Environmental Pollution 290 (2021) 118126

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Environmental Pollution
journal homepage: www.elsevier.com/locate/envpol

Identification of heavy metal pollution in estuarine sediments under

long-term reclamation: Ecological toxicity, sources and implications for
estuary management☆
Lixia Niu a, b, Jiayi Li c, Xiangxin Luo a, b, *, Tao Fu a, Ou Chen a, Qingshu Yang a, b
a
School of Marine Engineering and Technology, Sun Yat-sen University (Guangzhou)/Southern Laboratory of Ocean Science and Engineering, Zhuhai, China
b
Institute of Estuarine and Coastal Research, Guangdong Provincial Engineering Research Center of Coasts, Islands and Reefs, Guangzhou, China
c
School of Geography and Planning, Sun Yat-sen University, Guangzhou, China

A R T I C L E I N F O A B S T R A C T

Keywords: Sediment samples were collected to clarify the effect of changing sedimentary environment under long-term
Heavy metals reclamation on heavy metals (Cr, Zn, Pb, Cu, Cd, and Ni) in a partially mixed estuary (Modaomen) of the
Sedimentary environment Pearl River Delta. The ecological toxicity and source apportionment of these metals were discussed as well. The
Ecological toxicity
metal species during the 2010s (as 2015, 2018) was more enriched than that during the 2000s (as 2003) and
Source apportionment
Estuary
1990s (as 1991). This estuary overall suffered from a “moderate-to-high” pollution status. The element Cd was a
major concern for the ecosystem’s health because of its high toxicity. Sediment quality guidelines suggested that
adverse biological effects were likely to be caused by Cu and Cd in the early adjustment stage, while the threats
to marine organisms caused by the elements of Cu, Cr, Zn, and Ni were elevated during the 2010s. Two receptor
models of PCA-MLR and PMF quantified the source types and contributions of these heavy metals. Strong in­
tensity of industrial activities coupling with agricultural applications and import of adjacent seas were respon­
sible for the enriched accumulation of heavy metals in sediments. Metal source apportionment would help to
control the metal input into the estuary; identifying the role of sedimentary environment on heavy metals can
inform the sediment quality management in the estuary.

1. Introduction
Estuary is a transitional zone between river and ocean, providing
many important ecosystem functions and services (Boicourt, 1983; Guen
et al., 2019). The estuarine zones tend to be receptors and sinks of
anthropogenic pollutants such as nutrients, PAHs, and heavy metals
(Kumar et al., 2015; Guo et al., 2020; Bantan et al., 2020). In which,
heavy metal pollution has become a prime focus for environmental
scientists due to their environmental characteristics of abundance,
persistence, bio-accumulation, ecological toxicity, and
non-biodegradation (Papagiannis et al., 2004; Machado et al., 2016;
Truchet et al., 2020). Heavy metals exist in various environmental
media such as soil, suspended particulate matter, water, organism, and
sediment. The levels of heavy metals dissolved in water are relatively
low (Wang et al., 2012; Kumar et al., 2020; Xie and Wang, 2020), while
suspended particulate matter is a main carrier for heavy metals (Yao
et al., 2016; Zeng et al., 2020). Sediment has a large capacity to store
heavy metals, often acting as a reservoir/sink; and also, potentially re­
leases the heavy metals into the water column, causing a secondary
pollution to environment (Pekey, 2006; Yi et al., 2011; Ahmad et al.,
2020; Xiao et al., 2021). The distribution characteristics of sediment
metal species are highly correlated with sediment properties because of
absorption capacity and hydrological connectivity as a external forcing
(Bantan et al., 2020; Li et al., 2020; Jia et al., 2021). The role of sedi­
mentary environment should be considered for a better understanding of
the heavy metal accumulation in the estuarine sediments (Krupadam
et al., 2007; Ye et al., 2012; Bi et al., 2017). However, a knowledge gap
of how sedimentary environment influences the characteristics of heavy
metals in estuary is still developing. And more studies are needed to
reveal the transportation of heavy metal pollution in sediments from an

This paper has been recommended for acceptance by Dr Hefa Cheng.

☆

* Corresponding author. School of Marine Engineering and Technology, Sun Yat-sen University (Guangzhou)/Southern Laboratory of Ocean Science and Engi­
neering, Zhuhai, China.
E-mail address: luoxx6@mail.sysu.edu.cn (X. Luo).

https://doi.org/10.1016/j.envpol.2021.118126
Received 13 June 2021; Received in revised form 30 July 2021; Accepted 5 September 2021
Available online 7 September 2021
0269-7491/© 2021 Elsevier Ltd. All rights reserved.
L. Niu et al.
estuarine environment to a marine coastal zone.
The potential sources of heavy metals are both from the natural
geochemical weathering of soil and rocks and human-induced sources
such as agricultural fertilization, mineral mining, and industrial pro­
duction (Pekey, 2006; Jia et al., 2020; Zhao et al., 2020). There are
several commonly used methods to identify the source origins of heavy
metals in the environment, for example, positive matrix factorization
(PMF; (Comero et al., 2014; Deng et al., 2018)), principal component
analysis (PCA; (Wang et al., 2018; Salim et al., 2019; Wu et al., 2021;
Xiao et al., 2021)). In the present work, the applications of multivariate
statistical techniques (e.g., PMF, PCA, enrichment factor) are introduced
to identify the natural and anthropogenic sources of heavy metals in
sediments of a partially mixed estuary (Modaomen) of the Pearl River
Delta (PRD; Fig. 1).
The Modaomen Estuary contributes a lot of sediments from the West
River to the shape and formation of the PRD. The widely known huge
projects implemented in the Modaomen Estuary are the reclamation
development since 1980s. These projects have changed the coastlines,
sedimentary environment, and biogeochemical cycles in that area.
Heavy metals in this estuarine mixing zone are dynamic because of
intense anthropogenic perturbations from surrounding urban areas.
Previous studies have discussed the distribution characteristics of heavy
metals in sediments of the Pearl River Estuary (Chen et al., 2012; Zhao
et al., 2017; Zhang et al., 2017; Wang et al., 2020); researcher have
assessed the metal pollution in sediments/soils of the PRD (Bai et al.,
2011; Gu et al., 2014; Lin et al., 2018; Lu et al., 2020); while limited
reports on heavy metal pollution in this typical Modaomen Estuary are
found (Huang, 1993; Liu et al., 2019; Jia et al., 2021) and no reports
have discussed the metal pollution under the long-term reclamation in
this estuary. The impact of changing sedimentary environment on the
characteristics of sediment heavy metal pollution is firstly documented.
Fig. 1. Location of the Pearl River Delta in China (a) and sketch map of the Modaomen Estuary and distributions of functional water areas (b), and sampling sites (c).
The inner and outer zones of the estuary are approximately divided by the 5-m isobath line, which corresponds to the dominated roles of river discharge and marine
current, respectively.
2
Environmental Pollution 290 (2021) 118126
Moreover, long-term monitoring of metal pollution provides an useful
indicator of evaluating anthropogenic input and predicts the ecological
toxicity to the estuarine ecosystems.
For this purpose, the objectives of this study are designed to: (1)
examine the spatiotemporal trends of heavy metals (Cr, Zn, Pb, Cu, Cd,
and Ni) in the estuarine sediments under the long-term reclamation; (2)
analyze the effect of changing sedimentary environment on the heavy
metals; (3) evaluate the ecological toxicity using the compared pollution
indices; and (4) quantify the source contributions of heavy metals using
PCA-MLR and PMF and provide effective implications for estuary
management. These systematic investigations will gain an in-depth
understanding of the pollution status and anthropogenic pressures on
metal species.
2. Study site and data collection
2.1. Site description
The Pearl River (Zhujiang) deliveries the waters into the South China
Sea via eight river mouths (as Humen, Jiaomen, Hongqimen, Hengmen,
Modaomen, Jitimen, Hutiaomen, and Yamen) (Fig. 1). In which, the
discharge at the Modaomen is the largest, accounting for 80% of the
total. The estuary is a typical ecological environment fragile area and is
approximately divided into two zones according to the 5 m isobath line,
inner and outer estuary. Both sides of the Modaomen Estuary are located
in the Zhuhai Special Economic Zone and close to Macau. The aquatic
environment in that area has been threatened with the heavy metal
pollution as a consequence of the rapid population growth (Pan and
Wang, 2012; Zhao et al., 2017). Many industrial and agricultural areas
are distributed along the Modaomen channel (Fig. 1b), which would
contribute much to the metal sources.
L. Niu et al. Environmental Pollution 290 (2021) 118126

The high intensity of human perturbations has been detected over
the past decades, such as the typical extensive reclamation projects
implemented in the Modaomen Estuary (Fig. S1a, Supplementary Ma­
terial). The long-term variations of water and sediment between 1971
and 2019 also reflected the degree of human interference (Fig. S1c). The
sediment load showed a sharp decline. Three periods were then divided
according to the sediment trend, stable period (1971–1982), mutation
period (1983–2000), and adjustment period (2001-present). These pe­
riods were corresponded to the extensive reclamation projects in the
Modaomen Estuary.
2.2. Sample collection, instrumental analysis, and quality assurance/
quality control
Our research group (Institute of Coastal and Estuarine Research, Sun
Yat-sen University) conducted two field surveys in the Modaomen Es­
tuary in September 2003 and March 2015, combining the limited data in
1991 (Huang, 1993), 2008 (Xie et al., 2012), and 2018 (Liu et al., 2019;
used to explore the correlations between heavy metals and sediment
properties. The pollution assessment indices (contamination index, po­
tential ecological risk, geo-accumulation index, enrichment factor, and
sediment quality guidelines) are introduced to quantify the degree of
heavy metal contamination in sediments and their ecological toxicity to
the marine organisms. Principal component analysis (PCA) is used to
examine the correlations among heavy metals and to identify their po­
tential sources (Ip et al., 2007; Gu et al., 2014; Yang et al., 2014; Zhao
et al., 2017, 2020). The related factor scores of PCA, calculated by
regression method, help to understand the associations of environmental
variables. The PCA uses the principal factor scores to identify source
types while multiple linear regression (MLR) identifies the contribution
rate of each source (Li et al., 2015; Deng et al., 2018; Salim et al., 2019;
Zhang et al., 2020; Wu et al., 2021). Each variable is standardized for
units prior to the PCA-MLR analysis. Data preparations for PCA-MLR are
performed using the statistical package IBM SPSS Statistics 26 for
Windows. The calculation of PCA-MLR is as following:
∑
m

Jia et al., 2021). Sampling sites were displayed in Fig. 1 and spanned y= ai xi + a0 (1)
from 21.958◦ to 22.160◦ N and 113.367◦ -113.557◦ E. Surface sediment
i=1

samples (0–5 cm) were densely collected from the inner and outer
Modaomen Estuary using a grab sampler, 37 samples in 2003 and 76 in
2015. Samples were stored into the pre-cleaned polyethylene bags and
were shipped to the laboratory for further analysis.
Sediment properties were analyzed using a Mastersizer 2000 laser
diffraction particle size analyser (size range 0.02–2000 μm; Malvern,
United Kingdom). Digestion of sediments, with an acid mixture (HCl-
HClO4-HNO3), was conducted in a heating block. The grain sizes were
grouped as follows: >0.06 mm (sand), 0.004–0.06 mm (silt), and
<0.004 mm (clay). The measurement of the heavy metals was deter­
mined by inductively coupled plasma optical emission spectrometry
(ICP-OES, PE Optima 5300DV, America) (Liang et al., 2018).
The heavy metal recovery process followed a strict quality assur­
ance/quality control. A standard material of Guangdong water system
sediment composition GBW07312 (GSD-12) was used to guarantee
analytical accuracy and precision. The recovery rates were between 95%
and 110%. All of the experimental reagents were at an analytical grade
or higher. Duplicates and blank samples were used for quality control.
The method detection limit was 0.055 mg kg− 1 for Cu, 0.01 mg kg− 1 for
Cd, 0.246 mg kg− 1 for Zn, 0.006 mg kg− 1 for Pb, 0.003 mg kg− 1 for Ni,
and 0.028 mg kg− 1 for Cr. Relative standard deviations of less than 10%
for multiple measurements were acceptable. The summary of heavy
metal contents and sediment properties was shown in Table 1.
3. Methodology
In this study, multivariate statistical techniques are applied to
investigate the characteristics of heavy metal pollution in sediments of
the Modaomen Estuary. Spatial distributions of variables are plotted
with Golden Software surfer 13.0. The coefficient of variance (Cv) is
used to describe the spatial variability. Pearson’s correlation analysis is
where y indicates the concentration of heavy metal i (as Ci); m is the
number of influencing factors; ai is the normalized regression coeffi­
cient; xi is the factor score; and a0 indicates the regression constant. The
contribution rate (ci) of each source is derived as follows:
ai
ci (%) = ∑ × 100 (2)
ai
Another receptor model of positive matrix factorization (PMF)
quantifies the contributions of pollution sources (Comero et al., 2014;
Zhang et al., 2018). The PCA-MLR explains less than 100% of the in­
formation, while the PMF can represent 100% of all the information. The
PMF analysis is performed using the PMF 5.0 model from the United
States Environmental Protection Agency (EPA). According to the user
guide, the PMF calculation is as follows:
p
∑
xij = gik fkj + eij , (i = 1, 2, …, m; j = 1, 2, …, n) (3)
k=1
where xij is the concentration of metal species j measured in sample i and
eij is the residual for each sample. The sample data are divided into two
matrices: factor contribution matrix (gik) and factor profile matrix (fkj).
The PMF uses the least squares method to obtain the optimal matrices gik
and fkj. The sample concentration and uncertainty are both involved in
the PMF. The uncertainty values are defined as:
Unc = (5/6) × MDL, (Ci < MDL)
√̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅
̅
Unc = (errorfraction × concentration)2 + (0.5 × MDL)2 , (Ci > MDL)
(4)
The optimal matrices gik and fkj are obtained until a minimum value
of objective function (Q) is found. Q is defined as:

Table 1
Summary of heavy metal pollution and sediment properties in the estuary.
Variable Abbreviation Unit 2003 2015 Sample analysis

mean SD Cv mean SD Cv
1
Copper Cu mg kg− 85.51 34.62 40% 40.08 13.25 33% Inductively coupled plasma mass
1
Zinc Zn mg kg− 130.44 108.8 83% 254.68 154.99 61% spectrometry
1
Nickel Ni mg kg− 7.97 2.34 29% 29.68 6.77 23%
1
Lead Pb mg kg− 15.23 17.42 114% 38.8 10.12 26%
1
Chromium Cr mg kg− 24.62 15.89 65% 84.59 22.64 27%
1
Cadmium Cd mg kg− 1.7 1.24 73% 0.88 0.48 54%
Median diameter Md – 5.93 1.72 29% 5.37 1.61 30% Mastersizer 2000
Clay – % 32.22 13.54 42% 20.09 9.78 49%
Silt – % 31.4 29.58 94% 46.53 21.11 45%
Sand – % 42.23 14 33% 33.37 29.58 89%

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L. Niu et al. Environmental Pollution 290 (2021) 118126

∑m ∑ n (
eij
)2 values. The maximum concentrations of Zn, Cr, Pb, and Ni observed in
Q= (5) 2015 were higher than in 2003 by 96% (Zn), 272% (Cr), 155% (Pb), and
Uncij
244% (Ni). Cu, Zn, and Cd varied significantly over the estuary, with Cv
i=1 j=1

values of 33% (Cu), 61% (Zn), and 54% (Cd). The Cv values of Ni (23%),
4. Results
Pb (26%), and Cr (27%) were non-significant, demonstrating that these
metals may have different sources. Heavy metals collected in the Mod­
4.1. Characteristics of heavy metals in the estuarine sediments
aomen Estuary in 2018, a period of current adjustment, had the pattern
Zn (171.90 ± 37.72 mg kg− 1) >Cr (126.78 ± 28.41 mg kg− 1) >Pb
The mean concentrations of heavy metals in sediments of the Mod­
(56.22 ± 10.64 mg kg− 1) >Cu (37.78 ± 7.69 mg kg− 1) >Ni (37.11 ±
aomen Estuary under the long-term reclamation are shown in Fig. 2. In
6.83 mg kg− 1) >Cd (1.12 ± 1.04 mg kg− 1). In 2018, the mean concen­
the early adjustment period of 2003, significant differences in the spatial
trations of all heavy metals exceeded their background values.
distributions of heavy metals were detected between the sampling sites
Heavy metal concentrations in sediments of the Modaomen Estuary
(Table S1, Supplementary Material). The mean concentration of heavy
were comparable with those reported in the Pearl River Estuary (Ip
metal pollution followed the order of Zn (mean ± SD, 130.44 ± 108.8
et al., 2007; Ye et al., 2012; Chen et al., 2012; Zhao et al., 2017), the
mg kg− 1) >Cu (85.51 ± 34.62 mg kg− 1) >Cr (24.62 ± 15.89 mg kg− 1)
Yellow River Estuary (Bi et al., 2017), the Changjiang River Estuary (Bi
>Pb (15.24 ± 17.42 mg kg− 1) >Ni (7.97 ± 2.34 mg kg− 1) >Cd (1.70 ±
et al., 2017), and other estuarine systems in the world (Coxon et al.,
1.24 mg kg− 1). The metal levels in that period varied from 7.03 to
2016; Jahan and Strezov, 2018; Islam et al., 2018; Chen et al., 2021;
388.29 mg kg− 1 for Zn, 29.24–140.51 mg kg− 1 for Cu, 2.36–64.36 mg
Jeong et al., 2021; Ota et al., 2021). The comparisons are shown in
kg− 1 for Cr, 1.29–80.65 mg kg− 1 for Pb, 4.09–13.93 mg kg− 1 for Ni, and
Table S3, Supplementary Material.
0.14–4.58 mg kg− 1 for Cd. The mean concentrations of Zn, Cu, and Cd
Using the 5 m isobath line, the estuary displayed different charac­
exceeded their background values (CNEMC, 1990), and Pb, Ni, and Cr
teristics between the inner and outer zones, the inner zone under the
were within their background values. Heavy metal distributions showed
influence of riverine input and the outer zone under the influence of
different degrees of spatial variability regarding to the coefficient of
marine forcing. In 2003, Cu, Zn, Pb, and Cd were higher in the outer
variance of each variable. The Cv values ranged from 29% to 114%
estuary than that in the inner estuary. Cr showed higher values in the
(mean 68%), indicating significant variability in the estuary.
inner estuary, indicating that Cr could be largely attributed to riverine
A different pattern of heavy metal pollution was detected during the
input. The concentration of Ni in the two zones was similar, implying
middle adaptive adjustment period of 2015. The concentrations of
that river discharge and marine currents equally influenced Ni. In 2015,
heavy metals at the sampling sites are provided in Table S2 and Fig. S2,
Zn and Pb were higher in the inner estuary than the outer estuary, but
Supplementary Material. The sequenced of trace metals was Zn (254.68
the other elements showed the reverse trend. In 2018, all of the metal
± 154.99 mg kg− 1) >Cr (84.59 ± 22.64 mg kg− 1) >Cu (40.08 ± 13.25
elements had higher concentrations in the inner estuary than the outer
mg kg− 1) >Pb (38.80 ± 10.12 mg kg− 1) >Ni (29.68 ± 6.77 mg kg− 1)
zone. These findings indicated that heavy metal contamination in the
>Cd (0.88 ± 0.48 mg kg− 1). The concentrations of Cu, Zn, Ni, Pb, and Cr
estuary at different periods was a reflection of the interactions of the
were far higher than Cd, ranging from 15.78 to 62.96 mg kg− 1 Cu,
sedimentary environment, geographical factors, river discharge, marine
95.78–819.46 mg kg− 1 Zn, 16.73–42.55 mg kg− 1 Ni, 22.04–75.99 mg
current, and anthropogenic influences. Urban activities coupled with
kg− 1 Pb, 45.50–133.88 mg kg− 1 Cr, and 0.28–2.77 mg kg− 1 Cd. In 2015,
agricultural chemicals can increase the amounts of heavy metals in the
the mean concentrations of all heavy metals exceeded their background

Fig. 2. Box diagrams of heavy metal concentrations in sediment of the Modaomen Estuary in the early (a, 2003, n = 37), middle (b, 2015, n = 76), and present
adjustment stage (c, 2018, n = 10), in which, the data was fitted by the symmetric log-normal distributions.

4
L. Niu et al. Environmental Pollution 290 (2021) 118126

inner estuary (Bai et al., 2011); more heavy metals might be released 4.2.1. Assessment of potential ecological risk
into the water from the sediments when the marine current strongly The contamination index (CI) and comprehensive ecological risk
interacted with the riverine inflow (Huang, 1993; Feng et al., 2017). index (RI) are widely applied for evaluating the marine sediment
The transport route of Cd exhibited a different trend, indicating that pollution and ecological toxicity of heavy metals (Hakanson, 1980; Yi
it was from a different source. As a priority pollutant, Cd would pose a et al., 2011; Li et al., 2014). These pollution indices are expressed as
high toxicity even at a low concentration. The highest concentration of follows:
Cd was concentrated in the middle estuary. It showed a relative decrease
CI = Ci /Bi (6)
in 2015 and 2018 compared to its level in 2003. The locations with the
highest Cd varied due to the changing location of the central sandbars of
Ei = Ti × CI (7)
the Modaomen Estuary.
∑
n

4.2. Heavy metal pollution and ecological toxicity RI = Ei (8)

i

The pollution assessment results of heavy metals in sediments be­

where Ci indicates the measured concentration of heavy metal i; Bi
tween 2003 and 2018 are presented in Fig. 3 and Table S4-S6 (Supple­
means the background value of heavy metal i (Zn, Cu, Pb, Ni, Cd, and Cr
mentary Material).
as 47.3 mg kg− 1, 17 mg kg− 1, 36 mg kg− 1, 18.2 mg kg− 1, 0.056 mg kg− 1,
and 50.5 mg kg− 1, respectively; (CNEMC, 1990)); Ei means the potential
ecological index of heavy metal i; and Ti indicates the toxicity coefficient

Fig. 3. Pollution assessment of heavy metals in the estuarine sediments in 2003 (a, d, g, j), 2015 (b, e, h, k), and 2018 (c, f, i, l).

5
L. Niu et al.
(Zn, Cu, Pb, Ni, Cd, and Cr as 1, 5, 5, 5, 30, and 2, respectively). The
pollution levels of CI are classified as: no pollution if CI < 1; slight
pollution if CI at a range of 1–3; moderate pollution if at 3–5; and serious
pollution if CI > 5 (Li et al., 2014). For RI, four pollution levels are
classified: low contamination where RI < 95, moderate contamination
where larger than 95 and less than 190, considerable contamination
when RI at a range of 190–380, and very high contamination where
larger than 380 (Hakanson, 1980).
Overall, the values of CI for Ni, Pb, and Cr were all lower than 4,
indicating a low toxic risk to ecosystem’s health. Cd showed a high
toxicity to marine organisms. In the early adjustment period of 2003
(Fig. 3a and Table S4), the sequence of mean CI followed the order Cd >
Cu > Zn > Pb > Cr > Ni. The highest CI was Cd and the lowest was Ni.
The CI values for “moderate to high pollution” for Cu accounted for
81%. Correspondingly, some of the Ei values for Cu indicated moderate
pollution (16%). For the comprehensive ecological index (RI) of these
heavy metals, shown in Fig. 3d, “moderate to very high pollution”
accounted for 81%. The RI represented the sensitivity of marine or­
ganisms to toxic pollutants and illustrated the potential ecological risk
caused by heavy metals in sediments. The RI values of heavy metals were
clearly associated with the degree of anthropogenic disturbance (Lu
et al., 2020).
In 2015 (Fig. 3b and Table S5), the order of the mean CI was Cd > Zn
> Cu > Pb > Cr > Ni. The CI values for moderate pollution (larger than
3) were 32% (Cu), 31% (Zn), 1% (Pb), and 70% (Cd). The Ei suggested
that the ecological severity of heavy metal contamination decreased in
the sequence Cd > Cu > Pb > Ni > Zn > Cr (Fig. 3e). All the Ei values of
Cu, Zn, Ni, Pb, and Cr were lower than 40, indicating slight pollution.
However, all the Ei values for Cd were larger than 40, indicating mod­
erate to severe pollution. With respect to the RI index for all heavy
metals, 92% indicated moderate to very high pollution.
In 2018 (Fig. 3c and Table S6), the CI value for Cd at “moderate to
very high” pollution accounted for 60% of the results. For Pb, moderate
and higher pollution accounted for 20%. The metal species Cu, Zn, Ni,
and Cr were at low and very low pollution levels. All the Ei values for Cd
were larger than 40 (Fig. 3f), indicating that the Cd contamination in the
estuary poses a toxic threat to the marine organism and ecosystem’s
health. Based on the RI, this estuary was moderately to highly polluted
at 90% of the sampling sites and the remainder of the sampling sites
(10%) were at very high pollution levels.
Comparing these periods, the ecological toxicity of Cu decreased
over time while the risks for the other elements increased. The lowest
(53.68) and highest (740.06) values of RI appeared in 2003, which was
consistent with the CI and Ei values for Cd. The potential ecological risk
of surface sediments in the Modaomen Estuary was mainly caused by Cd.
Therefore, Cd should be used as a priority pollutant for environmental
pollution control in this estuary. This estuarine zone is a catchment area
for land-based pollutants. The medium to strong ecological risk level
might reflect the impact of human activities on the estuary ecosystem.
4.2.2. Assessment of geo-accumulation index
The geo-accumulation index (Igeo) is used to evaluate the marine
sediment pollution (Muller, 1969; Bai et al., 2011; Li et al., 2014; Lu
et al., 2020). This pollution index is expressed as following:
Igeo = log2 [Ci / (K × Bi )] (9)
where K indicates the background matrix correction factor (taken 1.5).
The classification of Igeo is recognized at six contamination grades (Bai
et al., 2011): no contamination where Igeo less than 0, slight contami­
nation where larger than 0 and less than 1, moderate contamination
where Igeo larger than 1 and less than 2, moderate to strong contami­
nation when larger than 2 and less than 3, strong contamination when
larger than 3 and less than 4, strong to extreme contamination where
larger than 4 and less than 5, and extreme contamination where Igeo >5.
All of the lowest Igeo values for heavy metals excluding Cu were
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Environmental Pollution 290 (2021) 118126
detected in the early adjustment period. The highest Igeo values for Cd
and Cu appeared in 2003, for Zn and Pb in 2015, and for Cr and Ni in
2018. The Igeo sequence in 2003 was Cd > Cu > Zn > Pb > Cr > Ni. In
2015 it was Cd > Zn > Cu > Pb > Cr > Ni. In 2018 it was Cd > Pb > Cu
> Zn > Cr > Ni.
Ni and Cr were mostly categorized as “unpolluted” because of Igeo <0.
Cu Igeo values corresponded with “moderate to strong pollution” status in
2003, “slight to moderate pollution” status in 2015, and “slightly
polluted” status in 2018. Moderate to more severe Cu pollution (Igeo >1)
occurred in 84% of the sampling sites in 2003 and 32% in 2015.
Therefore, Cu pollution decreased during the adjustment period in the
Modaomen Estuary. The Igeo value for Zn correlated with a “slight to
moderately polluted” status in 2003, “slight to moderately strong
polluted” status in 2015, and “unpolluted to slightly polluted” status in
2018, with the corresponding percentages of 11%, 31%, and 0% for a
moderate pollution status. As with Cu, the pollution level of Zn
decreased from the early adjustment period to present time. The Pb Igeo
value corresponded to an “unpolluted to slightly polluted” status at most
of the sampling sites in the early and middle adjustment period. How­
ever, Pb was at “slightly to moderately polluted” levels in 2018. Overall,
the sampled sediments were heavily contaminated by Cd, which was
consistent with the CI and Ei results. These Cd Igeo values indicated
“moderate or higher pollution” status for 68% of the sampling sites in
2003, 68% in 2015, and 60% in 2018. Strong Cd pollution occurred at
54% of the sampling sites in 2003, 14% in 2015, and 30% in 2018. Based
on the Igeo quantitative statistical analysis, Cd accumulated in sediments
of the Modaomen Estuary to a high degree after the reclamation/man­
agement projects, which had a significant adverse effect on the aquatic
organisms. Cu and Zn contaminated the sedimentary environment only
moderately, and Cr and Ni showed low toxicity in this estuary.
4.2.3. Assessment of enrichment factor
The enrichment factor (EF) is introduced to assess the pollution
levels and to determine whether the sediment metals are of natural or
anthropogenic input (Jahan and Strezov, 2018; Liu et al., 2019; Lu et al.,
2020). The EF value larger than 1 indicates anthropogenic factor, and
the EF value less than or close to 1 is treated as mainly of a natural origin
(Sutherland, 2000; Hu et al., 2013; Lu et al., 2020). The calculation of EF
is described as:
/
(Ci Cref )in− situ
EF = / (10)
(Bi Cref )reference
where Cref means the reference concentration of heavy metal for
normalization purposes. The element Al is mostly used for marine
sediment normalization since it represents aluminosilicates (Yang et al.,
2014; Liu et al., 2019). Al is supposed to behave conservatively in
normal marine environments. The background value of Al is 85.9 mg
kg− 1 (CNEMC, 1990). The classification of EF values is suggested as
(Sakan et al., 2009; Liu et al., 2019): no enrichment where EF < 1; minor
enrichment if 1 <EF < 3; moderate enrichment if 3 <EF < 5; moderately
severe enrichment if 5 <EF < 10; severe enrichment if 10 <EF < 25; very
severe enrichment where 25 <EF < 50; and extremely severe enrich­
ment where EF > 50.
Most of the EF values for Cr (89%), Ni (100%), and Pb (92%) in the
early adjustment period of 2003 were less than 1 (a minor enrichment
level; Fig. 3j), indicating these metals were of natural origins. Cu showed
a “moderate to severe enrichment” level in 2003, occurred in 75% of the
sampling sites. At more than a half of the sampling sites (62%) Zn was
categorized as having minor to slight enrichment and at the remainder
of the sampling sites it was “moderate to severe enrichment”. Cd was the
most enriched element, categorized as “moderate to extreme severe
enrichment”, occurred in 97% of the sampling sites.
In the middle and current adaptive adjustment periods of 2015 and
2018, the EF values for Cr, Ni, Pb, and Cu showed “minor to slight
enrichment” at most sites in the estuary, depicted in Fig. 3k-l. Moderate
L. Niu et al.
or higher Zn pollution occurred in 78% of the sampling sites in 2015 and
70% in 2018. The enrichment level of Cd was much higher than other
metal species. It was totally classified as moderate to severe enrichment
in 2015 (4.88–47.62) and 2018 (6.89–67.14). Severe Cd pollution
occurred in 73% of the sampling sites in 2015 and in 80% in 2018.
In summary, these findings indicated that the EF values for Cu and Cd
in the early adjustment period implied an anthropogenic origin, Ni
showed a natural forcing, whereas other heavy metal species were
controlled mainly by a mixed source. For the middle adjustment period,
the EF values implied anthropogenic sources for Zn and Cd and mixed
sources for Cu, Pb, Ni and Cr. For the current Modaomen Estuary
adjustment period, the EF values suggested that the anthropogenic
sources for these metals were the dominant.
4.2.4. Assessment of sediment quality guidelines
Sediment quality guidelines (SQGs) provides two target values: ef­
fects range low (ERL, 10th percentile of the data) and effects range
median (ERM, 50th percentile) (Liu et al., 2019; Tian et al., 2020; Zhang
et al., 2021). The values of ERL and ERM are used to assess sediment
quality with respect to adverse biological effects. Their values provide
qualitative guidelines on identifying the sediments as toxic or non-toxic
to aquatic organisms. The levels of heavy metals less than ERL are
treated as non-harmful, concentrations larger than ERM are viewed as
frequently harmful, and concentrations in the range of ERL–ERM are
considered to be occasionally harmful (Long et al., 1995; MacDonald
et al., 1996, 2000).
Table S7 (Supplementary Material) shows the toxicity assessment for
heavy metals in sediment and SQGs from published literature on this
highly anthropogenically influenced Modaomen Estuary. Specifically, in
2003, Cu occasionally posed a threat to aquatic organisms at most (95%)
sampling stations. The concentrations of Ni, Pb, and Cr were mostly
lower than the ERL, which implied that adverse biological effects from
Ni, Pb, and Cr rarely occurred. Almost one half (46%) of the Cd levels
were less than the ERL, and the remaining half (54%) were larger than
the ERL but lower than the ERM. In the middle adjustment period of
Fig. 4. Particle property and median grain size of the surface sediments in 2003 (a, d), 2015 (b, e), and 2018 (c, f).
7
Environmental Pollution 290 (2021) 118126
2015, Pb and Cd were likely to pose no risk of harm to aquatic envi­
ronment. Cu, Cr, Zn, and Ni were likely to occasionally show adverse
biological effects at most sites. Finally, 17% of the Zn levels were
frequently associated with adverse biological effects. In 2018, all of the
Ni and most of Cu, Zn, Pb, Cr levels occasionally caused toxic responses
in marine organisms. Cd showed rare harmful to marine organisms in
this estuary, accounted for 67%. Overall, Cu and Cd were likely to show
adverse biological effects in 2003, Cu, Cr, Zn, and Ni were the factors of
concern in 2015, and Cr, Ni, Cu, Zn, and Pb might be the threats to
marine organisms in 2018.
5. Discussion
5.1. Effects of sedimentary environment on the heavy metals
The Modaomen reclamation/management projects were an effective
way of relieving population pressure in the surrounding urban zones.
However, population growth resulted in increased concentrations of
heavy metals due to the urban activities (Bai et al., 2011). The recla­
mation projects in the estuary have significantly changed the sedimen­
tary and aquatic environments. These changes influenced the
accumulation process of heavy metals in sediments (Zhang et al., 2017).
The West River carried the sediment to the Modaomen Estuary. The
flow rate dropped sharply due to the horizontal diffusion at the river
mouth. The coarse particles settled and formed the Modaomen sandbar.
Fig. 4 shows the change in sedimentary environment during the
adjustment phases that began after the extensive reclamation projects in
the Modaomen Estuary. In the early adjustment period, the surface
sediments were mainly composed of clay (13.6–75.4%, mean 42%), silt
(6.6–61.3%, mean 32%), and sand (1.3–98.2%, mean 31%). The fine
sand was distributed mainly in the shoal of the Modaomen sandbar. In
2015, surface sediments consisted mainly of sandy clay (47%). Sand
accounted for 33% of the material and silt accounted for 20%. The grain
size near the sandbar was the coarsest, and the sediment size gradually
became finer to the sea. The median diameter of sediment near the
L. Niu et al.
sandbar (below the 5 m isobath) was far greater than in the outer es­
tuary. High levels of heavy metals (e.g., Cu, Ni, and Pb) appeared at the
5–8 m isobath of the Modaomen estuary (Fig. S2, Supplementary Ma­
terial). In 2018, the sediment had a high proportion of silt (54%). This
study of sedimentary environments reflects the impacts of anthropo­
genic and natural processes on depositional processes (Li et al., 2000;
Yang et al., 2014).
In general, fine particles were important carriers of trace metals (Ip
et al., 2007; Hu et al., 2013; Yao et al., 2016). Fig. 5 shows the PCA
correlations between the content of heavy metals and sediment prop­
erties in the Modaomen Estuary. In 2003, three components were
extracted and explained 80% of the total variance. PC1 (accounting for
36%) was dominated by the sediment texture, PC2 (28%) was highly
influenced by Cu, Cd, Ni, and Zn, and PC3 (16%) was associated with Pb
and Cr. The Pearson’s correlations (p < 0.05) indicated that Cu was
significantly correlated with clay and Cr was closely correlated with
sand and silt (Table S8, Supplementary Material). However, the corre­
lations between other elements and sediment properties were not
significant.
In 2015, three components were extracted and explained 84% of
total variance. In PC1, Cu, Ni, and sediment texture were the contribu­
tors, accounting for 54% of the total variance. PC2 was influenced
mainly by Cd and Pb, and accounted for 16% of the total variance. In
PC3, Zn and Cr contributed the most. The Pearson’s correlation results
showed that Cu, Pb, Cr, and Ni were significantly correlated with the
sediment texture. Zn and Cd behaved differently in that their distribu­
tions had relatively weak correlations with sediment texture. In 2018,
two factors were extracted and explained 95% of total variance. Sedi­
ment properties and metal species were the main contributors in PC1
(49%) and PC2 (46%), respectively. The amount of Cu, Cr, and Ni had
significant correlations with sediment properties.
In summary, a change in the sedimentary environment of the Mod­
aomen Estuary was detected under the long-term reclamation. Coarse
Fig. 5. Factor analysis results between sediment properties and heavy metals in the estuary (a, 2003; b, 2015; c, 2018).
8
Environmental Pollution 290 (2021) 118126
particles were mined for the reclamation projects. Therefore, fine par­
ticles were observed in the central estuary, which became coarser to the
sea. Clay was the main sediment component in the early and middle
adjustment periods and silt was the dominant material in the present
adjustment period. Other environmental factors (e.g., hydrodynamics,
pH, and organic matter) as well as binding capacity could also affect the
distribution of heavy metals in sediment (Yu et al., 2001; Krupadam
et al., 2007; Kumar et al., 2015; Machado et al., 2016; Li et al., 2020).
The adsorption capacity of heavy metals was positively correlated with
the surface area of particles, making the finer particles (e.g., silt and
clay) the leading materials for metal elements (Coxon et al., 2016). The
pollution patterns of accumulating metal species were regulated jointly
by the interactions of the sedimentary environment, riverine input,
marine forcing, and human activities (Feng et al., 2017; Xie and Wang,
2020; Jia et al., 2021). The adaptive adjustment of the estuary stability
under the long-term reclamation is still developing.
5.2. Source apportionment using PCA-MLR and PMF
5.2.1. PCA-MLR
Heavy metals in the superficial sediments of the Modaomen Estuary
have been shown to pose some threat to aquatic organisms and eco­
system’s health. Therefore, it is very important to identify the pollution
sources. In this estuary, heavy metals were imported through two main
pathways (Huang, 1993; Huang et al., 2018; Liu et al., 2019): (1) the
pollutants were transported through the main tributaries and river
networks; and (2) they were imported from the adjacent seas (e.g., Pearl
River Estuary, South China Sea). PCA-MLR determined the most com­
mon pollution sources and contribution rates of heavy metals in the
Modaomen Estuary (Table 2; and Fig. S3, Supplementary Material). The
PCA-MLR generated two factors for the three adjustment periods (2003,
2015, and 2018), with eigenvalues >1.0. These factors captured the
most important information in the raw data.
L. Niu et al. Environmental Pollution 290 (2021) 118126

Table 2 Pb (Lin et al., 2018; Zeng et al., 2020). Atmospheric deposition and soil
Source identification of heavy metals in the estuarine sediments using PCA-MLR erosion are also potential sources of Pb (Ip et al., 2007). Prior studies
and PMF. have reported that Cr originated mainly from natural sources in the PRD
PCs Eigenvalue Variance PCA- PMF (Huang, 1993; Hu et al., 2013) but that agricultural pollution also
MLR contributed to Cr (Wuana and Okieimen, 2011). Moreover, Cr was
2003 PC1 2.88 45% Cu, Zn, 2003 Factor Zn significantly correlated with other heavy metals (i.e., Cu and Cd) (Li
Ni, Cd 1 et al., 2020). PC2 thus portrayed a mixed source and accumulation in the
PC2 1.49 28% Pb, Cr Factor Pb estuarine sediments, heavily correlated with industrial wastewater, fuel
2
combustion, and the transport from the Pearl River Estuary.
Factor Cu, Cd
3 In 2015, PC1 (48% of the total variance) had high positive loading of
Factor Cr, Ni Cu, Ni, Cd, and Pb. These four elements contributed 84.3% (Cu), 82.7%
4 (Ni), 84.8% (Cd), and 75.8% (Pb) of the pollution sources. PC2 (25% of
2015 PC1 3.13 48% Cu, Ni, 2015 Factor Cd total variance) demonstrated a strong positive loading for Zn and Cr,
Cd, Pb 1
PC2 1.21 25% Zn, Cr Factor Cu, Pb,
with corresponding contribution rates of 93.1% and 70.5%. These two
2 Cr, Ni elements closely correlated with each other. The EF results showed that
Factor Zn Zn and Cd were mainly from anthropogenic input; Cu, Pb, Ni and Cr
3 originated from a mixed natural and anthropogenic source. In 2018, PC1
2018 PC1 3.32 53% Cu, Ni, 2018 Factor Pb
(53% of total variance) demonstrated a strong positive loading for Cu,
Cd, Cr 1
PC2 1.66 30% Zn, Pb Factor Cd Ni, Cr, and Cd, with the source contributions of 79.1% (Cu), 84.8% (Ni),
2 97.7% (Cr), and 75.5% (Cd). PC2 (30% of total variance) had a positive
Factor Cu, Zn, loading for Pb and a negative loading for Zn, with contribution rates of
3 Cr, Ni 63.9% (Pb) and 81.9% (Zn).
Overall, the source types of heavy metal pollution (except Cd) were
In the early adjustment period of the estuary, the first two principal different at these periods due to characteristics of each element and the
components accounted for 73% of the total variance. PC1 (45% of the sedimentary environment. The element Cd showed an anthropogenic
total variance) was highly correlated with Cu, Zn, Ni, and Cd, with the factor under the long-term reclamation. Cu implied “anthropogenic-
contribution rates of 77.6%, 82.4%, 91.1%, and 62.8%, respectively. mixed-anthropogenic” forcing during three stages; Ni had “natural-
Significant correlations were exhibited by the paired elements of Cu, Zn, mixed-anthropogenic” source; Zn showed “mixed-anthropogenic-
Cd, and Ni (R = 0.47–0.87), indicating that this group had similar anthropogenic” input; Cr and Pb suggested “mixed-mixed-anthropo­
contamination levels and/or similar pollution sources. Previous studies genic” input during those periods.
have suggested that Cu, Cd, and Zn were typically associated with (Huang, 1993) reported potential sources of heavy metal pollution in
anthropogenic input (Li et al., 2000; Zhou et al., 2004; Bai et al., 2011; 1991 in the Modaomen Estuary during the Modaomen reclama­
Hu and Cheng, 2013). Both EF and Igeo results suggested that Cd and Cu tion/management project based on PCA results (Table S9, Supplemen­
were influenced by anthropogenic input, Zn was a mixed source, and Ni tary Material). In that study, Cr was associated with transport from the
was mainly from a natural source. The city of Jiangmen, located in the Pearl River Estuary; Cd and Pb were mainly from the river basin; and Cu
lower reach of the West River, is one of the largest industrial cities along and Zn originated from industrial wastewater and transported within
the river. Some industrial and agricultural areas were also detected the river channels.
along the Modaomen channel (Fig. 1). Heavy metals in industrial
waste-water were adsorbed on the suspended solids (e.g., fine sand) and 5.2.2. PMF
were migrated to the estuary. Cu and Zn were the dominant. Addition­ The positive matrix factorization (PMF) model was also used to
ally, the use of chemical fertilizer in agricultural production and sewage quantify the potential sources of heavy metals in this estuary. PMF,
irrigation could markedly dedicate to heavy metal contamination such combined with Pearson’s correlation results, determined the number of
as Zn, Cu, and Cd (Mamat et al., 2014; Zhao et al., 2017). (Huang et al., factors. Twenty iterations were performed to improve the accuracy,
2018) have reported that Zn, Cu, and Cr were mainly from industrial considering the concentration and uncertainty data. Fig. 6 and Table 2
wastewater and agricultural pollution in the Pearl River Delta. Parent show the factor profiles of heavy metals achieved by PMF in the Mod­
rocks and emissions from vehicles have increased the concentration of aomen Estuary. Four factors were detected in the early adjustment
Ni (Hu et al., 2013; Antoniadis et al., 2017). Other related investigations period. The first factor showed high loading of Zn with a contribution
also reported that Ni was abundant in mining wastewater (Li et al., rate of 83.6%. Zn has been linked to industrial wastewater. Therefore,
2014). Therefore, PC1 could be interpreted as a mixed source mainly the first factor was designated as industrial source. The second factor
distributed to industrial wastewater, agricultural pollution, and parent was characterized by Pb with a contribution rate of 89.5%. According to
material. the EF value, 92% of the Pb was of natural origin in 2003. Therefore, the
The second principal component (PC2, accounting for 28% of the second factor was designated as atmospheric deposition. The third fac­
total variance) in 2003 included the high loading of Pb and Cr, with the tor, which was highly correlated with Cu and Cd, was considered to be
contribution rates of 92.4% Pb and 87.4% Cr. Pb and Cr negatively agricultural application and traffic. The fourth factor, characterized by
correlated with each other (R = − 0.35). Non-significant correlations Cr and Ni, was distributed to transportation of the adjacent seas and
between Pb and other elements were detected, demonstrating a different lithogenic control. Therefore, the fourth factor was associated with a
pollution source. This data implied that these two elements had a similar mixed source of marine transportation and parent material.
contamination level but might originate from different sources. The EF Three factors were detected in 2015. The first factor was character­
values indicated that Cr and Pb were from a mixed source influenced by ized by Cd and designated as the traffic source. The second factor had a
anthropogenic and natural input. The wastewater from lead high loading of Cu, Pb, Cr, and Ni, and was treated as a mixed source of
manufacturing and electroplating industries had some amount of Pb. fuel/oil combustion and marine source. The third factor included a high
Water transportation facilities (e.g., ship pollution) also contributed a load of Zn, linked to industrial source.
significant amount of Pb. (Ip et al., 2007) suggested that Pb in the coastal Three factors were observed in 2018. The first factor was charac­
area came mainly from the PRE and the main tributaries. Human ac­ terized by Pb, indicating a fuel combustion source. The second factor
tivities such as fuel and oil combustion could lead to a massive release of had a high load of Cd, associated with a traffic source. The third factor
was characterized by Cu, Cr, Zn, and Ni. This pollution was associated

9
L. Niu et al.
Fig. 6. Factor profiles achieved by the PMF model in 2003 (Panel A), 2015 (Panel B), and 2018 (Panel C).
with a mixed source of industrial and marine transportation.
Source classifications obtained by the PCA-MLR and PMF are pre­
sented in Fig. 7. Overall, the results of these two models have some in
common. Compared with the PCA-MLR, PMF provided more details of
source apportionment. The PCA explained most of the raw information
(<100%), while the PMF represented all the information (100%).
Various sources were intended to industrial productions, import from
the Pearl River Estuary, traffic pollution, fuel combustion, and agricul­
tural applications. Among these pollution sources of heavy metals, in­
dustrial activity was the main contributor. In 1991, 2003, Cr and Ni
were mainly imported from the Pearl River Estuary. The Pearl River
Estuary collected the suspended particulate solids in several waterways
of the East River, North River, and West River. These suspended par­
ticulate solids were likely transported to the Modaomen Estuary because
of the influence of southwestern coastal currents. These suspended
solids might adsorb a large amount of heavy metals released from cities
such as Dongguan and Guangzhou, of which Cr was the most prominent
(Huang, 1993). However, in 2015 and 2018, the sources for Cr and Ni
were of mixed natural and anthropogenic input. The contribution rates
of Cu, Zn, Cr, and Cd increased between 2003 and 2018, indicating that
the role of human activities in heavy metal pollution increased
10
Environmental Pollution 290 (2021) 118126
gradually.
5.3. Implications for estuary management
The heavy metals in the estuarine sediments were transported and
transformed because of the strong influences of hydrodynamics and
aquatic environment (Xie and Wang, 2020). The Modaomen Estuary
acted as a major sink of contaminants in the surrounding ecosystems and
co-influenced by river inflows and waves. Generally, riverine input of
land-based pollutants migrated from the West River to the southwest
estuary, largely influenced by the Coriolis and coastal currents. The east
estuary, connecting to the Pearl River Estuary, was heavily contami­
nated by the metal species of Zn, Cu, Ni, Pb, and Cr, which implied that
the Pearl River Estuary would contribute to these heavy metals. The
outer estuary received a large amount of petroleum leakages from ship
transportation, which induced the storage and fixation of heavy metal
accumulation. Additionally, the saltwater intruded into the estuary or
the upper channels (>50 km during 1992–2012) might induce toxic
conditions. More toxic conditions of the sedimentary environment due
to the changes in hydrodynamics and anthropogenic pressures may have
resulted in the enrichment of Cu, Zn, Pb, and Cd (Ota et al., 2021).
L. Niu et al.
Fig. 7. Source classifications of heavy metals in the estuarine sediments with two receptor models of PCA-MLR (a, 2003; b, 2015; c, 2018) and PMF (d, 2003; e, 2015;
f, 2018).
The identification of heavy metal diffusion and transportation can
inform the water quality management in the estuary; the source
apportionment of metal elements helps to manage the source input. This
may allow financial bodies, such as government and estuary manage­
ment groups, to identify that the sediments would have a greater adverse
effect on marine organisms or human health. The stability of the Mod­
aomen Estuary is still developing under the long-term reclamation.
Seasonal fertilizer applications in agricultural productions carry a large
number of heavy metals into the river basin. The river-tide-wave in­
teractions encourage/discourage the diffusion and transportation of
heavy metals. Urban activities (e.g., industrial application, domestic
sewage, fuel combustion) contribute more to metal accumulation in the
estuarine sediments.
With the continuous development of manufacturing industry in the
south China, the metal productions still resulted in heavy metal pollu­
tion (Wang et al., 2020). Accordingly, management practices, such as
ordered and standardized human activities may help to control the
metal pollution. Additionally, the estuarine-specific management that
accounts for spatiotemporal variation in sedimentary environment is
required for the management of trace metal input. Therefore, extensive
monitoring of heavy metal pollution in the aquatic environment should
be continued for a better understanding of source apportionment. Clean
production processes should be developed for the sustainable develop­
ment of the ecosystems’ health in the Pearl River Delta.
6. Conclusions
Heavy metal contamination were evaluated in the Modaomen Estu­
ary of the Pearl River Delta. Heavy metals varied significantly in the
estuary (p < 0.05) with sites and times, largely influenced by the sedi­
mentary environment and the geochemical properties of the metals. The
mean concentrations of Cu and Cd in 2018 showed a decreasing trend
with respect to 2003. The elements Zn, Pb, Cr, and Ni increased 32%,
269%, 415%, and 366%, respectively. All the concentrations of Zn, Cu,
and Cd exceeded their background values. The multivariate analysis
procedures were useful tools for the classification of the pollution levels.
Both EF and Ei showed moderate to very severe Cd contamination, and
the values of CI and Igeo displayed high ecological toxicity of Cu and Cd
in the estuary. The risk assessment results revealed that heavy metals
were accumulated to a high pollution level. PCA-MLR and PMF
11
Environmental Pollution 290 (2021) 118126
identified the source contributions of heavy metals. Various sources in
this estuary were distributed among industrial productions, import from
the Pearl River Estuary, traffic pollution, fuel/oil combustion, and
agricultural applications. Among these pollution sources of heavy
metals, industrial activity was the major contributor of heavy metals,
accounting for 29% in 2003, 28%, in 2015, and 38% in 2018, using PMF.
Overall, the principal acting mechanisms of heavy metal contami­
nation in sediments are different under the long-term reclamation. The
sedimentary environment has important ecological functions that in­
fluence the metal distributions. The accumulation of heavy metals and
their ecological toxicity to ecosystems’ health are the key aspects of
concern in that area. Limited discussion are focused on the effect of
sedimentary environment on the metal species of Cr, Zn, Pb, Cu, Cd, and
Ni. However, studies related to more metal elements and other influ­
encing processes (i.e., sea level rise, saltwater intrusion, atmospheric
deposition) should be explored for a better understanding of the dy­
namic mechanisms of heavy metals in the highly anthropogenically
influenced estuary. It is also necessary to formulate countermeasures for
protecting the estuarine ecosystems of the Pearl River Delta.
Funding
This work was supported by the National Key R&D Program of China
(grant number 2016YFC0402601) and the National Natural Science
Foundation of China (grant number 51709289).
CRediT author statement
Lixia Niu, Writing-Original Draft, Conceptualization, Formal anal­
ysis; Jiayi Li, Investigation; Xiangxin Luo, Writing-Original Draft, Soft­
ware, Visualization; Tao Fu, Data Curation; Ou Chen, Formal analysis;
Qingshu Yang, Supervision, Project administration.
Declaration of competing interest
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.
L. Niu et al.
Acknowledgments
The authors would like to thank the research group of the Institute of
Estuarine and Coastal Research (Sun Yat-sen University) for conducting
the filed surveys. The authors also thank LetPub (www.letpub.com) for
its linguistic assistance during the preparation of this manuscript.
Appendix A. Supplementary data
Supplementary data to this article can be found online at https://doi.
org/10.1016/j.envpol.2021.118126.
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