.056 0.078
Y 1.034 0.114 0.006 0.010 0.152 0.056 0.325 0.010 0.004 0.000 0.000
Ce 3.374 0.406 0.021 0.039 0.523 0.194 0.897 0.036 0.021 0.000 0.000
Pr 0.496 0.051 0.002 0.004 0.061 0.023 0.115 0.004 0.002 0.000 0.000
Nd 2.240 0.191 0.009 0.019 0.243 0.090 0.439 0.017 0.007 0.000 0.000
Sm 0.360 0.040 0.002 0.004 0.048 0.018 0.090 0.005 0.002 0.000 0.000
Eu 0.072 0.010 0.001 0.001 0.011 0.004 0.023 0.002 0.000 0.000 0.000
Gd 0.320 0.032 0.002 0.003 0.042 0.016 0.080 0.003 0.001 0.000 0.000
Tb 0.039 0.004 0.000 0.000 0.005 0.002 0.010 0.000 0.000 0.000 0.000
Dy 0.190 0.020 0.001 0.002 0.026 0.010 0.053 0.002 0.001 0.000 0.000
Ho 0.033 0.004 0.000 0.000 0.005 0.002 0.010 0.000 0.000 0.000 0.000
Er 0.099 0.011 0.001 0.001 0.014 0.005 0.030 0.001 0.001 0.000 0.000
Tm 0.012 0.001 0.000 0.000 0.002 0.001 0.004 0.000 0.000 0.000 0.000
Yb 0.077 0.009 0.001 0.001 0.011 0.004 0.024 0.001 0.001 0.000 0.000
Lu 0.014 0.002 0.000 0.000 0.002 0.001 0.005 0.000 0.000 0.000 0.000
Th 0.679 0.064 0.003 0.007 0.079 0.030 0.171 0.019 0.004 0.000 0.000
Mg 2637.4 2202.8 768.3 720.6 1508.5 999.11 3355.6 0.000 0.000 20,370. 9775.8
Na 721.31 388.28 74.03 76.24 269.99 140.08 238.7 1234.2 910.70 39,015.0 13,787.1
 Environ Sci Pollut Res

Table 2 (continued)

Liaoyuan mining area Country side Water

Elements (Hancheng) (Hancheng) (μgL−1)

Grass Ornamental Corn flour Wheat flour Other food Grass (1 Km Wheat flour Corn flour
1 plants 3 4 5 Average from mining Hancheng Countryside
2 of area)
3, 4, 5

Fe 2353.4 371.580 40.50 41.49 305.3 129.08 985.6 66.052 88.16 190.74 212.7
K 8948.4 12,524.0 3101. 2518.2 8413.6 4677.7 15,994.4 78.720 29.585 1509.50 894.6
Ca 18,518.0 183.3 266.4 3807.9 1419.2 31,520.0 3634.0 3508.5 57,750.0 56,343.0
14,-
174.
Al 4182.4 433.3 40.55 164.5 497.4 234.15 1507.56 402.70 150.4 24.771 1.773
SiO2 215.26 223.1 8855.5 9326.3
Sb 0.071 0.035
B 43.600 13.467
SAL‰ 0.545 0.385
EH mv 0.000 23.600
TDS 550,000. 430,083.3
SO4 100,670. 64,895.8
HcO3 255.37 240.43
Cl 32.66 37.559

‰ = Parts per trillion (ppt)

Other food: Garlic bolt, Brassica campestris seed, Chinese red pepper, rice,
Fruit trees wood, local egg, local pig meat, Hickory (Carya), potatoes, persimmon, millet

in agriculture soil were 194.8, 0.6, 7.4, and 83.4, while in
mountain soil 216.2, 0.8, 21.7, and 92.7 in mgKg−1, respec-
tively. Similarly, the Cr distribution in the grass, ornamental
plants, corn flour, wheat flour and other foodstuffs of
Liaoyuan mining and Hancheng counties were 19.8, 6.3,
0.5, 1.3, and 3.7 mgKg−1, respectively. The respective distri-
bution of Cd in grass 0.5, ornamental plants 0.045, corn flour
0.11, wheat flour 0.17 and other foodstuffs 0.036 in mgKg−1,
respectively. The distribution of Pb, Ni, Cd, Cr, V, Se, As, and
U in coal and coal waste and plants-food were given in Fig. 2.
The Pb distribution in the grass, ornamental plants, corn flour,
wheat flour and other foodstuffs were 21.4, 1.8, 0.05, 0.057,
and 1.0 mgKg−1, respectively. The average distribution of Ni
in grass 6.6, ornamental plants 2.07, corn flour 0.25, wheat
flour 0.3 and other foodstuffs 0.7 in mgKg−1, respectively.
However in countryside, the average concentration of Cr in
grass, wheat flour and in corn flour were 12.1, 0.9, 0.6, Cd 0.5,
0.28, 0.01, Pb 7.8, 0.19, 0.13, and Ni were 3.5, 0.25, and 0.5
mgKg−1, respectively (Tables 1 and 2, SF and Fig. 2). The
mode of occurrence for Ti are complex but the common
source is clay and titanium oxide (brookite, rutile, anatase
etc.,) (Ward 2002). The mode of occurrence of Ba is Barite
(BaSO4), Barytocelestine, witherite (BaCO3), gorceixite and
some carboxylic group (Bytnar and Makowska 2017). The
mode of occurrence of Pb is Galena (PbS), sulfate, carbonate,
and silicate (Lu et al. 2004), while the mode of occurrence of
Li mostly occurs with clay minerals, detrital micas and tour-
malines (Finkelman et al. 2018).
Besides the TTE, major elements composition were also
abundant in Shaanxi Liaoyuan coal mining areas and country-
side. The respective concentration of major elements coal,
coal gangue, coal slime and coal ash were given in Table 1,
while the concentration in plants and food were given in
Table 2.
Radioactive elements
During coal extraction and processing, the natural radio-
active elements were also contributed to the environment
caused many irregularities. The magnitude of Bismuth
(Bi) in coal gangue, coal slime, raw coal and coal ash
were 0.4–2.7, 0.5–1.2, 0.38–1.3, and 0.5–1.87 mgKg−1,
respectively (Table 1 and SF). By comparing with a pre-
vious study conducted on coal in the USA (Finkelman
1993) and China (Dai et al. 2005), Bi were 0.001 and
0.0005 mgKg−1, respectively. The mode of occurrence
of Bi in the coal is fusinite and semifusinite (Parzentny
and Róg 2017). The detected contents (mgKg−1) in moun-
tain soil were 0.2–0.5 (average 0.35) and in agriculture
soil 0.12–0.7 (average 0.45) at Hancheng counties,
Environ Sci Pollut Res
Fig. 2 Geospatial distribution of selected elements of coal and coal wastes and plants & food (mgKg−1) in Hancheng and countryside, Shaanxi
Shaanxi province, which is comparatively higher than the
SEPAC (1995) (0.37 mgKg−1). The average Bi concentra-
tions in the Hancheng grass 0.5 mgKg −1 , ornamental
plants 0.07 mgKg−1, corn flour 0.002 mgKg−1, wheat
flour 0.003 mgKg−1, and foodstuff 0.03 mgKg−1, respec-
tively. By comparing with Hancheng County, the Bi con-
centration in countryside grass 0.155 mgKg−1, wheat flour
0.003 mgKg−1 and corn flour 0.001 mgKg−1, respectively.
The Bi content (avg.) in groundwater of Hancheng was
0.001 μgL−1 and countryside 0.0001 μgL−1 (Table 2).
The average uranium (U) concentration in coal gangue
3.6 mgKg−1, coal slime 5.4 mgKg−1, raw coal 4.9 mgKg−1
and coal ash 5.7 mgKg−1. The average U concentration in
agriculture soil was 1.6 mgKg−1, mountain soil 1.7 mgKg−1,
while China soil standard is 3.03 mgKg−1 (SEPAC 1995). The
mode of occurrence of U is organic matter, pitchblende,

coffinite, brannerite and lignite coal (Chen et al. 2017). The
average U contents in the grass, ornamental plants, corn flour,
wheat flour, and foodstuff were 0.16, 0.017, 0.002, 0.003 and
0.021 mgKg−1, respectively in Hancheng area, while in the
countryside, uranium contents in the grass, wheat flour, and
corn flour were 0.08, 0.003 and 0.0031 mgKg−1, respectively.
Uranium concentration (average) in Hancheng and country-
side groundwater were 3.54 μgL−1 and 2.89 μgL−1, respec-
tively. Thorium (Th) concentration (average) in coal gangue,
coal slime, raw coal, coal ash, agriculture and mountain soil
were 14.6, 17.2, 17.7, 19.2, 9.9, and 8.1 mgKg−1, respectively.
The average Th concentration in the Hancheng grass 0.6, or-
namental plants 0.06, corn flour 0.003, wheat flour 0.007 and
foodstuff 0.079 in mgKg−1, respectively, while Th in the coun-
tryside grass 0.17, wheat flour 0.019, and corn flour 0.004 in
mgKg−1, respectively. Uranium and Th mostly associated
with uranium-bearing minerals (Hower et al. 2016). While
the anthropogenic source of radioactive elements especially
U, Th, and Bi are mining, milling, nuclear fuels.
Additionally the mobility of radioactive elements in an envi-
ronment mostly associated with organic matter (Bednar et al.
2007). The high concentration of radioactive elements may
affect the fetal development while also affect soil and ecosys-
tem (Sztajnkrycer and Otten 2004).
Elemental composition in coal-ash
Potentially toxic trace elements were also abundant in the fine
and coarse ash of Tatang Power Plants as well as in
Fig. 3 Evaluation of anions and
cations significance in
groundwater
Environ Sci Pollut Res
spontaneous burning ash of the mining counties. Among the
TTE, the average Se concentration in coarse ash, fine ash and
in spontaneous burning ash were 12.3, 11.9, and 8.6 mgKg−1,
respectively, While As concentration (average) in coarse ash
26.2-mgKg−1, fine ash 16.9-mgKg−1 and in spontaneous
burning ash 9.8-mgKg−1. Similarly, in coarse ash, fine ash
and in spontaneous ash the average concentration of Cr was
145, 96, 159, Pb 66.9, 32.9, 36.4, V 167.9, 145.5, 100.7, and
Zn 800, 1031, 5228 in mgKg−1, respectively (SF). The aver-
age contents of major oxides in ash (average of all types of
Ash) were 20.9, 3.1, 3.6, 2.0, 0.5, 2.3, 0.02, 0.07, 0.7 and
41.4% for Al2O3, CaO, Fe2O3, K2O, MgO, Na2O, MnO,
P2O5, TiO2, and SiO2, respectively. The abundance of some
precious elements (in Ash) i.e. In 0.2, Ga 56.2, Be 5.4, Bi
1.08, and U 5.7 in mgKg−1, respectively (Table 1 and SF).
Groundwater ionic concentration
The trace elements in groundwater of both areas were under
the standard permissible level of WHO (2004), while cations
and anions concentration were higher but having no WHO
permissible standard value (Table 2). The anions cations dis-
tribution pattern showed (Fig. 3), that groundwater has a high
concentration of SO4 almost 95%, while Ca were in between
40 and 96% and Mg was up to 20%. The integrated trilinear
diamond diagram revealed that the groundwater has a some-
what high concentration of Ca, Mg, and SO4 and was detected
to cause permanent hardness. The high tendency of permanent
hardness in groundwater is due to the anthropogenic or
Environ Sci Pollut Res
geogenic inputs, but the geogenic evidence is stronger than
anthropogenic because all other elements are under the per-
missible level of WHO (2004). Yan et al. (2013) reported that
the bedrocks and aquifer materials are the principal and frac-
tional source of elemental contents in groundwater that is
mostly associated with parental rocks. Hardness is caused
due to the occurrence of anions (Cl−, SO42−, HCO3− and
CO32-) and Cations (Ca2+ and Mg2+), while Na+ causes pseu-
do hardness (Sadashivaiah et al. 2008). The metallic cations
react with anions to damage the kidney filter, teeth, block the
skin pores and bumpy body, while some evidence also indi-
cates to activate heart problems. Hard water has a low buffer-
ing capacity and high corrosive property resulting damages
iron materials (Azevedo et al. 2006).
Loss on ignition and organic carbon abundance
The optimum percentile of moisture before LOI in coal
gangue, coal slime raw coal and coal ash were 0.36, 3.3,
0.58, and 0.51%, respectively, while the moisture content in
mountain and agriculture soil were 1.18 and 1.3%, respective-
ly. The moisture contents in soils represent the suitability and
possibility of the plantation. The average loss on ignition of
coal gangue, coal slime, raw coal, coal ash, mountain soil and
agriculture soil were 26.2, 37.6, 43.8, 25.2, 21.2, and 15.8%,
respectively (Table 1). The respective concentration of LOI in
coarse ash was 4.57, fine ash 5.7, spontaneous ash (far from
coalmine) 17.8, spontaneous ash (from coalmine) 58.2 and
spontaneous ash (from gangue place) 27.8% (SF). This un-
burnt carbon in the ash is due to the improper function of
powers plants, while in spontaneous burning areas are due to
decaying of radioactive elements, through which a significant
portion of energy is wasted.
The post-mining activity is also very important, among
them; only soil organic carbon is under consideration for af-
forestation. The average bulk density (BD) of agriculture soil
was 1.2007 g/cm3 and mountain soil was 1.68 g/cm3. The
average abundance of soil organic carbon (SOC) in agriculture
soil and mountain soil were 25.03 and 14.99 ton/ha. The status
of SOC and BD in agriculture soil is suitable for all type of
cropping and plantation, while SOC in mountain soil was not
sufficient to support all type of plants.
Discussions
Pollution prominence
The study observed great variation in the TTE concentration
from region to region and sample to sample. The pollution
related to TTE in the mining areas were higher than the coun-
tryside. The major elements mostly do not count in pollution,
but the extremely high level of major elements may cause
harmful impacts in the compound form rather than single el-
ements (Hussain et al. 2015). The higher concentration of the
major oxide was generally processed through GAI and their
result were: According to GAI, MnO caused no pollution,
Fe2O3 caused slight pollution, CaO moderate pollution,
MgO moderate-sever pollution and SiO2 caused severe pollu-
tion, while rest of the elements caused extreme pollution
(Table 3). By comparing with a previous study of Ren et al.
(2006) and Tang and Huang (2004) conducted in China, the
current study coal and coal wastes elemental contents were
high caused extreme pollution. In mountain soil, Cao, Zn,
and Cd caused extreme pollution, Na2O caused moderate-
sever pollution, Se, Cr, and Ni caused moderated pollution,
Al2O3, K2O, MgO, and Ga caused slight pollution, while re-
maining elements caused no pollution. Aluminum is mostly
associated with kaolinite, illite, while some old literature re-
ported zeolites, phosphates, crandallite group, sulfates, oxides,
feldspars, gibbsite, boehmite, diaspore (Finkelman 1981;
Finkelman et al. 2018). In agriculture soil, Zn caused extreme
pollution, Cd caused moderate-sever pollution, Cao caused
moderate pollution, MgO, Na2O, Se, Cr, Li, Ni, and Ga
caused slight pollution, while the remaining all elements
caused no pollution or low pollution (Table 3). The geospatial
distribution of Pb, Ni, Cd, Cr, V, Se, As, and U in soil and
water were given in Fig. S1. The tendency of GA and pollu-
tion in coal and coal wastes was extremely high followed by
mountain and agriculture soil. The comparative study of GA
exposed, that high accumulation of elements or their com-
pounds in surrounding environment is ultimately disrupting
the soil quality, deteriorate food crops and water composition,
damage air quality and causing various disease in humans (He
et al. 2005b; Muhammad et al. 2011).
The abundance of Vanadium (V) in Chinese coal ~9.10 Bt
(reserves), but its concentration in the coal and coal waste was
ranged 16.8 to 167.9 mgKg−1 in Hancheng area, which is
significantly higher than the earth upper continental crust of
0.097 mgKg−1 (Rudnick and Gao 2004), world coal 0.025
mgKg−1 (Ketris and Yudovich 2009), USA 0.022 mgKg−1
and in China coal 35.05 mgKg−1. While V in Liaoyuan
coalmine was lower than the industrial economic value of
7000 mgKg−1 (China Statistical Bureau 2014; Ren et al.
2006; Tang and Huang 2004). The abundance of Rare Earth
Elements (REE) such as Sc, Y, Ce, Pr, Nd, Sm, Eu, Gd, Tb,
Dy, Ho, Er, Yb, and Lu were lower than the concentration of
that element in the upper continental crust (JeffersonLab
2007; Kennish 2000; McLennan 2001). However, all the toxic
and heavy metals were higher in Liaoyuan coalmine than
Earth Crust Abundance value. In major elements, Al2O3,
K2O, Na2O, TiO2, and SiO2 were abundant in Liaoyuan
coalmine, while CaO, Fe2O3, MgO, and MnO were lower
than the earth crust abundant value (Table 1). It was reported
that Se and tellurium (Te) has been depleted from the earth
crust to form volatile hydride (JeffersonLab 2007; Kennish
Table 3 Environmental and health risk assessment related to trace and toxic elements exist in surrounding environment

Elements Risk to Environment Geo-accumulation of contaminants Risk to water Average daily intake
(GRI) mgKg−1 bw/d

Coal and Agriculture soil Mountain soil Coal and Agriculture soil Mountain soil Hancheng Country side Hancheng Country side
coal wastes coal wastes
Adult Child Adult Child

Al2O3 8.13 1.45 1.85 5.42 0.968 1.235 0.124 0.057 10.546 0.001 1.140 1.216
CaO 3.06 3.407 7.54 2.04 2.272 5.025 0.288 0.315 51.273 13.217 3.727 3.806
Fe2O3 1.91 0.947 1.15 1.27 0.631 0.77 0.038 0.041 5.946 44.291 0.328 0.349
K2O 8.513 0.897 1.72 5.67 0.597 1.149 0.1006 0.089 41.568 52.619 18.91 20.16
MgO 5.53 1.534 2.45 3.7 1.022 1.635 0.2037 0.199 10.700 3.103 6.446 6.823
Na2O 25.16 2.27 5.97 16.8 1.513 3.978 0.1950 0.150 3.603 7.666 1.440 1.455
MnO 1.252 0.547 0.631 0.83 0.364 0.421 0.00068 0.0021 0.200 0.005 0.125 0.134
P2O5 0 0.005 13.04 0.056 14.02 14.95
TiO2 2283.3 1.109 1.23 1522.2 0.739 0.823 0.0029 0.0043 0.229 0.013 0.005 0.005
SiO2 6.37 4.25 0.305 0.302 0.455 0.450
Se 3656.9 2.106 3.49 2437.9 1.404 2.33 0.020 0.0225 0.0044 0.0038 0.0005 0.0005
As 2742.1 0.934 0.83 1828.1 0.623 0.55 0.027 0.030 0.004 0.128 0.0004 0.0004
Ba 4199.5 0.677 0.92 2799.7 0.451 0.611 0.153 0.164 0.123 0.062 0.018 0.019
Cr 8295.9 2.902 3.54 5530.7 1.935 2.363 0.194 0.233 0.055 0.059 0.005 0.005
Cu 780.8 1.107 1.058 520.6 0.738 0.705 0.0033 0.0025 0.055 0.006 0.017 0.018
La 1334.5 0.664 0.627 889.7 0.443 0.418 0.006 0.026 0.0002 0.0001
Li 3611.9 2.121 1.112 2407.9 1.414 0.741 0.025 0.214 0.001 0.001
Mo 780.3 0.321 0.362 520.2 0.214 0.241 0.0751 0.0545 0.005 0.019 0.003 0.004
Ni 2466.2 2.795 3.447 1644.2 1.86 2.298 0.088 0.097 0.018 13.91 0.002 0.0023
Pb 3340.7 0.264 0.84 2227.1 0.18 0.557 0.0011 0.00067 0.053 0.001 0.001 0.0014
Sc 1360.9 0.527 0.614 907.3 0.351 0.409 0.001 0.299 0.000 0.000
Sr 1661.8 0.807 1.389 1107.9 0.538 0.926 0.303 0.266 0.030 0.030
V 811.1 0.661 0.81 540.76 0.44 0.541 0.03033 0.034 0.012 0.288 0.000 0.000
Zn 112,866 37.65 88.9 752.44 25.1 59.29 0.0288 0.0916 0.271 0.003 0.144 0.154
Cd 2075.8 5.930 8.243 1383.9 3.95 5.49 0.01 0.01602 0.001 0.004 0.00012 0.00012
Co 1104.8 0.811 0.85 736.6 0.541 0.567 0.00105 0.00154 0.004 0.000 0.000 0.000
Tl 6870.9 0.647 0.82 4580.7 0.431 0.546 0.00027 0.00014 0.000 0.013 0.000 0.000
Cs 8210.4 0.638 0.86 5473.6 0.425 0.58 0.012 0.000 0.005 0.005
Ga 3396.9 1.67 1.907 2264.6 1.116 1.273
In 0.89 1.102 0.59 0.735 0.000 0.034 0.000 0.000
Environ Sci Pollut Res
Table 3 (continued)

Elements Risk to Environment Geo-accumulation of contaminants Risk to water Average daily intake
(GRI) mgKg−1 bw/d

Coal and Agriculture soil Mountain soil Coal and Agriculture soil Mountain soil Hancheng Country side Hancheng Country side
Environ Sci Pollut Res

coal wastes coal wastes

Adult Child Adult Child

Rb 8403.7 0.948 1.202 5602.1 0.632 0.802 0.031 0.000 0.018 0.019
U 313.6 0.498 0.591 209.1 0.33 0.394 0.1181 0.1006 0.001 0.002 0.000 0.000
Bi 1668.1 1.089 0.947 1112.1 0.727 0.63 0.001 0.000 0.000 0.000
Be 1863.9 0.928 0.923 1242.7 0.619 0.63 0.00056 0.00059 0.000 0.003 0.000 0.000
Y 893.6 0.723 0.69 595.7 0.482 0.458 0.003 0.009 0.000 0.000
Ce 1213.8 0.767 0.69 809.3 0.511 0.465 0.009 0.001 0.000 0.000
Pr 1050.6 0.881 0.78 700.4 0.587 0.518 0.001 0.006 0.000 0.000
Nd 1398.4 0.969 0.84 932.3 0.646 0.559 0.006 0.001 0.000 0.000
Sm 1401.0 0.961 0.845 934.1 0.641 0.56 0.001 0.000 0.000 0.000
Eu 1519.7 0.907 0.927 1013.1 0.605 0.618 0.000 0.001 0.000 0.000
Gd 1224.9 1.011 0.904 816.6 0.674 0.603 0.001 0.000 0.000 0.000
Tb 1202.2 0.884 0.817 801.5 0.589 0.545 0.000 0.001 0.000 0.000
Dy 1109.9 0.671 0.644 739.9 0.45 0.423 0.000 0.000 0.000 0.000
Ho 1064.7 0.62 0.605 709.8 0.419 0.403 0.000 0.000 0.000 0.000
Er 1219.2 0.61 0.613 812.8 0.409 0.409 0.000 0.000 0.000 0.000
Tm 1025.1 0.579 0.59 683.4 0.39 0.393 0.000 0.000 0.000 0.000
Yb 1017.7 0.569 0.60 678.5 0.379 0.401 0.000 0.000 0.000 0.000
Lu 1009.0 0.58 0.61 672.7 0.389 0.408 0.000 0.002 0.000 0.000
Th 2455.1 0.66 0.59 1636.8 0.442 0.393 0.002 0.000 0.000 0.000
Sb 0.0142 0.014 0.000 0.000 0.000 0.000
B 0.0436 0.036 0.002 0.001 0.001 0.001
SO4 0.40268 0.2784 3.471 3.432 2.400 2.373
HCO3 0.00051 0.00057 0.009 0.009 0.010 0.010

2000), but the Se in Liaoyuan coalmine was higher than the
abundance value as well as another international study
(Seredin and Finkelman 2008; Taylor and Konhauser 2011).
The distribution of CaO, K2O, and Na2O in coal gangue,
coal slime, raw coal and coal ash were 12.5–65%, MgO and
Fe2O3 were 4–25%, while Al2O was highly abundant in be-
tween 35 and 75%, approximately (Fig. 4a). The mode of
occurrence for Fe is ferroselite and eskebornite (Dai et al.
2015), sulfides, micas, carbonates, silicates, oxides, sulfates,
phosphates (messelite) (Finkelman et al. 2018). The distribu-
tion CaO, K2O, and Na2O in both agriculture and mountain
soil were ranged 30–65% approximately, but the abundance in
mountain soil was high as compared to agriculture soil.
However, MgO and Fe2O3 in soil were ranged 8–25%,
Al 2 O 3 were 25–50%, approximately (Fig. 4b). While
assessing the distribution and abundance of major oxides in
soils and coals, it was found that the cations origin in the
Hancheng counties and countryside were due to geogenic
because of similar significance. To understand overall
Fig. 4 Distribution and abundance of anions cation in the environment
Environ Sci Pollut Res
prominence of major oxides and their evolution to the
environment, it was observed, that the major oxide of the
current study was high drastically high as compared to Kunli
et al. (2005) study conducted on the Permo-Carboniferous
coals of north China plate (Fig. 5).
Risk to environment
In the recent past, there have been abundantly increasing the
TTE in the soil, plants and water, which came from degraded
mineralized rocks and anthropogenic activates (Hussain et al.
2015; Kunli et al. 2005). Risk assessment related to coal and
coal wastes revealed that CaO and MnO caused moderate risk,
Fe2O3 and MgO caused considerable risk, while remaining all
elements caused very high risk to the environment. Whereas
in mountain soil, Al2O3, Fe2O3, K2O, MgO, TiO2, Cu, Li, Sr,
Ga, In, and Rb caused moderate risk (1 ≤ Cf < 3). Selenium,
Cr, Ni and Na2O caused considerable risk (3 ≤ Cf < 6), CaO,
Zn, and Cd caused very high risk to the environment, while
remain elements caused low risk to the environment (Cf < 1).
In agriculture soil, Al2O3, MgO, Na2O, TiO2, Se, Cr, Cu, Li,
Ni, Ga, Bi, and Gd were caused moderate risk, CaO and Cd
caused considerable risk, Zn caused very high risk, while the
remaining all the elements caused low risk to environment
(Table 3). The mountain and agriculture soil near the coal
mining area were almost similar in response to environmental
contamination and risk (Fig. 6), while comparably higher than
Banat et al. (2005); Khan et al. (2010).
In the Hancheng areas, Se contamination factor (Cf) in the
grass, ornamental plants, corn flour, wheat flour, and foodstuff
were 4.5, 11.4, 2.9, 2.8 and 2.9, respectively. It is obvious, that
grass and ornamental plants (growing in mining garden) were
at very high risk (Cf ≥ 6), while remaining food samples
batches were in moderate to considerable risk (1 ≤ Cf < 3).
In the countryside, Se contamination caused moderate risk to
grass, wheat and corn flour (Cf = 1.2, 2.01 and 1.4, respective-
ly). Arsenic in coal and coal wastes caused very high risk
(Cf ≥ 6), in soil (both mountain and agriculture soil) caused
low contamination and low risk (Cf < 1), which were below
the carcinogenic risk when compared with Ai et al. (2007) and
Li et al. (2012). Similarly, Bi in coal and coal caused severely-
extreme pollution and risk. In agriculture and mountain soil,
Bi caused moderate risk. In Hancheng County, Bi caused high
risk to grass and other food, while moderate risk to ornamental
plants, corn flour and in wheat flour as compared to the
countryside.
The U and Th in the coal and coal wastes caused high risk,
while in agriculture and mountain soil caused low risk
(Table 3). In Hancheng mining regions, Th in the grass, wheat
flour and in foodstuff caused considerable to high risk and
contamination, while in the countryside, it caused high risk
to foodstuff and moderate risk to corn flour and grass (Fig. 6).
It was reported that high concentration of radioactive and trace
Environ Sci Pollut Res

Fig. 5 Comparison of major

oxides in Permo-Carboniferous
coal with the previous study

elements in surrounding environment is extremely harmful to 2007). The appearance of overall environmental risk charac-
human health, water bodies and food crops (Ghose and Majee terization was, Coal and wastes > Plants > Food > Mountain

Fig. 6 Geochemical composition

and comparison of environmental
and health risk valuation in
surrounding areas

soil > Agriculture soil. By comparing the risk intensities in
between Hancheng and countryside, the Hancheng counties
are prone to high risk as compared to the countryside (Fig. 6).
Risk to humans
In Hancheng counties, arsenic concentration was more abun-
dant in coal and coal wastes, however, the soil has a similar
significance in both Hancheng and countryside. Similarly, ar-
senic in grass and ornamental plants of mining areas were
higher than the Chinese soil standard value, while As contents
in corn flour, wheat flour and in foodstuff of both Hancheng
counties and countryside were lower than the Chinese refer-
ence value (As = 0.5 for Cereal products & 0.2 grain and their
products mg/Kg−1) (GB 2012). By observing the impacts on
human beings, a total average daily intake of As by adults was
0.004 and children was 0.13 mgKg−1 bw/d in Hancheng,
while in the countryside it was 0.0001–0.0 mgKg−1 bw/d
adult-children, respectively. According to health risk assess-
ment, the HQ in Hancheng was 0.002–0.085 and in country-
side 0.00023–0.00025 for adult-children, respectively, which
is considerably lower than the As toxicity level of 0.5 mgKg−1
bw/d as well as cancer and non-cancer risk level (HQ < 1).
Currently, arsenic caused no cancer risk and non-cancer risk
while in future, the risk will be high as shown in Fig. 7 and
synergistic impacts (Arsenosis or other related health prob-
lems) will be higher in children than adults. In 2005,
Chinese government campaigned to ban all those coalmines
where As concentration is greater than 0.1 mgKg−1 (Chen
et al. 2014; Jack et al. 2003; Sun et al. 2014). The policy
was flopped due to energy crises and coalmines still a have a
role in endemic arsenicosis, skin cancer, lung cancer, black
foot disease, liver, and bladder cancer in some of the regions
in China (Tseng et al. 2002; Yu et al. 2007).
Fig. 7 Evaluation of carcinogenic
and Keshan and Kashin-Beck
disease risk
Environ Sci Pollut Res
The average Se contents in coal gangue, coal slime, raw
coal and coal ash were considerably higher than the threshold
value of China (Ren et al. 2006; Tang and Huang 2004), USA
(Finkelman 1993) as well as from normalized earth crust
abundance (0.05 mg/Kg) (Siyue and Zhang 2010). The ob-
served Se contents in agriculture and mountain soil were 3.5-
fold and 2.3-fold (respectively) higher than the China soil
standard (0.29 mgKg−1) and earth crust abundance value
(GB 2012; JeffersonLab 2007; Kennish 2000). By estimating
Se intake, ADI in Hancheng counties were 0.0044–0.0038
mgKg−1 bw/d adult-children respectively, while in country-
side 0.00049–0.00053 mgKg−1 bw/d adult-children, respec-
tively, which considerably lower than the optimum dose of
0.06–0.075 mgKg−1 bw/d (Hurst et al. 2010; Sun et al.
2016). The current study claimed the Se risk (due to low
availability to human) would be higher in the countryside
compared to Hancheng (Fig. 7). In the study areas, rock for-
mation belongs to Permo-Carboniferous Permian strata which
have low Se contents than the optimum level, which influ-
ences asthma and especially Keshan and Kashin-beck disease
(cardiomyopathy) (Cai et al. 2015; Chen 2012; Luo 2011; Zhu
et al. 2004).
In Hancheng counties, the ADI of Cr was 0.055–0.059, Cd
0.001–0.004, Ni 0.018–13.9, Pb 0.05–0.01, Fe 5.9–44, V
0.012–0.28, Co 0.004–0.0001, Mn 0.200–0.005 etc. adult-
children, respectively. While in countryside, ADI of Cr was
0.005–0.005, Cd 0.00, Ni 0.002–0.002, Pb 0.001–0.001, Fe
0.33–0.35, V 0.00, Co 0.00 and Mn 0.12–0.13 etc. adult-chil-
dren, respectively. Among the radioactive elements, ADI of U
was 0.001–0.002, Bi 0.0001–0.0 and Th 0.002–0.0 mgKg−1
bw/d by adult-children, respectively, in the Hancheng
counties, while in the countryside, the ADI of U, Bi and Th
were negligible (0.0 mgKg−1 bw/d) (Table 3). Among all the
trace elements, the majority were higher than Chinese refer-
ence standard for food (GB 2012) as well as previous studies
Environ Sci Pollut Res
(Ren et al. 2006, Tang and Huang 2004). By evaluating health
risk (at Hancheng regions), Cr, Cu, Mn, Pb, Ti, Cd, Co, Th,
Fe, Al and Mo causing non-cancer risk to a human with high
morbidity in Children than an adult. However, As, Bi and
other remaining elements causing neither cancer nor non-
cancer risk to humans (Fig. 6).
Mitigation options
It is obvious, that coal mining creates a lot of problems includ-
ing soil, water and air pollution, food contamination and land
degradation. By removing these problems through natural
ways, the study proposed the afforestation option. For this
purposes, the soil organic carbons (SOC) were determined in
the mountain and agriculture soil of Hancheng counties. The
SOC in mountain soil were ranged 7.5–26.1 (average 14.99),
while in agriculture soil were 14–50 (average 25.03) ton/ha,
respectively. The current stock of SOC in agriculture and
mountain soil were 32-fold and 53-fold (respectively) lower
than Cai et al. (2015). The lower SOC in mountain soil is due
to either degradation of mountain soil or dumping of the
mountain soil through mining wastes. By growing local tree’s
forest and green grasses in the mining areas will considerably
improve the SOC in soil environment and surely minimize the
atmospheric carbon and TTE (Chojnacka et al. 2005).
Besides the afforestation, a sustainable utilization is also
efficient option to maintain the new products and reuse coal
wastes in cement framework, bricks, land reclamation, filling
mine trench, road construction, and economic benefit areas. It
was reported, that utilization of wastes from coal mining and
washing were 24.7% and 57.4% in 1999 and 2003 respective-
ly, while in the USA and Britain it was more than 90%
(CCICED 2009; Zhang et al. 2008). However, in 2009,
Teifa coalfield utilize 37% of coal wastes to produce 1.6 bil-
lion brick account for 49.43 million RMB/year (Fan et al.
2013). Utilization not only reduces the coal wastes but also
reduced elemental contamination and environmental risk.
Conclusions
The study concluded that coal gangue, coal slime, raw coal
and coal ash of the current study have a significantly high
level of elemental pollutants than the previous study of
China and USA. However, the elemental pollutants in agricul-
ture and mountain soil have a similar significance, which is
comparably higher than the Chinese soil standard. The ele-
mental contents in the grass and ornamental plants of
Hancheng area were higher than the countryside. The magni-
tude of elements in corn, wheat, and other foodstuff was com-
parably higher in Hancheng than the countryside. The ground-
water contamination in mining area and countryside were be-
low the WHO water quality standard. The decreasing level of
elements in coal and coal wastes were; current study > China
(coal and coal waste) > USA (coal and coal waste), while in
soil; mountain soil > Agriculture soil, in food & plants;
Hancheng county > countryside, while in water;
WHO>Hancheng> countryside.
In Hancheng County, a series health risk were observed
related to TTE. The ADI (mgKg−1bw/d) of Se, As, Cr, Cd,
Ni, Pb etc., were 0.004–0.0038, 0.004–0.13, 0.055–0.06,
0.001–0.004, 0.018–13.91, 0.05–0.001 adult-children respec-
tively. While in countryside, ADI of Se 0.0005–0.00053, As
0.0004–0.0045, Cr 0.005–0.0052, Cd 0.00012–0.00012, Ni
0.002–0.0023, and Pb 0.001–0.0014 in mgKg−1 bw/d adult-
children, respectively. In both areas, selenium was below the
optimum level of 0.06–0.075 mgKg−1 bw/d. The Se and As
(carcinogenic) risk were higher to children than adults in both
Hancheng and countryside. Similarly, Cr, Cu, Mn, Pb, Ti, Cd,
Co, Th, Fe, Al, and Mo caused non-cancer risk, while As, Ba,
Sr, U, Sb, and B causing neither cancer nor non-cancer risk to
humans. In both areas, the health risk was higher, but children
are more exposed to risk than adults are.
Similar, the environmental risks in mining area were high
as compared to the countryside. The integrated risk trend at
Hancheng was Coal & coal wastes caused high risk, food &
plants faced moderate-high risk, while mountain and agricul-
ture soil are prone to low-considerable rick. The pollution in
the study areas was high which is dangerous to human health
and environment. The study suggested that coal wastes utili-
zation, safely dumping and post-mining plantation (local
plants species) would surely minimize the extent of contami-
nants and environmental risk to greater extent.
Acknowledgments The National Basic Research Program of China
(Grant No. 2014CB238906), the National Natural Science Foundation
of China (Grant Nos. 41172310 and 41472322) and CAS-TWAS Ph.D.
fellowship, supported this study. We are grateful to Mr. Gao Bolin and the
workers of Liaoyuan Coalmine, Hancheng coal mining Bureau, for their
permit and help us to collect the samples in their Coalmine field. The
authors are highly grateful to local guileless residents of Hancheng,
Shaanxi, for them allow us to go to their homes and farming fields to
collect samples of food, drinking water and soil.
Compliance with ethical standards
Conflict of interest The authors have no conflict of interest.
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