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Journal of Environmental Management 304 (2022) 114228

Contents lists available at ScienceDirect

Journal of Environmental Management


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

Source apportionment and health risk assessment of chemicals of concern


in soil, water and sediment at a large strontium slag pile area
Da Ding, Lingya Kong, Dengdeng Jiang, Jing Wei, Shaohua Cao, Xuwei Li, Liping Zheng,
Shaopo Deng *
State Environmental Protection Key Laboratory of Soil Environmental Management and Pollution Control, Nanjing Institute of Environmental Sciences, Ministry of
Ecology and Environment, Nanjing, 210046, China

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

Keywords: Strontium (Sr) is an alkaline earth metal that has adverse effects on bone tissue, but received little attention
Chongqing compared to other often-studied metals. This study analyzed the contents/concentrations of Sr, barium (Ba),
Nemerow index sulfate (SO42− ), sulfide (S2− ), and six common metals in 209 multi-media samples, including slag, soil,
Positive matrix factorization
groundwater, surface water, and sediment, collected at a large Sr slag pile area. Sr was the dominant chemical of
Monte Carlo simulation
concern (COC) in the soil and groundwater, with contents/concentrations being 35.50–32200 mg/kg and
0.57–152 mg/L, respectively, much higher than those reported in previous research. Contents/concentrations of
all COCs in the surface water and sediment were relatively low, except Sr content in the sediment near the slag
pile. The LogKd value of Sr was calculated to be lower than those of common metals, indicating relatively high
mobility of Sr in the aquatic environment. Contamination assessment using Nemerow index indicated near half of
the soil and groundwater sampling locations, especially those within and near the slag pile, were heavily
contaminated, and Sr was the dominant COC. The positive matrix factorization model suggested four sources for
the COCs in soil, including Sr slag pile/SrCO3 production, agricultural activities, industrial activities, and natural
sources, with contribution rates of 66.88%, 5.28%, 7.5%, and 20.34%, respectively. Monte Carlo simulation-
based probabilistic health risk assessment revealed that the non-carcinogenic risk of groundwater, and the
carcinogenic risk of soil and groundwater, were unacceptable. Notably, Sr was the unique COC posing non-
carcinogenic risk among the COCs studied. Our results provide the scientific support needed for managing Sr
point source impacted area.

1. Introduction Elevated uptake of Sr is associated with disorders of bone tissue, teeth,


liver, and brain, especially abnormal bone development in the children
Strontium (Sr) is an alkaline earth metal, an analogue of calcium (Ca) when skeletons are developing (Khandare et al., 2020; Musgrove, 2021;
and barium (Ba). In nature, Sr is found as minerals of celestite (SrSO4) Pathak and Gupta, 2020). Due to the concerns over the hazards of Sr to
and strontianite (SrCO3). SrCO3 can also be prepared synthetically from human health, since 2013, the United States Environmental Protection
SrSO4 by direct conversion or black ash method (Zoraga and Kahruman, Agency (USEPA) proposed the Lowest Concentration Minimum
2014). SrCO3 is often applied in various industries, such as ceramics, Reporting Level for Sr in drinking water to be 0.3 μg/L (USEPA, 2015).
paint pigments, fluorescent lights, and medicines (Pathak and Gupta, The USEPA also set Regional Screening Levels (RSLs) for Sr in soil to be
2020). In geochemical process, Sr behaves similar to Ca due to their 47,000 mg/kg and 420 mg/kg for residential soil and groundwater
similar chemical properties. Sr is highly mobile in surface water, protection, respectively (USEPA, 2021). The United States Geological
groundwater and sediments, and can also migrate to the atmosphere via Survey (USGS) developed a Health-Based Screening Levels of 4 mg/L for
rock weathering, migration of dust particles with wind, resuspension Sr in drinking water (Norman et al., 2018). Canada published a
processes, etc. (Pathak and Gupta, 2020). drinking-water quality guideline of 7 mg/L for Sr, specifically to protect
Humans are exposed to Sr mainly through drinking water and dietary infants and children (Health Canada, 2019). The Ministry of Ecology and
intake, while air inhalation is insignificant (Pathak and Gupta, 2020). Environment of the People’s Republic of China (MEE) has listed SrCO3

* Corresponding author.
E-mail address: dsp@nies.org (S. Deng).

https://doi.org/10.1016/j.jenvman.2021.114228
Received 27 September 2021; Received in revised form 30 November 2021; Accepted 1 December 2021
Available online 15 December 2021
0301-4797/© 2021 Elsevier Ltd. All rights reserved.
D. Ding et al. Journal of Environmental Management 304 (2022) 114228

into the high pollution products inventory (Production No. process, possible COCs associated with SrCO3 production included Sr,
2601220206) (MEE, 2021), but has not set up screening levels for Sr. Ba, sulfate (SO42− ) and sulfide (S2− ) (SrSO4 sometimes contains Ba)
Although the above potential hazards and regulations, Sr receives much (Alderton, 2021).
less attention as compared to other more often-studied metals to date.
SrSO4 + 2C = SrS + 2CO2 (1)
The environmental occurrence of Sr has been characterized in
several large-scale regions. Sr concentrations were reported to be
SrS + CO2 + H2 O = SrCO3 + H2 S (2)
0.001–13.6 mg/L in European rivers, and 0.4–1.5 mg/L in US surface
water (Watts and Howe, 2010). El-Sayed and Salem (2015) recorded Sr The plant closed in 2008, which had been operated for 15 years with
concentrations ranging from 0.630 to 1.213 mg/L in surface Nile water SrCO3 production capacity of about 12,000 t/y. During operation, about
and groundwater in South West Cairo. Sr concentrations were reported 190,000 t Sr slag was stockpiled within the plant area, covering an area
to range from 0.001 to 1.35 mg/L in drinking water in Western Australia of about 8800 m2. A river was adjacent to the plant area, and the areas
(Hinwood et al., 2015), and 0.06–1.69 mg/L in Xi’an, Northwest China surrounding the plant were mostly farmland, where several small-scale
(Zhang et al., 2018a). Rinklebe et al. (2019) reported the 50th percentile facilities were located in.
value was 105.9 mg/kg for soil in Floodplain soils across Central Elbe Samples were collected from August to September 2018. The sam­
River, Germany. However, at present, little is known about the occur­ pling locations were shown in Fig. 1. Briefly, depth-discrete slag (n =
rence of Sr at a Sr point source impacted area. 28), depth-discrete soil (n = 153), groundwater (n = 13), surface water
The chemicals detected in environment typically originate from (n = 8), and sediment (n = 7) samples were collected, including paired
multiple sources (Hu et al., 2020). Multivariate statistical analyses, such soil-groundwater (n = 10) and surface water-sediment (n = 7) samples.
as correlation analysis (CA) and principal component analysis (PCA), are The depth-discrete slag and soil samples were collected from a 10 m drill
often used to calculate the relationships among chemicals and group core drilled out by a percussion drilling rig. Groundwater monitoring
chemicals with similar sources (Hu et al., 2020). The positive matrix wells were constructed using a percussion drilling rig. Groundwater
factorizing (PMF) model recommended by the USEPA is a factor samples were collected by Bailers, after pumping out three times the
analysis-based receptor model that can get the non-negative source volume of water that was in the well. Surface water and sediment
contribution of each sample and apportion the source contribution to samples were collected by polypropylene bottles and a grab sampler,
each chemical (USEPA, 2014). PMF can be used in combination with CA respectively. All samplers were rinsed with methanol and ultrapure
and PCA to give reasonable and quantitative information about the water before sampling. QA/QC throughout the sampling campaign fol­
potential sources of chemicals (Dong et al., 2019; Hu et al., 2020; Ran lowed the Guidance for Quality Assurance and Quality Control for In­
et al., 2021). vestigations at Key Industries and Enterprises Sites (No. 1869–2017)
In addition, most existing health risk assessments were based on (MEE, 2017).
deterministic values for the input parameters. However, the variations
of input parameters may either under- or over-estimate the risk level.
Monte Carlo simulation can estimate the exposure and risk values with 2.2. Chemical analysis
cumulative probability via iterating calculations with random param­
eter value. Monte Carlo simulation, followed by sensitivity and uncer­ Target analytes included SrCO3 production-related chemicals (Sr, Ba,
tainty analysis, can perform a more realistic risk assessment and has SO42− and S2− ) and six metals, including arsenic (As), cadmium (Cd),
been proved to be one of the most useful approaches for probabilistic copper (Cu), nickel (Ni), lead (Pb) and zinc (Zn). All analyses were
risk assessment (Huang et al., 2021; Mukherjee et al., 2020; USEPA, conducted at the SEP Analytical Technology (Shanghai) Co, Ltd. which
2001; Zhang et al., 2018a). In this study, these advanced data analysis is certificated by the Shanghai Bureau of Quality and Technical
approaches were applied to achieve more accurate results. Supervision.
The largest Sr deposit in Asia has been found in Chongqing, China, Contents/concentrations of Sr, Ba, Cu, Zn, Ni, Pb and Cd were
and several SrCO3 production factories have been built in this city analyzed by inductively coupled plasma mass spectrometry (ICPMS-
(Chongqing Geological Survey, 2014). Accordingly, the site of a former 7900, Agilent, USA). As content/concentration was analyzed by atomic
SrCO3 production plant (now a large Sr slag pile area) in Chongqing was fluorescence spectrometer (AFS-9800, Beijing Haiguang Instrument,
taken as a case to (1) characterize the contents/concentrations of China). SO42− content in soil and sediment was determined following
chemicals of concern (COCs) in the slag, soil, groundwater, surface the titration method of NY/T 1121.18–2006. SO42− concentration in
water and sediments at the Sr slag pile area; (2) evaluate the contami­ water was analyzed by ion chromatography (Dionex™ ICS-600, Thermo
nation level using specific contamination assessment indices; (3) explore Fisher, USA). S2− contents/concentration in water, soil and sediment
and quantify the source contributions via a combination approach of CA, was determined following the methylene blue spectrophotometric
PCA, and PMF models; (4) assess the human health risk via a probabi­ method of HJ 833–2017, using an ultraviolet–visible spectroscopy (Cary
listic method. It should be noted that Sr has stable and radioactive iso­ 100, Agilent, USA). Detailed sample pre-treatment procedures and the
topes, and this study addressed the stable Sr. This work aims to fill the method detection limits (MDLs) were provided in Text S1 and Table S1,
knowledge gap of occurrence, source and risk of Sr at a Sr point source respectively, in Supporting Information.
impacted area, and to propose management options for policymakers to Field blanks, transport blanks, and analytical blanks were conducted
make decisions, guidelines and regulations. for each sample batch, and the contents/concentrations of target analyte
in the blanks were all below the MDLs. Standard sample recoveries
2. Materials and methods ranged from 91% to 114%, and the relative standard deviation was less
than 5%.
2.1. Study area and field sampling

The study area was a site of a closed SrCO3 production plant (now a 2.3. Data analysis
Sr slag pile area) and its surrounding area in Chongqing, China. The
closed plant formerly adopted the black ash method to produce SrCO3, 2.3.1. Contamination assessment indices
using SrSO4 as raw material. Firstly, SrSO4 was roasted with coke at Pollution index (PI) were calculated to evaluate the contamination
about 1100 ◦ C to form SrS which is then leached in water. Next, the Sr- level for individual metal using Eq. (3), and Nemerow index (NI) were
containing solution was reacted with CO2 to precipitate SrCO3. The main calculated to assess overall contamination level for all metals in soil and
process can be expressed as Eqs (1) and (2). According to the production water using Eq. (4) (Chen et al., 2019):

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D. Ding et al. Journal of Environmental Management 304 (2022) 114228

Fig. 1. Sampling locations of slag, soil, groundwater, surface water, and sediment.

Ci factor contributions matrix gik, factor profiles matrix fkj, and a residual
Pi = (3)
Si matrix eij:
√̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅ p

( )2
(Pi(max) )2 + Pi(ave) Xij = gik fkj + eij (6)
NI = (4) k=1
2
where i, j, and k are the numbers of samples, COCs and, sources,
where Ci is the COCs content/concentration (mg/kg or mg/L), Si is the
respectively. Xij is the content of chemical j in sample i (mg/kg); gik is the
limit value set by environmental administrations to protect the envi­
contribution of source k to sample i; fkj is the amount of COC j from
ronment and human health (e.g., screening levels, environmental
source k. Factor contributions and profiles are derived by minimizing
quality standards or drinking water regulations, unit mg/kg or mg/L).
the objective function Q:
The classification criteria of NI were provided in Table S2.
∑n ∑ m ( )2
eij
2.3.2. Surface water-sediment partition coefficient Q= (7)
i=1 j=1
uij
To understand the transport and fate of COCs in the aquatic envi­
ronment, the partitioning behavior of COCs between surface water and where m is the number of COCs studied, n is the number of samples, uij is
sediments were investigated by calculating the solid-water partition the uncertainty of jth COC in ith sample, which is calculated from the
coefficient Kd (L/kg): COC content, MDL, and the measurement uncertainty. If the COCs
Cs contents were greater than MDL, uij was calculated as:
Kd = (5) √̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅
Cw
Uij = (Errorfraction × concentration)2 + (0.5 × MDL)2 (8)
where Cs and Cw are the COCs content/concentration in sediments (mg/
kg) and surface water (mg/L), respectively. According to the model recommendation, data below the MDL would
be replaced with the value of MDL/2, and the associated uij was calcu­
2.3.3. Statistical analysis lated as:
All statistical analyses were performed in the statistical program 5
SPSS v22.0 (IBM, USA) and R (v 4.1.0) (Houyun Huang et al., 2021). The uij = × MDL (9)
6
contents/concentrations below MDL were replaced by MDL/2 for sta­
The bias and uncertainty of the solution obtained were further
tistical purposes (Feng et al., 2020). Figures were plotted in Origin
assessed using two error estimation methods: classical bootstrap (BS)
(2018). ArcGIS 10.5 was used for map delineation. ArcGIS inverse dis­
and displacement of factor elements (DISP). All calculations follow the
tance weighting interpolation was applied to interpolate the spatial
US EPA PMF 5.0 User Guide (USEPA, 2014).
distribution of NI in the soil and groundwater.

2.5. Probabilistic health risk assessment


2.4. PMF model
The non-carcinogenic and carcinogenic health risks for the COCs in
In this study, PMF was applied for quantitative source apportion­ soil and groundwater were estimated according to the USEPA health risk
ment. PMF decomposes the matrix of observed content of COCs Xij into assessment model (USEPA, 2001), including exposure assessment and

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D. Ding et al. Journal of Environmental Management 304 (2022) 114228

risk assessment. The population was grouped into children and adults Smirnov Test, which was required to perform the Monte Carlo simula­
due to their physiological and behavioral differences. Soil exposure tions (Table S6).
pathways were considered to include ingestion, dermal contact, and
inhalation. Groundwater exposure pathways were considered to include 3. Results and discussion
ingestion and dermal contact.
The non-carcinogenic risk was characterized as hazard quotient (HQ) 3.1. Contents/concentrations of COCs in slag leachate, soil, and
and hazard index (HI). The carcinogenic risk (CR) was characterized as groundwater
CR and total carcinogenic risk (TCR). If HQ or HI is greater than 1, there
are potential non-carcinogenic risks. If CR or TCR exceeds 1E-4, it in­ Fig. 2 displayed the box plots of the contents/concentrations of COCs
dicates humans suffer from cancer risks, whereas CR or TCR below 1E-6 detected in slag leachate, soil, groundwater, surface water, and sediment.
is generally considered to pose negligible carcinogenic risks (Huang Table S7 provided the summary statistics, including detection frequency,
et al., 2021; USEPA, 2001; Xu et al., 2018). Equations of exposure and minimum, maximum, mean, standard deviation, coefficient of variation
risk assessment were provided in Text S2. The exposure and toxicity (CV), median, limit value, and over-limit rate. The mean contents/concen­
parameters were provided in Table S3-S5. trations and over-limit rates of four SrCO3 production-related COCs (i.e., Sr,
Crystal Ball 11.1.24 (Oracle, USA) was used to perform the Monte Ba, SO42− , and S2− ) generally exceed other COCs in all media (Fig. 2,
Carlo simulations for probabilistic human health risk assessment, using Table S7). Moreover, the concentrations of all detected Sr in the slag leachate
2D simulation tools with 10,000 trials. The statistical distributions of the samples exceed the limit value of groundwater. These results exhibited the
COCs contents/concentrations were determined under Kolmogorov- impacts from the Sr slag pile on the COCs detected in this area.

Fig. 2. Box plots of COCs contents/concentrations in (a) slag leachate, (b) soil, (c) groundwater, (d) surface water, (e) sediment. The over-limit rates of COCs were
presented with blue font. (For interpretation of the references to colour in this figure legend, the reader is referred to the Web version of this article.)

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D. Ding et al. Journal of Environmental Management 304 (2022) 114228

Sr had the highest mean content among all COCs in the soil, and of other metals from a review of 245 literature conducted by Allison and
showed high spatial variation (CV = 187.67%) which was due to the Allison (2005), the LogKd value of Sr was lower than those of common
high Sr contents detected in some soil samples. Ba had high over-limit metals (Table 1), which indicated Sr had higher aquatic mobility than
rate (55.56%) but relatively low mean content and CV (55.42%), indi­ other metals (Allison and Allison, 2005; Ashayeri and Keshavarzi,
cating its relatively uniform spatial distribution. Fig. S1 showed vertical 2019). Sr has been characterized by moderate mobility in soils and
distribution of the contents of Sr, Ba, SO42− and S2− in the depth-discrete sediments via adsorbing on components of soils and sediments such as
soil samples, and high contents were mainly detected between 0.5 m and iron oxides, clay minerals, and organic matter (Pathak and Gupta,
6 m, suggesting their vertical transport capacities were limited. The 2020). In summary, the COCs contents/concentrations in the surface
highest Sr contents (32,200 mg/kg) occurred in the soil sample S19-5 m, water and sediment were relatively low, except for the sediment near the
which was also loaded by the highest Ba content (615 mg/kg). Addi­ slag pile.
tionally, high Sr content was detected in the corresponding groundwater
sample GW13 and the nearby sediment samples of SW3 and SW4. S19/
GW13 was about 30 m northwest to the Sr slag pile and about 30 m 3.3. Contamination assessment
southeast to the river. These findings implied a potential Sr transport
pathway: Sr transport northwest from the slag pile toward the river. Sr Based on the above results, the contents/concentrations and over-
contents in the soil of this study were higher than those reported in limit rates of COCs were relatively high in the soil and groundwater,
previous research, such as some mine and tailing sites, the Chinese while those were low in the surface water. The NI and PI values are
background value for urban soil, and the worldwide average value typically used to assess metal contamination, hence they were calculated
(Table S8) (Cheng et al., 2014; Jiang et al., 2021; Kabata-Pendias, 2011; to evaluate the contamination level of the metals in soil and water in this
Ran et al., 2021). The contents of Sr and Ba in about half of the soil area (Kowalska et al., 2018). Since depth-discrete soil samples were
samples exceeded the USEPA RSL values for groundwater protection, collected (more than one soil sample at a sampling location), NI was
but not exceeded the values for residential soil. This implied that Sr and calculated for each soil sample and the maximum NI at each soil sam­
Ba in the soil may pose risks to groundwater while not to human health. pling location was reported to represent the worst scenario (Riviere
In the groundwater, the mean concentrations of Sr and SO42− were et al., 2019). According to the NI values of soil, 47.37% of soil sampling
two to three orders of magnitudes higher than those of other COCs, and locations were classified as heavy contamination (NI > 3), and the areas
76.92% and 38.46% of Sr and SO42− exceeded their limit values, within and close to the slag pile got even higher PLI scores (Fig. 3a). In
respectively. The highest Sr concentrations (152 mg/L) occurred at terms of individual COC, the median PI sequence for the COCs in soil was
GW2, which was located within the Sr slag pile. The second high Sr Ba > Sr > As > Ni > Cd > Pb > Cu (Fig. S2). The median PI value for Ba
concentration (61.1 mg/L) occurred at GW13, which was corresponding exceeded 1, corresponding to the over-limit rate of 55.56% for Ba in the
to the soil sample S19-5 m having the highest Sr concentration. Sr soil. Sr got the highest 75th percentile and maximum PI values (max
concentrations in the groundwater in this area were much higher than 76.67), exhibiting dramatic Sr contamination at certain sampling
those reported in previous research, such as a semi-arid region of east locations.
India, the drinking water in Xi’an, China, and the drinking water and Similar to the soil, 46.15% of groundwater samples were classified as
groundwater in the United States (Table S8) (Gerke et al., 2013; Mus­ heavy contamination (NI > 3), and the areas within and close to the slag
grove, 2021; Zhang et al., 2018a). Overall, Sr had relatively high con­ pile got higher PLI scores (Fig. 3b). In terms of individual COC, the
tents/concentrations and over-limit rates in both soil and groundwater. median PI sequence for COCs in groundwater was Sr > Cd > Ba > As >
Further investigations and actions should be taken in this area and other Pb > Cu > Zn. The median PI value for Sr exceeded 1, corresponding to
sites regarding manufacturing of Sr compounds. In addition, there is a the over-limit rate of 76.92% for Sr in the groundwater. Other than Sr
call for updating and extending the current Chinese limit values for Sr and Ba, the maximum PI for As exceed 1 in both soil and groundwater,
and other less-studied chemicals. and the over-limit rates for As in soil and groundwater were 5.88% and
7.69%, respectively, which may result from the historical application of
3.2. Surface water-sediment partition As-containing fertilizers and pesticides (Gong et al., 2020; Hu et al.,
2020). The maximum NI and PI for surface water were 0.15 and 0.21,
All COCs in the surface water samples were detected at relatively low respectively, classified as safe. Overall, near half of the soil and
concentrations, distributed evenly (CV < 40%), and did not exceed any groundwater sampling locations, especially those within and near the Sr
limit value. Sr concentrations in the surface water of this study slag pile, were assessed to be heavily contaminated, which was sug­
(0.26–0.32 mg/L, mean 0.29 mg/L) were close to or lower than those gested to be priority areas for environmental management. Sr was the
reported in other studies, such as US surface water, European rivers, and dominant COC in both soil and groundwater in this area and deserved
surface water in South West Cairo (Table S8) (El-Sayed and Salem, 2015; closer attention.
Watts and Howe, 2010).
The COCs contents in the sediment were also relatively low, except Table 1
the Sr contents in the sediment close to the slag pile. Sr contents in the Median value of LogKd of COCs derived from
sediment samples SW3 and SW4 were 820 mg/kg and 1250 mg/kg, this study and other literature.
respectively, higher than those of other samples and those listed in other COCs LogKd (L/kg)
studies. Maurya and Kumari (2021) reported the maximum Sr content
Pb 5.1
was 996.25 mg/kg in the sediment of Gulf of Kachchh, India. Wang et al. Ni 4.0
(2016) found the Sr content was 42.5–768 mg/kg (mean 318 mg/kg) in Sb 4.0
the sediments of Chaohu Lake, China. Zn 3.7
Sediment can act as a sink to adsorb and store Sr. LogKd values were Se 3.6
Ba 3.4
calculated to quantify the affinity of COCs for the particulate phase, As 2.5
using the contents/concentrations in the paired surface water and Mo 2.5
sediment samples. High LogKd values indicate that the COC is prefer­ Sr 2.4
entially retained by the sediment, conversely low values suggest that the SO42- 0.3
COC mostly remains in water where it is available for transport and Note: Sr, Ba, and SO42− were from this study,
geochemical or biological reactions (Anderson and Christensen, 1988; while other metals were from (Allison and
Ashayeri and Keshavarzi, 2019). Compared to the median LogKd values Allison, 2005).

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D. Ding et al. Journal of Environmental Management 304 (2022) 114228

Fig. 3. Distribution of Nemerow index of (a) soil and (b) groundwater.

3.4. Sources apportionment 2020). PCA extracted four factors with eigenvalue >1, explaining
78.39% of the total variance. Accordingly, the factor number was set to
Due to the soil and groundwater contamination, potential sources for four in the PMF model, with over 93% prediction residuals normally
the COCs in soil and groundwater were explored and quantified. Firstly, distributed between − 3.0 and 3.0. The linear fit equation of the pre­
Kaiser-Meyer-Olkin (KMO) measure of sampling adequacy and Bartlett’s dicted and measured COCs contents was y = 1.04x-174.25, R2 = 0.99. BS
test of sphericity in PCA were conducted to test the suitability of the and DISP models were performed to further estimate the uncertainties in
content/concentration data for factor analysis. KMO index >0.5 and the modeled solution. A total of 100 bootstrap runs were performed, and
Bartlett’s test being significant (p < 0.5) is considered to be suitable for approximately 90% of the base factors were reproduced in the BS model
factor analysis (Williams et al., 2010). For soil, KMO was 0.621 (>0.5) (R2 > 0.6) (Table S10), and no factor swaps were observed in the DISP
and Bartlett’s test was significant (p < 0.01), implying a stable and model. The above results indicated that the four-factor PMF solution was
reliable solution. KMO was 0.326 (<0.5) for groundwater, indicating it stable (Fei et al., 2020). The factor profiles of PCA and PMF were shown
was not suitable for factor analysis. Therefore, source apportionment of in Table S11. Fig. 4a and b displayed the factor fingerprints and con­
COCs in groundwater was not further analyzed. Then Pearson correla­ tributions of individual factors to the COCs. To further verify the PMF
tion analysis was performed to initially explore the relationships be­ results, the factor contributions from PMF model were correlated with
tween the COCs studied. Significant positive correlations and relatively the Pearson correlation coefficients of COCs (Fig. 4c).
high coefficients were found in the group of Sr, Ba, SO42− and S2− , and Factor 1 from PCA and PMF included Sr, Ba, SO42− and S2− , which
the group of Cu and Ni (p < 0.01, r2 > 0.4), indicating the group COCs were associated with the Sr slag pile and historical SrCO3 production
may have common sources (Table S9) (Ghaffari et al., 2021). processes. Hence, Factor 1 was designated as Sr slag pile/SrCO3 pro­
In practice, PCA is often used to select the optimal number of factors duction, with a contribution rate of 66.88% to the COCs detected in the
before PMF analysis (Dong et al., 2019; Gelfand et al., 2017; Hu et al., soil. As mentioned earlier, the concentrations of detected Sr in the slag

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D. Ding et al. Journal of Environmental Management 304 (2022) 114228

Fig. 4. (a) PMF factor fingerprints of COCs, (b) PMF contributions of individual factor to COCs, (c) PMF factor contributions and Pearson correlation analysis.

leachate samples exceeded the limit value of groundwater. These results minerals, oxidation of sulfide minerals, and rainfall (Torres-Martinez
imply that removing the Sr slag can prevent and control further soil and et al., 2020). Factor 4 from PMF model was selected to be natural
groundwater contamination. Other researchers also found point sources sources, with a contribution rate of 20.34%. Overall, four sources
had large contributions to the chemicals detected in the surrounding contributed to the COCs detected in the soil, with Sr slag pile/SrCO3
environment. A municipal solid waste incinerator was reported to have a production being the primary source. Zhang et al. (2018b) also reported
contribution of 36.08% for heavy metals in the surrounding soil (Ma that the metal contents in an abandoned lead-acid battery plant zone
et al., 2018). Cheng et al. (2020) applied PMF and identified five sources were affected by various industrial and agricultural factors. PCA and
for heavy metals in the soil near large, open-pit coal mines. Four of the PMF generated similar results, while with minor differences. The
sources were related to mining activities, having a total contribution inter-model differences have been reported in previous research, which
rate of 62.8%. can be caused by the different theoretical procedures employed by the
Factor 2 from PCA was mainly related to Cu, Ni and Cd, while PMF two models (Huang et al., 2018; Salim et al., 2019; Sofowote et al., 2008;
included high loadings of Pb and moderate loadings of Cu, Ni and Cd. Pb Zhang et al., 2020).
typically originated from vehicular emissions and industrial discharges,
such as mining and smelting, coal burning, and waste incineration. Cu,
Ni and Cd were considered to be closely linked to the industrial zones 3.5. Probabilistic health risk assessment
(Dong et al., 2019; Huang et al., 2021; Shen et al., 2017). Therefore,
Factor 2 was chosen to represent industrial activities, with a contribu­ 3.5.1. Non-carcinogenic and carcinogenic risks
tion rate of 7.5%. Near half of the soil and groundwater sampling locations were
Factor 3 from PCA mainly included Ba, Cd, and As, while PMF was evaluated to be heavily contaminated and thus may pose risks to human
weighted primarily on As and moderately on Ba, Cd, Cu and Ni. Agri­ health. The non-carcinogenic and carcinogenic risks of children and
cultural application of fertilizer, pesticides, feed additives, and sewage adults exposed to the COCs in soil and groundwater through different
irrigation generally provides considerable amounts of As, Cd, Cu and Ni pathways were assessed using Monte Carlo simulation. The probability
(Dong et al., 2019; Fei et al., 2020; Hu et al., 2020). It has been reported distribution for HI and TCR was shown in Fig. 5. Summary statistics of
As, Cu, Ni and Cd were the common metals accumulated in Chinese risk levels were provided in Table S12. According to the probability
farmland (Gong et al., 2020; Zhang et al., 2015). Phosphate fertilizers distribution curves, children had higher probabilities than adults for HI
were found to have high contents of Ba (Ahlgren et al., 2012). Thus, > 1 or TCR > 1E-4, thus ought to be paid more attention. The HQ and CR
Factor 3 may be associated with agricultural activities, with a contri­ for individual COCs with different exposure pathways were presented in
bution rate of 5.28%. Fig. S3. Oral ingestion was the predominant exposure pathway for most
Factor 4 from PCA was mainly Pb, while that from PMF was mainly COCs, and dermal contact was dominant for Cd (due to its high ratio of
SO42− . High levels of SO42− mostly from natural sources, such as sulfate RfDo/RfDd of 100). At the same time, inhalation was insignificant for all
COCs. Accordingly, the residents should avoid ingesting and contacting

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D. Ding et al. Journal of Environmental Management 304 (2022) 114228

Fig. 5. Probability distribution for hazard index (HI) of (a) soil and (b) groundwater, and for total carcinogenic risk (TCR) of (c) soil and (d) groundwater. The red
area represents HI > 1 or TCR > 1E-4. (For interpretation of the references to colour in this figure legend, the reader is referred to the Web version of this article.)

the local soil and groundwater to minimize health risks. duration, adherent factor, soil/groundwater ingestion rate, and COCs
For non-carcinogenic risks, the mean and 95th percentile HI values contents/concentrations (e.g., Sr, As, Cd and Ni) (Fig. S4). The sensi­
of the COCs in soil for children and adults were both below 1, indicating tivity analysis results revealed that a better definition of these parame­
the COCs in soil barely pose non-carcinogenic risks to human health. ters could result in a more accurate risk assessment.
However, the 95th percentile HI values of the COCs in groundwater for Although Monte Carlo simulation was employed to quantify the
children and adults both exceed 1, implying the COCs in groundwater uncertainties of the health risk assessment, certain uncertainties
posed non-carcinogenic risks to human health. In terms of individual remained in this study. The input parameters of ingestion rate, skin area,
COC in groundwater (Fig. S3a, b), only the HQ value of Sr exceeded one. and body weight were obtained from Chinese statistical data. However,
It was much higher than those of other COCs, indicating Sr was the some other parameters were the recommended values from USEPA (e.g.,
unique COC in groundwater, posing a non-carcinogenic risk. Abnormal exposure duration and exposure time), which were not specific to the
bone development may occur for children if the groundwater is used as a Chinese population. Moreover, the exposure pathway of groundwater
drinking source. These results were consistent with the USEPA RSL inhalation was not considered in this study due to the unavailability of
values. Sr contents in soil did not exceed the RSL value for residential toxicological data. Therefore, a more accurate assessment can be further
soil but exceeded groundwater protection. carried out by considering these additional factors.
For carcinogenic risks, the mean and 95th percentile TCR values of
the COCs in soil and groundwater for children and adults both exceed 3.6. Management options
1E-6, and most TCR values surpass 1E-4, suggesting the COCs in soil and
groundwater posed carcinogenic risks to human health. For individual To better prevent and control contamination and risk, several man­
COCs in soil, CR of As, Cd and Ni in soil and Cd in groundwater for agement options were proposed. Firstly, to remediate the contaminated
children exceed 1E-4 (Fig. S3c, d). High carcinogenic risks induced by soil and groundwater and prevent further environmental deterioration,
these carcinogenic metals were also found in the park soil of Shanghai, slag/soil excavation and off-site treatment combining groundwater
China, and the groundwater of eastern China coastal zone (Huang et al., pump and treat are feasible short-term removal actions under high time
2021; Wang et al., 2021). In summary, Sr was assessed as the unique constraints. The excavated slag and soil can be sent to a cement kiln,
COC posing a non-carcinogenic risk, and As, Cd and Ni posed carcino­ which solidifies metals into cement products (Wang and Tang, 2018).
genic risks to human health, which need further responses. The pumped groundwater can be treated via adsorption, chemical pre­
cipitation, ion exchange, membrane technology, solvent extraction, etc.
3.5.2. Sensitivity analysis and uncertainty analysis (Liu et al., 2017). If long-term responses are allowed, phytoremediation
Sensitivity analysis was carried out to recognize the most influential would be an economical and environmentally friendly strategy for the
variables contributing to the output risk values. The dominant variables contaminated soil and groundwater (Pathak and Gupta, 2020).
were generally consistent for all output results, including exposure Then, more attention should be paid to less-examined chemicals. In

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D. Ding et al. Journal of Environmental Management 304 (2022) 114228

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