Process Safety and Environmental Protection 132 (2019) 73–81

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Process Safety and Environmental Protection

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

Estimation of soil pH using PXRF spectrometry and Vis-NIR

spectroscopy for rapid environmental risk assessment of
soil heavy metals
Mengxue Wan a,b,c,e , Mingkai Qu a,c , Wenyou Hu a , Weidong Li c , Chuanrong Zhang c ,
Hang Cheng d , Biao Huang a,∗
a
Key Laboratory of Soil Environment and Pollution Remediation, Institute of Soil Science, Chinese Academy of Sciences, Nanjing, 210008, China
b
University of Chinese Academy of Sciences, Beijing, 100049, China
c
Department of Geography, University of Connecticut, Storrs, CT, 06269, USA
d
School of Resource and Environmental Sciences, Wuhan University, Wuhan, 430079, China
e
Key Laboratory of Geospatial Technology for Middle and Lower Yellow River Regions (Henan University), Ministry of Education, Kaifeng 475004, China

a r t i c l e i n f o a b s t r a c t

Article history: Environmental risk of heavy metals (HMs) in soil is commonly assessed by the different risk screening val-
Received 8 July 2019 ues of HMs under different pH based on soil environmental quality standards. To explore and establish a
Received in revised form 5 September 2019 reliable, rapid and cost-effective method for detailed soil environmental quality survey with high-density
Accepted 20 September 2019
sampling in the large-scale area is of significance for theoretical and practical research. In present study,
Available online 24 September 2019
using data from Yunnan Province, China, rapid analysis of soil HMs were conducted via portable X-ray
fluorescence (PXRF) spectrometry, and that of soil pH was estimated by applying PXRF and visible near-
Keywords:
infrared reflectance (Vis-NIR) spectroscopy data to partial least-squares regression (PLSR) and support
Soil pH
PXRF
vector machine regression (SVMR). Then we compared soil HM contamination grades calculated by con-
Vis-NIR ventional laboratory analysis data with those of rapid analysis data. It was found that soil HMs (i.e., As,
Data fusion Pb, Cu, and Zn) were successfully estimated by PXRF with high coefficient of determination (R2 ) above
Soil heavy metals 0.97 (P < 0.001). SVMR with fused sensor dataset (here PXRF and Vis-NIR) provided the best predictive
Environmental risk assessment model for soil pH estimation (R2 = 0.86; the ratio of performance to deviation (RPD) = 2.21; the ratio of
performance to interquartile distance (RPIQ) = 3.09). The Kappa coefficient of the classification was 0.91,
a very high-level consistency between the assessment of soil HM contamination grades calculated by
rapid analysis data and that of conventional laboratory analysis data. Therefore, our study suggested a
promising method to rapidly detect soil HM contamination under different pH intervals, which would
considerably reduce the financial burden of detailed soil HM survey great sampling number in large-scale
areas.
© 2019 Published by Elsevier B.V. on behalf of Institution of Chemical Engineers.

1. Introduction
Soil heavy metal (HM) pollution has been a matter of great con-
cern globally (Li et al., 2017; Qu et al., 2018; Yang et al., 2019).
Heavy metals accumulated in soils could be toxic for many organ-
isms and affect the vegetable quality and food security, posing a
severe threat to human health (Hu et al., 2017b; Tian et al., 2017;
Tong et al., 2019). Therefore, completing detailed soil HM survey at
Abbreviations: PXRF, portable X-ray fluorescence; RPD, residual prediction devi-
ation; RPIQ, the ratio of performance to interquartile distance; SVMR, supportvector
machine regression; PLSR, partial least-squares regression; SG, Savitzky-Golay; SNV,
standard normal variate transform; Vis-NIR, visible near-infrared reflectance.
∗ Corresponding author.
E-mail address: bhuang@issas.ac.cn (B. Huang).
a large scale is critical to assess the environmental risk of soil HMs
in a time- and cost-saving manner.
Conventionally, the environmental risk of soil HMs is com-
monly assessed using different pH intervals to determine the joint
thresholds of soil HMs according to soil environmental quality stan-
dards. Currently, soil HMs are usually determined using laboratory
analytical methods, such as inductively coupled plasma-mass spec-
troscopy (ICP-MS), inductively coupled plasma atomic emission
spectrometry (ICP-AES), atomic fluorescence spectrometry (AFS)
and atomic absorption spectrophotometry (AAS) (Li et al., 2018;
Wang et al., 2018; Zhang et al., 2017). These techniques are highly
accurate but time- and cost-consuming, especially for detailed soil
HM surveys with high sampling density in the large scale (Hu et al.,
2017a; Ran et al., 2014). Recently, the application of portable X-
ray fluorescence (PXRF) to soil analysis was sanctioned first by

https://doi.org/10.1016/j.psep.2019.09.025
0957-5820/© 2019 Published by Elsevier B.V. on behalf of Institution of Chemical Engineers.
74 M. Wan, M. Qu, W. Hu et al. / Process Safety and Environmental Protection 132 (2019) 73–81

the USEPA (2007) in method 6200 and most recently by the Soil et al., 2018). Therefore, to get robustness and reliability in predic-
Survey Staff (2014). Moreover, PXRF has been widely used to deter- tion, the choice of an appropriate model is an essential factor for
mine soil HMs and assess soil environmental risk because of its successful prediction, especially for sensor data fusion with a large
accuracy and rapidity (Chakraborty et al., 2017; Horta et al., 2015; number of potential predictor variables (Nawar et al., 2016).
Qu et al., 2019; Weindorf et al., 2014, 2012; Yang et al., 2018). This study was conducted with 138 surface soil samples in Yun-
Wan et al. (2019) applied PXRF to determine As, Pb, Cu, and Zn nan Province, China. The specific objectives are as follows: (1) to
at relatively low concentration and found significantly positive investigate the feasibility of Vis-NIR, PXRF and sensor data fusion
correlations between the ex-situ PXRF results and conventional lab- (PXRF + Vis-NIR) for rapid characterization of soil pH; (2) to com-
oratory analysis results for both certified reference materials and pare, by using different sensor data sets, the performance of the
soil samples. Therefore, PXRF has potential to determine soil HMs traditional linear method PLSR with that of the non-linear method
concentrations ex-situ as a rapid and nondestructive tool, espe- SVMR; (3) to verify the application of PXRF for effectively quanti-
cially when attempting to quantify HMs with high sampling density fying soil HMs (As, Pb, Cu, and Zn); and (4) to rapidly assess soil
in a large-scale area. environmental risk based on pH and HMs with rapid and non-
Moreover, soil pH is traditionally measured either colorimetri- destructive analysis. The ultimate goal is to find an optimal rapid
cally or electrometrically in the laboratory (Zhang and Gong, 2012). method of soil pH characterization and HM determination to save
It may strongly impact the relative availability of plant nutrients, time and cost for rapid soil environmental risk assessment with
microbial activity, and toxicity of contaminants and accumulation high-density sampling in a large-scale area.
of toxic materials. Therefore, it is one of the most critical soil prop-
erties for soil survey and assessment of soil environmental quality.
2. Materials and methods
More importantly, there is a tremendous need for simultaneous
soil HMs and pH measuring methods with comparable accuracy to
2.1. Study area and soil sampling
rapidly assess soil environmental risk (Hu et al., 2017a; Shepherd
and Walsh, 2002). With the development of proximal soil sensing
The study was conducted in Yunnan Province, located in the
technology, not only PXRF could measure multiple soil elements
southwest China between longitude 97 to 105 ◦ E and latitude 20 to
rapidly (Kilbride et al., 2006; Wan et al., 2019; Yang et al., 2018)
28 ◦ N. Because of great difference in elevation from 93 to 5396 m
but also pH could be simultaneously predicted by multiple linear
above sea level, Yunnan Province comprises seven different climate
regression (MLR) directly with PXRF-measured elements (Sharma
zones, including north tropical, south subtropical, middle subtrop-
et al., 2014). While, visible near-infrared reflectance (Vis-NIR) spec-
ical, northern subtropical, warm temperate, middle temperate, and
troscopy was also used to predict soil pH by partial-least squares
plateau climatic zones, which reflect climatic effects of insolation,
regression (PLSR) (Hu et al., 2017a). However, a single sensor can-
monsoon, and elevation. The annual average temperature in Yun-
not always provide comprehensive information for soil properties
nan ranges from 5 ◦ C in the north to 24 ◦ C in the south, and the
effectively because of the complex nature of soils. Thus, methods
annual rainfall is between 800 and 1200 mm mostly falling from
with multiple sensor fusion and advanced models have been used
May to October. The whole province is highly mountainous and
to improve the prediction of some soil properties. Wang et al. (2013)
rugged landscape, giving rise to high biodiversity with tropical, sub-
reported that using a Fourier transform near-infrared (FT-NIR)
tropical, temperate and even frigid plant species. With the area of
spectrometer and a PXRF analyzer with data fusion improved the
390,000 km2 of Yunnan Province, factors affect the soil formation,
prediction of soil texture. Aldabaa et al. (2015) proved that applica-
including climate, organisms, topography, and parent materials,
tion of PXRF combined with Vis-NIR and remotely sensed spectral
vary substantially across space and time, allowing for the develop-
data could potentially improve the prediction of soil salinity. Wang
ment of many soil types including Ferrosols, Andosols, Anthrosols,
et al. (2015) demonstrated that merging the PXRF and Vis-NIR
Gleyosols, Isohumosols, Argosols, Cambosols and Primosols accord-
datasets improved the power of predictive models, as indicated
ing to Keys to Chinese Soil Taxonomy (2001).
by improved residual prediction deviation (RPD) and R2 statistics.
With the consideration of soil types and transportation condi-
Given the success of these previous investigations, we hypothesize
tions, the spatial distribution of sampling locations was arranged as
that similar approaches of sensor data fusion would be feasible to
shown in Fig. 1, according to the actual performance. In this study,
predict soil pH when the PXRF and Vis-NIR data were available for
138 surface soil samples were collected from the top layer of the
rapid soil environmental risk assessment. If the fused sensor data
corresponding soil profiles down to a depth of 120 cm or the rock,
(PXRF and Vis-NIR) could be efficiently used as a proxy for soil pH
across the Yunnan Province. The depths of the top layers varied,
characterization, it would result in substantial saving in cost and
according to the observable differences in soil color, texture, struc-
time for the rapid assessment of soil environmental risk.
ture, or other characteristics. Each soil sample, approximately 1 kg,
The linear technique of partial least-squares regression (PLSR)
was composed of five sub-samples within the top layer. The gravels
is one of the most widely used techniques and has a good capacity
and plant debris were hand-picked, and the soils were air-dried at
to handle data multicollinearity and estimate attributes between
room temperature. Then the soil was separated into three parts and
the spectral and soil properties (Vasques et al., 2008; Wold et al.,
crushed to pass through < 2 mm, < 0.25 mm, and < 0.150 mm sieves,
2001). Nonetheless, PLSR is restricted by its linearity assumption
and stored in paper bags, respectively, for the further analysis. Air-
among variables. Support vector machine regression (SVMR) is a
dried and sieved soils were used to minimize effects of variation
relatively new non-linear method and has been used in classifica-
in soil moisture, particle size and non-uniformity on reflectance
tion and multivariate calibration problems (Chang and Lin, 2011).
(Bendor et al., 1999; Silva et al., 2018).
Previous studies showed that this non-linear regression model
outperformed linear models because the relationships between
spectral data or elemental concentrations and soil characteristics 2.2. Conventional laboratory analysis
are rarely linear in nature, especially for large-scale areas with a
wide variability of soil properties (Araújo et al., 2014; Lucà et al., Soil pH was measured using a soil/water ratio of 1:2.5 with a pH
2017). When dealing with a heterogeneous sample set in which soil meter (PHS-3C, Shanghai, China), and standard reference materials
composition may vary considerably, the precision of linear regres- were used for the data quality control (Zhang and Gong, 2012).
sion techniques decreases because of the non-linear nature of the For HM analysis, soil samples were digested in HNO3 −HClO4 -
relationship between spectral data and the dependent variable (Xu HF (Zhuang et al., 2009), and analyzed for Pb, Cu, and Zn using
 M. Wan, M. Qu, W. Hu et al. / Process Safety and Environmental Protection 132 (2019) 73–81
Fig. 1. Distribution of sampling sites in Yunnan Province, China.
inductively coupled plasma-mass spectroscopy (ICP-MS; American
Thermo Scientific, X7). Arsenic was digested in aqua regia (HNO3 :
HCl = 3:1) and analyzed by atomic fluorescence spectrometry (AFS;
Beijing Jitian Instruments Co., Ltd. production, AFS-820) (Xu et al.,
2013).
2.3. Rapid analysis using proximal sensing techniques
The rapid estimation of soil HMs and pH using proximal sensing
techniques can be influenced by the instrument environments, soil
particle sizes, moisture and geographical distribution of samples
(Chang et al., 2005; Wang et al., 2013). Therefore, controlled mois-
ture and temperature for the scanning environment were set in the
laboratory to help to obtain more accurate results than in-situ mea-
surement methods. Moreover, the soils were air-dried and sieved
to the same size before scanning in the same laboratory environ-
ment, the negative influences of particle size and moisture could
be minimized.
Portable X-ray fluorescence (PXRF) spectrometry (NITON XLt
960, UK) was applied to determine elemental contents in this study
following the manufacturer’s instructions and the recommenda-
tions of the Method 6200 (USEPA, 2007). It was conducted with
a 40 kV X-ray tube with Ag anode target excitation source, and a
silicon PIN-diode with a Peltier cooled detector. Prior to sample
analysis, the PXRF was calibrated by the manufacturer’s sets. Then,
the soil surface was directly scanned by PXRF in Geochem mode,
and results of each sample were calculated by averaging three par-
allel measurements automatically for analysis and output in Excel
format (Hu et al., 2014). Geochem mode consisted of three beams
operating sequentially. Each beam was set to scan for 30 s so that
each scan could be completed in 90 s. The standard soil GSS-3 was
used to test the accuracy after every twenty samplings’ scans.
Soil samples were oven-dried at 45 ◦ C for 24 h prior to spec-
tra collection. Reflectance spectra were measured in the visible
and near-infrared (Vis-NIR) range of 350–2500 nm using Cary 5000
75
(Agilent Technologies, CA) under controlled laboratory conditions.
It took about 3.5 min to scan one sample, and for each subset of
50 samples, two samples were randomly chosen for replicate mea-
surements. The variation between replicates was less than 0.3%.
Spectra were sampled at 1-nm intervals with resolution narrower
than 0.048 nm in the visible range (350–700 nm) and narrower
than 0.2 nm in the NIR range (700-2,500 nm) to obtain 2151 wave-
lengths. Detailed information about the Cary 5000 spectrometer
and protocols of spectra measurements can be found at Zeng et al.
(2016).
2.4. Data preparations for pH prediction
2.4.1. PXRF data
The instrument was capable of detecting various elements,
including Ca, Fe, Mn, Cr, Ni, Cu, Zn, Pb, As, K, Ti, V, Rb, Sr, Zr, Nb,
Si, and Al in soil samples. Elemental data in this study were higher
than the detection limit. And the elemental data were then log-
transformed (Sharma et al., 2014).
2.4.2. Vis-NIR data
The pretreatment of the spectral data was performed using
Unscrambler 9.3 (Camo Software AS, Oslo, Norway). Spectral
reflectance (R) was transformed to absorbance (A) by the equation
A = log10 (1/R) before modelling. Data redundancy was reduced by
selecting every tenth band in every ten bands. The remaining 216
wavebands were smoothed through an 11-point Savitzky-Golay
(SG) filter with the first derivative using a second-order polynomial
with a window size of 10 wavelengths to reduce the baseline vari-
ation and improve the spectral features (Savitzky and Golay, 1964).
Derivatives were applied either alone or combined with (i) standard
normal variate transform (SNV), which reduced the particle-size
effect, or (ii) with multiplicative scatter correction (MSC), which
removed light scattering variation in the reflectance spectroscopy
(Martens and Naes, 1989). Each preprocessing data was then cal-
76 M. Wan, M. Qu, W. Hu et al. / Process Safety and Environmental Protection 132 (2019) 73–81

ibrated for soil pH determination using PLSR and SVMR models. Table 1
Assessment of standard reference on soil heavy metal.
Overall, the SG, SNV, and MSC transforms did not improve the accu-
racy of the models (data not shown), and the results presented pH As Pb Cu Zn
below were from the SG smoothing using the first derivative with mg kg−1
a second-order polynomial in conjunction with MSC. Risk control standard pH ≤ 5.5 40 70 50 200
for soil contamination 5.5 < pH ≤ 6.5 40 90 50 200
2.4.3. Sensor data fusion in China 6.5 < pH ≤ 7.5 30 120 100 250
(GB15618-2018) pH > 7.5 25 170 100 300
The elemental concentrations measured by PXRF (18 variables)
and the reflectance data by Vis-NIR (216 variables) were fused into
one dataset - PXRF + Vis-NIR (234 variables). Table 2
Grades of soil heavy metal pollution (Han et al., 2018; Zhang et al., 2017).
2.5. Multivariate models for soil pH prediction
Class SPI NCPI Grade

Both the two single sensor datasets and the one fused sensor
dataset were each divided into two subsets for calibration and val-
idation. The whole dataset (n = 138) was sorted in a descending
order according to soil pH value; then the middle one of every three
adjacent samples in the sequence were regarded as the validation
set (n = 46) and the remaining two thirds as the calibration dataset
(n = 92).
Partial least-squares regression (PLSR) and support vector
machine regression (SVMR) models were performed to establish
the relationship between pH and sensor data matrix using the PLS
Toolbox version 8.02 (Eigenvector Research, Inc., Wenatchee, WA,
USA) under MATLAB version R2016a (The MathWorks, Inc., Nat-
ick, MA, USA). In PLSR and SVMR models, Y was the matrix of soil
pH measured by conventional laboratory analysis, and X was the
sensor data matrix.
PLSR is a widely used linear multivariate regression method for
relating soil properties and spectral data (Wold et al., 2001). The
compression and regression steps are integrated in PLSR, and the
new orthogonal factors by reducing dimensional space and noise
of spectral variables, namely latent variables (LVs), are determined.
The optimal number of LVs, which are used to optimize the covari-
ance between soil property and spectral data in PLSR modelling, are
determined after the minimum root mean squared error (RMSE) is
obtained by leave-one-out cross-validation. Then the extracted LVs
are used as the linear combination of the predictor variables.
SVMR is a new nonlinear regression method, commonly applied
in classification and regression due to its high speed of computing
and excellent performance (Bao et al., 2017; Vapnik, 1999). The raw
data are reduced to support vectors through SVM, and a support-
vector network maps the input vectors into a high-dimensional
feature space via some nonlinear mapping to construct an optimal
hyperplane for nonlinear regression. The epsilon-SVM algorithm
and radial basis function (kernel function) were used for modeling
in this study. The radial basis function kernel parameter (␥) and cost
parameter (C) were fine-tuned by a systematic grid search method,
and the optimal parameters were determined after the minimum
root mean squared error (RMSE) was obtained by leave-one-out
cross-validation.
In this study, six modeling modes were performed as follows:
1 First, soil pH was predicted by both PLSR and SVMR using single
sensor datasets of log-transformed PXRF elemental data.
2 Next, soil pH was predicted by both PLSR and SVMR using single
sensor datasets of pretreated Vis-NIR spectral data.
3 Finally, soil pH was predicted by both PLSR and SVMR using the
fused sensor dataset.
2.6. Accuracy assessment of prediction models
The measured values soil HMs and pH were compared with
the corresponding estimated values using simple linear regression
analysis. The performances of the different models were eval-
uated using the indices including the RMSE, the coefficient of
1 SPI≤ 1 NCPI≤ 0.7 Safety
2 1 < SPI ≤ 2 0.7 < NCPI≤ 1.0 Alert
3 2 < SPI ≤ 3 1.0 < NCPI≤ 2.0 Slight pollution
4 3 < SPI ≤ 5 2.0 < NCPI≤ 3.0 Moderate pollution
5 SPI > 5 NCPI> 3.0 Severe pollution
determination (R2 ), and the ratio of performance to deviation resid-
ual prediction deviation (RPD) and the ratio of performance to
interquartile distance (RPIQ). The RPD index is the standard devi-
ation (SD) divided by the RMSE (Chang and Laird, 2002; Shepherd
and Walsh, 2002). The RPIQ is the ratio of the interquartile distance
to the RMSE (Bellon-Maurel et al., 2010).
2.7. Soil heavy metal contamination assessment
To evaluate the feasibility of rapid soil environmental risk
assessment, soil contamination grades, assessed by rapid analysis
data (PXRF measured HMs and PXRF and Vis-NIR predicted pH),
were compared with those of conventional laboratory analysis in
this study. Single pollution index (SPI) for each HM was used to
evaluate the effect of each HM on soil contamination and Nemerow
composite pollution index (NCPI) was used to assess the influence
of high concentration HMs on soil environmental quality. The pollu-
tion thresholds for each soil HM were decided based on four-group
pH intervals according to the soil environmental quality standards
in China (GB15618-2018) (Table 1). SPI is calculated by
Ci
SPI = (1)
Si
where Ci is the concentration of soil heavy metal i and Si is the
threshold of i. NCPI is calculated by

(SPI max )2 + (SPI mean )2
NCPI = (2)
2
where SPI max is the maximum value among SPI values of each HM
and SPI mean is the mean SPI of each heavy metal.
As NCPI was used to classify the soil HM pollution, they were
divided into different grades according to different values (Table 2).
Kappa coefficient was used to verify the intra rater-reliability of
environmental risk assessment based on conventional laboratory
analysis data and rapid analysis data. The Kappa coefficient was
calculated as Eq. 3:
Po − Pe
Kappa = (3)
1 − Pe
where Po is observed agreement, and Pe is chance agreement
(Kraemer, 2014; Thompson and Walter, 1988). The value of Kappa
coefficient is between -1 and 1. Kappa < 0.4 indicates poor consis-
tency, 0.4 ≤ Kappa < 0.75 for acceptable consistency, Kappa ≥ 0.75
for satisfactory consistency (Landis and Koch, 1977).
 M. Wan, M. Qu, W. Hu et al. / Process Safety and Environmental Protection 132 (2019) 73–81 77

Fig. 2. Box-plots, histograms and descriptive statistics of measured pH data. Min.: minimum, Max.: maximum, SD: standard deviation, CV: coefficient of variation, n: the
number of soil samples.

Table 3
Descriptive statistics of heavy metals determined by conventional laboratory
analysis.

Heavy metals Min. Max. Mean SD CV

. . .. . .. . .. . . mg·kg−1 . . .. . .. . .. . .

Cu 5.84 331.63 50.59 47.87 0.95

Zn 24.49 858.47 103.73 87.89 0.85
Pb 14.19 489.86 46.74 52.46 1.12
As 5.97 217.33 32.42 33.24 1.03

Table 4
Correlation statistics relating the elemental contents of PXRF to soil pH.

Elements pH Elements pH Elements pH

Ca 0.820** Zn 0.173** Rb 0.008

Fe −0.001 Pb 0.145** Sr 0.458**
Mn 0.229** As 0.041 Zr −0.234**
Cr −0.028 K 0.208** Nb −0.136**
Ni 0.166** Ti −0.090* Al −0.270**
Cu 0.044 V −0.085* Si −0.116**
*
Correlation is significant at the 0.05 level (2-tailed).
**
Correlation is significant at the 0.01 level (2-tailed).

3. Results and discussion

3.1. Descriptive statistics
The summary statistics of soil pH measured by conventional lab-
oratory analysis for the whole, calibration and validation datasets
were provided in Fig. 2. The calibration data ranged from 4.12 to
8.59 with a mean value of 5.99, and the validation data ranged from
4.25 to 8.32 with an average of 5.99. Overall, the soil pH values of
both calibration and validation datasets were similar to the whole
dataset with a wide range from 4.12 to 8.59, from acidic to alkaline,
demonstrating that they represented the whole dataset well.
The summary statistics of soil HMs measured by conventional
laboratory analysis were provided in Table 3. The mean values of
As, Pb, Cu, and Zn were 32.42, 46.74, 50.59, and 103.73 mg kg−1 ,
respectively. The CV values of As, Pb, Cu, and Zn were between
0.85–1.12, much higher than 0.75, which were in the state of rel-
atively high variation. The SD of As and Pb were higher than their
corresponding mean value, thus indicating a high variation, espe-
cially for Pb having the highest CV of 1.12. This demonstrated that
soil formation factors, especially for the parent materials, in Yun-
nan Province varied dramatically. The parent materials, which are
the main source of the elements, should contribute to the corre-
lations between soil pH and some elements. Table 4 showed that
Fig. 3. Mean soil reflectance spectra at different pH values from soils in Yunnan
Province, China: (a) raw spectra; (b) first derivative spectra.
there were significant differences in correlations between soil pH
and each of Ca, Mn, Ni, Zn, Pb, K, Ti, V, Sr, Zr, Nb, Al, and Si, with Ca
having the highest positive correlation coefficient of 0.820 at the
significance level of 0.01, which might be contributed to the good
predictive ability of PXRF data.
The raw and preprocessed Vis-NIR spectra of soil samples at
different wavelengths representing different intervals of pH val-
ues (from acid to alkaline) were summarized in Fig. 3. The overall
shapes of the raw spectra in different pH intervals were gen-
erally broad and smooth. The first derivative of the reflectance
enhanced the spectral features compared with the raw reflectance.
As reported, the three absorption regions at approximately 1400,
1900, and 2200 nm are related to the O H stretching, H O H bend-
ing, and the clay lattice Al−OH absorption band (Stenberg et al.,
2010). Given that multiple linear regression with PXRF data and
auxiliary input data (clay content, sand content, organic matter
content) provided the best predictive model (Sharma et al., 2014),
the improvement of pH prediction based on fused sensor data in
78 M. Wan, M. Qu, W. Hu et al. / Process Safety and Environmental Protection 132 (2019) 73–81

Table 5
Comparison of classification of heavy metal contamination grades based on conventional laboratory analysis data and rapid analysis data.

Prediction-based classification Safety Alert Slight Moderate Severe Total Accuracy of prediction-based
Pollution Pollution Pollution classification (%)

Lab-measurement-based classification
Safety 63 6 1 0 0 70 90
Alert 5 20 3 0 0 28 71
Slight Pollution 3 2 19 1 0 25 76
Moderate Pollution 0 0 2 5 3 10 50
Severe Pollution 0 0 0 1 4 5 80
Total 71 28 25 7 7 138
Accuracy of method classification (%) 89 71 76 71 57 Kappa Coefficient: 0.80
Safety 66 3 1 0 0 70 94
Alert 3 23 2 0 0 28 82
Slight Pollution 1 1 22 1 0 25 88
Moderate Pollution 0 0 1 9 0 10 90
Severe Pollution 0 0 0 0 5 5 100
Total 70 27 26 10 5 138
Accuracy of method classification (%) 94 85 85 90 100 Kappa Coefficient: 0.91

Fig. 4. Scatter plots of lab-measured pH vs predicted pH using different data sets and analysis methods (PLSR and SVMR) for surface soils (validation dataset, n = 46). The
dotted lines are the 1:1 line and the red lines are the regression lines. The colored regions in the six subplots represent 95% prediction confidence intervals. (For interpretation
of the references to colour in this figure legend, the reader is referred to the web version of this article).

this study might be due to the spectral response to the soil organic
matter and clay.
3.2. Soil pH estimation using different sensor datasets
For the linear regression method PLSR, the soil pH was pre-
dicted with R2 = 0.68, 0.34, and 0.58, RPD = 1.50, 0.70, and 1.13, and
RPIQ = 2.01, 0.81, and 1.37 for validation dataset through PXRF, Vis-
NIR, and fused sensor data, respectively (Fig. 4). The correlations
between soil pH and certain elements might lead to the acceptable
performance of the linear regression (PLSR) based on PXRF dataset
(Sharma et al., 2014). While, the poor performance of PLSR based on
Vis-NIR dataset might be caused by the indirect spectral response
to soil pH (Stenberg et al., 2010). Since it was difficult for Vis-NIR
spectroscopy alone to provide a proper soil characterization, the
poor correlation between the Vis-NIR spectra and the soil pH might
complicate the PLSR analysis, leading to the decreased prediction
accuracy based on the fused dataset.
Compared with PLSR, the nonlinear regression method SVMR
improved the predictions of soil pH from PXRF, Vis-NIR, and fused
sensor dataset with R2 = 0.80, 0.75, and 0.86, RPD = 2.03, 1.74, and
2.21, and RPIQ = 3.01, 2.50, and 3.09 for validation dataset, respec-
tively. Substantial improvement in predicting soil pH by SVMR over
PLSR is likely attributable to the nonlinear relationships between
soil characteristics that were not captured by PLSR (Webster, 2000).
Moreover, the application of the nonlinear regression method
ignored the step of selecting the specific elements for linear regres-
sion, leading to a better performance of SVMR. Therefore, when only
PXRF data were available, SVMR was effective to predict soil pH
with reasonable accuracy in our study area. However, Sharma et al.
(2014) reported that multiple linear regression (MLR) with PXRF
and auxiliary data (clay, sand, organic matter) could improve the
prediction of soil pH. But these auxiliary data also need conven-
 M. Wan, M. Qu, W. Hu et al. / Process Safety and Environmental Protection 132 (2019) 73–81
Fig. 5. Correlations of heavy metals concentrations between rapid analysis and laboratory analysis for surface soils in Yunnan Province, China. The dotted lines are the 1:1
line and the red lines are the regression lines. The colored regions in the six subplots represent 95% prediction confidence intervals. (For interpretation of the references to
colour in this figure legend, the reader is referred to the web version of this article).
tional laboratory analysis, which was time- and cost-consuming.
Moreover, Vis-NIR is widely used to predict soil clay, sand, and
organic matter (Nawar et al., 2016; Sharma et al., 2014; Zeng et al.,
2016). But the correlation between the standalone Vis-NIR spectra
and the soil pH is poor, yet we found that this dataset could provide
valuable auxiliary data for PXRF to improve the prediction. There-
fore, SVMR could be a preferred method for pH prediction based
on sensor data fusion (PXRF + Vis-NIR), which further proved their
values in rapid soil pH estimation.
3.3. Soil heavy metals estimation using PXRF
The detection limit of As, Pb, Cu and Zn determined by PXRF
(NITON XLt 960, UK) were 7 mg kg−1 , 8 mg kg−1 , 15 mg kg−1 , and
12 mg kg−1 , respectively (Wan et al., 2019), which were lower than
the lowest risk screening values for soil contamination according to
the soil environmental quality standards in China (GB15618-2018,
2018). Moreover, Wan et al. (2019) verified the quality of PXRF
data to be “definitive” in the small-scale area. Therefore, based on
the accuracy and precision, this study applied PXRF to verify its
feasibility of measuring soil HM (As, Pb, Cu, and Zn) concentrations
with higher variability in the large-scale area. The results showed
determination coefficients (R2 ) for As, Pb, Cu and Zn were 0.97,
0.99, 0.98 and 0.98 (P < 0.00 1), respectively (Fig. 5). The consistent
79
results demonstrated that it was reasonable to use PXRF to rapidly
measure soil HMs in both small-scale area and large-scale area.
3.4. Rapid assessment of the environmental risk of soil heavy
metals
Compared with above different pH predictions, pure PXRF
dataset and fused sensor dataset (PXRF + Vis-NIR) with SVMR were
used to estimate pH (as predicted pH) of soil samples, respec-
tively, and then they were classified by pH intervals into four
classes (pH < 5.5, 5.5–6.5, 6.5–7.5, > 7.5) according to the standard
of soil environmental quality in China (GB15618-2018), as well as
pH measured by conventional laboratory analysis. The rapid envi-
ronmental risk assessment of soil HMs was performed by rapid
analysis data (PXRF measured HMs and predicted pH). While the
conventional environmental risk assessment was performed by
conventional laboratory analysis for estimating soil HMs and soil
pH. The accuracies of classification from NCPI results were verified
using the Kappa coefficient, based on rapid analysis data and con-
ventional laboratory analysis data. Results of this comparison were
shown in Table 5.
According to the results of conventional laboratory analysis for
the 138 surface soil samples, the number of different grades of com-
prehensive contamination, including safety, alert, slight pollution,
moderate pollution, and severe pollution, were 70, 28, 25, 10, and
80 M. Wan, M. Qu, W. Hu et al. / Process Safety and Environmental Protection 132 (2019) 73–81
5, respectively (Table 5). The accuracies of prediction classification
based on PXRF predicted pH results were 90%, 71%, 76%, 50%, and
80% for soil composite contamination grades, including safety, alert,
slight pollution, moderate pollution, and severe pollution, respec-
tively. Meanwhile, the accuracies of method classification were
89%, 71%, 76%, 71%, and 57%, respectively. The Kappa coefficient
of classification was 0.80, above 0.75, which indicated the assess-
ment of HM contamination results based on PXRF measured HMs
and PXRF predicted pH had a satisfactory consistency with these
based on conventional laboratory analysis (Table 5). When there
were only PXRF data available, it could be acceptable to use PXRF
measured HMs and PXRF predicted pH for rapidly classifying soil
HM contamination grades.
PXRF + Vis-NIR improved the accuracies of prediction classi-
fication substantially to 94%, 82%, 88%, 90%, and 100% for soil
composite contamination grades of safety, alert, slight pollution,
moderate pollution, and severe pollution, respectively. The accu-
racies of method classification were improved to 94%, 85%, 85%,
90%, and 100%, respectively. The improved accuracy of classifi-
cation should be due to the improved pH prediction. Both the
accuracy of prediction-based classification of severe pollution and
that of method classification were 100%, demonstrating that the
“hot spots” could be identified in a time- and cost-saving manner.
Moreover, the Kappa coefficient of classification was 0.91, higher
than that of pure PXRF predicted pH, highlighting the usefulness of
using both PXRF and VIS-NIR. These results proved the feasibility of
rapidly classifying soil HM contamination grades using estimated
soil pH and HMs.
Furthermore, using predicted soil pH to gain the joint thresh-
olds of soil HMs could rapidly accomplish soil environmental risk
assessment. Considering that the Kappa coefficient of the classifi-
cation of HM contamination grades was above 0.80, it was feasible
and reasonable to use PXRF individually or in combination with
Vis-NIR to effectively assess soil environmental risk of HMs with
reasonable accuracy. Therefore, the results proved the effectiveness
of single sensor data (PXRF) and fused sensor data with nonlinear
regression SVMR in pH prediction, which could further serve for the
rapid assessment of soil environmental risk with HMs measured
by PXRF, making the rapid soil survey of high-density sampling
feasible. Although the rapid analysis was promising ex-situ, fur-
ther studies on a survey of soil HMs with high-density sampling
at a large scale should be focused on the in-situ assessment of soil
environmental risk. And soil pH and HM analysis in-situ have to
overcome the negative influence of moisture and particle size (Hu
et al., 2014).
4. Conclusion
This study used two different regression methods, the linear
PLSR and nonlinear SVMR, to predict soil pH via PXRF or Nis-VIR
sensor individually and the fused sensor dataset (PXRF + Nis-VIR).
The results showed that PXRF can be used to predict soil pH
through SVMR with reasonable accuracy based either on pure ele-
mental data (R2 = 0.80; RPD = 2.03; RPIQ = 3.01) or in fusion with
Vis-NIR data (R2 = 0.86; RPD = 2.21; RPIQ = 3.09), which makes
non-destructive pH measurement possible. Simultaneously, it was
found that PXRF measured values and lab-measured values (i.e.,
As, Pb, Cu, and Zn) have relatedly significant positive correlations
(P < 0.001) with R2 > 0.97. Moreover, the relatively high Kappa coef-
ficient of 0.91 demonstrated that assessment of the environmental
risk of soil HMs using PXRF measured HMs and predicted pH is
almost identical to those of conventional laboratory analysis. We,
therefore, recommend the use of fused sensor data to estimate
soil pH and PXRF to measure soil HMs for rapidly assessing soil
environmental risk.
Acknowledgments
This work was supported by the National Key Research and
Development Program (Grant No. 2018YFC1802601), the Key Fron-
tier Project of Institute of Soil Science, Chinese Academy of Sciences
(Grant No. ISSASIP1629), the National Science and Technology Basic
Special Program (2014FY110200A10) and the China Scholarship
Council. The authors thank Professor Ganlin Zhang and Doctor Rong
Zeng for providing the visible near-infrared reflectance (Vis-NIR)
spectroscopy data of soil samples in this study area.
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