Accepted Manuscript

Title: A modified receptor model for source apportionment of

heavy metal pollution in soil

Authors: Ying Huang, Meihua Deng, Shaofu Wu, Jan Japenga,

Tingqiang Li, Xiaoe Yang, Zhenli He

PII: S0304-3894(18)30345-5
DOI: https://doi.org/10.1016/j.jhazmat.2018.05.006
Reference: HAZMAT 19372

To appear in: Journal of Hazardous Materials

Received date: 21-11-2017

Revised date: 26-4-2018
Accepted date: 2-5-2018

Please cite this article as: Huang Y, Deng M, Wu S, Japenga J, Li T, Yang X, He Z,

A modified receptor model for source apportionment of heavy metal pollution in soil,
Journal of Hazardous Materials (2010), https://doi.org/10.1016/j.jhazmat.2018.05.006

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A modified receptor model for source apportionment of heavy

metal pollution in soil

Ying Huanga, Meihua Denga, Shaofu Wub, Jan Japengaa, Tingqiang Lia,*, Xiaoe Yanga,*, Zhenli

Hec

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The affiliation and address of the authors
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Ministry of Education Key Laboratory of Environmental Remediation and Ecological Health,

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College of Environmental and Resource Sciences, Zhejiang University, Hangzhou 310058,

China
b

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Shaoxing Station of Agricultural Technique Popularization, Shaoxing 312000, China
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c
University of Florida, Institute of Food and Agricultural Sciences, Indian River Research and
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Education Center, Fort Pierce, FL 34945, USA
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*Corresponding author: Dr. Xiaoe Yang, Ministry of Education Key Laboratory of

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Environmental Remediation and Ecological Health, College of Environmental and Resource

Sciences, Zhejiang University, Hangzhou, 310058, China, Tel: +86-571-88982907 Fax:

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+86-571-88982907
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E-mail: xeyang@zju.edu.cn; litq@zju.edu.cn

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Graphical abstract

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Highlights


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A new model (PCA-MLRD) for soil heavy metal source apportionment was build.

 Multiple linear regression with content and distance was used to quantify source
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contributions.

 It can identify the specific sources as well as their influence extents.

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 It performed better prediction and more practical source identification than APCA-
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MLR and PMF.

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Abstract
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Source apportionment is a crucial step toward reduction of heavy metal pollution in soil.

Existing methods are generally based on receptor models. However, overestimation or

underestimation occurs when they are applied to heavy metal source apportionment in soil.

Therefore, a modified model (PCA-MLRD) was developed, which is based on principal

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component analysis (PCA) and multiple linear regression with distance (MLRD). This model

was applied to a case study conducted in a peri-urban area in southeast China where soils were

contaminated by arsenic (As), cadmium (Cd), mercury (Hg) and lead (Pb). Compared with

existing models, PCA-MLRD is able to identify specific sources and quantify the extent of

influence for each emission. The zinc (Zn)-Pb mine was identified as the most important

anthropogenic emission, which affected approximately half area for Pb and As accumulation,

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and approximately one third for Cd. Overall, the influence extent of the anthropogenic

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emissions decreased in the order of mine (3km) > dyeing mill (2km) ≈ industrial hub (2km)

> fluorescent factory (1.5km) > road (0.5km). Although algorithm still needs to improved,

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the PCA-MLRD model has the potential to become a useful tool for heavy metal source

apportionment in soil.

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Keywords
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Heavy metal; source apportionment; PCA-MLRD; PMF; APCA-MLR
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1. Introduction
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In recent years, Chinese citizens have become concerned about heavy metal pollution of
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soil, to which food safety and human health are related [1-3]. According to the 2014 National

Soil Pollution Investigation Bulletin of China, 16.1% of arable soils have been contaminated,
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and heavy metal was the most important pollutants, sites with concentrations exceeding the

standard value of As, Cd, Hg, Pb, Zn, chromium (Cr), and copper (Cu) were 2.7%, 7.0%, 1.6%,
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1.5%, 0.9%, 1.1%, and 2.1%, respectively [4,5]. Source apportionment is an important tool for

prevention and reduction of soil pollution by heavy metals. Research is needed to tackle issues

like high spatial heterogeneity of heavy metals in soil, complexity and diversity of source

emissions, and the lack of monitoring information [6]. Current methods for source

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apportionment can be grouped into source identification and quantification. The former is to

identify major pollution sources using geographic information system (GIS), principal

component analysis, and cluster analysis [7-11], whilst the latter performs quantitative analysis

using receptor models, which were originally developed for source apportionment of pollutants

in the atmosphere [12-15]. Receptor models can identify and quantify source contributions

based on chemical and physical characteristics of pollutants in sources and receptors. The

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existing receptor models include chemical mass balance (CMB), positive matrix factorization

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(PMF), absolute principal component analysis followed by multiple linear regression (APCA-

MLR), potential source contribution function (PSCF), and UNMIX [16-19].

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Chemical mass balance (CMB) is a fundamental receptor model based on the concept of

mass balance [20]. In this model, linear regression is used to develop balance equations of

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pollutants in source and receptor using both source profiles and ambient data. It is the most
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accurate model, but the application of CMB model is limited due to unavailability of source
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profiles [21]. Based on CMB, more sophisticated statistical approaches have been developed
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and source contributions can be quantified with ambient pollutant contents. The first

application of this model was reported by Hopke et al. (1976), who used factor analysis to
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identify the major sources of pollutants in aerosol particles [22]. Several models were

subsequently developed, and the most widely used ones are APCA-MLR and PMF. The APCA-
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MLR model is based on principal component analysis (PCA) and multiple linear regression
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(MLR) [23-26]. In this model, PCA is used to reduce data dimensionality by replacing a large
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set of corrected variables with less independent variables so that major factors can be identified

[27]. Then the MLR with ambient contents and factor scores is performed to quantify the
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contribution from each factor. The PMF is employed to decompose a matrix of sample data

into two matrices: factor contributions and factor profiles. These two matrices can be

transformed into exact source profile matrix and source contribution matrix [28,29]. In recent

years, these two models have been widely applied to air pollution and lately to soils and
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sediments [6,30-32].

A critical step of source apportionment with receptor models is the interpretation of source

profiles and their assignment to practical emission sources. For air pollution, source signatures,

seasonal variations, and wind direction are usually used [33]. But source interpretation

becomes more difficult when applied to heavy metals in soil. Firstly, due to physical, chemical,

and biological migration, a definitive signature may not exist [34]. Secondly, there is no

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significant seasonal variations of heavy metal in soil. Thirdly, contribution of point sources

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changes with distance. There are three ways for heavy metal emitting from anthropogenic

sources to the surrounding soil: heavy metal-enriched exhausted gases, effluent and solid

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wastes. During atmospheric deposition, heavy metal in exhausted gases can fall to the soil

surface with rain or as dry deposits. Although some elements are not volatile, they can be

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absorbed in aerosol particles and transported to further areas via long-distance circulation.
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Runoff water and effluents/storm water from contaminated sites can transport heavy metals to
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the surrounding areas. Solid wastes are often stacked around, and heavy metal can be infiltrated
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into soil with leachates and/or land disposal of the wastes. Previous studies reported that soil

heavy metal content decreased with increasing distance from roads or mines [35]. In addition,
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in order to separate factors, factor matrix is always rotated, which may lead to rotational

ambiguity [36]. This problem becomes a critical shortcoming in source apportionment in soils,
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since a minor contributor of heavy metal in one place could be a major contributor in other
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places. For example, the contribution from soil parent materials is usually underestimated.
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Therefore, it is necessary to modify receptor models when applied to heavy metal source

apportionment in soils.
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This study was aimed to develop a modified model that can be applied to heavy metal

source apportionment in contaminated soils. The model was verified using the data of heavy

metal contents in the topsoil samples collected from a peri-urban area in southeast China, where

soil pollution is severe due to exposure to multiple emission sources. The modelling outcome
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was compared with APCA-MLR and PMF for their performance.

2. Material and methods

2.1 Sample collection and chemical analysis

One hundred and fourteen soil samples were collected from a peri-urban area of 12×10

km2 in southeast China between December 2014 and February 2015, where an abandoned lead-

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zinc (Pb-Zn) mine was located, and two high ways (G104 and S24) passed through. In addition,

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a large industrial hub was located in the central east, consisting of several plastic factories.

Small factories were distributed along the high ways, including dyeing mills, textile mills and

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a fluorescent factory. Soil samples were collected with stainless steel augers, as a sampling

grid of about 1×1 km2. Each sample (approximately 1.5 kg fresh soil) was composited with

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five topsoil cores, one collected at the center and four in the surrounding area, and the sampling
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sites were located using a portable GPS. The location of the study area and sampling sites are
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presented in Fig. 1. In laboratory, the soil samples were air-dried, passed through a 100-mesh
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polyethylene sieve and stored in a desiccator prior to analysis.

After soil samples were digested in a closed poly-tetrafluoroethylene system with a

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mixture of HNO3 (5 mL) – HF (1 mL) – HClO4 (1 mL) at 180 ˚C for 10 hours, concentrations

of aluminum (Al), calcium (Ca), chromium (Cr), copper (Cu), magnesium (Mg), manganese
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(Mn), sodium (Na), vanadium (V), zinc ( Zn ), iron (Fe), and lead (Pb) in the digester were
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determined using inductively coupled plasma optical emission spectrometry (ICP-OES,

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Thermo 6300, USA) and concentration of cadmium (Cd) determined using inductively coupled

plasma-mass spectrometry (ICP-MS, Agilent 7500a, USA). Mercury (Hg) and arsenic (As)
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were analyzed using atomic fluorescence spectrometry (AFS, AFS-230E Haiguang Analytical

Instrument Co., Beijing, China) after the soil samples were digested with 5 mL aqua regia and

5 mL deionized water on a water bath at 100 ˚C for 4 hours. Sample replicates, reagent blanks,

and standard reference materials (GBW07429, the National Research Center for Certified
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Reference Materials of China) were included in each batch of analysis for quality assurance.

The recovery of spiked standard for each element was from 90 to 110%. The detection limits

of Al, Ca, Cr, Cu, Mg, Mn, Na, V, Zn, Fe, and Pb were 0.1, 0.01, 0.01, 0.01, 0.02, 0.02, 0.2,

0.01, 0.006, 0.03, and 0.05 mg/kg, respectively. The detection limits of Cd, Hg and As were

0.1, 0.04 and 0.04 μg/kg.

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2.2 Source apportionment models

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2.2.1 Absolute principal component analysis followed by multiple linear regression (APCA-

MLR)

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This model is based on the assumption that total content of contaminant is equal to the

sum of contributions from all individual pollutant sources. The algorithm of this model is

shown below:
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𝑋𝑖𝑘 −𝐶𝑖
𝑍𝑖𝑘 = (1)
𝜎𝑖
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𝑍𝑖𝑘 = ∑𝑝𝑗=1 𝑊𝑖𝑗 𝑃𝑗𝑘 (2)
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(𝐴𝑃𝐶𝑆)𝑗𝑘 = 𝑃𝑗0 − 𝑃𝑗𝑘 (3)

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𝑋𝑖𝑘 = ∑𝑝𝑗=1 𝐴𝑖𝑗 (𝐴𝑃𝐶𝑆)𝑗𝑘 (4)

where 𝑋𝑖𝑘 is the content of ith element in the kth sampling site; 𝐶𝑖 is the average content; 𝜎𝑖
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is the standard deviation; 𝑍𝑖𝑘 is the normalized matrix of elemental content, j is the number of

factors; 𝑊𝑖𝑗 is the factor loading matrix, which is the coefficient matrix of the components
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relating each factor to its element content and 𝑃𝑗𝑘 is the factor score matrix, defined as the

value of the jth source’s components on each sampling site k. 𝑃𝑗0 is the factor score matrix in
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a “zero” pollution site, where all elemental contents are equal to 0, (𝐴𝑃𝐶𝑆)𝑗𝑘 is the absolute

principal component scores. 𝐴𝑖𝑗 is the linear regression coefficient matrix for the ith element

of jth factor. The contribution of each source is calculated using 𝐴𝑖𝑗 and (𝐴𝑃𝐶𝑆)𝑗𝑘 .

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2.2.2 Positive matrix factorization (PMF)

Positive matrix factorization is a typical receptor model recommended by United States

Environmental Protection Agency (US EPA) for source apportionment of airborne pollutants

with the following equation [33,34]:

𝑋𝑖𝑘 = ∑𝑝𝑗=1 𝐺𝑖𝑗 𝐹𝑗𝑘 + 𝐸𝑖𝑘 (5)

where 𝑋𝑖𝑘 has the same meaning as in equation (1); 𝐹𝑗𝑘 is the contribution matrix of jth source

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factor for k number of samples; 𝐺𝑖𝑗 is the source profile for ith element for jth source factor and

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𝐸𝑖𝑘 is the residual error matrix. Factor contributions and profiles are derived by the PMF model

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minimizing the objective function Q:

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𝐸𝑖𝑘 2
Q = ∑𝑛𝑖=1 ∑𝑚
𝑘=1( ) (6)
𝑈𝑖𝑘

where 𝑈𝑖𝑘 is uncertainty of the ith source factor for kth sample. The calculation method for

𝑈𝑖𝑘 is referred to US EPA (2014) [37]. U

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2.2.3 The modified model (PCA-MLRD)

The modification is based on the assumption that total content of contaminant is equal to
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the sum of contributions from each individual source. Since the spread character of these metals

from emission sources to soil follows decreases with distance, the contribution can be
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quantified with the distance between sampling sites and the sources. In addition, this model is

based on complete emission inventory and detailed survey of regional socio-economic

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activities. Figure 2 shows the detail flowchart of this model, where PCA is used to identify

potential sources and source contribution can be calculated through MLR with heavy metal
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content and distance from the source:

𝑋𝑖𝑘 = ∑𝑝𝑗=1 𝐵𝑖𝑛 𝐷𝑛𝑘 (7)

where 𝐷𝑛𝑘 is the distance from sampling sites to sources; 𝐵𝑖𝑛 is the regression coefficient

matrix of the distance to sources; 𝑛 is the number of sources. As shown in Figure 2, 80% of

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the samples were randomly chosen to build the model, and the left 20% samples were for

verification. In addition, PCA is sensitive to outliers, in order to reduce the fluctuation,

excessive content of elements were used instead of original contents. The excessive content

can be calculated based on Enrichment Factors (EF) as follows [38]:

[𝑀]
( )
[𝐶] 𝑆𝑜𝑖𝑙
EF = [𝑀] (8)
( )𝐶𝑟𝑢𝑠𝑡
[𝐶]

[𝑀]
[𝑀]𝑒𝑥𝑐𝑒𝑠𝑠𝑖𝑣𝑒 = [𝑀]𝑠𝑜𝑖𝑙 − [𝐶]𝑠𝑜𝑖𝑙 ( )𝐶𝑟𝑢𝑠𝑡 (9)

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𝐶

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where [𝑀] is the content of trace element, and [𝑀]𝑒𝑥𝑐𝑒𝑠𝑠𝑖𝑣𝑒 is the excessive content , [𝐶] is

[𝑀]

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content of crustal reference element; ( [𝐶] )𝑆𝑜𝑖𝑙 is the concentration ratio of the trace element

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[𝑀]
to crustal reference element in the collected soil samples, and ( [𝐶] )𝐶𝑟𝑢𝑠𝑡 is the background

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ratio of trace metal to crustal reference element. With the extracted factor loading matrix and
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factor score matrix, potential emissions were screened. Then source assumption was made by
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comparing the spatial distribution of factor score matrix with the location of potential emissions.
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In the multiple linear regression, not only the original distance matrix was used, the distance

metric was also transformed with various mathematical algorithms to find the best fitting. The
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mathematical algorithms used in this study include logarithmic transformation and reciprocal

transformation conducted with the inverse distance weighting method (Supplementary

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Material). In order to avoid collinearity, stepwise regression was used in MLR. In model

verification, 𝑅 2 > 0.5 was used to filter all element models, and the best models were selected
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based on their fitting of the measured contents with mean-square error (MSE) and recognition

of the most contaminated sites where management priority should be given. With the regression
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model, the contribution of each source was quantified, and the influence extend was calculated.

2.3 Data analysis

Data pre-processing and transformation were conducted with Microsoft Excel 2003. PCA

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and MLR were conducted with SPSS 18.0. Principal components with eigenvalues > 1 were

retained (Kaiser criterion). Varimax rotation was used to minimize the number of elements with

a high loading on one component [39]. The multiple regression was performed with a forward

stepwise. The analysis of PMF was conducted with PMF 5.0 (US EPA 2014) [37]. The

resolution was attained when there was no big reduction of Q with increasing factor number.

The distribution of heavy metal content, and source contribution were analyzed with ArcMap

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10.0 with inverse distance weighted interpolation.

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3. Results and discussion

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3.1 Heavy metal pollution in the studied area

Majority of the studied elements in soil had relatively wide ranges, high standard deviation

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(SD) and high coefficients of variation (CV), especially for As, Hg, Pb, Cd (Table 1). The
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geometric means of Hg, Pb and Cd contents in the soil samples were higher than the second
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standard threshold values in the Chinese Environmental Soil Quality Standards (GB 15618-
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2008) [40], and were several times of the background values [41]. Overall, more than half of

the sampling sites were contaminated with Cd and As, and one third of the soils were
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contaminated with Hg and Pb. On the contrary, Cr, Cu, V and Zn contents were not significantly

higher than background values. Contents of Ca, Fe, Mg, Mn, Cu, Al and Zn were all below
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background values. To further assess the degree of trace element pollution, the Index of geo-
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accumulation (Igeo) was calculated (Supplementary Material). The result showed that Pb, Hg,
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Cd were moderately contaminated in the order of Pb＞Hg＞Cd, and As was uncontaminated

to moderately contaminated, while the other elements were uncontaminated (Table. S1).
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Therefore, it is necessary to identify pollution sources of Cd, Pb, Hg, and As for management

purposes.

3.2 Source apportionment by the APCA-MLR and PMF model

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 Four factors were selected by the APCA-MLR and PMF model. The source profiles and

source contributions generated by these two models are presented in Fig. S1 and 3. There was

relatively high overlapping of both source profiles and source contributions. Factor 1 obtained

from both models was strongly representative for Al, Ca, Mg, Na and Fe. Factor 2 had high

loading of V, Zn, Cr, and Fe, while there was minimal difference regarding As. Factor 3 from

the APCA-MLR model had high loadings of Pb, Cd and As, while factor 3 from the PMF

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model was dominated by Pb and Cr. Factor 4 from both models had high loadings of Cu, Cd,

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and Hg. Earlier studies showed that Fe, Al, Na, V, and Cr were highly characteristic of soil

parent materials [42,43]. Zinc, Cu, Ca, Mg were more related to fertilizers and agrochemicals

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[44,45]. Lead and Cd were linked to traffic emission [46]. Imperato et al (2003) reported that

industrial plants together with traffic were responsible for enrichment of Cu, Cr, Pb, and Zn in

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soil [47]. Metal mining was also an important emission source of Pb and Cu [48,49]. According
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to the obtained source profiles, factors 1 and 2 represented natural and agricultural sources,
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factors 3 and 4 were more associated with traffic emission and industrial/mining inputs.
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Considering the socio-economic activities in this area, the two high ways (G104 and S24), the

Pb-Zn mine, the industrial hub and small plants contributed to factors 3 and 4. According to
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the four identified factors, it can be shown that: 1) in the APCA-MLR model, 100% of Cd and

Hg were related to traffic and industrial emissions; 28% of Pb was originated from natural and
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agricultural sources with the remaining 72% from traffic and industrial emissions; 40% of As
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may come from natural and agricultural sources with the remaining 60% from traffic and
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industrial emissions. 2) In the PMF model, 100% of Pb, Cd, and Hg were originated from traffic

and industrial emissions, while 100% of As came from natural and agricultural source.
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3.3 Source apportionment by the PCA-MLRD model

In the PCA model, V was selected as a crustal reference element since it is the signature

of soil parent materials, and the content of V is similar to the natural background value. The
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result showed that model calculations using excessive contents were more reliable as compared

to the original contents in PCA (Supplementary Material). Three principal components were

obtained, jointly accounting for approximately 70% of the total variance. PC1 was responsible

for the variance of Al, Ca, Mg, Mn, Na, Fe, Zn and a part of Cr; PC2 was the main factor for

Pb, As, Cu and a part of Cd pollution; and PC3 was the major factor for Hg, Cd and As pollution.

Spatial distribution of the three absolute principal component scores was shown in Figure S2,

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and used for source interpretation by comparing with the location of potential emissions (Figure

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S2). It can be clearly noticed a non-point distribution of PC1 and a significant point distribution

of PC 2. The higher scores of PC2 were located around the Pb-Zn mine. There were two higher

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scoring points for PC3, one is located in the industrial hub and the other along the northern

stretch of road S24. Therefore, traffic emissions (G104 and S24), the Pb-Zn mine, the industrial

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hub, and small factories along the roads were identified as potential anthropogenic sources.
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The distances from sampling sites to sources were calculated and the distance transformed with
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the inverse distance weighting method (with m = 5/3) resulted in the best result (Supplementary
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Material). Finally, the MLR models for As, Cd, Hg, Pb were developed as follows:
1 1 1
[𝐴𝑠]𝑒𝑥𝑐𝑒𝑠𝑠 = 74.74 × + 44.54 × + 35.37 × 𝑅 2 = 0.54
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5 5 5
3
𝐷𝑚𝑖𝑛𝑒 3
𝐷43 𝐷53

1 1 1 1
[𝐶𝑑]𝑒𝑥𝑐𝑒𝑠𝑠 = 2.66 × 5 + 2.38 × 5 + 1.43 × 5 + 0.08 × 5 𝑅 2 = 0.54
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3
𝐷𝑚𝑖𝑛𝑒 3
𝐷106 𝐷53 3
𝐷𝑆24

1 1 1 1
[𝐻𝑔]𝑒𝑥𝑐𝑒𝑠𝑠 = 0.70 × 5 + 0.56 × 5 + 0.46 × 5 + 0.06 × 5 𝑅 2 = 0.59
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3
𝐷industrial 𝐷53 3
𝐷106 3
𝐷𝑆24
hub
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1 1
[𝑃𝑏]𝑒𝑥𝑐𝑒𝑠𝑠 = 560.40 × 5 + 217.92 × 5 𝑅 2 = 0.65
3
𝐷𝑚𝑖𝑛𝑒 3
𝐷43
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Where the subscript ‘mine’ represents the Pb-Zn mine; ‘industrial hub’ means the industrial

hub; ‘5’ represented a small dyeing mill, and ‘106’ represented a big dyeing mill; ‘43’

represented a fluorescent factory; and ‘S24’ represented the provincial road.

Six individual point and polyline sources were identified as significant anthropogenic

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emission sources for As, Cd, Hg, and Pb pollution in the studied area. Together with

background contribution values, the contribution from each source to As, Cd, Hg, Pb was

determined (Fig. 4). For soils in the central part, parent materials had minimal influences, the

increased metal contents were mainly resulted from anthropogenic emissions. Overall, parent

materials were the biggest contributor, accounting for nearly 40% of the total variance for each

heavy metal. The biggest anthropogenic emission was the Pb-Zn mine, which has spread Pb

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out to 4 km away, and had influence on As and Cd for approximately 3 km from the center.

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The fluorescent factory was also an anthropogenic source for Pb, but its influence was less than

mine. Mercury, Pb, and As are the common additives in fluorescent lamp production, and the

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emission from the fluorescent factory was reported to contaminate soils within 1.5 km [50].

The mine, two dyeing mills and the provincial road (S24) contributed to the higher Cd contents

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in the order of: the Pb-Zn mine/the bigger dyeing mill (3 km)＞the smaller dyeing mill (1.5
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km) ＞the provincial road (500 m). In dye products, Cd, Cu, and other metals are common
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additives and their concentrations are higher in waste water and sludge [51]. The industrial hub,
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which housed several plastic factories, was a major emission source for Hg. Plastic production
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is the major Hg consumer in China, and Hg is contained in exhaust gases, effluents and solid

waste of plastic factories [52]. In order to control soil pollution, emissions from the Pb-Zn mine,
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two dyeing mills, the fluorescent factory, the provincial road, and the industrial hub should be

monitored and isolated or discontinued.

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3.4 Comparison with commonly used receptor models

The comparison between measured contents of heavy metals and the calculated values
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with the three models indicated that the APCA-MLR and PCA-MLRD model performed better

than the PMF model for Hg, As, Cd, and Pb. The APCA-MLR model fitted better in the middle

range of heavy metal contents, while, the PCA-MLRD model fitted better on severely polluted

sites (Fig. 5). The points with high contents in the distribution map were well identified with
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PCA-MLRD model. In addition, in APCA-MLR and PMF model, the fitting of Pb, Cd, Hg,

and As was poor, as compared with Al, Ca, and Mg (Fig. S3). This is because contaminants

(like Cd, Hg, As, Pb in this area) are mainly influenced by anthropogenic emissions, whereas

uncontaminated elements (Al, Ca, Mg, Fe, etc.) are more determined by parent materials and

agricultural emissions. Therefore, priority was given to those uncontaminated elements both in

factor analysis and source quantification. This problem was solved in the PCA-MLRD model

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by separate regression with metal content and distance, leading to best fitting for each

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contaminated element.

The advantages of the modified model over other existing models include: 1) the problem

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of rotational ambiguity being avoided, as over-rotated factor scores were not used in the

contribution quantification; 2) being able to identify specific anthropogenic sources; and 3)

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providing useful source interpretation, based on the match of factor distribution and potential
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source location. The interpretation of source profiles in existing receptor models was always
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based on identified source signatures. However, not all sources have unique signatures, and the
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source signatures were changeable. For example, lead was not allowed as an additive to petrol

in China since 1996, leading to reduced Pb emission from traffic, but Pb was still regarded as
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a tracer for traffic emission in the interpretation of source profiles [53]. In addition, the data

inconsistency caused by outliers is reduced using excessive content instead of measured

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content, and the model output verification using an additional 20% data rendered the results
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more reliable. However, there are also potential disadvantages with the modified model. Firstly,
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the contributions of non-point sources cannot be quantified. Secondly, comprehensive research

of the local information is needed for the studied area, such as background values of heavy
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metals, local industrial activities, and potential anthropogenic emission sources. Thirdly, the

algorithm should be further improved, and better methods for distance transformation is desired.

4. Conclusion
14
 Principal component analysis followed by multiple linear regression with distance from

sampling sites to sources (PCA-MLRD) provides more reliable and accurate results than

traditional receptor models when applied to source apportionment of heavy metal pollution in

contaminated soils. It can detect specific anthropogenic emission sources for each pollutant

and quantify their contributions and geographical impact ranges, which is useful for pollution

control and management. The identified anthropogenic sources for As, Cd, Hg and Pb pollution

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in the studied area were a Pb-Zn mine, two dyeing mills, a fluorescent factory, a provincial

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road, and an industrial hub. Emissions from the mine, the industrial hub and the bigger dyeing

mill have an impact up to approximately 3 km from the center of the source. Therefore, in order

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to reduce heavy metal emission, the emissions from these sources should be monitored and

isolated or removed. However, there are still shortcomings of this newly developed model, for

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example, cannot quantify the contribution from non-point sources (such as agricultural
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emissions). Nonetheless, this model is a useful tool for heavy metal pollution management of
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agricultural soils, particularly in the areas with severe pollution by multiple emission sources.
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Acknowledgments
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This study was financially supported by key projects from Science and Technology Bureau of

Zhejiang Province (Grant # 2015C02011; Grant # 2015C03020), key research program from
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Ministry of Science and Technology of China (Grant # 2016YFD800805), and the Fundamental
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Research Funds for the central Universities of China.

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15
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Figure legends
Figure 1. Map of study area and location of sampling sites.
Figure 2. The flowchart of model modification processes (PCA-MLRD).
Figure 3. Source contributions to trace metals of each factor generated by the APCA-MLR and PMF
model.
Figure 4. Spatial distribution of pollution sources (%) for As, Cd, Hg, Pb, and their total contribution
to the study area.

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Figure 5. Comparison of measured heavy metal contents with calculated values (mg/kg) from the

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three models.

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Figure 1. Map of study area and location of sampling sites.

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20
 Start
Start Randomly
Randomly choosing
choosing 80%
80% samples
samples to
to build
build model
model

Element
Element content
content matrix
matrix X
X (i×k)
(i×k)

Data
Data prepartion
prepartion Element
Element excess
excess content
content matrix
matrix X excess (i×k)
Xexcess (i×k)

Normalized
Normalized element
element content
content matrix
matrix ZZ (i×k)
(i×k)

Principal
Principal component
component analysis
analysis (PCA)
(PCA) ZZ == W
W ×× PP

Factor
Factor loading
loading matrix
matrix W
W (i×j);
(i×j); Factor
Factor score
score matrix
matrix PP (j×k)
(j×k)

Spatial
Spatial distribution
distribution of
of PP (j×k)
(j×k)

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Source
Source screening
screening
Comparing
Comparing with
with local
local geographical
geographical information
information

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source
source assumption
assumption

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Distance
Distance calculation
calculation D
D (n×k)
(n×k)

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Distance
Distance transformation
transformation D
D
Contribution
Contribution
quantification
quantification Multiple
Multiple linear
linear regression
regression X excess =
Xexcess =BB ×× D
D

Comparing
Comparing with
with No
No U
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estimated
estimated content
content
Yes
Yes
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Varification
Varification with
with the
the other
other 20%
20% sampling
sampling sites
sites
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Model
Model verification
verification
Comparing
Comparing with
with No
No
estimated
estimated content
content
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Yes
Yes
End
End Export
Export source
source and
and contribution
contribution

Figure 2. The flowchart of model modification processes (PCA-MLRD).

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Figure 3. Source contributions to trace metals of each factor generated by the APCA-MLR and PMF
model.

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Figure 4. Spatial distribution of pollution sources (%) for As, Cd, Hg, Pb, and their total contribution to the study area

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Figure 5. Comparison of measured heavy metal contents with calculated values (mg/kg) from the three models.
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Table 1. Summary of element content in 114 soil samples in the study area (values in mg/kg).

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Element Cr Cd Hg Pb As Cu Zn Al Ca Fe Mg Mn Na V
Minimum 5.44 0.18 0.08 19.24 0.11 18.51 28.88 30982 2222 11469 7001 196.5 9468 55.88

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Median 74.97 0.82 0.46 169.12 23.87 29.41 93.00 54226 5546 33210 5510 364.8 10186 108.4
Maximum 189.00 5.45 2.18 512.26 109.55 79.00 201.18 129966 12002 57354 17824 825.9 24346 211.0

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Geometric
69.11 0.80 0.43 157.17 18.24 29.82 90.89 47755 4301 29974 5032 367.2 8570 90.14
Mean
Arithmetic
76.19 1.24 0.54 182.67 29.55 31.77 96.80 53272 5558 31583 6127 386.2 9801 93.02

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Mean
SD 29.69 1.11 0.39 97.16 24.14 11.87 34.35 23070 4443 9710 3952 120.6 4470 31.38
CV % 38.97 89.25 72.69 53.19 81.70 37.37 35.48 43.31 79.95 30.74 64.50 31.24 45.61 27.76

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Skewness 0.50 1.31 1.77 0.88 0.94 1.42 0.69 0.40 4.47 0.08 2.16 0.61 0.31 0.51
Kurtosis 1.48 1.37 3.76 0.62 0.48 3.59 0.31 -0.01 27.64 -0.40 9.28 1.05 -0.11 0.57
Standard a 300 0.5 0.5 80 25 100 250
Background b
Igeo c
69.70
-0.60
0.20
1.41
ED 0.10
1.54
32.50
1.70
6.20
0.97
29.20
-0.55
89.90
-0.57
67700
-1.09
6140
-1.10
27650
-0.47
9350
-1.48
491.0
-1.00
11500
-1.01
85.00
-0.50
a
The second standard threshold value of Chinese Environmental Soil Quality Standards (GB 15618-2008) [40], with 6.5＜pH＜7.5.
b The
background value of this area was adapted from ref. 41.
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c
The calculation of Index of geo-accumulation (Igeo) can be seen in Supporting Information.
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