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Environmental Pollution
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a r t i c l ein fo abstract
Article history: In China, the cadmium (Cd) levels in paddy fields have increased, which has led to the excessive uptake of
Received 15 September 2017 Cd into rice grains. In this study, we determined the physicochemical properties of soil samples, including
Received in revised form the pH, soil organic matter (SOM) content, cation exchange capacity (CEC), and total Cd content (Cd soil) in
21 January 2018
order to establish a quadratic discriminant analysis (QDA) model for assessing the risk of Cd in rice and
Accepted 27 January 2018
to calculate its prior probability. Decision tree and logistic regression models were also estab - lished for
comparison. The results showed that the accuracy rate was 74% with QDA, which was significantly higher
than that obtained using the decision tree (67%) and logistic regression (68%) models. The correlation
Keywords:
coefficients between the soil pH and the other three factors (CEC, SOM, and Cd soil) were higher in the
Cadmium
Decision tree inaccurate set than the accurate set, whereas the correlation coefficients were smaller in the inaccurate
Logistic regression set than the accurate set.
Paddy field © 2018 Elsevier Ltd. All rights reserved.
Quadratic discriminant analysis model
https://doi.org/10.1016/j.envpol.2018.01.088
0269-7491/© 2018 Elsevier Ltd. All rights reserved.
X. Wang et al. / Environmental Pollution 236 (2018) 366e372 367
2013) has shown that the Cd in this region is mainly derived from
1 1 the metallurgical industry, chemical industry, and sewage
dk ðxÞ ¼ log pðkÞ — log.Sc . — ðx — mc ÞT S—c 1 ðx — mc Þ; (1)
2 2 irrigation.
In addition, severe Cd pollution in the soil means that there is a
where k is the predicted class, x is the set of measurements, mc is high risk of Cd absorption by paddy rice, which is the dominant
the mean vector, p(k) is the prior probability, and Sc is the crop (7.09×105 t/y of rice from 1.35 ×105 ha of land) in this region
covariance matrix. because of the suitable subtropical humid monsoon climate with an
In the present study, we developed a QDA model for assessing the average annual temperature of 17.4 ○ C and mean annual precipi-
risk of Cd in rice based on the total Cd content of the soil (Cdsoil), tation of 1300 mm.
physicochemical properties (pH, SOM, and cation exchange ca-
pacity (CEC)), and the calculated prior probability. We also estab-
lished decision tree and logistic regression models for comparison. 2.2. Locations of sampling plots
Fig. 1. Map of Xiangtan County showing the locations of the sampling plots.
368 X. Wang et al. / Environmental Pollution 236 (2018) 366e372
samples and obtain brown rice grains. The rice grains were then q
1 þ e—q x
cleaned three times with deionized water, oven dried to constant
weight at 60 ○C, and passed through a 0.25-mm sieve. where q is the mean vector comprising the soil pH, SOM, Cd soil, and
The pH of each soil solution was measured potentiometrically CEC.
(water:soil slurry ratio ¼1:2.5) using a pH meter (PB-10, Sartorius,
Go€ttingen, Germany). The SOM contents were determined using
2.4.3. Model verification
the WalkleyeBlack method (Nelson et al., 1982). The CEC was
Finally, in order to calculate the accuracy of the data fitting by
measured using 1 M NH4OAc buffered at pH 7.0 (USDA, 1996),
the QDA, decision tree model, and logistic regression model, 30
where a soil sample weighing 2 g was digested with an acid
groups of data were randomly selected from the testing set and
mixture containing concentrated HNO3, HF, and HClO4 at a ratio of
repeated 50 times to compare the effectiveness of the model fitting
1:2:1, and then analyzed with a flame atomic absorption spectro-
procedure.
photometer (AA240, Varian, Palo Alto, CA, USA). A brown rice grain
sample weighing 1 g was digested using an acid mixture containing
concentrated HNO3 and HClO4 at a ratio of 9:1, before analyzing 3. Results and discussion
with an atomic absorption spectrometer (AA800, PerkinElmer,
Norwalk, CT, USA) in a graphite furnace. 3.1. Regional monitoring results and classic assessment model
2.4. Model description In general, a higher value for Cd soil can lead to a greater value for
Cdrice. However, a clear relationship between Cd soil and Cdrice has not
In this study, all of the models were constructed using Matlab been reported previously (Li et al., 2003). To verify this rela-
2012a, and statistical analyses were performed with Origin 9.0 and tionship, Cdsoil is plotted versus Cdrice in our study region in Fig. 2.
IBM SPSS Statistics 20.0 software. For the data shown in Fig. 2, Pearson's correlation coefficient was
only 0.168, thereby indicating the lack of a linear correlation
between Cdsoil and Cdrice in this study. We also used the Cd con-
2.4.1. QDA model
centrations comprising the limitation II level standard of the Chi-
We used the data set obtained in 2012 to calculate the prior
nese Soil Environmental Quality Standard (SQS) and the Chinese
probability for the QDA model, and the data sets from 2013 to 2014
Food Safety Standard (FQS) as cut-off rules to obtain four quad-
were employed as the training set and testing set, respectively. It
rants: N1 where Cdsoil > SQS and Cdrice > FQS; N2 where Cdsoil ≤ SQS
should be noted that the number of data used in the training set was
and Cdrice > FQS; N3 where Cdsoil ≤ SQS and Cdrice ≤ FQS; and N4
actually 330 after eliminating noise and outliers.
where Cdsoil > SQS and Cdrice ≤ FQS.
The QDA model is given by Eq. (2):
1
h i
p j2pS j— 2 exp — 1ðx — m ÞT S—1ðx — m Þ 10
i i 2 i 0 i
Critical line y = 0.724+0.663x
i¼0 ij Sij 2
— 2ð — iÞ Si ð — iÞ R2 = 0.168
pðy ¼ ijx;qÞ¼ P n h io ;
—1 1x
Cd concentration in brown rice / FQS
i¼1
p 2p exp m T —1 x m
(2) 8
(2) 8
N2=12 N1=309
The cycle was repeated until the complete decision tree was generated
N =11 N =204
2.4.2. Comparison of models and it was then clipped to obtain an optimal deci- sion tree:
3 4
0
0 2 4 6 8 10
Cd concentration in soil / SQS
Fig. 2. Distributions of Cd in soil (Cdsoil) and Cd in rice grains (Cdrice). The vertical
line is a critical line showing whether Cdsoil exceeded the Chinese Soil
Environmental Quality Standard (SQS). The horizontal line is a critical line
indicating whether Cdrice exceeded the Chinese Food Safety Standard (FQS).
X. Wang et al. / Environmental Pollution 236 (2018) 366e372 369
trations of Cd in both the soil and rice relative to the safety stan- data from 2012:
dards differed in nearly 40% of the paired samples.
Ni
Previous studies have suggested that Cd rice is correlated well p ¼ ; (6)
1
h ðx (5)
Þ¼
q
1 þ EXPð8:0529 — 1:5615pH þ 0:1404SOM þ 0:2804Cdsoil — 0:4127CECÞ
The second was a decision tree model, which is a classifier and and it indirectly affected Cdrice via pH, SOM, and CEC.
not a mathematical model. Thus, there was no equation for the According to the results obtained by the QDA model, the accu-
decision tree model and its classification process is shown in Fig. 3 racy rate was 74% (Fig. 5), which was higher than that for the de-
instead. cision tree or logistic regression models. Similar conclusion could be
According to tests of 50 groups, the accuracy rate for the deci- drawn by comparing to the researches of Xu et al. (2016), Adams et
sion tree model was 67% and that for the logistic regression model al. (2004) and Guo et al. (2007). Also, the accuracy rate of QDA
was 68% (Fig. 4). Both of these percentages were larger than 60%, model was almost the same with some neural network models (Liu
which was the proportion represented by (N1þN3) in the whole et al., 2011).
samples. In terms of the model's stability, the standard deviation of the
accuracy rate was 0.032 with QDA, and the results were 0.035 and
0.025 for the decision tree and logistic regression models, respec-
3.2. QDA model for Cd risk assessment tively. Thus, there were no significant differences among the three
models according to the 95% confidence intervals.
Many other factors could be introduced to further improve the We also analyzed the characteristics of the error data for the QDA
accuracy of the assessment models, where some region-specific model. Fig. 6 shows the sites where the QDA model obtained the
factors might affect the transfer of Cd from the soil to food crops, opposite results compared with the actual results.
including the crop species or breed, meteorological conditions, soil According to the results obtained by analysis of variance, there
physicochemical properties (excluding the pH, SOM, and CEC, such were no significant differences (p < 0.05) in the pH, CEC, SOM, or
as Fe, Mn, Si, Ca, and Se), agricultural management practices, and Cdsoil in the accurate set and inaccurate set for the QDA model. In
geographical differences (Zhao et al., 2015; Song et al., 2015; Ye et addition, the correlation analysis results (Table 3) showed that the
al., 2012; Kheir et al., 2010; Sarwar et al., 2010). Xu et al. (2016). correlation coefficients between the soil pH and the other three
suggested that certain prior conditions can be used to enhance the factors (CEC, SOM, and Cdsoil) were higher in the inaccurate set than
reliability of a model for assessing the risk of Cd accumulation in the accurate set, whereas the correlation coefficients were smaller in
rice. the inaccurate set than the accurate set. This indicates that the QDA
In this study, we used the historical rate in this region of Cd rice model might make an incorrect prediction if the relationship
exceeding the specified standard as the prior probability. Therefore,
Table 1
pH, soil organic matter (SOM), cation exchange capacity (CEC), Cd in soil (Cd soil), and Cd in rice grains (Cd rice) in each year. Minimum, maximum, and average (in brackets)
values are presented.
2012 4.6e7.8 (5.5) 28.3e71.1 (44.3) 7.49e20.29 (12.76) 0.13e7.70 (0.64) ND*e3.20 (0.38)
2013 4.8e7.7 (5.7) 36.6e55.1 (45.2) 10.94e14.19 (12.69) 0.17e2.80 (0.60) NDe3.31 (0.40)
2014 4.8e6.3 (5.4) 38.4e52.1 (45.9) 10.97e14.16 (12.62) 0.30e1.70 (0.71) 0.04e3.31 (0.61)
Fig. 3. Decision-tree for predicting Cd in rice grains (Cdrice) based on soil properties (where Cds is Cd in soil and Cdr is Cdrice).
Fig. 4. Path analysis for soil properties with different limits on Cd in rice grains.
Table 2
Parameters in the quadratic discriminant analysis (QDA) model. Cd soil: Cd in soil and Cdrice: Cd in rice grains.
Table 3
Analysis of correlations between soil properties in the accurate set and inaccurate
set. SOM: soil organic matter; Cd soil: total Cd content in soil; CEC: cation exchange
capacity.
Fig. 5. Accuracy rates for the quadratic discriminant analysis (QDA), decision tree
(DTA), and logistic regression (LRA) models after testing 50 times.
Fig. 6. Assessment of the results obtained by the quadratic discriminant analysis model using data from 2014.
372 X. Wang et al. / Environmental Pollution 236 (2018) 366e372
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