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Marine Pollution Bulletin 146 (2019) 893–899

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Marine Pollution Bulletin


journal homepage: www.elsevier.com/locate/marpolbul

Baseline

Distribution and ecological risks of heavy metals in river sediments and T


overlying water in typical mining areas of China
⁎ ⁎
Ming Chen , Fengguo Li , Meixia Tao, Lanwen Hu, Yanli Shi, Youcun Liu
Jiangxi Key Laboratory of Mining & Metallurgy Environmental Pollution Control, Jiangxi University of Science and Technology, No.156, Hakka Ave, Ganzhou, Jiangxi
341000, PR China

A R T I C LE I N FO A B S T R A C T

Keywords: The distribution and potential ecological risks of eight heavy metal elements including Cr, Cu, Zn, As, Cd, Pb, Hg,
Metal mines and W in the overlying water and sediments of the Taojiang River were investigated. The concentrations of eight
Taojiang river heavy metals were measured by inductively coupled plasma mass spectrometer (ICP-MS), and the distribution
Overlying water coefficients were exploited to estimate the partition coefficient between overlying water and sediment phases,
Sediments
which were subsequently used to establish the potential ecological risk of heavy metals in sediments. The results
Heavy metals
revealed that the contents of Pb (33.47 μg·L−1), Cd (153.03 μg·L−1) and Hg (1.12 μg·L−1) in the water samples
Ecological risk
exceeded threshold values as proposed by the limits of the class III environmental quality standard. On the other
hand, Cr, Cu, Zn, As, and Pb within sediments were below threshold limits.

In recent years, most socio-economy, urban and industrial activities sediments. For instance, the distribution, migration and transformation
generate tons of pollutants (solid, liquid and gas) which then enter into processes of Hg, Cr, Cu, Zn, As. within the Yangtze estuary, Pearl river,
various types of environmental ecosystems. Among these pollutants, Yongming river and Chao-hu lake were widely explored (Liu et al.,
heavy metals are the most important components for some of these 2007; Gong et al., 2017; Tang et al., 2017; Li et al., 2019). However,
industrial wastes. However, those industrial wastes which contain high due to the high toxicity, high potential accumulation effect, non-bio-
level of heavy metal pollutants were discharged into environments degradability and long-term existence within the food chain (Li et al.,
without proper treatments or recovery operations. A large number of 2014Ai et al., 2018), these heavy metals have become important pol-
heavy metals accompanied with solid or liquid wastes are subsequently lution issues that require urgent, extensive and drastic measures.
discharged into the natural ecosystems, predominantly river bodies, can In recent years, due to pollution treaties and policies signed on by
result in serious negative effects on water toxicity, eutrophication and developed countries, the ecological safety of heavy metals has aroused
destruction of aquatic lives. Besides industries, significant concentra- extensive attention. China is currently one of the major producer,
tions of heavy metals were reported to have come from non-point consumer and exporter of a number of heavy metals including tungsten,
sources, mining activities, agriculture fields, and atmospheric deposi- which may result in high potentials to cause severe pollution problems
tion (Yang et al., 2015; Zhang et al., 2017). What is worth to mention is if left unattended (Varol, 2011; Koutsospyros et al., 2011). Conse-
that livestock manure, poultry manure, pesticides and fertilizers also quently, a substantial number of government departments and agencies
contain cadmium, mercury, copper, zinc and other heavy metals upon across the world have funded studies on the ecotoxicity and toxic me-
the river (Chai et al., 2012; Chen et al., 2015). Therefore, improper chanism of heavy metals (particularly tungsten) in order to promote the
treatment of such wastes to recover or remove heavy metals will sub- formulation of relevant standards and regulations (Gao and Chen, 2012;
sequently enter into river bodies, which then can be subject to migra- Dietrich et al., 2018). As indicated above, China is not exception so far
tion and transformation processes, including adsorption, desorption, as heavy metal pollution is concerned. For instance, heavy metal
precipitation, and biological absorption, in waterbodies, sediments and mining is very prevalent within the Taojiang River basin located in
organisms. Furthermore, heavy metals can be accumulated in organ- Gannan County, Jiangxi province of China.
isms through food chain circulation, threatening human health (Zhang In the early periods of a decommissioned mine, heavy metals in-
et al., 2013). A number of studies have established extensive dynamics cluding lead, cadmium, arsenic, copper and zinc are often washed off
and relationship of these heavy metals between waterbodies and from wastewater and slag into surrounding river by rain runoff leading


Corresponding authors.
E-mail addresses: jxlgdx@qq.com (M. Chen), 792512371@qq.com (F. Li).

https://doi.org/10.1016/j.marpolbul.2019.07.029
Received 31 March 2019; Received in revised form 9 July 2019; Accepted 12 July 2019
Available online 26 July 2019
0025-326X/ © 2019 Elsevier Ltd. All rights reserved.
M. Chen, et al. Marine Pollution Bulletin 146 (2019) 893–899

to serious pollution problems in waterbodies and associated ecosystems estuary were conducted in rainy season (Jun) from 2017. Twelve (12)
(Jing et al., 2016; Liu et al., 2017; Mohammadreza et al., 2018). For samples points were established in the estuarine area (Fig. 1). Twelve
instance, previous studies showed that the aquatics lives within the sampling sites were arranged with full consideration of domestic water
southern part of Jiangxi province are heavily destroyed. Taojiang River intakes, wastewater discharges, hydrology and river bed tributaries in
is one of the headwaters of the Ganjiang River and is also on the path of the sampling section. Water samples were collected using a 500 mL
the construction of the Jiangxi and Guangdong canals planned by the polyethylene plastic bottle, which was rinsed 3–4 times using the cor-
state, which makes the pollution control of the Taojiang River basin responding water before samples were taken. The pH of the water was
particularly essential. analyzed on site using a portable pH meter, followed by addition of
Therefore, this research proposed the Quannan section of the proper amount of nitric acid until pH ≤ 2. The sediments were col-
Taojiang River as the research site, and explored the distribution lected by multi-point mixing method. A stainless-steel grab sampler was
characteristics and potential ecological risks of eight heavy metal ele- used to collect sediments in the depth of 0–20 cm beneath the sediment-
ments including Cr, Cu, Zn, As, Cd, Pb, Hg and W in the overlying water water interface, then samples were stored on ice bag until being re-
and sediments. The proposed studies on the transport and biochemical turned to the laboratory as soon as possible.
transformation processes of the heavy metals in the water-sediment Water samples were filtered using filter membrane (0.45 μm) and
interface of Taojiang River are expected to (1) provide theoretical heavy metal contents were measured using an inductively coupled
support and scientific basis for the pollution control project of Taojiang plasma mass spectrometry (ICP-MS Agilent 8800) (Bednar et al., 2010),
River; (2) evolve ecological risk management support/scheme of the and the standard sample (GSB07) provided by the Ministry of En-
river basin as a reference to secure fact for the design and construction vironmental Protection Standard Sample Research Institute was used
of the Ganyue Canal. for quality control. Three parallel Water samples were analyzed, and
Sampling campaigns to collect sediment in the Taojiang River the results showed that the RSD of all elements was < 10%, which was

Fig. 1. Location of sampling sites.

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M. Chen, et al. Marine Pollution Bulletin 146 (2019) 893–899

Table 1 Cs
Kd =
Grading standards of potential ecological risk. Cw (1)
Risk level Slight Medium Strong Very strong Extremely strong −1 −1
where, Cs/(mg·kg ) and CW/(mg·L ) are the contents of heavy metals
in the solid phase (sediment) and liquid phase (dissolution), respec-
Er < 30 30–60 60–120 120–240 > 240
RI < 100 100–200 200–400 > 400 tively, when the system reaches equilibrium.
The potential ecological risk index method is a biological method
proposed by Hankinson, which is employed to evaluate the potential
in accordance with the requirements. According to the experimental risk of heavy metal pollution in soils and sediments, based on com-
results, the recoveries of various heavy metals in the analysis were prehensively considerations of various factors, such as the synergy of
within the allowable range of national standard reference materials. various heavy metal elements, toxicology, heavy metals pollution, and
The reagents used throughout the analytical process were all grade- environmental sensitivity to heavy metals (Han et al., 2018). Quanti-
grade pure, and deionized water was used. tative classification of the extent of potential ecological hazards of
The sediment samples were naturally dried, and the impurities such heavy metals' pollution, which is widely used in environmental impact
as gravel, shells, animals and plant residues were removed. The sedi- assessment, was conducted not only to evaluate the ecological risk of
ment samples were grounded using an agate mortar and sieved through sediments by individual heavy metals, but also to investigate the
a 200-mesh nylon sieve and stored in a polyethylene bottle. The sedi- comprehensive ecological risk of various heavy metals on sediments.
ment sample was used for chemical analysis, which consists of digesting Both expressions are as follows:
aliquots of 5 g by adding 5 mL a solution 4:1 of HNO3:HClO4 to the
Csi
samples during 3 h at 140 °C (Yap and Pang, 2011). After the samples RI = ∑ Eri = ∑ Tri × Cri = ∑ Tri ×
were cooled, the content of each tube was diluted to 25 ml with double Cbi (2)
distilled water. The digested samples were then filtered. The con- i
where, Cs is the measured value (mg·kg ̇
−1
) of ith heavy metal in the
centrations of Cr, Cu, Zn, As, Cd, Pb, Hg, and W were determined for sediment, and Cbi is the background value of element i in the sediment
each sample using ICP-MS, with sediment standard substance (GBW- environment. In this study, the background values of heavy metals in
07309) was used for quality control during the analysis process. Three the sediments of the Yangtze River system were selected as references.
parallel samples were set up and the reference material recoveries of Cri is the pollution factor of the ith heavy metal and Tri is the toxicity
the sediments were basically between 89% and 109%, with relative coefficient of the ith heavy metal, which reflects the toxicity of heavy
standard deviations within 10%. The quality of the analytical procedure metals and the sensitivity of water bodies to heavy metals. The toxicity
was assessed based on the recovery measurements of China's national coefficients of Cr, As, Cd, Cu, Zn, Hg and Pb, were 2, 10, 30, 5, 1, 15,
geography (HJ/T166-2004). All the glasswares (bottles, tubes, etc.) and 5 (Wang et al., 2015; Umbonal et al., 2016), respectively. There is
used in this study were acid washed by 10% nitric acid (HNO3) for at little data available regarding the toxicity coefficient of tungsten;
least two days, and then soaked and rinsed with deionized water therefore, this study did not evaluate the potential ecological risk as-
(Mohamed et al., 2019). sociated with tungsten. As a potential ecological risk factor for heavy
The partition coefficient of a pollutant in the particulate-water metals in sediment, Eri is a comprehensive potential ecological risk
phases refers to the ratio of concentrations of this pollutant in these two index for multiple heavy metals in sediment. The specific grading
phases at equilibrium (Zhao et al., 2015). The distribution coefficient, standards are shown in Table 1 (Han et al., 2018).
which was used as an important physicochemical characteristic para- The contents of heavy metals in the overlying water bodies are
meter to describe the behavior of pollutants in the water environment, within the limits of the class I and III environmental quality standards
comprehensively reflects the migration ability of the pollutants be- in the river (Table 2). The average mean values and spatial variations of
tween the water phase and the particulate matter phase and potential eight heavy metals in water samples at 12 sampling sites were shown in
ecological hazards that may exist. The conversion of heavy metal pol- Fig. 2. As shown in Table 2, the contents of As in all water samples were
lutants from the liquid to the solid phase mainly depends on the ad- lower than the class I environmental quality standard in the river, and
sorption effect produced by sediments. The adsorption of heavy metals the contents of W at all sampling sites were lower than the Russian
in sediments and suspended matter is achieved through ion exchange, fishery river and lake water quality standards. The concentrations of Cr,
exclusive adsorption, non-exclusive adsorption, and complex adsorp- Cu and Zn were between the class I and the class III environmental
tion (Huang et al., 2018). The sediment is a carrier of heavy metals in quality standard in the Taojiang river. Additionally, the concentrations
rivers, influencing the adsorption of heavy metals. Meanwhile, due to of Pb, Cd, and Hg exceeded the class III environmental quality standard
the physical and chemical conditions at the water-sediment interface, values by 8%, 33%, and 67%, respectively, indicating that all of these
the heavy metals adsorbed by the sediments can be released again into metals exceeded the standards with Hg which poses the most serious
the overlying water, causing secondary water pollution. This study, the threat in particular. The Hg contents in the overlying water at four
distribution coefficient was employed to qualitatively analyze the sampling points (Nanjing Section, Zhong Tan section, Longxi Reservoir
ecological hazards of heavy metals in water. The following expression and the Tong Zi-gang section) were below the class III environmental
described the distribution coefficient: quality standard. In addition, the Hg content in the water of the Longxi

Table 2
Contents of heavy metals in the overlying water of the Taojiang River (μg·L−1).
Heavy metal element

Cr As Cd Cu Zn Hg Pb Wa

The class I environmental quality standard in the river 10 50 1 10 50 0.05 10 8


The class III environmental quality standard in the river 50 50 5 1000 1000 0.1 50
Water sample heavy metal content range (N = 12) 0.03–24.3 0.7–12.5 0.2–178 38.1–191 54.9–159 0.01–4.5 0.7–257 0.01–1.25
Average 10.5 3.24 19.4 153.03 101.2 1.12 33.47 0.35
More than class I standard limit/% 67 0 58 100 100 83 33 0
More than class III standard limit/% 0 0 33 0 0 67 8

a
Tungsten's standard limits refer to the Russian fishery rivers and lakes water quality standards.

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M. Chen, et al. Marine Pollution Bulletin 146 (2019) 893–899

Fig. 2. Profile of heavy metals concentrations in overlying water of the Taojiang River.

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M. Chen, et al. Marine Pollution Bulletin 146 (2019) 893–899

Table 3
Heavy metals contents of river sediment (mg.kg−1).
Heavy metal element

Cr Cu Zn As Cd Hg Pb W

TEC 43.4 31.6 121 9.79 0.99 0.18 35.8 –


Background values 82a 35a 78a 9.6a 0.25a 0.08a 27a 1.8a
Heavy metal content range 7.02–80.4 23.53–55.6 44.94–212 6.26–27.2 0.2–65.8 0.07–6.6 8.33–107.2 4.42–54.5
Average value 38.94 43.09 156.8 15.95 9.09 1.7 48.72 17.56
Percentage of TEC limit exceeded/% 33 83 92 92 67 92 83 –
Percentage over background value/% 0 83 92 92 92 92 83 1

a
Background values of heavy metals in the sediments of the Yangtze River system were selected; no studies have investigated the TEC values of tungsten, so no
analysis was performed.

Reservoir was lowest, which was primarily because it is a reservoir area and the Dajishan is greatly affected by the Dajishan tungsten mine
and protected drinking water source of a class I. Therefore, there is (Chen et al., 2015). Except for the source of Taojiang, the Zn, As and Pb
relatively less human-induced pollution. The contents of Hg in the other contents of the other 11 sampling points exceeded the threshold values,
eight sampling sites exceeded the standard, with Xiao-mu river had the which can be explained by the relatively rich background mineral re-
highest value which can be explained by the influence from domestic sources at these areas. The Cd contents in the Dajishan Section and
refuse, domestic wastewater and aquaculture development in the sur- Zhongtan Section greatly exceeded the threshold value, which were
rounding residential areas. The Cd contents in the overlying water of mainly affected by aquaculture and mining. The maximum content of
Dajishan, Nanting, Zhongtan and Chenglong sections, were obviously Pb was attained in Tongzigang, which was primarily affected by ex-
higher than the standard with Zhongtan being the highest. The averages haust emissions from transportation. Moreover, Hg and W were rela-
of other heavy metal elements were within the class III environmental tively high in the Dajishan section and Chenglong section. The highest
quality standards. content of W in the Dajishan section was mainly because of mining of
The concentrations and pollution levels and the spatial distributions the Dajishan tungsten mine. When combined with the comparison of
of the investigated eight heavy metals in sediments of the studied 12 the contents of the eight heavy metals with threshold values and TEC
sites were shown in Table 3, and Fig. 3, respectively. As shown in values, the pollution status of W in the study area was most serious,
Table 3, the Cr content did not exceed the threshold value, but the indicating that it was directly affected by mining and smelting at the
seven other heavy metals at most sampling points exceeded the Dajishan tungsten mine. In addition, Zn, As and Hg, may be due to the
threshold values. When compared with the threshold effect con- development of tungsten mining, smelting, aquaculture and fruit in-
centration (TEC), the Cr exceeded the standard value by the lowest dustry. Cr is the least contaminated of the eight heavy metals.
amount, while Zn, As, and Hg exceeded the limit by the greatest values. The distribution coefficients of eight heavy metals between river
Because of a lack of research regarding the TEC value of W, compar- water and sediments were shown in Fig. 4. The log Kp values of Cr, As,
isons between W and TEC were not made. The concentrations of the Cd, Cu, Zn, Hg, Pb, and W were 3.9 ± 0.91, 3.84 ± 0.38,
eight heavy metals in the source of the Taojiang river were the lowest 2.99 ± 0.61, 2.47 ± 0.26, 3.19 ± 0.21, 3.67 ± 0.91, 3.7 ± 0.67
(Fig. 3), mainly because it was less affected by man-made pollution. The and 4.93 ± 0.66, respectively, indicating that the sediments have a
highest concentration of Cr is from the Jindong section, possibly be- strong ability to accumulate heavy metals. Because of the different
cause the development of aquaculture at the sampling sites, and the physical and chemical properties among heavy metals, the distribution
discharge of pesticides and fertilizers and aquaculture wastewater in- coefficients of heavy metals in the water-solid phases differed (Deng
crease the chromium level. The concentrations of Cu in Reshui Village, et al., 2016). The order of the heavy metals by sediments was W >
Dajishan, Zhongtan and Jinlong sections greatly exceeded the threshold Cr > As > Pb > Hg > Zn > Cd > Cu in this paper. Among these,
value. It may be related to the development of farms or aquaculture, particulates had the highest adsorption capacity for W and posed the
greatest risk. Moreover, the partition coefficient of W was about one
order of magnitude higher than that of Cr, As, Pb, Hg and Zn wand two
orders of magnitude higher than Cd and Cu. Based on a study conducted
by Jinn et al. (1992), the majority of heavy metal ions in river water are

Fig. 3. Spatial distribution of heavy metals at the sampling point. Fig. 4. Partition coefficient of heavy metal elements in river sediments.

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Table 4 wastewater slag from smelting activities. Zhongtan is close to fishery


Ecological risk of heavy metals in river sediments. breeding areas and forest farms, and is affected by human aquaculture
Er RI and cutting activities. The Chenglong section is adjacent to a brick
factory, which discharges a large amount of domestic refuse into the
Cr Cu Zn As Cd Hg Pb water surface as well as air pollution into the region. Overall, the results
indicate that there is a strong ecological risk in the study area.
1 0.2 3.4 0.6 6.5 24.0 13.1 1.5 49.3
2 0.7 7.3 2.1 12.8 84.0 165.0 6.8 278.7 In this study, the concentrations and distributions of 8 heavy metals
3 0.7 7.9 2.0 12.2 2904.0 1237.5 7.7 4172.0 in the overlying water and sediments of 12 sampling sites along the
4 0.9 6.0 2.0 28.3 136.8 393.8 6.8 574.6 Taojiang River were investigated. Based on our results, the following
5 1.2 5.7 1.8 13.2 136.8 311.3 7.3 477.3 conclusions were made:
6 0.8 7.0 2.0 14.1 7896.0 41.3 4.8 7966.0
7 0.6 5.3 2.5 19.7 64.8 202.5 8.6 303.9
8 1.1 6.2 2.5 19.7 278.4 202.5 19.9 530.3 (1) The contents of As in water samples of all the 12 sites at Quannan
9 1.6 6.1 2.3 17.0 278.4 183.8 14.4 503.6 Section of the Taojiang River were lower than the threshold value
10 0.8 4.5 1.6 13.2 67.2 52.5 8.7 148.4 suggested in the class I environmental quality standard (China),
11 2.0 7.7 2.7 23.5 518.4 161.3 10.1 725.6
whereas the Cr levels were observably below the class III environ-
12 0.9 6.8 2.1 19.0 694.8 858.8 11.7 1594.0
Slightly polluting 1 1 1 1 0.08 0.08 1 0.08
mental quality standard (China). In addition, the Cu and Zn levels
percentage/% were within the class I and class III environmental quality stan-
Medium pollution 0 0 0 0 0.00 0.17 0 0.08 dards. The concentrations of all the studied heavy metals, with an
percentage/% exception of Cr, in the sediments of 12 sampling sites were higher
Strong pollution 0 0 0 0 0.25 0.00 0 0.17
than the values for Yangtze River. Particularly, Pb, Cd, and Hg
percentage/%
Very strong pollution 0 0 0 0 0.17 0.42 0 0.67 posed the greatest threat to the environment. Notably, W con-
percentage/% centration exceeded threshold value at all 12 sampling points.
Extremely strong 0 0 0 0 0.50 0.33 0 (2) The estimated distribution coefficients revealed that the sequence
pollution
of heavy metal enrichment in the Taojiang rivers was
percentage/%
W > Cr > As > Pb > Hg > Zn > Cd > Cu, and the adsorp-
tion capacity for W was also the highest.
adsorbed, which is related to the characteristics of suspended particles (3) Based on Hakanson's potential ecological risk assessment, the po-
with small particle size, large specific surface area, many surface ad- tential ecological risk degree of heavy metals in sediments from the
sorption sites, and more reactive functional groups. The logKp value of 12 sampling sites was Cd > Hg > As > Pb > Cu > Zn > Cr.
heavy metals in the Yellow river was significantly lower than that re- Among the 12 sampling points, Taojiang River was the only site
ported for other rivers because of the influence of sand and high particle that posed slight pollution indicted by the RI value of < 100 There
strength. Tang found that Cr, Pb, Hg, and Zn in river sediments pri- were strong ecological risks at all other sampling sites in the study
marily exist in a residue state, resulting in a large partition coefficient in area.
the sediment-overlying water, which is consistent with the results of the (4) The W contents in the overlying waters of the 12 sampling points
present study (Tang et al., 2015). Suspended particles in the river en- were lower than the Russian river standards for fishery and river
vironment are the major carriers of heavy metals and play important water quality, whereas the W contents in the sediments exceeded
roles in their migration and transformation. the threshold value. The value of W was the highest among the
As shown in Table 4, the potential ecological risk values of seven water-sediment distribution coefficients, causing the greatest risk
heavy metals in the river sediments from the 12 sampling sites was among the studied metals.
Cd > Hg > As > Pb > Cu > Zn > Cr. Although the contents of Cd
and Hg were not high, their ecological risk were highest because of the Credit authorship contribution statement
strong toxicity coefficient. The ecological risk (Er) values of Cr, Cu, Zn,
As, and Pb in the sediments at the 12 sampling sites were all < 30, Ming Chen: Funding acquisition, Project administration,
indicating that the pollutions of these elements are low. Cd in Taojiang Supervision, Validation. Writing - review & editing. Fengguo Li:
was the only element with the Er value < 30, which suggested that it Conceptualization, Investigation, Formal analysis, Writing - original
was in a slight pollution level. The Er values of Cd in the remaining 11 draft, Writing - review & editing. Meixia Tao: Data curation, Writing -
sampling points are all > 60, and they are in strong, stronger, or ex- review & editing. Lanwen Hu: Resources, Writing - review & editing.
tremely strong pollution levels. The most serious pollution was in the Yanli Shi: Investigation, Writing - review & editing. Youcun Liu:
Dajishan River and Zhongtan, which have mainly been affected by Funding acquisition, Writing - review & editing.
tungsten mining and smelting and aquaculture. The Er value of Hg at
the Taojiang source was < 30, indicating slight pollution, while the Acknowledgements
remaining 11 sampling sites were polluted to a certain extent. The
Dajishan section and Chenglong section had the strongest pollution This study was supported by a project grant from the National
levels, primarily as a result of mining, aquaculture, urban household Natural Science Foundation of China (Grant No. 51664025, 41861002).
domestic waste and wastewater, as well as development of the fruit We thank Kara Bogus, PhD, from Liwen Bianji (Edanz Group China)
industry. (www.liwenbianji.cn/ac) for editing the English text of a draft of this
Among the 12 sampling points, only the RI value at the source of the manuscript. We thank PHILIP ANTWI, PhD, from Jiangxi University of
Taojiang was < 100, indicating slight pollution. The low value was Science and Technology (E-mail: kobbyiean@yahoo.co.uk) for critically
mainly because the impact of human activities on this section of river is reading and revising the manuscript.
relatively small. The Xiaomu river had an RI value of < 200, indicating
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