Geoderma 405 (2022) 115399

Contents lists available at ScienceDirect

Geoderma
journal homepage: www.elsevier.com/locate/geoderma

Assessing toxic metal chromium in the soil in coal mining areas via
proximal sensing: Prerequisites for land rehabilitation and
sustainable development
Jingzhe Wang a, Xianjun Hu d, Tiezhu Shi a, b, Li He c, *, Weifang Hu e, Guofeng Wu a, b
a
MNR Key Laboratory for Geo-Environmental Monitoring of Great Bay Area & Guangdong Key Laboratory of Urban Informatics & Shenzhen Key Laboratory of Spatial
Smart Sensing and Services, Shenzhen University, Shenzhen 518060, China
b
School of Architecture & Urban Planning, Shenzhen University, 518060 Shenzhen, China
c
College of Mechatronics and Control Engineering, Shenzhen University, 518060 Shenzhen, China
d
School of Electronic Engineering, Naval University of Engineering, Wuhan 430033, China
e
Institute of Agricultural Resources and Environment, Guangdong Academy of Agricultural Sciences, Guangzhou 510640, China

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

Handling Editor: Cristine Morgan The rapid and accurate determination of soil chromium (Cr) is crucial for preventing toxic element pollution in
soils and ensuring ecological security. Proximal sensing technology uses visible and near-infrared (Vis-NIR)
Keywords: diffuse reflectance spectroscopy, which has been demonstrated to be a viable approach for monitoring soil Cr
Soil pollution mapping concentrations. However, at trace levels, soil Cr is not especially spectrally active, thus limiting the practical
Soil chromium (Cr)
application of using corresponding spectral data for quantifying soil Cr concentrations. In this study, we hy­
Proximal soil sensing
pothesized that fused proximal sensing and soil auxiliary attributes (including organic matter (OM) and pH)
Auxiliary soil attributes
Three-band spectral indices (TBI) could improve estimation of Cr concentrations in the soil. Additionally, the introduction of best-fit variogram
Variogram model models was theoretically possible to improve spatial visualization. To address these hypotheses, we collected 168
soil samples from the open coal mine area in the Eastern Junggar Basin, China. Fractional-order derivative (FOD)
pretreatment and optimal band combination methods were implemented for spectral data mining and the
derivation of spectral parameters, respectively. Soil Cr estimation models were calibrated with a partial least
squares (PLS) approach through four designed strategies with different predictors: (I) full Vis-NIR variables, (II)
effective three-band spectral indices (TBIs), (III) the effective TBIs and OM, and (IV) the effective TBIs, OM, and
the pH. The results suggest that FOD could identify abundant spectral variability. Compared with full Vis-NIR
variables, the effective TBIs can effectively magnify the subtle spectral signals concerning soil Cr. The optimal
estimation model was determined as Strategy IV, indicating that the introduction of soil auxiliary attributes (pH
and OM) can improve the estimation performance of the model; notably, the coefficient of determination (R2)
and ratio of performance to interquartile distance (RPIQ) were 0.87 and 2.68, respectively. Based on the optimal
semivariance model, we used kriging interpolation to map regional soil Cr. In the study area, the soil Cr dis­
tribution features strong spatial dependence and strong associations. Our study might inspire further research on
soil contamination mapping based on proximal Vis-NIR sensors.

1. Introduction
1.1. Background
Toxic metal contamination in the soil is a global environmental issue,
and a notable threat to ecological systems and human well-being
(McBratney et al. 2014). Chromium (Cr) and its compounds are
widely used in the coal, steel, electroplating, and tanning industries;
therefore, Cr has become a typical pollutant of toxic metal contamina­
tion pollution in China, especially in coal industrial areas and mining
wastelands (Gao and Xia 2011; Wang et al. 2011). In addition, Cr is one
of the most harmful toxic elements, causes severe human health impli­
cations (Ellis et al. 2002).
Considering its various sources and high toxicity, Cr has been defined

* Corresponding author at: College of Mechatronics and Control Engineering, Shenzhen University, 518060 Shenzhen, China.
E-mail address: heli@szu.edu.cn (L. He).

https://doi.org/10.1016/j.geoderma.2021.115399
Received 14 December 2020; Received in revised form 9 August 2021; Accepted 11 August 2021
Available online 25 August 2021
0016-7061/© 2021 Elsevier B.V. All rights reserved.
J. Wang et al.
as a priority monitoring and control pollutant according to the Chinese
government (Hu et al. 2020; Xu et al. 2019). Referring to the “Outline of
the 13th Five-Year Plan for Land and Resources (2016–2020)”, over
5000 km2 of the geological environment of historical mines needs to be
restored, and the reclamation of mining wastelands (ecological reha­
bilitation) is an increasing need (Zhou and Cao 2020). Mining waste­
lands are preferred for agricultural production after ecological
restoration in China (Gao and Xia 2011). However, land rehabilitation
may cause secondary toxic metal contamination based on the filling
materials and restricted technologies used (Cao 2007).
The two main valence states for Cr in soils are Cr(III) and Cr(VI) (Xu
et al. 2019). The Cr(VI) state is toxic and can be taken up by plants,
accumulated in plants, and be absorbed by humans where it has carci­
nogenic effects. Overlying plants including grain crops and other cash
crops, may be affected by Cr (Liu et al. 2017; Shi et al. 2018a). Conse­
quently, it is a foreseeable consequence that this specific toxic metal will
be absorbed and then accumulate in the human body and/or wildlife via
the food chain (Hong et al. 2019c). Therefore, there is a tremendous
need to identify Cr-contaminated soil and further assess Cr concentra­
tions. As a first step to obtaining a sustainable solution to toxic metal
contamination in the soil and controlling the corresponding eco-
environmental impacts, quantitative assessments are needed for land
rehabilitation and sustainable development (Minasny and McBratney
2010). Therefore, it is imperative to be able to rapidly, accurately, and
reliably characterize the soil Cr concentrations for possible remediation.
Compared with regular field investigations, proximal sensing tech­
nology uses visible and near-infrared (Vis-NIR) diffuse reflectance
spectroscopy methods, which have been demonstrated to be eco-friendly
and accurately relate spectral reflectance information to specific soil
properties (Jia et al. 2021; Wan et al. 2020). The development of
proximal sensing and remote sensing technologies has provided reliable
approaches for monitoring soil Cr concentrations in time- and cost-
saving modes (Shi et al. 2018a). Related studies in the fields of pedo­
metrics, spectral pedology, and environmental science have been con­
ducted (Hu et al. 2020; Viscarra Rossel et al. 2006b).
1.2. Related works
Since 1997, many studies have assessed and/or retrieved concen­
trations of toxic metals in the soil via proximal sensing (Malley and
Williams 1997; Shi et al. 2014a; Shi et al. 2018a). Based on the test
objects and media, current main approaches can be summarized as
direct approaches, indirect approaches and integrated approaches.
1.2.1. Direct approaches
Some toxic metal elements in the soil can be adsorbed by soil organic
matter, clay minerals, iron manganese oxides, and carbonate minerals.
These soil components can lead to changes in the soil spectral shape and
reflectance and display specific spectral absorption features (Liu et al.
2018; Mustafa et al. 2020). The correlation between cuprum (Cu) and
the reflectance spectrum is mainly affected by organic matter (OM);
those of lead (Pb), zinc (Zn), cobalt (Co), and nickel (Ni) are mainly
affected by clay minerals and iron manganese oxides. Wu et al. (2007)
have investigated the spectral response by adding known amounts of
heavy metals into soil. The results showed that the spectral features for
heavy metals only appear in the Vis-NIR region for transitional elements
at very high concentrations, although it is rarely found in common
natural soils. These above mechanisms lay the foundation for moni­
toring toxic metal contamination in the soil based on diffuse spectral
reflectance. A direct approach, as the term suggests, is to assess the
concentrations of soil toxic metals based on in situ and laboratory
spectral measurements at high spectral resolutions in the visible, near-
infrared, mid-infrared, and thermal infrared regions (Cheng et al.
2019). Notably, spectral reflectance can be directly obtained from a
spectroradiometer. Subsequently, a quantitative inversion model can be
established by integrating laboratory-based toxic metal concentrations
2
Geoderma 405 (2022) 115399
and the selected sensitive wavelengths (Horta et al. 2015; Shi et al.
2014a; Shi et al. 2018a).
In essence, the spectral estimation of soil Cr concentrations is a
typical application of quantitative remote sensing. However, the number
of environmental variables in a model calibration system is commonly
much larger than that for remote sensing observations, and the nature of
inversion is an ill-posed inversion problem (Liang et al. 2012). In terms
of soil, Cr is not a decisive element in forming the soil reflectance
spectrum. Consequently, Baveye and Laba (2015) noted that a persistent
Vis-NIR myth seems to exist in proximal soil sensing. To overcome this
specific ill-posed inversion problem, some studies have focused on reg­
ularization methods, including the introduction of multisource data and
prior knowledge and the integration of multiple data-mining algorithms
(Wang et al. 2020; Xu et al. 2019).
1.2.2. Indirect approaches
In most toxic metal-polluted areas, the concentrations of metals in
the soil are measured at low or trace levels, moreover, some metals are
featureless in raw spectral reflectance (Wu et al. 2007; Xia et al. 2007).
Considering these challenges, some scholars have developed new
assessment methods. Specifically, researchers have developed indirect
approaches to quantitatively or qualitatively assess toxic metal elements
in the soil (Gholizadeh and Kopačková 2019; Zhang et al. 2020a). Such
estimations are not directly obtained based on a target toxic metal.
Currently, there are two main types of indirect methods: (1) those that
consider the potential relationships between pollutant-related materials
and target toxic metals and (2) those based on the reflectance spectra of
vegetation.
The toxic metal elements in the soil are often associated with soil
physiochemical properties (Hong et al. 2019c). For example, heavy
metal ions in the soil can easily form stable compounds with OM through
chelation or complexation. Exogenous heavy metals entering the soil can
also be adsorbed by soil clay minerals, iron oxides, and OM (Chakra­
borty et al. 2017; Wang et al. 2014). These related components have
significant spectral features; hence, indirect estimation via soil physi­
ochemical properties (OM, pH, and texture) and Vis-NIR spectroscopy is
feasible (Cheng et al. 2019; Wang et al. 2014).
Plants grown in polluted soil can absorb toxic metal elements via
their root systems, and the elements then accumulate in their organs
(stem, leaf, and spike) (Gholizadeh and Kopačková 2019). These toxic
metals lead to the destruction of carrier proteins in leaves, and further
inhibit plant growth (Shi et al. 2016). Accordingly, the changing levels
of leaf nitrogen, chlorophyll, and protein result in changes in the spectral
reflectance of the leaf and canopy (Zhang et al. 2020a). Some scholars
have also systematically investigated the physiochemical responses of
plants to toxic metal elements and established corresponding quantita­
tive retrieval models (Li et al. 2015; Shi et al. 2018a). Published studies
have shown that these indirect measurements of toxic metals provide
reliable prediction accuracy. Nevertheless, it is noted that the perfor­
mance of indirect approaches partly depends on the correlation between
the toxic metal elements and auxiliary attributes as well as the stress
severity to plants (Shi et al. 2018a; Zhang et al. 2020a). Related works
should only be performed if the prerequisites are met; otherwise, the
estimation accuracy may be unsatisfactory, furthering lead to error
accumulation.
1.2.3. Integrated approaches
The soil system, a natural system formed by long-term evolution, has
synergistic relationships between various physiochemical processes and
environmental variables that affect its development (McBratney et al.
2014). This relationship is summarized as a soil-landscape model and
such models can be used for the rapid characterization of toxic metals in
the soil (Minasny and McBratney 2016). Existing studies have shown
that the differences in landscape variables are closely related to regional
soil toxic metal contamination and can be summarized into some
soil–landscape correlation functions, such as Jenny’s model and the
J. Wang et al.
SCORPAN framework (McBratney et al. 2003). In terms of toxic metals,
some scholars have used the integrated approach to perform digital soil
mapping (DSM) and conduct the point estimation (Shi et al. 2018b;
Wadoux et al. 2020). Compared with direct and indirect approaches, the
integrated approach can not only estimate the attributes of the soil at a
point but also visualize toxic metal-polluted areas. However, the quan­
titative characterization performance is usually unsatisfactorily
restricted by soil auxiliary attributes with coarse spatiotemporal reso­
lutions (Tóth et al. 2016).
Vis-NIR spectral reflectance data are typical stored in large and
complex datasets characterized by ultrahigh spectral resolutions, many
wavebands, and abundant information (Ben-Dor et al. 1997; Viscarra
Rossel et al. 2006a). Therefore, effective spectral pretreatment steps are
crucial for enhancing the internal differences in spectral variables and
revealing key information (Liu et al. 2019; Nawar et al. 2016).
Fractional-order derivative (FOD) methods can reduce such complex
datasets and minimize the loss of spectral information (Abulaiti et al.
2020; Hong et al. 2019a; Wang et al. 2018a; Zhang et al., 2020b).
However, the integrated application of FOD methods and soil auxiliary
variables in the quantitative characterization of soil toxic metals based
on soil proximal sensing has not been explored. Close relationships exist
between Cr and different soil covariates (OM and pH) (Shi et al. 2014a).
To improve predictive ability, the potential concatenation of FOD-
pretreated Vis-NIR spectroscopy and auxiliary attributes is a highly
anticipated task. Moreover, existing studies often focus on point esti­
mation, but mapping the distribution soil properties is more useful for a
better decision making of soil resources (Jia et al. 2021).
1.3. Contributions
Inspired by these approaches, we hypothesize that fused proximal
sensing and soil auxiliary attributes can improve estimates of Cr con­
centrations in the soil. A precise variogram estimator is essential for
Fig. 1. Maps of the study area and the distribution of sampling sites (a: Xinjiang in China; b: Geographical location of the eastern Junggar coalfield; c: Soil sampling
sites across the study area; d: Typical landscape photograph of sampling sites (Photograph credit: Jingzhe Wang); and f: Sampling schema (four points)
within quadrat).
3
Geoderma 405 (2022) 115399
realizing spatial distribution mapping of soil Cr. Therefore, the intro­
duction of best-fit variogram models could improve the spatial visuali­
zation of results. Specifically, the main objectives of this study are (1) to
explore the potential of considering soil auxiliary information (OM and
pH) in soil Cr spectral estimation; (2) to compare the performance of
different modeling modes (introducing auxiliary attributes or not); and
(3) to produce a soil Cr map based on the integration of proximal sensing
and the kriging interpolation method. The main contributions of this
study include developing an integrated estimation methodology for
toxic metals (Cr) and applying the method in an arid mining wasteland.
2. Methodology
2.1. Study area
The study area, the eastern Junggar coalfield (also known as the
Zhundong coalfield) is well known for its massive coal reserves (over
3.9 × 1011 tons) and is the largest integrated coalfield in China, ac­
counting for approximately 7.2% of China’s total reserves (Imin et al.
2020). Previous geological surveys have revealed that local coal seams
are strongly associated with Cr elements (Zhou et al. 2010). The eastern
Junggar coalfield is located in the Gobi Desert region in the south­
western Karamaili Nature Reserve on the northern slope of the Tianshan
Mountains and adjacent to the eastern Junggar Basin in China. This
specific coalfield area is also named after its geographic location (Fig. 1a
and b). With an extremely arid continental climate, the study area re­
ceives scarce precipitation (183.5 mm yr− 1) and experiences intense
evaporation (2070.3 mm yr− 1). The average wind speed of the local
prevailing northwestern winds is 2.0 m s− 1, reaching a maximum of 16
m s− 1. The total area of the eastern Junggar coalfield is approximately
1.3 × 104 km2. Referring to the World Reference Base (WRB) soil clas­
sification, the local soil types are dominated by Skeletic and Yermic
(Imin et al. 2020; Nachtergaele et al. 2000). Local vegetation cover is
J. Wang et al.
extremely low (<10%), with the main plant types being Anabasis salsa
(C. A. Mey.) Benth. ex Volkens, Ephedra przewalskii Stapf, Haloxylon
ammodendron (C. A. Mey.) Bunge, concomitant extreme xerophytes such
as Salsola collina Pall., and Ceratoides latens (J. F. Gmel.) Reveal et
Holmgren, Iljinia regelii (Bunge) Korov., and Sarcozygium xanthoxylon
Bunge (Zeng et al. 2020). In recent years, the habitation of the eastern
Junggar Basin has attracted enormous governmental concern. As a
result, assessments of soil Cr are needed for regional land rehabilitation
and sustainable development.
2.2. Sampling and experiments
The soil sampling investigation was conducted in June 2019. The
sampling strategy was designed based on the land use/land cover, soil
types, soil surface characteristics, previous field sampling experience,
and accessibility of the study area to the designed investigation sites.
Each quadrat was set as 10 m × 10 m (Fig. 1e). At each sampling point,
four subsamples ranging from 0 to 20 cm were collected via a wooden
shovel. All subsamples were fully mixed to generate representative
composite samples, placed into sealed plastic bags and labelled. The
corresponding geographic coordinates were simultaneously recorded
with a portable high precision GPS (GARMIN Oregon 550, positioning
accuracy ≤ 5 m). Notably, the sampling campaigns including collection
and preservation, strictly complied with the Technical Specification for
Soil Environmental Monitoring (HJ/T 166–2004) released by the State
Environmental Protection Agency of China (2004) to avoid the potential
cross-contamination of collected soil samples.
Under laboratory conditions, all samples were air dried and ground.
Moreover, they were sieved to ≤0.15 mm and <2 mm for subsequent
chemical analysis and spectral measurements, respectively (Hong et al.
2019a). After appropriate pretreatments, all chemical measurements
were conducted immediately to reduce the potential effects of exposed
time/amounts/mixed time as possible. The OM content was determined
based on the potassium dichromate method. The soil Cr concentration
was determined using an atomic absorption spectrophotometer (Hitachi
Z-2000, Japan). The soil pH was determined at a solid/water ratio of
1:2.5 with a precise pH meter (Shanghai Leici, PHBJ-260, China) ac­
cording to the method of Bao (2005).
2.3. Spectral measurements and preprocessing
The spectral measurements of all pretreated soil samples obtained
with an ASD FieldSpec® 3 portable spectrometer (Malvern Panalytical,
Malvern, UK) installed in a dark room with controlled lighting condi­
tions. Detailed technical specifications of the spectroradiometer are
available at https://www.malvernpanalytical.com/en/products/prod
uct-range/asd-range. The detailed steps of sample preparation and the
geometric parameters of the spectrometer setup are as follows (Shi et al.
2014b). All soil samples were evenly placed in a contained with a 12-cm
diameter and a 1.8-cm depth. A standardized Spectralon white plate
with 99% reflectance was applied to calibrate the spectrometer before
each measurement. Measurements were made with a Hi-Brite Contact
Probe using a halogen bulb (color temperature of 2901 ± 10 K) for
illumination. The collected Vis-NIR reflectance spectra covered wave­
lengths from 350 nm to 2500 nm with a final spectral resolution of 1 nm.
Each sample was repeatedly scanned 10 times and then averaged to
create the representative spectrum. In this study, the spectral wave­
lengths were narrowed (400–2400 nm) to reduce the inherent high-
frequency noise of the spectrometer. Subsequently, the original reflec­
tance spectra were smoothed by the second-order Savitzky-Golay
method with a window size of 9 wavelengths. To further simplify the
spectral matrix and reduce redundant information, the spectral data for
each soil sample were downsampled at an interval of 10 nm prior to
spectral preprocessing (Zhang et al. 2021). Then, spectral pretreatment
with the FOD method was conducted.
The FOD algorithm can extend the common integer-order derivative
4
Geoderma 405 (2022) 115399
(IOD) to derivatives of any order and be used to obtain precise in­
terpolations between the 0-order derivative (original) and the IOD to
identify changes in the details of the spectrum for different IODs; this
approach has high application potential in reducing spectral noise and
increasing the resolution of spectral features (Wang et al. 2018a; Wang
et al. 2020). The Grünwald–Letnikov equation is a discrete definition
that is convenient for numerical calculations and highly computation­
ally efficient, so this specific formula is used in this study (Schmitt
1998). The related mathematical expressions of FOD are as follows:
( )∑(t− a)
1 h
Γ(q + 1)
dq f (x) = lim q
( − 1)m f (x − mh) (1)
h→∞ h m!Γ(q − m − 1)
m=0
where q represents the derivative order; h represents the step interval;
and t and a are the upper and lower limits of the fractional derivative
order, respectively.
The formula contains the gamma function (Γ(β)):
∫∞
Γ(β) = e− t tβ− 1 dt = (β − 1)! (2)
0
When a one-dimensional spectrum in the data interval of [a, t] is set
as f(λ), the wavelength interval is portioned into n equal divisions based
on the spectral step (h). Because the spectral data in this study had
already been resampled to a resolution of 10 nm, h was set to 1.
Consequently, the FOD formula from Eq. (1) can be defined as:
dq f(λ)
≈ f(λ) +( − q)f (λ − 1) +(− q)(− q+1)
f(λ − Γ(− q+1)
2) +⋯ +n!Γ(−
dλq 2 q+n+1) f(λ − n)
(3)
Notably, if λ is set to 0, 1, or 2, Eq. (3) represents the non-processed
original spectrum, the classic first derivative or the classic second de­
rivative, respectively. In this investigation, a total of nine FOD series
(from order 0.0 to 2.0) of the soil spectrum were calculated using Eq. (3)
to mine potential ‘hidden’ information.
Previous studies have demonstrated that spectral indices can reduce
the redundancy of the spectral matrix and be used to select sensitive
spectral parameters related to soil attributes (Tian et al. 2013; Wang
et al. 2019). A spectral index composed of three spectral bands is a better
representation than an index based on a single band or two band (Li
et al. 2014; Zhang et al., 2020b). In this study, five three-band spectral
indices (TBIs) are investigated at three wavelengths (R1 , R2 , andR3 ) over
the range of 400–2400 nm based on Eqs. (4)–(8). Moreover, the corre­
lation coefficients of the TBIs with the soil Cr are calculated. Five types
of TBIs were used to explore their relationships with Cr concentrations
and further extract the spectral parameters. It is noted that
R1 ∕= R2 ∕= R3 . For each potential combination, the TBI with the
maximum absolute correlation coefficient (|r|) with the Cr concentra­
tion is used to determine the optimal band combination and spectral
variables for subsequent estimation analysis. The optimal band combi­
nation algorithm was run by programming Eqs. (4)–(8) in MATLAB
2019b (MathWorks, Natick, MA, USA).
TBI1 (R1 , R2 , R3 ) = (R1 − R2 )/(R1 + R3 ) (4)
TBI2 (R1 , R2 , R3 ) = R1 /(R2 × R3 ) (5)
TBI3 (R1 , R2 , R3 ) = (R1 − R2 )/(R1 − 2R2 + R3 ) (6)
TBI4 (R1 , R2 , R3 ) = R1 /(R2 + R3 ) (7)
TBI5 (R1 , R2 , R3 ) = (R1 − R2 )/(R2 − R3 ) (8)
2.4. Modeling strategies and statistical analysis
In this study, the Kennard-Stone algorithm was employed to establish
the calibration and validation datasets. Based on the concept of this
specific partitioning algorithm, two-thirds of the whole dataset was
J. Wang et al.
selected as calibration dataset (n = 112); therefore, the remaining
samples (n = 56, accounting for one-third of the data) were regarded as
the validation dataset. Additionally, we conducted an analysis of vari­
ance (ANOVA), as proposed by Levene (1960) to examine the data dis­
tributions for both partitioned sub datasets and prove reasonable
statistical status between them.
The partial least square (PLS) method is one of the most widely
adopted regression strategies in spectral modeling (Viscarra Rossel et al.
2006a). The PLS approach was developed from principal component
regression and can simultaneously model predictive multiple dependent
variables, reduce dimensionality and avoid multicollinearity (Nawar
et al. 2016; Wold et al. 1983). Compared with the conventional multi-
linear regression (MLR), PLS is a more appropriate approach for cali­
brating models with severe collinearity in the independent variables
(spectral data in this study), particularly in cases where the sample size
is small (Wang et al. 2019). In this study, PLS analysis is employed to
assess the potential relationships between dependent and independent
variables. Leave-one-out cross-validation is used to prevent model
overfitting and improve the performance of the model. In this study, we
designed four modeling strategies for the quantitative assessment of soil
Cr concentrations (Table 1). To evaluate the performance of the cali­
brated models, several statistical parameters were compared between
laboratory measurements and model-estimated values based on the in­
dependent validation set: the coefficient of determination (R2), root
mean square error (RMSE), and the ratio of performance to the inter­
quartile range (RPIQ). RPIQ is a highly effective measure, especially of
asymmetric (nonnormal) behavior (Bellon-Maurel et al. 2010).
In addition to the common local accuracy of the estimation models,
we investigated variograms to support kriging interpolation. Variograms
were introduced to examine the spatial structures of the lab- and model-
based soil Cr in the study area. The dependence of soil Cr in space was
evaluated through a variogram analysis using semivariance values. The
related formula is shown in Eq. (9):
1
∑N(h) 2 In terms of the spectral dimension, we identified and selected the
γ(h) = 2N(h) α=1 [E(xi ) − E(xi + h) ] (9)where γ(h) represents the
average semivariance of the soil Cr, h represents the lag (distance be­
tween pairs), N(h) is the number of paired sampling points based the lag
h, and E(xi ) and E(xi +h) represent the observed values of soil Cr at the
given locations of xi and xi + h, respectively. Specifically, x is the co­
ordinate location of the point. Variograms provide evidence of spatial
autocorrelation if the semivariances are lower at small lags than at
larger lags, i.e., sampling locations located close to each other display
similar values. Common variogram models, i.e., spherical, circular,
exponential, and gaussian models were tested in this study (Oliver and
Webster 2014). In this step, we also conduct the independent validation
(n = 56) to fairly assess the performance of semivariogram function. The
best fit model with lowest value of RMSE was selected for subsequent
analysis. More detailed descriptions of variogram analysis and the
kriging method are available in previous studies and will not be repeated
here (Chakraborty et al. 2017; Oliver and Webster 2015).
In this study, all mathematical calculations and geostatistical
Table 1
Detailed specifications of the applied modeling strategies and the corresponding
input variables used in this study.
Strategies Predictor variable Detailed concept
I Full Vis-NIR 400–2400 nm
variables
II Effective TBI The selected optimal spectral band combination
based on the maximum correlation coefficient (|
r|) for soil Cr
III Effective TBI + Optimal spectral band combination and soil
OM organic matter contents
IV Effective TBI + Optimal spectral band combination, soil organic
OM + pH matter contents and soil pH
NOTE: Vis-NIR represents visible and near-infrared diffuse reflectance spec­
troscopy, TBI represents three three-band spectral index.
5
Geoderma 405 (2022) 115399
operations were performed via the packages of PLS (version 2.7–3),
geoR (version 1.8–1), gstat (version 2.0–7), and corrplot (version 0.84)
in the R platform (version 3.4.0) (Pebesma and Heuvelink, 2016; R
Development Core Team 2019; Ribeiro et al., 2007; Wei et al. 2017).
3. Results
3.1. Exploratory data analysis
The statistical descriptions of the soil Cr concentrations (mg kg− 1) of
the 168 collected soil samples are summarized in Table 2. For the entire
dataset, the Cr concentration varied between 14.31 and 110.07, with an
average of 53.67 mg kg− 1. The mean Cr concentration was twice higher
than the Xinjiang soil background value (49.30 mg kg− 1). According to
the pollution level (78 mg kg− 1) in China’s Soil Environmental Quality
Control Standards (GB36600-2018), 122 samples showed different de­
grees of Cr pollution, with pollution rate of 72.62%. The data approxi­
mately obey a normal distribution with a relatively small coefficient of
variation (CV) of 0.34. In terms of the dataset partitions, the results of
Levene’s test suggested that the homogeneity between the calibration
and validation datasets was significant at the 0.05 significance level (p
= 0.97). The OM and pH values varied from 0.26 to 33.37 g kg− 1 and
7.60 to 10.60, respectively. The mean pH value indicated that the
regional surface soil is strongly alkaline.
To further investigate the estimation performance based on Vis-NIR
data and auxiliary information, we explore the internal correlations
among different soil parameters (Fig. 2). It is obvious that Cr was
significantly correlated with OM with a correlation coefficient (r-value)
of 0.517 (p < 0.001). In addition, a significant negative correlation was
observed between Cr and pH (r = − 0.254, p < 0.01), whereas no sig­
nificant correlation relationship between pH and OM was detected (r =
− 0.081). These results suggest that soil Cr estimation may benefit from
the selected soil auxiliary information (OM and pH).
major wavelength based on Pearson correlation analysis. Considering
the sample size (n = 168), the P-value thresholds for statistical signifi­
cance of 0.01 and 0.001 were 0.201 and 0.255, respectively. Fig. 3 il­
lustrates the sensitive wavelengths of different soil parameters over the
spectral range of 400–2400 nm. The correlations between Cr and the
FOD processed spectra for all wavelengths were calculated, and the
maximum absolute correlation for the 0.75-order reflectance was 0.51.
Moreover, the important spectral wavelengths of soil Cr (400–760 nm
and 1800–2300 nm), OM (580–1000 nm and 2000–2400 nm), and the
pH (880–1860 nm and 2070–2400 nm) partly overlapped. In other
words, some similar spectral ranges were identified, suggesting that the
arduous spectral estimation of spectrally featureless Cr can be improved
by considering the effects of soil auxiliary parameters. Consequently, the
OM and pH were introduced during the modeling process in subsequent
model calibrations.
3.2. Spectral feature detection
In this study, we performed FOD calculations for each smoothed
continuous spectrum to detect spectral features (Fig. 4). The spectral
features, including absorption and wave band shapes, are wide and
considerably overlap; therefore, the corresponding explanations of the
original reflection spectra are difficult to establish. As the FOD
increased, the FOD reflectivity of the general spectral range narrowed
and tended to 0, suggesting that spectral baseline drift and mixed
overlapping peaks are gradually eliminated to some extent. The com­
parison of results makes it clear that the FOD-pretreated spectrum can
express the variations in spectral details. That is, this specific spectral
preprocessing approach improves the analytical resolution and further
magnifies the spectral absorption valleys, especially at wavelengths of
1600–2100 nm. These characteristics indicate that the FOD processing
of the segmented spectrum was effective, and it is possible to extract
J. Wang et al. Geoderma 405 (2022) 115399

Table 2
Descriptive statistics of soil Cr and the related auxiliary information.
Count Minimum Mean Median Maximum Standard deviation Interquartile range Coefficient of variation Skewness
− 1
Cr (mg kg ) Entire 168 14.31 53.67 54.02 110.07 18.37 23.12 0.34 0.11
Calibration 112 14.31 53.34 56.11 110.07 18.46 23.24 0.35 − 0.04
Validation 56 18.04 54.32 52.15 105.00 18.35 23.05 0.34 0.45
OM (g kg− 1) 168 0.26 6.39 3.31 33.37 6.63 6.87 1.03 1.93
pH 168 7.50 9.04 9.10 10.50 0.83 1.40 0.09 –

NOTE: OM represents organic matter. Calculating the coefficient of variation for the pH is not statistically significant because the pH is an interval variable.

Fig. 2. Scatter matrix based on the correlations among the soil Cr concentration, pH, and OM (n = 168). Solid red lines indicate fitting curves. The double asterisks
(**) indicate p < 0.01 and the triple asterisks (***) indicate p < 0.001.

Fig. 3. Distribution of sensitive wavelengths based on the correlation coefficients (r) between various soil parameters and raw wavelengths (400–2400 nm). The
color blue represents the corresponding selected wavelength and statistical significance (p < 0.01).

effective spectral information. The absorption peaks (500 nm, 1413 nm, foundation for subsequent spectral modeling.
and 2200 nm) affected by organic components and clay minerals, such To understand the spectral features and synergy among multiple
as smectite, kaolinite, and illite, can provide crucial information on soil bands in detail, we traversed all wavelengths within the Vis-NIR region,
constituents. These abovementioned investigations also laid the thus preserving all potential combinations of the three separate spectral

6
J. Wang et al. Geoderma 405 (2022) 115399

Fig. 4. Average FOD spectral curves of the collected soil samples from order 0.0 to 2.0 (increment of 0.25 per step). The black solid line and colored shaded region in
each subfigure represent the average reflectivity and spectral standard deviation, respectively.

bands. Correspondingly, the contour map of the correlations (r) between rather than the original reflectance.
the Cr concentration and six forms of the TBI for different FOD spectra
were analyzed (Table 3 and Fig. 5). Similar to the distribution of sen­
3.3. Model performance and comparison
sitive wavelengths from Fig. 3, the obtained important bands selected
based on the TBIs were mainly concentrated within the regions of
In this study, the predictor variables of various modeling strategies
400–700 nm and 1700–2400 nm. The optimal result was generated by
are defined in Tables 2 and 3. To investigate whether the application of
TBI1 based on 0.75-order reflectance spectra (max |r| = 0.68). The
TBIs can improve the model, the PLS model was employed to calibrate
correlation coefficient was improved by 0.12 compared to that of the
the estimation models, and the results were compared for four different
original reflectance (0-order). Additionally, TBI1 generated the most
modeling strategies. Thus, a total of 36 PLS models (nine FOD orders and
band combinations (n = 4). In terms of the results based on various FOD
four strategies) were calibrated based on the designed variable pre­
reflectance spectra, the maximum correlation coefficients (|r|) of the
dictors and soil Cr concentrations as the input and response variables,
modes of 0-, 0.25-, 0.5-, 0.75-, 1-, 1.25-, 1.5-, 1.75-, and 2nd-order
respectively. The corresponding descriptive evaluation statistics are
reflectance were 0.58, 0.54, 0.62, 0.68, 0.64, 0.63, 0.63, 0.62, and
summarized in Fig. 6.
0.63, respectively. These results suggest that FOD pretreatment can
The introduction of spectral transformations improved model per­
provide additional detailed spectral parameters associated with soil Cr
formance. For example, in strategy I, the model based on the original

Table 3
Sensitive TBIs derived from the optimal band combination algorithm and FOD-pretreated spectrum (1D indicates the Pearson correlation between Cr and the
reflectance spectra, and the maximum absolute correlation coefficient (|r|) in bold indicates that the corresponding band combination is most effective in this study).
FOD 1D Optimal band combination and corresponding correlation coefficient (|r|)

TBI1 |r| TBI2 |r| TBI3 |r| TBI4 |r| TBI5 |r|

0 0.34 (R550-R470)/(R550- 0.56 R620/(R2180 × 0.54 (R550-R470)/(R550-2 × R1740 0.58 R1370/(R1710 + 0.53 (R650-R1920)/(R1920- 0.55
R620) R570) + R1670) R1050) R600)
0.25 0.37 (R1800-R1820)/ 0.54 R510/(R2630 × 0.46 (R950-R2280)/(R950-2 × 0.49 R1280/(R1620 + 0.44 (R2160-R940)/(R940- 0.47
(R1800-R1900) R1940) R2280 + R1180) R1070) R2310)
0.50 0.44 (R1960-R2210)/ 0.62 R2330/(R2320 × 0.61 (R1170-R1990)/(R1170-2 × 0.54 R2210/(R1900 + 0.56 (R890-R2000)/(R2000- 0.57
(R1960-R2300) R1430) R1990 + R950) R580) R1320)
0.75 0.51 (R1120-R850)/(R1120- 0.68 R1650/(R1310 × 0.49 (R1560-R1180)/(R1560-2 × 0.51 R1700/(R1390 + 0.54 (R2290-R1850)/ 0.57
R1950) R1210) R1180 + R740) R500) (R1850-R840)
1 0.50 (R750-R660)/(R750- 0.54 R1820/(R1230×R810) 0.64 (R2140-R1130)/(R2140-2 × 0.58 R1150/(R1840 + 0.56 (R640-R750)/(R750- 0.59
R1840) R1130 + R980) R780) R1300)
1.25 0.46 (R1970-R1410)/ 0.53 R1030/(R970 × 0.63 (R1440-R720)/(R1440-2 × 0.54 R2200/(R2290 + 0.55 (R470-R2380)/(R2380- 0.58
(R1970-R2290) R760) R720 + R1440) R1970) R800)
1.50 0.31 (R1000-R1200)/ 0.63 R1070/(R2180 × 0.54 (R2100-R830)/(R2100-2 × 0.61 R2150/(R1480 + 0.53 (R2080-R2240)/ 0.58
(R1000-R1690) R1290) R830 + R760) R1320) (R2240-R1640)
1.75 0.38 (R780-R2000)/(R780- 0.57 R1420/(R1040 × 0.58 (R1260-R410)/(R1260-2 × 0.62 R2000/(R1960 + 0.61 (R2200-R2330)/ 0.57
R1960) R1000) R410 + R700) R780) (R2330-R1820)
2 0.40 (R1650-R1970)/ 0.60 R490/(R1840 × 0.63 (R1510-R810)/(R1510-2 × 0.62 R1970/(R2260 + 0.60 (R590-R450)/(R450- 0.61
(R1650-R2260) R1690) R810 + R1540) R1650) R700)

7
J. Wang et al.
Fig. 5. Correlation between the Cr concentration and different TBIs for the entire dataset: (a) 0-order (raw data), (b) 0.25-order, (c) 0.5-order, (d) 0.75-order, (e) 1-
order (first-order), (f) 1.25-order, (g) 1.5-order, (h) 1.75-order, and (i) 2.0-order (second-order) derivatives. The right color bar in each subfigure is the range of
correlation (r) values, and the x-, y-, and z-axes are spectral wavelengths from 400 to 2400 nm.
spectrum (R2v = 0.67 and RMSEv = 10.47 mg kg− 1) was inferior to that
based on the 0.75-order spectrum (R2v = 0.79 and RMSEv = 8.98 mg
kg− 1). The results in Table 3 also confirm this finding. Generally, the
estimation performance of the model with strategy II (with effective TBIs
as predictor variables) was better than that for strategy I (with full Vis-
NIR variables as predictors), as reflected by the higher R2 and lower
RMSE values. This result suggested that the estimation models con­
structed considering TBIs were better than those based on the original
spectrum, regardless of whether FOD processing was performed. When
one soil auxiliary attribute (OM) was considered (strategy III), the
quantitative performance of the models improved, with satisfactory R2cv
(0.67–0.84) and R2v (0.71–0.84) values. When both soil auxiliary vari­
ables and effective TBIs were employed for the inputs (strategy IV), the
prediction accuracies of the model further increased. For each modeling
strategy, we selected the optimal quantitative model to illustrate the
relationships between the measured and estimated Cr concentrations
(Fig. 7).
Compared with the original spectrum (order = 0) and IOD spectrum
(i.e., the first-order and second-order derivatives), a specific FOD pre­
treatment could improve the estimation performance. Specifically, the
model based on 0.75-order reflectance spectra was optimal, with the
best prediction ability (R2cv = 0.84, RMSEv = 6.33 mg kg− 1, R2v = 0.87,
RMSEv = 7.34 mg kg− 1, and RPIQ = 2.68). Regarding the modeling
strategy, the 1:1 lines and confidence ellipses (95% confidence) for the
results of the PLS models based on the 0.75-order spectra were well
8
Geoderma 405 (2022) 115399
grouped along the actual 1:1 line. These fitted lines suggest that a strong
correlation exists between the laboratory-measured and estimated Cr
concentrations. However, it is noted that none of the calibrated models
yield high values of Cr (≥80 mg kg− 1) based on the selected predictors.
Among all the modeling schemes, the PLS models based on strategy IV
perform best. Moreover, the R2 and RMSE values, general statistical
indicators, between the calibration and validation datasets were similar
for all established models, highlighting the robust quantitative perfor­
mance of the models (neither overfitting nor underfitting occurs).
Consequently, these selected optimal models and outcomes were used
for the subsequent spatial visualization of soil Cr levels.
3.4. Spatial visualization of soil Cr levels
The spatial heterogeneity statistics of soil Cr are indispensable for
predicting its spatial distribution. The experimental semivariograms and
related parameters are illustrated in Fig. 8 and Table 4. For both the lab-
and model-based Cr concentrations, the corresponding fitted variograms
all follow exponential models with good fitting performance. The pa­
rameters of the variogram estimated from strategy IV (Fig. 8e) are
similar to those estimated for the real soil Cr concentration (laboratory-
based measurements, Fig. 8a) at the same locations, and the ranges,
nuggets, and structural variances are also similar. Moreover, the nugget/
sill ratios are much <25%, which reflects the strong spatial dependence
of regional soil Cr concentrations.
J. Wang et al. Geoderma 405 (2022) 115399

Fig. 6. Accuracy statistics for models based on four modeling strategies: (I) full Vis-NIR variables, (II) effective TBIs, (III) the combination of effective TBIs and OM,
and (IV) the combination of effective TBIs, OM and the pH. (a) Latent variables (LVs), (b) coefficient of determination for the calibration process (R2cv), (c) root mean
squared error (mg kg− 1) for the calibration process (RMSEcv), (d) coefficient of determination for the validation process (R2v), (e) root mean squared error (mg kg− 1)
for the validation process (RMSEv), and (f) the ratio of performance to interquartile distance (RPIQ).

Considering the satisfactory performance of the semivariogram
models, we produced soil Cr concentration maps (laboratory-based and
strategy IV model-based maps) by integrating the optimal semivario­
gram function and kriging method (Fig. 9). Both spatial distributions
exhibited similar distribution trends: lower values were concentrated in
the middle part of the study area, and prominently higher values were
mainly in observed the western part of the region, thus validating the
accuracy of the prediction model. By comparison, the western part of the
investigation area was not obviously contaminated, and low Cr con­
centrations were observed.
4. Discussion and perspectives
Over the past several decades, many scholars have suggested that
Vis-NIR reflectance spectroscopy is an effective approach for the mea­
surement of soil toxic metal concentrations (Gholizadeh and Kopačková
2019; Jia et al. 2021; Shi et al. 2014a). Considering the limited perfor­
mance of conventional linear models, an increasing number of studies
have suggested that advanced machine learning (ML) algorithms can
effectively capture both linear and nonlinear relationships between
specific soil properties and Vis-NIR datasets (Jia et al. 2021). Despite the
broad application of MLs in proximal soil sensing, there have long been
debates regarding their use and model interpretability (Padarian et al.
2020; Wang et al. 2018a). The corresponding uncertainties, including
strong randomness, overfitting and/or underfitting, are often
overlooked, which may significantly threaten the modeling accuracy
and robustness. Although our main interest is in the predictive perfor­
mance of the models, it is informative to interpret the structure of the
models. The machine learning algorithms are often considered “black
boxes” since the models derived from these algorithms are difficult to
interpret (Zhu et al. 2017). Even though some algorithms provide var­
iable importance measures, such as the RF and the Cubist, the magnitude
and direction of the predictor effects are unknown. It is obvious that
models built with PLS are easier to interpret. Under these conditions, we
aimed to mitigate some of the criticisms and explore the possibility of
perpetuating the Vis-NIR myth based on PLS (Baveye and Laba 2015).
Among the available spectral analysis methods, the FOD approach is
a powerful mathematical method that can highlight the differences in
spectral information (Wang et al. 2020). The development of the FOD
algorithm was based on the extension of the IOD method, and its ra­
tionality and excellent performance have been recognized (Abulaiti
et al. 2020). Many existing studies have shown that the FOD algorithm
can remove baseline drift and overlapping peaks from spectral data
(Hong et al. 2019a; Wang et al. 2018b; Zhang et al., 2020b). Moreover,
this algorithm can capture the details of spectral curves and improve the
estimation accuracy of soil characteristic values. Wang et al. (2018b)
and Hong et al. (2020) investigated the performances of the FOD
approach based on different parameters, such as the Pearson correlation,
peak signal-to-noise ratio (PSNR), and structural similarity index
(SSIM). These studies indicated that the FOD algorithm possesses the

9
J. Wang et al. Geoderma 405 (2022) 115399

Fig. 7. Scatterplots of the lab-measured versus estimated Cr concentration for PLS models with the optimal predictor variables based on four modeling strategies. The
blue, red, and black lines in each sub-figure represent the 1:1 line, fitted line and confidence ellipse with 95% probability, respectively.

Fig. 8. Empirical variograms of the soil Cr concentrations at 168 sites obtained from (a) laboratory-measured values and the corresponding estimated values with the
PLS model based on (b) strategy I, (c) strategy II, (d) strategy III, and (e) strategy IV, respectively.

capacity to gather information because the reflectance of the x-band of of the FOD method was feasible and effective for extracting spectral
the FOD spectrum is obtained by summing the reflectance of the other features, and the obtained correlation coefficient values at various FODs
bands with certain weights (Eqs. (1)–(3)). In this study, the application were generally better than those of raw data (Table 3). Commonly, the

10
J. Wang et al. Geoderma 405 (2022) 115399

Table 4
Parameters of the semivariogram models.
Model Range (km) Structural variance (Sill) Nugget Nugget/Sill ratio R2

Laboratory-measured Cr Exponential 14.53 1.01 0.02 2.24% 0.82

Estimated Cr for strategy I 20.39 0.88 0.15 17.43% 0.71
Estimated Cr for strategy II 25.59 0.88 0.19 21.20% 0.78
Estimated Cr for strategy III 11.85 0.97 0.00 0.28% 0.77
Estimated Cr for strategy IV 13.82 1.02 0.01 1.24% 0.80

Fig. 9. Distribution maps of soil Cr levels predicted with the kriging method based on (a) field measured values and (b) optimal PLS-estimated values for strategy IV.

corresponding weights are related to the spectral distance values
(Schmitt 1998). The FOD method uses the same metric. Based on the
mathematical definitions of the first derivative (slope of the spectrum)
and second derivative (curvature of the spectrum), we can consider the
FOD an effective indicator for quantifying the sensitivity to the slope and
curvature of a spectrum. The spectral shape of the collected soil samples
was relatively flat. In other words, the slope effect was more obvious
than that of the curvature. Consequently, the optimal FOD (0.75-order
derivative) was located in the range of low-frequency FODs (0–1). The
optimal band combination algorithm (based on TBIs in this study) tra­
verses all wavelength spectral signals, and through the combination of
two or more wavelengths, the spectral variation characteristics can be
strengthened and noise can be weakened. Many studies have adopted
this method but have mainly focused on conventional two-dimensional
spectral indices (difference index, normalized difference index, or ratio
index) rather than TBIs (Hong et al. 2019b; Wang et al. 2018b). Based on
the absolute value of the correlation coefficient (|r|), we explored and
selected the potential optimal band combination (Table 3 and Fig. 5).
Based on 0.75-order reflectance spectra, TBI1 ((R1120-R850)/(R1120-
R1950)) generated the optimal result (max |r| = 0.68). The results proved
that the FOD algorithm performed better than the IOD approach.
In existing studies of soil toxic metal estimation, scholars often paid
limited attention to soil auxiliary information. With reference to field
investigations and core concept of DSM, we designed four different

11
J. Wang et al.
modeling strategies and corresponding predictor variables in this study
(Table 1). Subsequently, we compared the performance of different
modeling modes (introducing auxiliary attributes or not). Among them,
we found that Strategy IV (Effective TBI + OM + pH) was superior to the
others. The improved performance mainly attributed to the introduction
of auxiliary covariates. In fact, we also attempted to estimate soil Cr
based on auxiliary attributes independently without spectral informa­
tion. Not unexpectedly, the accuracy was poor (R2v = 0.542, RMSEv =
12.25 mg kg− 1, and RPIQ = 1.48), indicating that approximate 50% of
the Cr information was still not captured. Correspondingly, this specific
model was excluded from this study. According to (Hong et al. 2019c), it
is suggested that using auxiliary attributes to enhance the predictive
performance may be promising, but Vis-NIR spectroscopy is indispens­
able. Soil study is usually considered to be a multi-factor problem
(Viscarra Rossel et al. 2006b). Therefore, estimation merely using
auxiliary attributes is undesirable, and proximal soil sensing (especially
for Vis-NIR spectroscopy) is still crucial and attractive in Cr estimation.
It was obvious that the full Vis-NIR variables and effective TBI are more
comprehensively reflecting the soil properties, which includes not only
OM and pH but also texture and clay minerals (Minasny and McBratney
2016; Rossel and Behrens, 2010). Therefore, we believe using Vis-NIR
variables and effective TBI can better estimate the soil Cr than merely
using auxiliary attributes.
In soil systems, Cr is strongly associated with OM and the pH via the
metal complexation effect (Shi et al. 2018a). The first reaction process
when Cr enters the soil is adsorption. Many external factors affect the
adsorption behavior of Cr, such as the soil type, OM level, pH, clay
mineral content and amounts of active iron and aluminum oxides (Wu
et al. 2007). Specifically, variations in the pH may affect the form of and
binding reactions involving soil Cr. As the major provider of variable
charges, OM has a direct influence on the absorption of chromium ions
in the soil. Humic acid is an essential component of OM. The contained
carbonyl, carboxyl, and hydroxyl groups mainly contribute to the
negative surface charge of the soil (Jia et al. 2021; Rossel and Behrens,
2010). In fact, Chromium is a low mobility element, especially under
moderately oxidizing and reducing conditions and near-neutral pH
values. In soil, Cr behavior is governed by pH, redox potential (Eh), and
soil organic matter. Its adsorption by clay is also highly dependent on
pH. Cr(VI) adsorption decreases with increasing pH, and Cr(III)
adsorption increases with increasing pH. The dominant effect of organic
matter is the stimulation of the reduction of Cr(VI) to Cr(III), the rate of
which increases with soil acidity (Kabata-Pendias 2004; Salminen et al.
2005). In general, whether it is OM, pH, or soil texture that connect
potentially toxic elements to spectral data, the spectral estimation of soil
Cr is mainly dependent on its correlation with the spectrally active
components, unless the Cr is present at very high concentrations
(>4000 mg kg− 1).
In this study, FOD pretreatment and optimal band combination
methods were implemented for spectral data mining and the derivation
of spectral parameters, respectively. These operations avoided intro­
ducing too many irrelevant variables, resulting in a decrease in model
accuracy. PLS, a traditional but effective regression approach, was uti­
lized to establish soil Cr estimation models for four designed modeling
schemes on the above basis. The results showed that the model based on
the combination of TBIs and soil auxiliary information is promising (R2v
= 0.87 and RPIQ = 2.68). The differences between max |r| and R2 values
may be attributed to the potential outliers in different dataset. More­
over, many previous studies have investigated the spectral behavior
and/or responses with auxiliary components in a tailing, stream sedi­
ment, and soil before constructing the models (Jeong et al., 2018; Lim
et al. 2019; Shin et al. 2019). Although these models were all site specific
and the equations established in one study cannot extend to other sites
with different metal types and soils, these results indicate that geological
processes associated with formation of soils and tailings are the major
controlling factors of spectral responses to heavy metal contamination.
Similar to aforementioned published results, the Cr is closely associated
12
Geoderma 405 (2022) 115399
with auxiliary covariates in an arid region (eastern Junggar coalfield).
Therefore, there are clear spectral estimation mechanisms that support
the use of soil auxiliary attributes such as the OM and pH levels in
spectral estimation in this study.
Geostatistical methods can be effectively applied to analyze the
characteristics of the spatial distribution structures of regional variables,
and the variance function is commonly used. Under appropriate prior
assumptions, kriging based on the prior covariance produced the best
linear, unbiased prediction of the median. Moreover, kriging is among
the most common practical methods applied in spatial analysis studies
(Oliver and Webster 2015). Therefore, we predicted the spatial distri­
bution of Cr based on estimated values and a kriging interpolation
method with optimal semivariograms. The semivariogram models re­
flected the accuracy of the predicted spatial distribution of Cr in the soil.
The results indicated that the Cr distribution features strong spatial
dependence (Table 4). In addition, obvious Cr enrichment was detected
in the study area (Fig. 9). The eastern Junggar coalfield is located in the
Gobi Desert region in the southwestern Karamaili Nature Reserve with
extreme environmental conditions. Prior to production activities related
to coal mining, the study area was not exposed to human disturbances;
therefore, the local soil was under natural conditions. Heavy industry
has been promoted in the recent past, and industrial discharges from the
local metal smelting, raw material, and manufacturing industries are
considered other primary sources (Imin et al. 2020). From the distri­
bution map and the results of previous studies and main contents in
regional coal deposit, we speculate that the variance in regional soil Cr is
affected by the parent soil materials and industrial discharge sources.
It is noted that the cost of OM and pH measurements in the labora­
tory are cheap and general institutes can measure them. However, we
still need more time to measure them in the laboratory (especially for
SOM) and therefore make the prediction of Cr not that rapid any more.
In this context, advanced proximal soil sensing technology and portable
X-ray fluorescence spectroscopy (pXRF) have become popular recently
(Wan et al. 2020; Xu et al. 2019). The technology in itself is well
established in the laboratory for geochemical and chemical analysis, but
it was only after its incorporation in a portable handheld device that it
became popular for fast, low cost, in situ environmental monitoring
including detecting the occurrence of higher concentrations of heavy
metals in the soil. The pXRF sensor provides adequate analytical accu­
racy and have been used successfully in existing studies (Horta et al.
2021; Ravansari et al. 2020; Shin et al. 2019). The ability to integrate
pXRF with Vis-NIR has displayed considerable potential to improve the
estimation performance for potentially toxic elements. Though not
considered in this study, we intend to do so in the future to joint use
pXRF with Vis-NIR data for long-term soil Cr mapping and believe we
could further reduce the potential uncertainty and improve the accuracy
of the predictions. To reduce potential uncertainty and further make
more solid predictions, we can investigate the geochemical homogeneity
condition of soil sample compositions based on X-ray diffraction (XRD)
analysis, inductively coupled plasma mass spectrometry (ICP-MS), and
pXRF measurements (Lim et al. 2019). Other than these aforementioned
works, we also intend to focus on conducting studies on the spatial
mapping of soil toxic metals based on advanced DSM technology to
obtain the optimal mapping strategy. Assessing the spatial distribution
of soil Cr is only the first step, how to protect local ecology and envi­
ronment and ensure the development of natural resources, ecological
governance, and achieve sustainable development is our ultimate goal.
5. Conclusion
In this study, we used the FOD algorithm to preprocess the spectral
dataset and investigated the potential for integrating soil auxiliary data
and optimal band combinations for soil Cr estimation. The FOD algo­
rithm was effectively used to process spectral curves, which improved
the resolution of the spectrum and illustrated detailed variations in
spectral features. In addition, the correlation coefficients of the
J. Wang et al.
constructed TBIs indicated that the FOD approach can increase the
correlation between soil Cr and spectral data. Our results indicated that
the introduction of soil auxiliary attributes (pH and OM) improved the
model estimation performance, with R2 and RPIQ values of 0.87 and
2.68, respectively, for the validation data set. The integration of the
proximal sensing and kriging interpolation methods yielded a soil Cr
map with satisfactory performance. In the study area, the soil Cr dis­
tribution features strong spatial dependence and strong associations.
Although Vis-NIR is of limited practical use in monitoring soil contam­
ination, we should be hopeful about its potential applications. This study
might inspire further research on soil contamination mapping in arid
regions based on proximal Vis-NIR sensors. The resulting conclusions
improve our understanding of the effects of FOD technology and soil
auxiliary covariates on the spectral estimation of soil Cr levels.
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.
Acknowledgments
The authors wish to thank Prof. Jianli Ding and Dr. Dong Zhang for
helping in providing helpful suggestions and sample collection. This
study was supported by the National Natural Science Foundation of
China (41890854 and 41701476), National Key Research and Devel­
opment Program of China (2019YFB2102703), Guangdong Basic and
Applied Basic Research Foundation (2020A1515111142), and China
Postdoctoral Science Foundation (2020M672776). The funders had no
role in study design, data collection and analysis, decision to publish, or
preparation of the manuscript.
References
Abulaiti, Y., Sawut, M., Maimaitiaili, B., Chunyue, M.a., 2020. A possible fractional order
derivative and optimized spectral indices for assessing total nitrogen content in
cotton. Comput. Electron. Agric. 171, 105275.
Bao, S., 2005. Soil and Agricultural Chemistry Analysis. China Agriculture Press, Beijing.
Baveye, P.C., Laba, M., 2015. Visible and near-infrared reflectance spectroscopy is of
limited practical use to monitor soil contamination by heavy metals. J. Hazard.
Mater. 285, 137–139.
Bellon-Maurel, V., Fernandez-Ahumada, E., Palagos, B., Roger, J.-M., McBratney, A.,
2010. Critical review of chemometric indicators commonly used for assessing the
quality of the prediction of soil attributes by NIR spectroscopy. TrAC, Trends Anal.
Chem. 29, 1073–1081.
Ben-Dor, E., Inbar, Y., Chen, Y., 1997. The reflectance spectra of organic matter in the
visible near-infrared and short wave infrared region (400–2500 nm) during a
controlled decomposition process. Remote Sens. Environ. 61, 1–15.
Cao, X., 2007. Regulating mine land reclamation in developing countries: the case of
China. Land Use Policy 24 (2), 472–483.
Chakraborty, S., Weindorf, D.C., Deb, S., Li, B., Paul, S., Choudhury, A., Ray, D.P., 2017.
Rapid assessment of regional soil arsenic pollution risk via diffuse reflectance
spectroscopy. Geoderma 289, 72–81.
Cheng, H., Shen, R., Chen, Y., Wan, Q., Shi, T., Wang, J., Wan, Y., Hong, Y., Li, X., 2019.
Estimating heavy metal concentrations in suburban soils with reflectance
spectroscopy. Geoderma 336, 59–67.
Ellis, A.S., Johnson, T.M., Bullen, T.D., 2002. Chromium isotopes and the fate of
hexavalent chromium in the environment. Science 295, 2060–2062.
Gao, Y., Xia, J., 2011. Chromium contamination accident in China: viewing environment
policy of China. Environ. Sci. Technol. 45, 8605–8606.
Gholizadeh, A., Kopačková, V., 2019. Detecting vegetation stress as a soil contamination
proxy: a review of optical proximal and remote sensing techniques. Int. J. Environ.
Sci. Technol. 16, 2511–2524.
Hong, Y., Chen, S., Liu, Y., Zhang, Y., Yu, L., Chen, Y., Liu, Y., Cheng, H., Liu, Y., 2019a.
Combination of fractional order derivative and memory-based learning algorithm to
improve the estimation accuracy of soil organic matter by visible and near-infrared
spectroscopy. CATENA 174, 104–116.
Hong, Y., Liu, Y., Chen, Y., Liu, Y., Yu, L., Liu, Y., Cheng, H., 2019b. Application of
fractional-order derivative in the quantitative estimation of soil organic matter
content through visible and near-infrared spectroscopy. Geoderma 337, 758–769.
Hong, Y., Shen, R., Cheng, H., Chen, S., Chen, Y., Guo, L., He, J., Liu, Y., Yu, L., Liu, Y.,
2019c. Cadmium concentration estimation in peri-urban agricultural soils: using
reflectance spectroscopy, soil auxiliary information, or a combination of both?
Geoderma 354, 113875.
13
Geoderma 405 (2022) 115399
Hong, Y., Guo, L., Chen, S., Linderman, M., Mouazen, A.M., Yu, L., Chen, Y., Liu, Y.,
Liu, Y., Cheng, H., Liu, Y.i., 2020. Exploring the potential of airborne hyperspectral
image for estimating topsoil organic carbon: effects of fractional-order derivative
and optimal band combination algorithm. Geoderma 365, 114228.
Horta, A., Malone, B., Stockmann, U., Minasny, B., Bishop, T.F.A., McBratney, A.B.,
Pallasser, R., Pozza, L., 2015. Potential of integrated field spectroscopy and spatial
analysis for enhanced assessment of soil contamination: a prospective review.
Geoderma 241-242, 180–209.
Horta, A., Azevedo, L., Neves, J., Soares, A., Pozza, L., 2021. Integrating portable X-ray
fluorescence (pXRF) measurement uncertainty for accurate soil contamination
mapping. Geoderma 382, 114712.
Hu, B., Shao, S., Ni, H., Fu, Z., Hu, L., Zhou, Y., Min, X., She, S., Chen, S., Huang, M.,
Zhou, L., Li, Y., Shi, Z., 2020. Current status, spatial features, health risks, and
potential driving factors of soil heavy metal pollution in China at province level.
Environ. Pollut. 266, 114961.
Imin, B., Abliz, A., Shi, Q., Liu, S., Hao, L.i., 2020. Quantitatively assessing the risks and
possible sources of toxic metals in soil from an arid, coal-dependent industrial region
in NW China. J. Geochem. Explor. 212, 106505.
Jeong, Y., Yu, J., Wang, L., & Shin, J.H., 2018. Spectral Responses of As and Pb
Contamination in Tailings of a Hydrothermal Ore Deposit: A Case Study of
Samgwang Mine, South Korea. Remote Sensing, 10.
Jia, X., O’Connor, D., Shi, Z., Hou, D., 2021. VIRS based detection in combination with
machine learning for mapping soil pollution. Environ. Pollut. 268, 115845.
Kabata-Pendias, A., 2004. Soil–plant transfer of trace elements—an environmental issue.
Geoderma 122, 143–149.
Levene, H., 1960. Robust Tests for Equality of Variances. Stanford University Press,
California.
Li, X., Liu, X., Liu, M., Wang, C., Xia, X., 2015. A hyperspectral index sensitive to subtle
changes in the canopy chlorophyll content under arsenic stress. Int. J. Appl. Earth
Obs. Geoinf. 36, 41–53.
Li, F., Mistele, B., Hu, Y., Chen, X., Schmidhalter, U., 2014. Optimising three-band
spectral indices to assess aerial N concentration, N uptake and aboveground biomass
of winter wheat remotely in China and Germany. ISPRS J. Photogramm. Remote
Sens. 92, 112–123.
Liang, S., Li, X., Wang, J., 2012. Advanced Remote Sensing. Academic Press, New York.
Lim, J., Yu, J., Wang, L., Jeong, Y., Shin, J.H., 2019. Heavy metal contamination index
using spectral variables for white precipitates induced by acid mine drainage: a case
study of Soro Creek, South Korea. IEEE Trans. Geosci. Remote Sens. 57, 4870–4888.
Liu, B., Ai, S., Zhang, W., Huang, D., Zhang, Y., 2017. Assessment of the bioavailability,
bioaccessibility and transfer of heavy metals in the soil-grain-human systems near a
mining and smelting area in NW China. Sci. Total Environ. 609, 822–829.
Liu, Y.i., Liu, Y., Chen, Y., Zhang, Y., Shi, T., Wang, J., Hong, Y., Fei, T., Zhang, Y., 2019.
The influence of spectral pretreatment on the selection of representative calibration
samples for soil organic matter estimation using Vis-NIR reflectance spectroscopy.
Remote Sens. 11, 450.
Liu, J., Zhang, Y., Wang, H., Du, Y., 2018. Study on the prediction of soil heavy metal
elements content based on visible near-infrared spectroscopy. Spectrochim. Acta
Part A Mol. Biomol. Spectrosc. 199, 43–49.
Malley, D.F., Williams, P.C., 1997. Use of near-infrared reflectance spectroscopy in
prediction of heavy metals in freshwater sediment by their association with organic
matter. Environ. Sci. Technol. 31, 3461–3467.
McBratney, A., Field, D.J., Koch, A., 2014. The dimensions of soil security. Geoderma
213, 203–213.
McBratney, A.B., Mendonça Santos, M.L., Minasny, B., 2003. On digital soil mapping.
Geoderma 117 (1-2), 3–52.
Minasny, B., McBratney, A.B., 2010. Methodologies for Global Soil Mapping. In:
Boettinger, J.L., Howell, D.W., Moore, A.C., Hartemink, A.E., Kienast-Brown, S.
(Eds.), Digital Soil Mapping: Bridging Research, Environmental Application, and
Operation. Springer, Netherlands, Dordrecht, pp. 429–436.
Minasny, B., McBratney, A.B., 2016. Digital soil mapping: A brief history and some
lessons. Geoderma 264, 301–311.
Mustafa, B.M., Al-Quraishi, A.M.F., Gholizadeh, A., Saberioon, M., 2020. Proximal Soil
Sensing for Soil Monitoring. In: Al-Quraishi, A.M.F., Negm, A.M. (Eds.),
Environmental Remote Sensing and GIS in Iraq. Springer International Publishing,
Cham, pp. 95–118.
Nachtergaele, F.O., Spaargaren, O., Deckers, J.A., Ahrens, B., 2000. New developments
in soil classification: world reference base for soil resources. Geoderma 96 (4),
345–357.
Nawar, S., Buddenbaum, H., Hill, J., Kozak, J., Mouazen, A.M., 2016. Estimating the soil
clay content and organic matter by means of different calibration methods of vis-NIR
diffuse reflectance spectroscopy. Soil Tillage Res. 155, 510–522.
Oliver, M.A., Webster, R., 2014. A tutorial guide to geostatistics: Computing and
modelling variograms and kriging. CATENA 113, 56–69.
Oliver, M.A., Webster, R., 2015. Geostatistical Prediction: Kriging. Basic Steps in
Geostatistics: The Variogram and Kriging. Springer International Publishing, Cham,
pp. 43–69.
Padarian, J., Minasny, B., McBratney, A.B., 2020. Machine learning and soil sciences: a
review aided by machine learning tools. Soil 6, 35–52.
Pebesma, E., Heuvelink, G., 2016. Spatio-temporal interpolation using gstat. R J. 8,
204–218.
R Development Core Team, 2019. R: A language and environment for statistical
computing. In: http://www.R-project.org.R.Foundation.for.Statistical.Computing.
Ravansari, R., Wilson, S.C., & Tighe, M., 2020. Portable X-ray fluorescence for
environmental assessment of soils: Not just a point and shoot method. Environment
International, 134, 105250.
J. Wang et al.
Ribeiro Jr, P.J., Diggle, P.J., Ribeiro Jr, M.P.J., Suggests, M., 2007. The geoR package.
R news 1, 14–18.
Rossel, R.A.V., Behrens, T., 2010. Using data mining to model and interpret soil diffuse
reflectance spectra. Geoderma 158, 46–54.
Salminen, R., Batista, M., Bidovec, M., Demetriades, A., De Vivo, B., De Vos, W.,
Duris, M., Gilucis, A., Gregorauskiene, V., Halamić, J., 2005. Geochemical Atlas of
Europe, Part 1 — Background Information, Methodology and Maps. Geological
Survey of Finland, Espoo.
Schmitt, J.M., 1998. Fractional derivative analysis of diffuse reflectance spectra. Appl.
Spectrosc. 52, 840–846.
Shi, T., Chen, Y., Liu, Y., Wu, G., 2014a. Visible and near-infrared reflectance
spectroscopy—an alternative for monitoring soil contamination by heavy metals.
J. Hazard. Mater. 265, 166–176.
Shi, T., Wang, J., Chen, Y., Wu, G., 2016. Improving the prediction of arsenic contents in
agricultural soils by combining the reflectance spectroscopy of soils and rice plants.
Int. J. Appl. Earth Obs. Geoinf. 52, 95–103.
Shi, T., Guo, L., Chen, Y., Wang, W., Shi, Z., Li, Q., Wu, G., 2018a. Proximal and remote
sensing techniques for mapping of soil contamination with heavy metals. Appl.
Spectrosc. Rev. 53, 783–805.
Shi, T., Hu, Z., Shi, Z., Guo, L., Chen, Y., Li, Q., Wu, G., 2018b. Geo-detection of factors
controlling spatial patterns of heavy metals in urban topsoil using multi-source data.
Sci. Total Environ. 643, 451–459.
Shi, Z., Wang, Q., Peng, J., Ji, W., Liu, H., Li, X., Rossel, R.A.V., 2014b. Development of a
national VNIR soil-spectral library for soil classification and prediction of organic
matter concentrations. Sci. China Earth Sci. 57, 1671–1680.
Shin, J.H., Yu, J., Wang, L., Kim, J., Koh, S.-M., Kim, S.-O., 2019. Spectral responses of
heavy metal contaminated soils in the vicinity of a hydrothermal ore deposit: a case
study of Boksu Mine, South Korea. IEEE Trans. Geosci. Remote Sens. 57, 4092–4106.
State Environmental Protection Agency of China (2004). Technical Specification for Soil
Environmental Monitoring (HJ/T 166–2004). In. Beijing: China Environmental Press
Beijing.
Tian, Y., Zhang, J., Yao, X., Cao, W., Zhu, Y., 2013. Laboratory assessment of three
quantitative methods for estimating the organic matter content of soils in China
based on visible/near-infrared reflectance spectra. Geoderma 202-203, 161–170.
Tóth, G., Hermann, T., Szatmári, G., Pásztor, L., 2016. Maps of heavy metals in the soils
of the European Union and proposed priority areas for detailed assessment. Sci. Total
Environ. 565, 1054–1062.
Viscarra Rossel, R.A., McGlynn, R.N., McBratney, A.B., 2006a. Determining the
composition of mineral-organic mixes using UV–vis–NIR diffuse reflectance
spectroscopy. Geoderma 137, 70–82.
Viscarra Rossel, R.A., Walvoort, D.J.J., McBratney, A.B., Janik, L.J., Skjemstad, J.O.,
2006b. Visible, near infrared, mid infrared or combined diffuse reflectance
spectroscopy for simultaneous assessment of various soil properties. Geoderma 131,
59–75.
Wadoux, A.-C., Minasny, B., McBratney, A.B., 2020. Machine learning for digital soil
mapping: applications, challenges and suggested solutions. Earth Sci. Rev. 210,
103359.
Wan, M., Hu, W., Qu, M., Li, W., Zhang, C., Kang, J., Hong, Y., Chen, Y., Huang, B., 2020.
Rapid estimation of soil cation exchange capacity through sensor data fusion of
portable XRF spectrometry and Vis-NIR spectroscopy. Geoderma 363, 114163.
Wang, Z.-X., Chen, J.-Q., Chai, L.-Y., Yang, Z.-H., Huang, S.-H., Zheng, Y.u., 2011.
Environmental impact and site-specific human health risks of chromium in the
vicinity of a ferro-alloy manufactory, China. J. Hazard. Mater. 190, 980–985.
Wang, J., Cui, L., Gao, W., Shi, T., Chen, Y., Gao, Y., 2014. Prediction of low heavy metal
concentrations in agricultural soils using visible and near-infrared reflectance
spectroscopy. Geoderma 216, 1–9.
14
Geoderma 405 (2022) 115399
Wang, J., Ding, J., Abulimiti, A., Cai, L., 2018a. Quantitative estimation of soil salinity by
means of different modeling methods and visible-near infrared (VIS–NIR)
spectroscopy, Ebinur Lake Wetland, Northwest China. PeerJ 6, e4703.
Wang, J., Ding, J., Yu, D., Ma, X., Zhang, Z., Ge, X., Teng, D., Li, X., Liang, J., Lizaga, I.,
Chen, X., Yuan, L., Guo, Y., 2019. Capability of Sentinel-2 MSI data for monitoring
and mapping of soil salinity in dry and wet seasons in the Ebinur Lake region,
Xinjiang, China. Geoderma 353, 172–187.
Wang, J., Shi, T., Yu, D., Teng, D., Ge, X., Zhang, Z., Yang, X., Wang, H., Wu, G., 2020.
Ensemble machine-learning-based framework for estimating total nitrogen
concentration in water using drone-borne hyperspectral imagery of emergent plants:
a case study in an arid oasis, NW China. Environ. Pollut. 266, 115412. https://doi.
org/10.1016/j.envpol.2020.115412.
Wang, X., Zhang, F., Kung, H.-T., Johnson, V.C., 2018b. New methods for improving the
remote sensing estimation of soil organic matter content (SOMC) in the Ebinur Lake
Wetland National Nature Reserve (ELWNNR) in northwest China. Remote Sens.
Environ. 218, 104–118.
Wei, T., Simko, V., Levy, M., Xie, Y., Jin, Y., & Zemla, J. (2017). Corrplot: visualization of
a correlation matrix. R package version 0.84. In: https://CRAN.R-project.org/pack
age=corrplot.
Wold, S., Martens, H., & Wold, H. (1983). The multivariate calibration problem in
chemistry solved by the PLS method. In (pp. 286-293). Berlin, Heidelberg: Springer
Berlin Heidelberg.
Wu, Y., Chen, J., Ji, J., Gong, P., Liao, Q., Tian, Q., Ma, H., 2007. A mechanism study of
reflectance spectroscopy for investigating heavy metals in soils. Soil Sci. Soc. Am. J.
71, 918–926.
Xia, X.Q., Mao, Y.Q., Ji, J.F., Ma, H.R., Chen, J., Liao, Q.L., 2007. Reflectance
spectroscopy study of Cd contamination in the sediments of the Changjiang River,
China. Environ. Sci. Technol. 41, 3449–3454.
Xu, D., Chen, S., Viscarra Rossel, R.A., Biswas, A., Li, S., Zhou, Y., Shi, Z., 2019. X-ray
fluorescence and visible near infrared sensor fusion for predicting soil chromium
content. Geoderma 352, 61–69.
Zeng, Q., Shen, L., Yang, J., 2020. Potential impacts of mining of super-thick coal seam
on the local environment in arid Eastern Junggar coalfield, Xinjiang region, China.
Environ. Earth Sci. 79, 88.
Zhang, Z., Ding, J., Wang, J., Ge, X., 2020b. Prediction of soil organic matter in
northwestern China using fractional-order derivative spectroscopy and modified
normalized difference indices. CATENA 185, 104257.
Zhang, Z., Ding, J., Zhu, C., Wang, J., Ma, G., Ge, X., Li, Z., Han, L., 2021. Strategies for
the efficient estimation of soil organic matter in salt-affected soils through Vis-NIR
spectroscopy: optimal band combination algorithm and spectral degradation.
Geoderma 382, 114729.
Zhang, S., Fei, T., You, X., Wan, Y., Wang, Y., & Bian, M., 2020. Two hyperspectral
indices for detecting cadmium and lead contamination from arice canopy spectrum.
Land Degradation & Development, n/a.
Zhou, J., Cao, X., 2020. What is the policy improvement of China’s land consolidation?
Evidence from completed land consolidation projects in Shaanxi Province. Land Use
Policy 99, 104847.
Zhou, J., Zhuang, X., Alastuey, A., Querol, X., Li, J., 2010. Geochemistry and mineralogy
of coal in the recently explored Zhundong large coal field in the Junggar basin,
Xinjiang province, China. Int. J. Coal Geol. 82, 51–67.
Zhu, X.X., Tuia, D., Mou, L., Xia, G.-S., Zhang, L., Xu, F., Fraundorfer, F., 2017. Deep
learning in remote sensing: a comprehensive review and list of resources. IEEE
Geosci. Remote Sens. Mag. 5, 8–36.