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The impact of natural weathering and mining on heavy metal

accumulation in the karst areas of the Pearl River Basin, China

Weihua Wu, Shuyi Qu, Werner Nel, Junfeng Ji

PII: S0048-9697(20)32997-1
DOI: https://doi.org/10.1016/j.scitotenv.2020.139480
Reference: STOTEN 139480

To appear in: Science of the Total Environment

Received date: 31 March 2020

Revised date: 14 May 2020
Accepted date: 14 May 2020

Please cite this article as: W. Wu, S. Qu, W. Nel, et al., The impact of natural weathering
and mining on heavy metal accumulation in the karst areas of the Pearl River Basin, China,
Science of the Total Environment (2020), https://doi.org/10.1016/j.scitotenv.2020.139480

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© 2020 Published by Elsevier.

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The impact of natural weathering and mining on heavy

metal accumulation in the karst areas of the Pearl River

Basin, China
Weihua Wu a*, Shuyi Qu a, Werner Nel b, Junfeng, Ji a

a
Key Laboratory of Surficial Geochemistry, Ministry of Education, School of Earth Sciences and

Engineering, Nanjing University, Nanjing 210023, PR China

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b
Dept. of Geography and Environmental Science, University of Fort Hare, Alice 5700, South Africa

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Abstract: This paper presents the heavy metal content in river water, sediment and
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bedrock in the karst area of the Pearl River Basin in China to evaluate the long-term
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impact of natural weathering and mining on the ecological environment. The results

show that Cd and As is 2–3 times more enriched within the carbonate bedrock of the
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Pearl River Basin compared to the upper continental crust (UCC), which is indicative
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of high geological background values. Within the river water of the upper reaches of
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the Diaojiang River (a tributary of the Pearl River), which flows through the Dachang

super-large orefield, Zn, As, Cd and Sb exceeds the environmental quality standards

for surface water (WQS) by more than an order of magnitude. Among these, Zn and

Cd sharply decreases to within the WQS in the lower reaches of the river, but the

content of As and Sb in the estuary is still several times higher than the WQS. Cd in

the sediments of the small carbonate watersheds and in the mainstream of the Pearl

River only present a low-moderate ecological risk. In contrast, severe heavy metal

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pollution of the sediments of the Diaojiang River Basin is observed. Even in the lower

reaches, remote from the mining area, the content of Pb, Zn, As and Cd in the

sediments is still two orders of magnitude higher than the soil background values. The

content of both Cd and As presents a very high ecological risk, indicating that under

the cumulative effect of high geological background values and mining, full

restoration of the ecological environment in the Diaojiang River Basin is a complex

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and long-term process.

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Keywords: Small carbonate watersheds; Diaojiang River; bedrock, river water,
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sediment; heavy metal elements; ecological risk
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1. Introduction

Heavy metal pollution in the farmlands of southwest China is severe due to

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geological and anthropogenic sources of metals and the excess rate of 8 inorganic
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pollutants, namely, cadmium (Cd), mercury (Hg), arsenic (As), copper (Cu), lead (Pb),
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chromium (Cr), zinc (Zn) and nickel (Ni) reaches 0.9–7.0% (Wong et al., 2002; Feng

and Qiu, 2008; Zhang et al., 2010, 2014; MEE and MNR, 2014; Chen et al., 2015; Liu

et al., 2019). Over 80% of the heavy metal content in the soil of the karst area of

southwest China are caused by high geological background values and pedogenesis

(China Geological Survey, 2015). However, human activities are also an important

cause of excessive levels of heavy metals in the environment. Waste materials emitted

from industrial activities such as mining, smelting, metallurgy and electroplating,

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sewage irrigation, irrational use of fertilizers in agriculture and livestock have caused

or exacerbated heavy metal pollution in cultivated land (Nriagu, 1996; Alloway et al.,

2013; Li et al., 2014). In the mining areas, metals in 33.4% of the soils exceed the

standard, and the main inorganic pollutants are identified as Cd, As, Zn and Pb (MEE

and MNR, 2014). In addition, the karst region of southwest China is also one of the

areas significantly affected by acid rain (e.g., Larssen et al., 2006; MEE, 2019).

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Studies have shown that acid rain not only changes the chemical composition, metal

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mobility and speciation of the soil (Wang et al., 2009; Li et al., 2015; Moharami and
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Jalali, 2015), but also affects the chemical weathering rate (Liu et al., 2016; Zheng et
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al., 2017; Huang et al., 2019; Zhu et al., 2020).
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Carbonate rocks are the dominant lithology in the upper and middle reaches of

the Pearl River Basin of China. The bedrock itself has low heavy metal content except
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for Cd and As (Wang et al., 2012; Qu et al., 2020), but the weathering rate of
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carbonate rocks is more than an order of magnitude higher than that of silicate rocks
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(Meybeck, 1987; Liu et al., 2011). As the carbonate rock weathers into soil, heavy

metal elements are rapidly released. It then migrates and enriches in the environment

through precipitation, adsorption and complexation. The weathering of carbonate rock

is one of the major causes of metal pollution in the karst areas of southwest China

(e.g., Ni et al., 2009; Zhao et al., 2015; Qu et al., 2020; Wen et al., 2020). In addition,

the black rock series (a combination of dark-black siliceous rocks, carbonate rocks,

mudstones and their corresponding metamorphic rocks, which contain more than 1%

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organic carbon and sulfide) are widely distributed in the south and southwest of China

(Fan and Zhang, 2004). The black rock series has formed some large/super-large

deposits and is an important source of metals/metalloids such as U, Mo, Ni, Mn, V,

Hg, Sb, Pb, Zn, W, Pt, Pd and Au (Fan and Zhang, 2004). The soil formed by the

black rock series contains a variety of toxic elements and these elements are a

potential source of heavy metal pollution (e.g., Peng et al., 2004; Tuttle et al., 2009;

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Park et al., 2010; Ling et al., 2015; Perkins and Mason, 2015; Derkowski and

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Marynowski, 2018). Notwithstanding these natural processes, improper treatment of
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abandoned mines and tailings can also cause further serious heavy metal pollution in
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adjacent agricultural soils, surface water and groundwater (e.g., Rodríguez et al., 2009;
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Larios et al., 2013; Queiroz et al., 2018; Rodríguez et al., 2018; Sun et al., 2018;

Wang et al., 2019).

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The Diaojiang River, a tributary of the Pearl River, is prime example of how
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extensive areas have been affected by heavy metal pollution (Song et al., 2003; Zhong
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et al., 2014; Bai et al., 2017). The basin famous for being the "hometown of

non-ferrous metals". The Dachang orefield located in the upper reaches of the

Diaojiang River has seen large scale development since the 1980s. The orefield has an

area of 168 km2 and includes 6 mines and more than 300 mineral processing points

(Song et al., 2003). Historically, waste water and tailings from mining and processing

plants have been discharged directly into the upper reaches of the Diaojiang River,

leading to serious environmental problems (Song et al., 2003; Zhong et al., 2014; Bai

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et al., 2017). However, rehabilitation of the Diaojiang River Basin started in 1996 and

the comprehensive rectification of the mining industry that began in 2001

discontinued the direct discharge of mineral processing wastewater and tailings. But

the long-term accumulated environmental problems in the basin still persist.

Here we present the data of heavy metals in river water, sediment and bedrock of

the Diaojiang River Basin and small carbonate watersheds of the Pearl River to (1)

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establish which heavy metals are mainly affected by the high geological background

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in karst areas in southwest China; (2) determine the effects of natural bedrock
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weathering and mining on heavy metal accumulation and (3) assess the ecological risk
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of heavy metals within the river water and riverbed sediments in the karst areas of the
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Pearl River Basin.

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2. Study areas
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The Pearl River Basin is located at E 102°14'–115°53' and N 21°31'–26°49', with

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a drainage area of 453,700 km2. The Pearl River originates from the Yunnan-Guizhou

Plateau and is divided into Nanpan River, Beipan River, Hongshui River, Qianjiang

River, Xunjiang River and Xijiang River sections from the headwater to estuary. The

Pearl River Basin is in a humid and rainy tropical-subtropical climate zone. The

average annual temperature are 14℃–22℃ and annual precipitation varies between

1200–2000 mm. Mountainous and hilly topography account for 94.5% of the basin’s

surface area and the basin is rich in mineral resources with reserves of more than 100

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million tons of mainly coal, tin, manganese, tungsten, aluminum and phosphorus

(Pearl River Water Resource Commission of the Ministry of Water Resource,

http://www.pearlwater.gov.cn; CCERL, 2013). On average, the exposed areas of

carbonate rock account for 40% of the Pearl River Basin, but this percentage roughly

doubles in the upper reaches of the river (Gao et al., 2009). The Diaojiang River is a

first-grade tributary of the Pearl River, with a total length of 220 km. It has an average

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river slope of 1.07 ‰ and a drainage area of 3632 km2. The Diaojiang River Basin has

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a subtropical monsoon climate with an average annual temperature of 16.9°C –
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22.5°C and annual average precipitation of 1470 mm. Rainfall in April to September
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accounts for more than 80% of the annual rainfall total. The basin is extremely rich in
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mineral resources with more than 20 non-ferrous metal deposits, of which the tin

reserves are rank first in China (CCERL, 2013). In recent years, unreasonable mining
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development has led to severe heavy metal pollution along the Diaojiang River.
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3. Material and Methods

During September 2017 and May 2018, river water, riverbed sediment and

bedrock samples were collected from small carbonate watersheds in the upper and

middle reaches of the Pearl River as well as in the Diaojiang River and the

mainstream of the Pearl River (Fig. 1, Table S1). The samples of the Pearl River

mainstream are after the confluence of the Nanpan River and Beipan River, before

and after the confluence of Diaojiang River, and before and after the confluence of

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Liujiang River. The carbonate watersheds are located in Yunnan, Guizhou and

Guangxi provinces respectively, including small watersheds with no industrial

activities and small watersheds flowing through mining areas. The portable

multi-parameter water quality analyzer (WTW 340i) and alkalinity TEST (Merck)

were used to measure pH value, water temperature and alkalinity. Water samples were

collected from the river bank and stored in precleaned polyethylene bottles with no

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headspace. Water samples were filtered through 0.45 μm Millipore filters. An aliquot

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of the filtered water was acidified to pH < 2 with ultrapure grade 1:1 nitric acid. Ca2+,
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Mg2+, Na+, K+ and Si were measured in filtered and acidified water with an
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inductively coupled plasma-optical emission spectrometer (ICP-OES 6300) in the
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Key Laboratory of Surficial Geochemistry, Ministry of Education, School of Earth

Sciences and Engineering, Nanjing University. The anions (F−, Cl−, NO3− and SO42−)
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in the filtered and unacidified water samples were measured using an ion
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chromatograph (ICS-1100). The measurement reproducibility was determined by

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repeated analysis of samples and standards, showing ± 5% precision for the cations

and the anions.

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Fig. 1; Table S1

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Riverbed sediment samples were collected at the riverbank by using a

pre-cleaned bamboo spade. Samples were put into clean polythene bags and taken

back to the laboratory for chemical analysis. Fresh outcrop rock samples were

collected from the mountains near the river water sampling sites, knocked off the

surface and stored in bag. Sediment and rock samples were air-dried and finely

ground to 200 mesh whereas 0.1 g (accurate to 0.0001 g) powder were dissolved in 6

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ml aqua regia (HCl + HNO3) on a hot plate to keep it at a boiling state for 2 h. After

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the digestion, the mixture was cooled to room temperature, and the extract was
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filtered through a filter paper and collected in a 50 ml flask for the analysis. Major
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element content of the riverbed sediment and bedrock samples was measured using
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XRF (ZSX Primus II) in the State Key Laboratory for Mineral Deposits Research,

School of Earth Sciences and Engineering, Nanjing University. Absolute errors of Si

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and Al are ±0.5% and ±0.2%, respectively, and relative errors of other elements are
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below 10%. The content of heavy metals was measured using Quadrupole-Inductively
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Coupled Plasma-Mass Spectrometry (Agilent 7900) in the Key Laboratory of

Surficial Geochemistry, Ministry of Education, School of Earth Sciences and

Engineering, Nanjing University. All samples were analyzed in duplicate with a

relative standard error (RSD) of ± 5%. The standard soil (GBW07425) specified by

the Chinese Academy of Geological Sciences was selected for the quality control, and

the recoveries for metal contents were between 90–105%.

We use the geoaccumulation index (Igeo) to assess the degree of change of heavy

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metals from bedrock to riverbed sediments during natural weathering. The Igeo was

first proposed by Müller (1969) and is widely used in the studies of sediments and soil

heavy metals (e.g., Audry et al., 2004; Chen et al., 2015):

C𝑖n
Igeo = log2 (1)
1.5B𝑖n

Where Cin refers to the content of heavy metal element i in the sample, and Bin

is the background content of the heavy metal element i. In this study, the average

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heavy metal content of bedrock in small carbonate watersheds are used as the

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background value to determine the enrichment degree of heavy metal elements in the
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process of bedrock weathering to sediment in the karst areas. Müller (1969) divided
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the geoaccumulation index and pollution level into seven levels (Table S2).
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Table S2
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The potential ecological risk index (RI) proposed by Hakanson (1980) is used to

quantitatively evaluate the ecological risk of heavy metals in sediments and soils. RI

is calculated by the following equations:

Cis
Eir = Tir (2)
Bin

RI= ∑ni=1 Eir (3)

Where Eir is the potential ecological risk factor of a single heavy metal element i,

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and T𝑖r is the toxic response factor of element i, 30, 2, 5, 5, 1, 10, and 5 for Cd, Cr, Ni,

Cu, Zn, As, and Pb, respectively. Bin is the background value of heavy metal i. In this

study, the strictest criteria of the Soil environmental quality Risk control standard for

soil contamination of agricultural land (GB 15618-2018) are used to assess the

ecological risk caused by natural weathering and mining activities in karst areas. The

evaluation criteria for Eir and RI are listed in Table S2.

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4. Results and Discussions
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4.1. Major and heavy metal elements in bedrock
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There are two types of bedrock samples collected in the watershed: carbonate
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rocks (limestone and dolomite) and ore in the mining area. The CaO content of

limestone is 47.2–54.2%, and for the dolomites the CaO content is 26.0–29.4% and
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the MgO content is 15.0–17.9%. There are slight differences in the heavy metal
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element content of limestone and dolomite (Table S3). Except for one limestone
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sample (ZJ–R29) at the source area of the Duliu River which show Zn content of 110

μg/g, the heavy metal content of other samples does not exceed 100 μg/g. The average

content of Cr, Ni, Cu, Zn, Cd, As and Pb is 13.7, 10.0, 6.48, 32.8, 0.23, 5.98 and 8.94

mg/kg, respectively. The content of Cr, Ni, Cu and Zn is significantly lower than that

of the Emeishan basalt and black rock series in the upper reaches of the Pearl River

(Qu et al., 2020). We normalize the average content of heavy metal elements in

carbonate bedrock to the upper continental crust (UCC) (Fig. 2). The average content

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of Cr, Ni, Cu, Zn and Pb in carbonate rocks is only approximately half of the UCC. In

contrast, the content of Cd and As is significantly higher than the UCC (on average 2–

3 times). In addition, the Cd content in karst rocks in the Pearl River Basin (average

0.23 μg/g in this study and 0.45 μg/g in Wen et al., 2020) is about an order of

magnitude higher than the world average for carbonate rocks (0.035 μg/g, Salomons

and Forstner, 2012), indicating high geological background values of these elements

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in the study area.

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Fig. 2; Table S3
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A sample of sphalerite ore (ZJ–R26) in the abandoned Chashan

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antimony-tungsten mine area has extremely high content of Cu (1244 μg/g), Zn

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(130154 μg/g), Cd (1311 μg/g) and As (651 μg/g), while the lead-zinc ore sample

(ZJ–R20) at Shanshulin is very high in Zn (54203 μg/g) and Pb (64320 μg/g).

However, Cr and Ni for both types of ore samples do not show enrichment when

compared to the carbonate bedrock. The content of Cr, Ni Cu and Zn in the coal

gangue samples (ZJ–R16 and ZJ–R19-1) is 1-2 orders of magnitude higher than that

of the carbonate bedrock, but there is little difference with regards to Cd, As and Pb.

Since the coal seams in the upper reaches of the Pearl River are basically intercalated

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in the Permian Emeishan basalt, the content of siderophile elements is relatively high.

Previous studies have also shown that the soils in some basalt areas in China have

significant excesses of Cr and Ni (Xie et al., 2012). Therefore, the large number of

sulfide deposits formed by the black rock series intercalated in the carbonate strata in

the upper reaches of the Pearl River increase the heavy metal content of Pb, Zn, As,

Cd and Sb, while the presence of the Permian basalt and coal seams lead to the

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enrichment of elements such as Cr, Ni and Cu.

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4.2. Major ions and heavy metals in river water and mine wastewater
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The material composition of rivers are complex and depend on the rock
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weathering in the basin, the contribution of human activities and the atmospheric

input (Galy and France-Lanord, 1999). In most cases, natural rock weathering
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processes do not produce significant enrichment of heavy metals and do not

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necessarily create geological pollution of the ecological environment. However,

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considerable ecological risks can develop when rock weathering occur in areas with

high geological background values of metals, such as during the weathering of widely

exposed black rock series in southwest China (Peng et al., 2004; Ling et al., 2015) and

the weathering of carbonate rocks with high Cd and As content (Ni et al., 2009; Wen

et al., 2020). Risk is also associated with the release of As during weathering (Xie et

al., 2014; Radkova et al., 2017). In addition, acid rain can significantly affect the rock

weathering rate. For example, when the average pH of acid rain is 4.91, the proportion

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of carbonate weathering caused by acid rain is 22%, and the weathering rate reaches

2.1 t/km2/y (Zhu et al., 2020). At an annual pH value of 3.94 to 4.70 the proportion of

carbonate weathering caused by acid rain is 36 ± 15% (Huang et al., 2019). When air

temperature is 25℃ and the pH value of acid rain is 5.6, the weathering efficiency of

pyrite reaches 105% (Zheng et al., 2017) and when pH decreased from 5.2 to 4.2, the

weathering efficiency of galena increased to 2208% (Zheng et al., 2018).

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The river water samples have a pH value of 7.8–8.54, which is slightly alkaline,

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reflecting the typical characteristics of a river in a karst area. Although a large amount
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of lime is used to neutralize acidic wastewater in the mining area, the pH is usually
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controlled so that it is above 5 (the online monitoring data of the wastewater treatment
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station showed pH = 5.33). Therefore, the heavy use of lime does not necessarily raise

the pH of the river water. The water temperature is 17.5–23.4 °C. The total dissolved
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solid (TDS) of river water is 139–1196 mg/L with an average of 410 mg/L (Table S4).
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Due to the influence of the Dachang super-large sulfide orefield, the TDS of the
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Diaojiang River is significantly higher than that of the small carbonate watersheds

which is only affected by natural weathering, and the mainstream of the Pearl River

affected by the dilution from large water discharge (Xu and Liu, 2007; Gao et al.,

2009). The total cation charge (TZ+) in those samples flowing through the mining area

are significantly higher than the total anion charge (TZ–). This is due to lime being

widely used in the neutralization of acidic wastewater in the mining areas, resulting in

a very high Ca2+ concentration (758–13300 μmol/L, average 2948 μmol/L) in the

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water samples, but without the correspondingly high HCO3– concentrations. There is

no correlation between Ca2+ and HCO3– (Fig. 3a), indicating that carbonate dissolution

is not the main reason for the high Ca2+ concentrations. For anions in the watersheds,

the SO42– concentration is 74.5–12323 μmol/L, with an average value of 1848 μmol/L.

SO42– concentrations show a very strong positive correlation with Ca2+ concentrations

(r2 = 0.90) (Fig. 3b). Since there is no gypsum in the basin, we speculate that the high

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SO42– concentrations in the water samples are predominantly derived from the

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influence of sulfide deposits. The mines use lime to treat acidic wastewater and
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discharge it into the river, which causes high Ca2+ concentrations in the river water
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and a strong correlation between Ca2+ and SO42–. In contrast, the correlation

coefficient between Ca2+ and HCO3– reaches 0.91 in small limestone watersheds
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unaffected by mining (Fig. 3c).

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Fig. 3; Table S4

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Of all the heavy metal elements, the concentrations of Cr, Ni and Cu are far

lower than the strictest Class I limit of China’s Environmental Quality Standards for

Surface Water (GB 3838-2002) as well as the Guidelines for Drinking Water Quality

4th ed (WHO, 2011) (hereinafter referred to as WQS) in both natural river water and

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mining wastewater. However, concentrations of Zn, As, Cd and Sb in the upper

Diaojiang River flowing through the mining area exceed the WQS to varying degrees

(several to tens of times). The water samples (ZJ–2 and ZJ–3) flowing through the

Lamo zinc ore tailings have Zn and As concentrations of 73.9–201 μg/L and 21.8–

44.1 μg/L, respectively. The water within the Lamo zinc ore itself (ZJ–5) has the

highest Zn (up to 2845 μg/L) and Cd concentrations (31.6 μg/L), and the second

of
highest As concentration (89.2 μg/L) of all the samples. Zn, Cd and As concentrations

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in the river water 3 km downstream from the ore (ZJ–6) are 1207 μg/L, 5.04 μg/L and
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116 μg/L, respectively. In mining areas, heavy metal concentrations in water decrease
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exponentially with an increase in distance from the mine due to the adsorption of
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sediments and the precipitation and complexation of heavy metals, and the

concentrations usually return to normal after ten kilometers (MacKenzie and Pulford,
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2002). Equally, the alkaline environment in karst areas also limits the activation and
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migration of cadmium and other toxic heavy metal elements, making them
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concentrate in the mine soils, plants and river sediments (Holmström et al., 1999). In

the Diaojiang River Basin, Zn and Cd concentrations in water decay very fast

downstream. The sample point ZJ–6 is less than 3 km downstream from ZJ–5 yet Zn

and Cd concentrations decrease by 58% and 84% respectively between the two

sample sites. When the middle reaches of the Diaojiang River is reached the

concentrations of Zn and Cd are already within the WQS. The compounds formed by

Zn and SO42–, Cl–, and NO3– are highly soluble and can be efficiently moved by water.

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However, if carbonate rocks are encountered during this migration, it can form zinc

carbonate precipitation with low solubility and it can also be adsorbed by colloids,

clay minerals, and hydroxide colloids of iron and manganese (Liu et al., 1984).

Cadmium has a similar geochemical behavior with zinc, but cadmium is more

sulphophil. With a large ion radius and a low energy coefficient, cadmium can

extensively remain in aqueous solution, but it begins to precipitate in a strongly

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alkaline environment (pH > 10). In addition, cadmium has a strong polarization

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ability and can be efficiently adsorbed by the colloidal solution of the soil, making it
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difficult to migrate. Like zinc, the precipitation of cadmium is mainly through the
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carbonate form, and the solubility of cadmium carbonate is lower than that of ZnCO 3,
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so it will precipitate before ZnCO3 (Liu et al., 1984). In contrast, the decrease of the

concentrations of As and Sb are much slower, and the concentrations are still 37.2
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μg/Land 32.1 μg/L before the Diaojiang River merges into the Hongshui River. The
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As concentration is less than the strictest Class I limit of GB 3838-2002 (50 μg/L), but
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three times the WHO standard for drinking water (10 μg/L). The concentration of

antimony was 6 times and 1.5 times higher than that of GB 3838-2002 and WHO's

drinking water standard, respectively. According to Igeo, this is moderate enrichment.

Unlike Zn and Cd, As and Sb are both multi-valence elements, which can form 3+ and

5+ cations. However, their distribution in nature and geochemical behavior are more

complex. It can not only form simple cations and anions, but also form complex

anions with oxygen, sulfur, selenium, tellurium, and complex cations (Liu et al.,

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1984).

It is worth noting that all water samples of the Diaojiang River have very low Pb

concentrations with the highest value being only 1.58 μg/L, and most of the samples

in the lead-zinc mining area do not exceed 0.1 μg/L. It is in sharp contrast with the

pronounced enrichment of Zn in the mining area. Lead and zinc are closely symbiotic

during the endogenous processes, but when the deposit is oxidized, the solubility of

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lead sulfate is only 0.041 g/L, which is 5 orders of magnitude lower than that of zinc

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sulfate. Therefore, the two elements separate during the weathering process: lead
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usually remains in situ to form secondary enrichment, and zinc migrates into the
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environment (Liu et al., 1984). Moreover, the displacement capacity of Pb to Ca is
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much higher than that of Zn. In the process of wastewater treatment with lime, more

Pb may be adsorbed and precipitated than Zn.

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It must be noted that although the Sb concentration in the drainage from

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wastewater processing station of antimony deposits (ZJ–27) has been well controlled
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with only 0.386 μg/L after treatment, the small watershed flowing through this mining

area still has very high Sb concentration (573–604 μg/L). Zn concentration in the

treated wastewater reaches 1105 μg/L, but it is extremely low in the watershed. In

comparison, although Zn concentration in the wastewater from the Shanshulin

lead-zinc deposit (ZJ–28) is controlled (92.6 μg/L), the Sb concentration in the

wastewater is high (up to 788 μg/L), but it is only 1.43–1.89 μg/L in the watershed

flowing through this deposit. Therefore, the wastewater treatment process in the

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mining area may cause the replacement of Zn by Sb.

In the mainstream of the Pearl River, the concentrations of heavy metal elements

in all water samples are lower than the WQS. It should be noted that the

concentrations of other heavy metals other than As and Sb are at least one order of

magnitude lower than the WQS. In contrast, As, Sb are basically in the same order of

magnitude as the WQS. In particularly, the concentrations of As and Sb reach 7.44

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μg/L and 4.81 μg/L (very close to the limit of the WQS) in the mainstream of the

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Pearl River after the confluence with the Diaojiang River. As mentioned-above, the
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migration of As and Sb in aqueous solutions does not show the tendency of rapid
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decay with distance like other heavy metals. In the karst area, the extensive
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distribution of carbonate rocks effectively buffer the acid drainage in sulfide deposits.

The increased pH enhances the dissolution of scorodite and As desorption from

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Fe-oxyhydroxides and goethite with zero point of charge (pHzpc) values of 8 and 6–7,
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resulting in As release to the water body (Borba et al., 2003 and therein references;
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Radkova et al., 2017). Sb and As display similar geochemical behavior in the

environment and are usually associated with sulfide deposits, but Sb has a greater

transport rate into solution than As (Liu et al., 1984; Armiento et al., 2016). This

needs to be considered when monitoring karst areas with sulfide deposits, especially

where As and Sb is easily desorbed into ground- and surface water as the pH value

increases.

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4.3. Major and heavy metal elements in riverbed sediments

The content of CaO in riverbed sediments of the small carbonate watersheds is

only 0.44–4.0% which indicate that Ca enters the solution phase during weathering.

Fe2O3 content reaches 2.05–20.9%, with an average of 12.9%. The average contents

of other heavy metal elements in the sediments of the small watersheds without

mining and the Pearl River mainstream are: Ni (70.4 and 37.9 μg/g), Cu (80.6 and

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39.1 μg/g), Zn (158 and 177 μg/g), Cd (0.61 and 0.87 μg/g), As (18.4 and 16.3 μg/g)

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and Pb (25.5 and 28.4 μg/g), respectively. The contents of heavy metal elements in
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topsoil samples (ZJ-T29) from a weathering profile near the source area of the Duliu
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River are close to these values. Compared with the small carbonate watersheds, the
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entire Diaojiang River Basin exhibits extremely high Zn (433–10911 μg/g, average

4314 μg/g), Pb (68.9–2957 μg/g, average 921 μg/g), Cd (3.04–124 μg/g, average 43.9
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μg/g) and As content (32.3–2229 μg/g, average 991 μg/g) in the riverbed sediments.
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Unlike the river water, the Diaojiang River sediments do not show a significant trend
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of decreasing content with distance downstream (Fig. 4). Contrasting to heavy metal

elements in river water, which can easily enter into the sediments and soils through

precipitation, adsorption and complexation and decreases their concentrations

downstream, heavy metals can be trapped in sediments for longer and have a lengthier

transport distance, unless environmental conditions such as oxidation-reduction and

pH change significantly. Even the sample ZJ–S10 (which is at a point before the

Diaojiang River merges into the Hongshui River) still shows extremely high Zn (3842

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μg/g), Cd (33.4 μg/g), As (788 μg/g) and Pb content (1799 μg/g). Two soil samples

(ZJ–T6) of corn fields near the Lamo zinc mine also show exceedingly high content

of Zn (3842 μg/g), Cd (33.4 μg/g), As (788 μg/g) and Pb content (1799 μg/g). In

addition, we conducted a rough random test on the soils with a portable XRF along

the downstream bank. The results also show a serious excess of these heavy metals

along the bank. Therefore, in contrast to the water body, heavy metal elements in river

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sediment shows significant large adsorption capacity, long transport distances and

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lasting action time and suggest that although most mining activities in the Diaojiang
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River Basin have been regulated during the past 30 years, ecological restoration still
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requires continuous efforts. The ~600 km mainstream of the Pearl River, from the
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confluence of the Nanpan River and Beipan River to the confluence of the Liujiang

River, show no obvious variations in the content of heavy metal elements and there is
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no increasing trend in content downstream. Despite the extremely high content of

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heavy metal elements in the Diaojiang River sediments, its influence on the
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mainstream of the Pearl River seems negligible. This is due to the relative small

amount of sediment transported by the Diaojiang River, which only accounts for 0.8%

of the sediment in the mainstream of the Pearl River (as measured by the Qianjiang

Hydrological Station ~100 km downstream from the confluence with the Diaojiang

River without other major tributaries). According to mass balance calculations the

highest content of Zn in the lower reaches of the Diaojiang River (3842 μg/g) only

contribute 28.6 μg/g to the content of Zn in the mainstream of the Pearl River.

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----------------------------------------------------------------------------------------------------

Fig. 4

----------------------------------------------------------------------------------------------------

In order to discuss whether the extremely high content of heavy metal elements

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in the sediments of the Diaojiang River Basin is universal, we compared it with the

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data from other basins in southwest China (Table 1). The results show that the
-p
Diaojiang River is the most extraordinary as the content of Pb, Zn, Cd and As are
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more than one order of magnitude higher than the content measured in other basins.
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The small watersheds with mining (this study) and the Huanjiang River (Deng et al.,

2017), which is tens of kilometers away from the Diaojiang River, has moderate Pb,
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Zn, Cd, and As contents (~10–30% of the Diaojiang). The contents of Pb, Zn, Cd and
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As measured in the Lijiang River, Hejiang River, the mainstream of the Pearl River,
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the wetland in Guangxi Province and the Chishui River (a tributary of the Yangtze

River, originating from the Yunnan-Guizhou Plateau) show no significant differences.

The content is similar to that small carbonate watersheds without mining in the upper

reaches of the Pearl River (this study). Even though the content is only 1–10% of the

heavy metal content measured in the Diaojiang River, it is still more than 1 to 2 times

higher than the average values for river sediment in China. This is indicative of the

considerable influence of the high geological background values in southwest China

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have on heavy metal content.

The content of Pb, Zn, Cd and As in the polluted farmland soil near the mining

area and the bank soil along the Diaojiang River (abbreviated as FBS) is also

extremely high (Table 1). In an assessment of the status of heavy metal pollution in

the whole Diaojiang River Basin (abbreviated as WDB), Bai et al. (2017) analyzed

840 soil data points and the results also showed serious pollution levels of these four

of
elements. The overall variation trend of the heavy metal elements Pb, Zn, Cd and As

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in soil is as follows: the content in the FBS is 1–2 orders of magnitude higher than
-p
that measured in the WDB, the content in the WDB is about twice that of the average
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of the entire Guangxi Province, and the average content in the Guangxi Province is
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almost double the soil average of China (Cd is an order of magnitude higher). This

evidence is significant for the environmental management and remediation of heavy

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metal pollution in the Pearl River Basin, and especially its tributary the Diaojiang
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River Basin, whose management should be given top priority.

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----------------------------------------------------------------------------------------------------

Table 1

----------------------------------------------------------------------------------------------------

4.4. Heavy metal enrichment and ecological risk assessment

The calculated Igeo is listed in Table S5 and Fig. 5. Within the small carbonate

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watersheds without mining activities, Zn is moderately enriched, and Cd, As and Pb

are slightly enriched. Cr, Ni and Cu in most watersheds are moderately-highly

enriched. Statistical analysis shows that there is a strong correlation between these

three elements (Cr, Ni and Cu) and Fe2O3, with correlation coefficients of 0.40 (p =

0.260), 0.90 (p = 0.000) and 0.86 (p = 0.001), respectively. The other four elements

have no obvious correlation with Fe2O3, which is consistent with previous studies

of
(Zhu and Li, 2004; Ni et al., 2009). Iron and manganese nodules are widely found in

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karst areas and the presence of these iron and manganese oxides is one of the main
-p
reasons for the enrichment of heavy metals (Ji et al., 2020). In the small watersheds
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with mining, the enrichment of heavy metal elements is also different according to the
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types of deposits. In the small watersheds that flow through lead-zinc deposit, Zn and

Pb are highly-extremely enriched. In the small watersheds flowing through abandoned

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coal mines, the enrichment of Cr, Ni and Cu is high. The small watershed flowing
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through antimony deposit shows the highest As enrichment of all samples (Igeo = 10.9,
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and Sb is not analyzed). As mentioned above, sulfide deposits mainly affect Pb, Zn,

Cd and As, but have little influence on Cr, Ni and Cu. In contrast, heavy metals in

small carbonate watersheds without mining are mainly affected by associated Permian

basalt and coal seams, which have high Cr, Ni and Cu content. Therefore, Igeo for Cr,

Ni and Cu in some small watersheds with mining is lower than in the watersheds

without mining. In the Diaojiang River Basin, Cr and Ni are moderately enriched, and

Cu is high to extremely enriched. Except for one sample in the source region, Zn, Cd,

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As and Pb are extremely enriched, and the Igeo of almost all samples was greater than

5. There is no doubt that the extreme enrichment of Zn, Cd, As and Pb in the

Diaojiang River sediments are mainly due to the long-term impact caused by mining

in the basin, and this impact can be seen throughout the whole basin. The enrichment

of heavy metals in the sediment samples in the mainstream of the Pearl River is

basically similar to that of the small carbonate watersheds without mining activities

of
(slight-moderate enrichment). As mentioned above, although the Diaojiang River

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Basin is extremely enriched in heavy metals, it has no obvious effect on the heavy
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metal content of the mainstream sediments after merging into the Pearl River.
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lP

----------------------------------------------------------------------------------------------------

Fig. 5; Table S5
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----------------------------------------------------------------------------------------------------
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The calculated Eir and RI are listed in Fig. 6 and Table S5. In the small

carbonate watersheds without mining activities, all heavy metal elements present a

low ecological risk except Cd, which present a low-high ecological risk. In some

small watersheds with mining activities, Cd is still the element with the most obvious

ecological risk (ranking from moderate to very high). Cr, Ni and Cu present a low

ecological risk in the Diaojiang River Basin while Zn has a low-moderate and Pb a

low-high ecological risk factor. The environmental problems stemming from Cd and

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As enrichment could be extremely prominent as both elements present a high- to very

high ecological risk. Except for one source sample, the values for Cd is an order of

magnitude higher than the extremely high ecological risk standard. In the mainstream

of the Pearl River, Cd presents a moderate ecological risk while the other heavy

metals present a low risk. A comprehensive ecological risk assessment of all seven

heavy metal elements in the river basin show that heavy metals present a low

of
ecological risk in the small carbonate watersheds without mining activities, a very

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high ecological risk in the whole Diaojiang River Basin, and a low to moderate
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ecological risk in the mainstream of the Pearl River. Considering that the Cd and As
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content in the carbonate bedrock of the Pearl River Basin is on average of 2-3 times
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higher than the UCC, the ecological risks of Cd and As in the small carbonate

watersheds without mining and the mainstream of the Pearl River are mainly
na

attributed to the high regional geological background values of the two elements. The
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very high ecological risks that these elements present in the Diaojiang River Basin are
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due to the combined effect of the high geological background values and the mining

activities found within the basin.

----------------------------------------------------------------------------------------------------

Fig. 6

----------------------------------------------------------------------------------------------------

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4.5. Effects of changes in hydrological characteristics on heavy metals in river water

and sediment

Temperature and precipitation are important factors affecting the chemical

weathering of rocks (e.g., Meybeck, 1987; White and Blum, 1995; Li et al., 2016).

Under the conditions of high temperature and abundant precipitation, the activity of

microorganism and respiration of plants are stronger in karst area, which promotes

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carbonate weathering. The formation of carbonate rock or calcite containing trace

ro
amounts of heavy metals such as zinc, cadmium and manganese is also related to the
-p
solubility affected by seasonal variations (Liu et al., 2017). The content of heavy
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metal elements is higher during the low-flow season in the Nanpan, Beipan and
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Hongshui River (Liu et al., 2017). Although the heavy metal content is lower during

the wet season, the flux is significantly higher due to the high water discharge. For
na

example, Zhen et al. (2016) proposed that the wet season (April-September)
ur

accounted for 70–75% of the annual heavy metal flux in the upper, middle and lower
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reaches of the Pearl River.

The data presented here was from sampling performed during September and

May, both of which belong to the high flow period (although not the highest which is

July and August). We estimate that the heavy metal content in the study area should

be higher during the dry season. For the upper reaches of the Diaojiang River where

water pollution from heavy metals is serious, the risk during the dry season may be

greater from the perspective of water resource security. Given higher heavy metal

26
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fluxes, the effect of heavy metals on the surrounding environment in the Diaojiang

River Basin is more significant in the wet season. As the heavy metal content in the

other watersheds in this study area is low, the influence of seasonal variation on these

watersheds is small. Since sediments reflect the long-term average of the crust in the

basin, the seasonal effect of heavy metal content is negligible.

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5. Conclusions

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The content of Cd and As in the carbonate bedrock in the upper reaches of the
-p
Pearl River Basin is on average 2–3 times higher than that of the UCC. The high
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elemental content is due to what can be typically termed as the high geological
lP

background values of heavy metals in the karst areas. These elevated geochemical

baseline levels are the most important reason for the environmental and ecological
na

risks that Cd and As pose in the whole Pearl River Basin.

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For the river water, the concentrations of heavy metals in the small carbonate
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watersheds and in the mainstream of the Pearl River are significantly lower than the

WQS. However, the concentrations of Zn, Cd, Sb and As in the upper reaches of the

Diaojiang River flowing through the Dachang super-large orefield exceed the WQS

by more than one order of magnitude. Among all the heavy metals measured, the

concentrations of Zn and Cd show sharp decline downstream from the point source. In

contrast, Sb and As show no obvious decay, and As and Sb also affect the mainstream

of the Pearl River after the Diaojiang River merges into the Pearl River.

27
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The ecological risk assessment of riverbed sediments within the small carbonate

watersheds without mining activities and the mainstream of the Pearl River shows that

only Cd presents an ecological risk, again due to the influence of the high geological

background values. However, for the Diaojiang River Basin, even ~200 km

downwards from the mining area, Cd and As still presents extremely high ecological

risks. Although the mining activities in the basin have been regulated for more than 30

of
years, the combined effect of the high geological background values of heavy metals

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in the bedrock and the historical ecological detrimental industrial activities in the
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early stages of mining can still be seen within the basin sediments. It is necessary to
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continue implementing the long-term solutions to this ecological challenge to mitigate
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against the heavy metal pollution in this very important river basin.
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Acknowledgements
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This work is supported by the National Key R&D Program of China (No.
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2017YFD0800301), the Natural Science Foundation of China (Grant No. 41373003,

41773007, 41761144058, 41730101) and National Research Foundation – South

Africa (No. 110777). Comments by five anonymous reviewers considerably improved

an earlier version of the paper.

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Weihua Wu: Conceptualization, Data curation, Investigation, Methodology, Validation

and Writing - Original Draft.

Shuyi Qu: Data curation, Investigation, Methodology

Werner Nel: Formal analysis, Writing- Reviewing and Editing.

Junfeng Ji: Supervision, Validation, Project administration

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Declaration of interests

☒ The authors declare that they have no known competing financial interests
or personal relationships that could have appeared to influence the work
reported in this paper.

☐The authors declare the following financial interests/personal relationships which

may be considered as potential competing interests:

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Fig. 1: Sampling map of the upper reaches of the Pearl River, small carbonate

watersheds and Diaojiang River. Number 1, from ZJ–19 to ZJ–20, ZJ–28; Number 2,

ZJ–21 to ZJ–22; Number 3, ZJ–32 to ZJ–39; Number 4, from ZJ–23 to ZJ–25, ZJ–29;

Number 5, ZJ–30 to ZJ–31; Number 6, ZJ–2 to ZJ–3; Number 7, ZJ–5 to ZJ–6, ZJ–

26.

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Fig. 2: The ratio of metal content in the carbonate bedrock relative to that in UCC.
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The box body is a value range of 25–75%. The upper and lower bars are the
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maximum and minimum values, respectively. The orange line is the average value.
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The average content of Cd and As in carbonate rocks is 2-3 times higher than that in

the UCC, while the content of other heavy metal elements is basically lower than that
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in the UCC.
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Fig. 3: (a), (b) Plots of Ca and HCO3 and SO4 in water samples from the basin. (c)

Plots of Ca and HCO3 in the small limestone watersheds.

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Fig. 4: The variation trend of heavy metals in river water (blue) and sediment (orange)

along the Diaojiang River. On the y axis, the units of water and sediment content are

μg/l and μg/g, respectively. The triangle label in the upper right is Sb.

Fig. 5: Geo-accumulation index (Igeo) of riverbed sediment relative to bedrock.

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Fig. 6: Potential ecological risk factors (Eir ) of single heavy metal element in riverbed
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sediments and overall ecological risk indices (RI) in river basin.
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Table 1. Comparison of heavy metal elements in this study with other river basin in
southwest China.
Cr Ni Cu Zn Cd As Pb
Samples Data sources
μg/g
Riverbed
Sediments
45.3-7 36.7-79 63.7-29 433-109 32.3-22 68.9-29
Diaojiang 3.04-124
7.6 .2 3 11 29 57 This study
River a
(43.9)
(64.2) (53.6) (151) (4314) (991) (921)
59.2-3 24.7-52 25.7-59 13.9-21. 22.1-45
Mainstream 114-254 0.53-1.40
10 .5 .8 9 .1 This study
of Pearl River (177) (0.87)
(121) (37.9) (39.1) (16.3) (28.4)

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Small 26.7-1 12.7-81 9.12-17 43.6-144 17.0-52. 7.16-10
0.30-3.91
watersheds 64 .6 4 5 1 99 This study
(1.62)

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with mining (70.8) (46.1) (62.6) (496) (27.9) (286)
Small 55.2-5 30.2-94 13.8-13 12.7-27. 16.0-60
72.7-248 0.29-1.77
watersheds 19 .4 4
(158)
-p (0.61)
3 .3 This study
no mining (208) (70.4) (80.6) (18.4) (25.5)
41.4-8 21.3-38 16.7-57 125-214 18.6-82 17.4-49
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Huanjiang 1.12-17.5 Deng et al.,
2.3 .9 .4 5 4 3
River (4.92) 2017
(57.6) (28.0) (27.1) (417) (95.4) (113)
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Beipan River Liu et al.,

128 62.6 63.1 300 2.32 n.a. 85.7
(n = 1) 2017
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Nanpan River Liu et al.,

58.7 25.6 28.3 69.3 0.51 n.a. 16.6
(n = 1) 2017
Nanpan River Xiong et al.,
(150) n.a. (80) (239) (4.52) (146) (101)
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(n = 20) 2017
31.2-9 21.0-56 10.2-44. 32.2-83
Lijiang River 79.8-213 0.34-3.94 Xu et al.,
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4.2 n.a. .4 1 .6
(n = 20) (142) (1.72) 2016
(56.4) (38.1) (18.1) (51.5)
Hejiang 1.4-45. 17.7-40
3-124 7.2-208 42-943 0.03-8.51 4.1-463 Ning et al.,
River 9 0
(44.3) (43.5) (188) (1.42) (83.1) 2017
(n = 41) (21.7) (78.5)
Mainstream
49-101 18-41 19-69 48-259 0.2-3.3 13-95 Liu et al.,
of Pearl (n = n.a.
(75) (30) (38) (162) (1.7) (47) 2019
12)
Middle and 4.32-6 1.17-77 1.42-36 5.83-13 6.40-93
14.8-179 0.01-2.42 Zhuang et
lower Pearl 6.6 .8 .1 6 .8
(60.1) (0.24) al., 2018
(n = 54) (19.6) (15.0) (14.7) (58.5) (28.9)
2.0-31 1.58-92.
Lower Pearl 1.1-352 11-1234 0.04-9.29 11-221 Zhao et al.,
5 n.a. 8
(n = 323) (42.9) (136) (0.84) (44.6) 2018
(55.2) (18.2)

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Huixian 32.3-2 16.0-58 19.5-53 0.052-1.2 5.96-54. 31.1-97

46.7-119
wetland 86 .9 .6 92 3 .1 Xiao et al.,
(77.1±1.
Guanxi (n = (114±2 (35.9±0 (31.1±0 (0.445±0. (21.5±0 (51.3±0 2019
38)
13) .64) .80) .46) 018) .65) .96)
Chishui River 13.0-99 5.12-12 1.56-11.
36.0-219 0.03-1.28 Yu et al.,
Southwest n.a. .5 0 6 n.a.
(91.9) (0.23) 2015
China (40.2) (37.4) (5.16)
River
sediments in
China
Shi et al.,
(Regional 54.0 23.0 20.0 67.0 0.13 9.0 23.0
2018
geochemical

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survey, n >
million)

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Soils

19.7-2 26.9-59 644-16 10049-3 6950-10 370-48

Diaojiang
-p 51.6-291
1.4 .4 85 5588 437 1 This study
River (171)
(20.6) (43.2) (1165) (22819) (8694) (425)
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Diaojiang
47.9-7 59.5-33 937-187 402-227 143-13
River 8.71-147 Song et al.,
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2.6 n.a. 0 00 00 60
Contaminated (56.6) 2003
(62.6) (164) (6637) (7717) (695)
land
Diaojiang 2.01-150 0.15-52 0.39-84
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0.10-44.0 Bai et al.,

River n.a. n.a. n.a. 8 8 7
(4.02) 2017
(n = 840) (232) (50.0) (50.9)
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70.1-7 18.0-20 13.3-15 0.323-0.4 21.3-27. 35.0-35

123-151
Duliu River 5.9 .2 .7 37 5 .8 This study
(137)
(73.0) (19.1) (14.5) (0.38) (24.4) (35.4)
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30.7-1 12.9-16 16.4-52

7.3-166 28.2-732 0.12-17.9
Guanxi 442 2 8 Wen et al.,
(42.6±2 (159±10 (1.49±2.0 n.a.
(n = 308) (194±1 (37.2±1 (58.6±5 2020
5.3) 9) 8)
67) 4.9) 4.1)
37.9-2 10.1-93 9.3-52. 17.2-70
Guanxi 28.6-272 0.05-2.56 5.1-51.5 Chen et al.,
32 .0 2 .7
(n = 1259) (111) (1.05) (23.7) 2015
(113) (37.7) (29.3) (42.4)
Average
background CNEMC,
61.0 26.9 22.6 74.2 0.097 11.2 26
values in 1990
China
a
Average value.

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Graphical abstract -p
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1. The carbonate bedrock in southwest China has a high background value of Cd and
As
2. Small carbonate watershed without mining presents a certain ecological risk of Cd
3. Metals pollution in upper Diaojiang River water has slight effect on downstream
4. The ecological risk of metals in most of Diaojiang River sediments is very high
5. The Pearl River shows the impact of human activity under high geologic
background.

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