Science of the Total Environment 897 (2023) 165511

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Science of the Total Environment

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

Hydrogeochemical and sediment parameters improve predication accuracy

of arsenic-prone groundwater in random forest machine-learning models
⁎
Wenjing Guo a,b, Zhipeng Gao a,b, , Huaming Guo a,b, , Wengeng Cao c
⁎
a
State Key Laboratory of Biogeology and Environmental Geology, China University of Geosciences, Beijing 100083, PR China
b
MOE Key Laboratory of Groundwater Circulation and Environmental Evolution, School of Water Resources and Environment, China University of Geosciences (Beijing), Beijing
100083, PR China
c
Institute of Hydrogeology and Environmental Geology, Chinese Academy of Geological Sciences, Shijiazhuang 050061, PR China

H I G H L I G H T S G R A P H I C A L A B S T R A C T

• The full random forest model well pre-

dicted groundwater arsenic (As) distribu-
tions.
• Better prediction was achieved when con-
sidering groundwater and sediment vari-
ables.
• Groundwater Fe(II) dominated all predic-
tive variables in As prediction.
• The model supports that As mobility was
primarily caused by Fe(III) oxide reduc-
tion.

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

Editor: Filip M.G.Tack The relative importance of groundwater geochemicals and sediment characteristics in predicting groundwater arsenic
distributions was rarely documented. To figure this out, we established a random forest machine-learning model to
Keywords: predict groundwater arsenic distributions in the Hetao Basin, China, by using 22 variables of climate, topographic fea-
Groundwater
tures, soil properties, sediment characteristics, groundwater geochemicals, and hydraulic gradients of 492 groundwa-
Arsenic
ter samples. The established model precisely captured the patchy distributions of groundwater arsenic concentrations
Hetao Basin
Random forest model
in the basin with an AUC value of 0.84. Results suggest that Fe(II) was the most prominent variable in predicting
Prediction groundwater arsenic concentrations, which supported that the enrichment of arsenic in groundwater was caused by
the reductive dissolution of Fe(III) oxides. The high relative importance of SO2− 4 indicated that sulfate reduction
was also conducive to groundwater arsenic enrichment in inland basins. Nevertheless, parameters of climate variables,
sediment characteristics, and soil properties showed secondly important roles in predicting groundwater arsenic con-
centrations. The other two models, which excluded parameters of groundwater geochemicals and/or sediment charac-
teristics, showed much worse predictions than the model considering all variables. This highlights the importance of
variables of groundwater geochemicals and sediment characteristics in improving the precision and accuracy of
predicting results. Future studies should probe a method constructing the random forest predicting model with high
precision based on the limited number of groundwater samples and sediment samples.

⁎ Corresponding authors at: School of Water Resources and Environment, China University of Geosciences (Beijing), Beijing 100083, PR China.
E-mail addresses: zpgao@cugb.edu.cn (Z. Gao), hmguo@cugb.edu.cn (H. Guo).

http://dx.doi.org/10.1016/j.scitotenv.2023.165511
Received 24 March 2023; Received in revised form 1 July 2023; Accepted 11 July 2023
Available online 12 July 2023
0048-9697/© 2023 Elsevier B.V. All rights reserved.
W. Guo et al.
1. Introduction
Arsenic (As) is a highly toxic and carcinogenic metalloid commonly
occurring in groundwater. The World Health Organization (WHO) has rec-
ommended an As guideline concentration of 10 μg/L in drinking water.
Long-term consumption of high-As groundwater (>10 μg/L) can cause se-
vere adverse health consequences, such as skin diseases, cancer, and cardio-
vascular diseases (Kapaj et al., 2006; Karagas et al., 2015). It has been
estimated that up to 220 million people in >70 countries and regions
were threatened by high-As groundwater around the world (Podgorski
and Berg, 2020), being mostly in the East and Southeast Asia,
e.g., Bangladesh (Huhmann et al., 2022), Cambodia (Richards et al.,
2019), China (Feng et al., 2022), India (Khan and Rai, 2022), Nepal
(Gyawali et al., 2022), Pakistan (Ur Rehman et al., 2022), and Vietnam
(Glodowska et al., 2021).
It is generally accepted that the occurrence of high-As groundwater is
the result of water-rock interactions, being primarily related to the reduc-
tive dissolution of As-bearing Fe(III) oxides under reducing conditions
(Guo et al., 2013). The process is intimately influenced by geomorphology,
stratigraphy, and hydrometeor factors (Chakraborty et al., 2022). For in-
stance, thick clays capping on the top of the aquifer may facilitate genesis
of high-As groundwater (Choudhury et al., 2018; Verma et al., 2016),
which is likely due to the fact that thick clay layer inhibits flushing of the
aquifer and thus favors accumulation of As in groundwater. This has also
been observed in the Hetao Basin, where heterogeneity of clay layers
caused by diversion and swing of the ancient Yellow River course since
the Late Pleistocene has resulted in considerable variations in groundwater
As concentrations (Cao et al., 2018). Furthermore, the combination of high
evapotranspiration, high aridity, high temperature, and low precipitation
increases the evaporation of groundwater, thereby aggravating the concen-
tration of As, especially in inland or enclosed basins with arid or semi-arid
climates (Alarcón-Herrera et al., 2013; Smedley and Kinniburgh, 2002). Ar-
senic desorption under weakly alkaline environments is also conducive to
groundwater As enrichment (Richards et al., 2019), which was considered
as the major cause of high-As groundwater in the arid Indus Plain with high
soil pH and high levels of soil organic carbon (Podgorski et al., 2017).
As stated above, the enrichment of groundwater As is generally the re-
sult of the synergy of many environmental factors. Due to the complex en-
richment mechanism of groundwater As, limited groundwater samples
cannot fully constrain the area hosting high-As groundwater. Prediction
models can provide information on locations of safe groundwater to gov-
ernment or managers by simultaneously considering distinct variables
(Erickson et al., 2021a, b). Therefore, predictions on distributions of high-
As groundwater via machine learning models have been increasingly con-
ducted at global (Cao et al., 2021; Podgorski and Berg, 2020), country
(Ayotte et al., 2017; Connolly et al., 2022; Lombard et al., 2021;
Mukherjee et al., 2021; Rodríguez-Lado et al., 2013; Tan et al., 2020),
basin (Fu et al., 2022), and regional scales (Kumar and Pati, 2022; Singh
et al., 2022). These models have included variables of climate
(e.g., precipitation, evapotranspiration, and temperature), soil, geology, hy-
drology, land use/land cover, and the topographic wetness index as predic-
tor variables (Cao et al., 2021; Nath et al., 2022; Wu et al., 2021; Podgorski
and Berg, 2020; Zhang et al., 2012). They coincidentally suggest that cli-
mate and soil variables played a crucial role in predicting high-As
groundwater distributions (Cao et al., 2021; Podgorski and Berg,
2020). Although climate and soil variables were commonly used in pre-
dictive models on groundwater As distributions, few studies have used
groundwater geochemicals and sedimentary characteristics as variables
to predict distributions of high-As groundwater. The ignorance of sedi-
mentary characteristics and groundwater geochemicals in the model
would limit the accuracy and precise of the predicting results. There-
fore, it is necessary to comprehensively consider those variables poten-
tially contributing to groundwater As enrichment to create a model with
high accuracy, which not only provides the reliable predicting of
groundwater As distribution but also helps to unravel the dominant fac-
tors controlling groundwater As mobility.
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Science of the Total Environment 897 (2023) 165511
There are many kinds of machine learning models for predicting the dis-
tribution of groundwater chemicals, including neural network models (Cao
et al., 2021), support vector machine learning models (Park et al., 2016),
boosted regression tree models (Erickson et al., 2021a, b), logistic regres-
sion models (Podgorski et al., 2017), and random forest machine learning
models (Podgorski and Berg, 2020). Random forest algorithm is an artificial
intelligence integrated learning algorithm that has developed rapidly in re-
cent years. It is a classification model that can generate an ensemble of de-
cision trees, which can be used to predict a binary class on the basis of the
associated independent variables. It can well handle the samples with
mixed data types, missing values, and outliers without increasing the com-
putation cost, thus greatly reducing the noise impact (Li et al., 2022). Since
the classification or regression is performed by repeatedly bisecting data,
the amount of computation is much lower than other machine learning
methods (such as neural networks and support vector machines)
(Ebrahimy et al., 2021). Because of the high tolerance to outliers in data se-
ries and the significantly higher accuracy of prediction results than other
commonly used algorithms, it has been extensively applied in natural sci-
ence research, especially in the field of hydrogeology (Ebrahimy et al.,
2021).
The Hetao Basin of Inner Mongolia is one of the areas affected by high-
As groundwater in China. Field investigation showed that groundwater As
concentrations were high up to 1480 μg/L, threatening around 300 thou-
sands residents in the basin (Deng et al., 2009). In the area, high-As ground-
water was thought to be related to soil properties (Tong et al., 2014),
sediment characteristics (Shen et al., 2018), climates (Jia et al., 2017),
and groundwater geochemicals (Guo et al., 2008). Geochemically, ground-
water As enrichment in the basin was primarily the result of the reductive
dissolution of As-bearing Fe(III) oxides, and was secondarily caused by As
desorption under weakly alkaline environments (Gao et al., 2020).
Recently, Fu et al. (2022) have used nine surface environmental variables
covering climatic and topographical features to predict the possibility of
high-As groundwater across the Hetao Basin based on a random forest
model. They found that the distributions of high-As groundwater increased
from the winter to the summer with the increases in temperature, rainfall,
and evapotranspiration. Nevertheless, synthetic effects of the above-
mentioned parameters on distributions of high-As groundwater are still un-
known, and deserve further investigations.
Therefore, the study aims to (1) develop a random forest prediction
model based on datasets of climate, topographic features, soil properties,
sediment characteristics, groundwater geochemicals, and hydraulic gradi-
ents to show the possibility distributions of high-As groundwater,
(2) rank model variables in determining distribution of groundwater As
concentrations, and (3) evaluate the importance of groundwater geochem-
icals and sediment characteristics in improving the prediction accuracy of
the established model.
2. Materials and methods
2.1. Study area
The Hetao Basin (40°10′-41° 20′N, 106° 15′-109° 30′E) is located in the
western part of Inner Mongolia, which is formed by the alluvial of the Yel-
low River and its tributaries (Fig. 1b). It is around 200 km long and 50 km
wide, with a total area of around 13,000 km2. The elevation of the basin is
around 1020–1050 m above the sea level. From south to north, it can be di-
vided into the Yellow River alluvial lacustrine plain and the piedmont
alluvial-proluvial inclined plain. The Hetao Basin has a typical arid and
semi-arid continental monsoon climate with little rainfall, which is unevenly
seasonally distributed. The average annual rainfall is from 130 to 220 mm,
being concentrated in June–September, while the annual average evapora-
tion is much stronger with around 1900–2500 mm (Guo et al., 2008).
Quaternary sediments are important stratigraphic components in the
Hetao Basin, and their thickness varies in different areas within the basin.
The Late Pleistocene (Q3) sediments have a thickness of 15–400 m, being
mainly composed of conglomeratic coarse sand, fine sand, and silty sand.
W. Guo et al.
Fig. 1. Locations of (a) the Hetao Basin and (b) the sampling sites, and (c) the stratigraphic profiles of the study area obtained from the constructed 3D geological model.
Locations of the stratigraphic profiles are provided in panel b.
It is the main aquifer where high-As groundwater occurs. The Holocene
(Q4) is a set of sediments transitioning from the lacustrine fluvial facies to
the Yellow River alluvial facies. The main lithology is the interlayer of yel-
low clay soil and silty sand, clay sand, sandy clay and clay, with a thickness
of 10–50 m. The Quaternary groundwater systems can be divided into two
groups: the shallow and deep aquifers. The shallow aquifers consist of
upper Pleistocene–Holocene alluvial–pluvial and alluvial–lacustrine sands
within depths up to around 40 m below the land surface (bls). The deep
aquifers are composed of middle Pleistocene lacustrine sands occurring at
depths >40 m bls, being separated by a thick blanket of clay layers from
the upper shallow aquifers (Guo et al., 2008).
2.2. Construction of the 3D geological model
A three-dimensional (3D) geological model of the Hetao Basin was de-
veloped to digitalize distribution of lithological settings. 204 boreholes
that are evenly distributed across the basin (Fig. S1), collected from Cao
et al. (2018), were used to construct the 3D geological model utilizing
ESRI ArcGIS Desktop software. Briefly, we first classified the lithologies
into four sediment groups, i.e., medium-coarse sand, loamy sand, silt-fine
sand, and clay. Secondly, stratigraphic division was made according to li-
thology and geological age. Subsequently, spatial interpolation of the stra-
tum lithology based on the classified sediment groups in different
boreholes was carried out. The cross-validation and accuracy comparison
were also performed to acquire the 3D geological model with high quality.
The stratigraphic profiles of 3D geological model are shown in Fig. 1c. The
3D geological model was eventually used to obtain variables of sediment
characteristics used in the predicting models.
2.3. Dataset of groundwater As concentrations
The dataset of groundwater As concentrations (n = 492) were compiled
from Cao et al. (2018) and Gao et al. (2022). All groundwater samples were
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Science of the Total Environment 897 (2023) 165511
collected from aquifers at depths from 2 to 120 m bls (Fig. S2). The samples
were uniformly distributed in the basin at a density of 0.041 km2/sample
(Fig. 1b). The As concentrations in groundwater samples varied widely
from below the detection limit (<0.01 μg/L) to 917 μg/L, with an average
and median concentration of 57.5 and 8.57 μg/L, respectively. Groundwa-
ter As data were classified into two groups: high-As groundwater
(>10 μg/L) and low-As groundwater (≤10 μg/L) (Fig. 1b). High-As ground-
water accounted for a proportion of 48.6 % among all groundwater sam-
ples.
2.4. Independent model variables
Parameters that may potentially influence groundwater As enrichment
based on previous studies (Bindal and Singh, 2019; Cao et al., 2021;
Podgorski and Berg, 2020) were selected as predictor variables. A total of
32 variables covering climate, topographic features, soil properties, sedi-
ment characteristics, groundwater geochemicals, and hydraulic gradients
were initially included as prediction variables of the model (Table S1).
Among these variables, datasets of climate, soil properties, and topographic
features are all continuous data in raster formats, which were acquired from
publicly available datasets, while groundwater geochemicals, sediment
characteristics, and hydraulic gradients are discrete data in vector formats.
Values of these continuous variables were extracted using point extraction
method to represent the data in the locations of groundwater sample in
ESRI ArcGIS Desktop software.
2.4.1. Climate data
Climate datasets include actual evapotranspiration (AET), precipitation
(PRE), temperature (TEM), and normalized difference vegetation index
(NDVI). The raw datasets of AET (Fig. S3a), PRE (Fig. S3b), TEM
(Fig. S3c), and NDVI (Fig. S3d) were compiled from the APPEEARS website
(https://appeears.earthdatacloud.nasa.gov/), with resolutions of 500 m,
2500 m, 2500 m, and 500 m, respectively. The summer data (June–August)
W. Guo et al.
in 2014 were collected, being consistent with the groundwater sampling
periods. Based on the surface energy balance model (SEBS) combined
with MODIS data, the summer evapotranspiration in the study area was
inverted, which made the evapotranspiration data more accurate and reli-
able (Ma et al., 2018). Some non-value grids in these datasets were proc-
essed utilizing nearby values for PRE, TEM, and NDVI data.
2.4.2. Soil properties
Datasets of soil properties mainly comprise coarse sand (volumetric per-
centage, 0 cm depth) (Fig. S4a), sand (weight percentage, 0 cm depth)
(Fig. S4b), clay (weight percentage, 200 cm depth) (Fig. S4c), silt (weight
percentage, 200 cm depth) (Fig. S4d), and fluvisols (Fig. S4e), which
were compiled from SoilGrids website (https://soilgrids.org/). These
datasets all have resolutions of 250 m.
2.4.3. Topographic features
Topographic features mainly include DEM (Fig. S5a), aspect (Fig. S5b),
and slope (Fig. S5c), which were obtained from the Spatial Geographical
Data Cloud website (http://www.gscloud.cn/) with resolutions of 90 m,
90 m, and 30 m, respectively.
2.4.4. Sediment characteristics
Aquifer sediment characteristics include lithology (loamy sand, fine sand,
and medium-coarse sand), geological age, the individual number of overlying
clay and sand layers, the individual thickness of overlying clay and sand
layers, and well depths. Well depths for groundwater sampling were compiled
from Cao et al. (2018) and Gao et al. (2022), which were used to extract the
individual number of the overlying clay and sand layers and the individual
thickness of the overlying clay and sand layers. All sedimentary datasets, ex-
cept for well depth, were obtained from the established 3D geological model
(Fig. 1c) by projecting the groundwater samples with varied well depths.
2.4.5. Groundwater geochemicals
Datasets of groundwater geochemicals, including pH, total dissolved
solids (TDS), Mn, Fe(II), K+, Na+, Mg2+, Ca2+, F−, Cl−, HCO−3 and SO4
2
−
concentrations, were compiled from Cao et al. (2018) and Gao et al.
(2022), being similar to groundwater As data.
2.4.6. Hydraulic gradient
Hydraulic gradient of each groundwater being sampled was obtained by
projecting groundwater sampling sites into groundwater contour map in
Zhang et al. (2013).
2.5. Development of the random forest machine learning model
A random forest model was constructed to produce possibility of high-
As groundwater distributions, which was implemented in the Python pro-
gramming language (version 3.8.5). During the modeling, all datasets
were randomly divided into the training set (75 %, n = 369) and the test
set (25 %, n = 123) to train the model and test the model performance, re-
spectively. To achieve maximum model accuracy and reliability, a recursive
feature elimination (RFE) method was used to perform feature selection
within the 10-fold cross-validation (CV). The number of decision trees
(hereafter as n_estimators), the maximum depth of the decision tree (here-
after as max_depth), and the maximum number of features that the random
forest allows a single decision tree to use (hereafter as max_features) are im-
portant parameters determining the accuracy and reliability of random for-
est models. Generally, higher numbers of decision trees (n_estimators) are
associated with better model results. Nevertheless, too many decision
trees can also lead to overfitting, thereby reducing the reliability of the
model. The square root of the number of predictors is calculated as the
values of max_features. The out-of-bag (OOB) samples, which refer to ap-
proximately one third of the data being not included during the random
sampling, were calculated for estimation of model error (Li et al., 2022).
A total of 22 predictor variables were finally selected (Table S1), which
were classified into five types: (1) climate variables (including AET, PRE,
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Science of the Total Environment 897 (2023) 165511
TEM, and NDVI); (2) soil properties (including Coarse sand (volumetric per-
centage, 0 cm depth), Clay (weight percentage, 200 cm depth), Silt (weight
percentage, 200 cm depth), Sand (weight percentage, 0 cm depth)); (3) sedi-
ment characteristics (including overlying clay thickness, overlying sand thick-
ness, and well depth); (4) groundwater geochemicals (including pH and
concentrations of Fe(II), Mn, Na+, Ca2+, Mg2+, Cl−, SO2− 4 and HCO− 3 );
and (5) others (including hydraulic gradient and DEM). These predictor var-
iables were ranked in the order of importance based on their average predic-
tive power within the model. This model was regarded as Model I. In the
Model I, datasets of groundwater As concentrations and 22 predictor vari-
ables described above (Table S1) were used to create a statistical prediction
model of high-As groundwater exceeding the WHO guideline of 10 μg/L.
In order to explore the roles of groundwater geochemicals and sediment
characteristics in improving the accuracy of the predicting model, we also cre-
ated another two models (Models II and III) to make comparisons with the
above developed model (i.e., Model I). The Model II was developed excluding
variables of groundwater geochemicals from Model I, and the Model III was
constructed excluding variables of both groundwater geochemicals and sedi-
ment characteristics from Model I. Variables in Model II were identical to
those in previous studies (Tan et al., 2020; Podgorski et al., 2020), in which
climate, soil properties, and sediment characteristics were mainly considered.
However, variables in Model III were analogous to those in Nath et al. (2022)
and Cao et al. (2021), in which climate and soil properties were mainly in-
cluded.
The predictor variables verified in the three models (Models I, II, and
III) were applied to predict distributions of the possibility of high-As
groundwater in the Hetao Basin using ESRI ArcGIS Desktop software.
Prior to producing the prediction maps, discrete predictor variables
(e.g., groundwater geochemicals and sediment characteristics) were first
interpolated using methods of inverse distance weighted (IDW) or radial
basis function (RBF) with resolutions of 500 m × 500 m. The method
showing low values of mean error and root mean square error (RMSE)
was finally chosen for the interpolation. The interpolation errors of each
predictor variable are shown in Table S2, where the interpolation method
used in this study was highlighted in bold.
2.6. Accuracy assessment and sensitivity analysis
Accuracy (ACC) and positive predictive value (PPV) were calculated to
evaluate the accuracy of the prediction model. The ACC was calculated as
the percentage of correctly predicted results among the total sample based
on Eq. (1). The PPV is the proportion of true positive samples to all predicted
positive samples according to Eq. (2). Both ACC and PPV are important and
indispensable metrics in model performance evaluation (Ebrahimy et al.,
2021). The accuracy of the prediction model can also be evaluated by the
model sensitivity (true positive rate) and specificity (true negative rate).
The true positive rate (TPR) reflects the ability of the model correctly classi-
fying high-As groundwater samples (Eq. (3)), and true negative rate (TNR)
measures its ability to classify low-As groundwater (Eq. (4)). A plot of the sen-
sitivity (i.e., TPR) and specificity (i.e., TNR) for all the outputs of model cutoff
values between 0 and 1 produces a receiver operating characteristic (ROC)
curve. The area under the curve (AUC) determines the predictive capability
of the model, which ranges from 0.5 (no predictive capability) to 1 (best pre-
dictive capability) (Tesoriero et al., 2017).
Accuracy ðACCÞ ¼ ðTP þ TNÞ=ðTP þ TN þ FP þ FNÞ (1)
Positive predictive value ðPPVÞ ¼ TP=ðTP þ FPÞ (2)
True positive rate ðTPRÞ ¼ TP=ðTP þ FNÞ (3)
True negative rate ðTNRÞ ¼ TN=ðTN þ FPÞ (4)
where, the true positive (TP) value shows the number of high-As
groundwater samples when the model accurately predicts the high-As
groundwater class (i.e., observed As concentration > 10 μg/L and predicted
W. Guo et al. Science of the Total Environment 897 (2023) 165511

Table 1
Confusion matrix for the Model I.
Confusion matrix Actual value

Positive Negative

Predictive value Positive TP FP

57 13
Negative FN TN
13 40

As concentration > 10 μg/L); the true negative (TN) value is the outcome
when the model accurately predicts the low-As groundwater class
(i.e., observed As concentration ≤ 10 μg/L and predicted As concentra-
tion ≤ 10 μg/L); the false positive (FP) value is a result when the model in-
accurately predicts the high-As groundwater class (i.e., observed As
concentration > 10 μg/L and predicted As concentration ≤ 10 μg/L); and
the false negative (FN) is a result when the model inaccurately predicts
Fig. 2. AUC value of performance evaluation parameters and the probability cut-off
the low-As groundwater class (i.e., observed As concentration ≤ 10 μg/L
point in Model I.
and predicted As concentration > 10 μg/L) (Schapire, 2001).

3. Results and discussion
3.1. Model performance metrics and prediction map of high-As groundwater
The best random forest model (i.e., Model I) was achieved when the per-
formance evaluation parameter of “n_estimators” was 447 and
“max_depth” was 9. The values of ACC and PPV calculated from the confu-
sion matrix shown in Table 1 were 0.79 and 0.81 (Table 2), respectively, in-
dicating a good prediction of the Model I. It should be noted that there was
no distortion of the ACC parameters since the numbers of high- and low-As
groundwater samples were approximately equal. The OOB score of the
overall model with a value of 0.84 suggests good model performance. In ad-
dition, TPR and TNR of the overall model reached values of 0.81 and 0.75,
respectively. This indicates that the model had high ability to predict both
high-As and low-As groundwater distributions (Bindal and Singh, 2019).
The AUC value of the Model I under the ROC curve was 0.84 (Fig. 2),
being relatively higher than other studies with values of 0.68–0.8 (Bindal
and Singh, 2019; Erickson et al., 2018; Fu et al., 2022; Podgorski et al.,
2017; Winkel et al., 2008; Zhang et al., 2012).
The obtained Model I was used to produce the possibility distribution of
high-As groundwater of the study area (Fig. 3). The high-risk distribution
areas of groundwater As with probability of 0.13–0.88 in the study area
are shown in Fig. 3a. This prediction map covered not only the areas with
known high-As groundwater, but also the areas that were not monitored
by field investigations. Areas with high-As groundwater of high probability
(>0.8) mainly distributed in the east part of the basin (Fig. 3a), covering an
area of 2334 km2. However, the predicted high-As groundwater with prob-
ability of 0.6–0.8 covered an area of 8073 km2. Furthermore, high-risk
areas with groundwater As concentrations exceeding 10 μg/L in the study
area were also identified by binary classification of the random forest
model based on the probability cutoff of 0.59 (Fig. 3b). The probability
cut-off was determined by the best trade-off between sensitivity and speci-
ficity (Fig. 2). The prediction results show that the high-As areas were con-
centrated in the depositional center of the Hetao Basin, especially in the
east of the basin (Fig. 3b). This may be due to the fact that aquifers within
the center of the Hetao Basin had sluggish groundwater flow and consisted
Table 2
The performance evaluation parameters of the Models I, II, and III.
Model I Model II Model III
OOB score 0.84 0.70 0.68
ACC 0.79 0.67 0.63
PPV 0.81 0.60 0.57
TPR 0.81 0.76 0.71
TNR 0.75 0.59 0.55
AUC 0.84 0.75 0.69
of lacustrine deposit with abundant organic matter (Guo et al., 2008),
which were conductive to groundwater As enrichment (Fendorf et al.,
2010). Predicted high-As groundwater with probability >0.59 covered an
area of around 10,597 km2, accounting for 70.3 % of the total area of the
study area (15,082 km2).
3.2. Ranking of model variables in Model I
The importance of distinct variables in predicting groundwater As concen-
trations was assessed by the random forest model (Fig. 4). Rankings of the rel-
ative importance of the predictor variables in the Model I suggest that high-As
groundwater in the Hetao Basin was the synergistic result of groundwater geo-
chemicals, sediment characteristics, climate, and soil properties.
3.2.1. Groundwater geochemicals
Dissolved Fe(II) concentration was the most prominent variable in
predicting groundwater As concentration in the basin (Fig. 4). This was ev-
idenced by the significantly higher dissolved Fe(II) concentrations in high-
As groundwater than those in low-As groundwater with a p value < 0.001
(Fig. S6a). The reductive dissolution of Fe(III) oxides in reducing environ-
ments was thus considered to be the main cause of groundwater As mobility
(Guo et al., 2014). Normally, Fe(III) oxides have a high affinity to As due to
their high specific area and positively charged surface sites at neutral to
weakly alkaline pH (Gao et al., 2020). During the reductive dissolution of
Fe(III) oxides in aquifers under reducing conditions, high-valence Fe(III)
is reduced to low-valence Fe(II) with better mobility. Simultaneously, the
released As(V) was reduced to As(III) with higher mobility, leading to
more As release into groundwater (Ayotte et al., 2017; Postma et al.,
2007). This is consistent with a large number of studies, showing that
groundwater As and Fe(II) concentrations were commonly positively corre-
lated (Perez et al., 2019; Zhou et al., 2022).
Groundwater SO2− 4 concentration was ranked as the third important
predictor in the Model I (Fig. 4). Statistical results showed that dissolved
SO2−4 concentration of high-As groundwater samples (average
306 mg/L, median 235 mg/L) were significantly lower than that of
low-As groundwater samples (average 401 mg/L, median 306 mg/L)
(p < 0.001) (Fig. S6c), indicating that lower SO2− 4 concentrations were
−
conducive to groundwater As mobility. The SO 2− 4 /Cl molar ratios,
which may reflect the extent of SO2− 4 reduction, were also significantly
lower in high-As groundwater than those in shallow groundwater
(p < 0.001) (Fig. S6d). This suggests that SO 2− 4 reduction facilitated
groundwater As enrichment (Liu et al., 2022), being possibly due to
the fact that H2 S and S 0, as products from SO 2− 4 reduction, can be
coupled to Fe(III) oxide reduction to cause As release from aquifer sed-
iments into groundwater from aquifer sediments (Guo et al., 2016), or
forming highly mobile thioarsenic species (Nghiem et al., 2023).

5
W. Guo et al. Science of the Total Environment 897 (2023) 165511

Fig. 3. (a) Probability distribution map of high As groundwater with As concentrations >10 μg/L and (b) high As-risk areas based on the probability cut-off point of 0.59 in the
Hetao Basin.

Fig. 4. The relative importance of 22 predictor variables from the Model I.

6
W. Guo et al.
Dissolved HCO− 3 concentration and the weakly alkaline groundwater
pH also played non-negligible roles in predicting groundwater As concen-
trations (Fig. 4). Groundwater HCO− 3 concentration ranged from 153 to
1739 mg/L in the study area, being significantly higher in high-As ground-
water (average 525 mg/L, median 483 mg/L) than those in low-As ground-
water (average 475 mg/L, median 433 mg/L) (p < 0.01) (Fig. S6e).
Similarly, the pH values of the high-As groundwater samples were also sig-
nificantly (average 7.95, median 7.85) higher than those of the low-As
groundwater samples (average 7.88, median 7.83) (p < 0.05) (Fig. S6f).
The presence of high concentration of HCO− 3 and high groundwater pH
may compete with As for the solid surface and induce the As desorption
into groundwater (Stachowicz et al., 2008; Stolze et al., 2019). The compe-
tition of HCO− −
3 and OH with As for sediment surface sites was evaluated
by utilizing As adsorption experiments and surface complexation model in
our previous study (Gao et al., 2020). It showed that higher HCO− 3 concen-
trations and pH values were associated with weaker As adsorption, which
supported the competition effect of HCO− 3 and pH on As adsorption.
Groundwater Mn concentration was identified as a predictor in Model I,
although its relative importance was much less than that of groundwater Fe
(II). Basically, groundwater Mn concentration can be a robust indictor of
Mn oxide reduction, which may also release As into groundwater
(Akintomide et al., 2021). Another possible explanation was that ground-
water As and Mn usually showed distinct depth distributions, demonstrat-
ing that shallower groundwater was typically characterized by higher Mn
and lower As concentrations compared to deeper groundwater (Ying
et al., 2017). Overall, the remarkably higher relative importance of dis-
solved Fe(II) than that of dissolved Mn suggests that the enrichment of As
in groundwater was more controlled by the reductive dissolution of As-
bearing Fe(III) oxides.
3.2.2. Variables of climate
Climate variables were also identified as crucial predictors on ground-
water As concentrations in Model I (Fig. 4), being consistent with previous
studies (Cao et al., 2021; Fu et al., 2022). In the study area, AET ranged
from 46.2 mm/month to 330 mm/month, being significantly higher in
high-As groundwater (average 268 mm/month, median 273 mm/month)
than those in low-As groundwater (average 255 mm/month, median
266 mm/month) (p < 0.001) (Fig. S7a). This indicates that high evapotranspi-
ration was associated with high probability of high-As groundwater (Alarcón-
Herrera et al., 2013; Smedley and Kinniburgh, 2002). According to the Model
I, the AET ranked as the second vital variable among all variables (Fig. 4),
which was consistent with previous studies suggesting much important contri-
bution of the AET to predict high-As groundwater distributions (Ayotte et al.,
2017; Cao et al., 2021; Fu et al., 2022; Nath et al., 2022; Podgorski and Berg,
2020). Furthermore, AET was usually positively correlated with the NDVI
(Wang et al., 2021), since higher NDVI may result in stronger evaporation
and transpiration of vegetation leaves, and therefore higher actual evapotrans-
piration (Wang et al., 2021). Therefore, the NDVI was also identified as an im-
portant predictor on groundwater As enrichment (Fig. 4).
Similarly, the TEM was also higher in high-As groundwater (average
23.6 °C, median 23.7 °C) than those in low-As groundwater (average
23.5 °C, median 23.5 °C) (p < 0.001) (Fig. S7b). Higher temperature pro-
motes stronger evapotranspiration and exacerbates drought. Therefore,
the combination of high evapotranspiration, high temperature, and low
precipitation may be responsible for high-As groundwater (Rodríguez-
Lado et al., 2013).
3.2.3. Sediment characteristics
The well depth was an important predictor of groundwater As concen-
trations. High-As groundwater was mainly distributed in shallow aquifers
with depths of <40 m bls, being consistent with high-As groundwater in
Southeast Asia (Fendorf et al., 2010). The reasons may be that shallow aqui-
fer sediments with younger geological ages were higher in reactivities of
As-bearing Fe(III) oxides and organic matter (Stuckey et al., 2016), and
readily received labile dissolved organic matter from surface water
(Erban et al., 2014).
7
Science of the Total Environment 897 (2023) 165511
Other sedimentary characteristics, including overlying sand thickness
and overlying clay thickness, showed relatively lower contributions to
groundwater As concentrations (Fig. 4). Statistical results show that the
overlying sand thickness (average 17.9 m) and the proportion of overlying
sand thickness to total thickness of sediment (average 74 %) of the aquifer
containing high-As groundwaters were slightly higher than those of the
low-As ones (average 15.1 m and 72 %, respectively) (Fig. 5). However,
the proportion of the thickness of overlying clay layers to total thickness
of the aquifer (average 26 %) was slightly lower in the aquifers containing
high-As groundwater than those of the low-As ones (Fig. 5b). This suggests
that deposit environments with thicker overlying sand and thinner clay
layers were favorable for the shallow groundwater to receive the recharge
of surface-derived organic matter, and thus facilitated the reductive dissolu-
tion of Fe(III)/Mn oxides (Gao et al., 2022; Li et al., 2014). Therefore, the
higher proportion of sand layers in the overlying aquifer sediments was
conducive to the formation of higher As groundwater.
3.2.4. Hydraulic gradients
The low hydraulic gradient was conducive to groundwater As enrich-
ment, although its importance was relatively low (Fig. 4). The flat topogra-
phy of the study area (Fig. S5) and low hydraulic gradient across the region
represent extremely low groundwater flow rate, which limited flush of
groundwater As out of the system (van Geen et al., 2008). Furthermore,
aquifers characterized by flat topography and low groundwater flow rate
usually had abundant finer-grained sediments enriched in As-bearing Fe
(III) oxides and organic matter (Guo et al., 2019), which thus exacerbated
As accumulation in the flat, low-lying areas during the Fe(III) oxide reduc-
tion (Gao et al., 2022).
3.3. Importance of groundwater geochemicals and sediment characteristics in As
predictions
Another two models (i.e., Models II and III) were constructed to explore
the importance of groundwater geochemicals and sediment characteristics
in predicting groundwater As distributions. The best Model II was achieved
when n_estimators = 320 and max_depth = 8. The performance evaluation
parameters of OOB score, ACC, PPV, and AUC were 0.70, 0.67, 0.60, and
0.75, respectively (Table 2). The probability cut-off point of the Model II
was 0.54 (Fig. 6c). According to this probability cut-off point and the pre-
dicted variables, the risk distribution map of high-As groundwater of the
study area was produced (Fig. 6a). The model III achieved the best predic-
tion when n_estimators = 141 and max_depth = 6. The obtained OOB
score, ACC, PPV, and AUC values were 0.68, 0.63, 0.57, and 0.69, respec-
tively (Table 2), with the probability cut-off point of 0.60 (Fig. 6d). The
risk distribution map of groundwater As of Model III is shown in Fig. 6b.
The importance of the variables in predicting groundwater As concentra-
tions of Models II and III is shown in Fig. S8.
According to the performance evaluation parameters, the precision and
accuracy of the Model I were the highest among the three models, followed
by the Model II and the Model III. The Model III, excluding variables of
groundwater geochemicals and sediment characteristics, showed the low-
est predicting precision (e.g., the lowest AUC values of 0.69). In the
Model III, climate parameters (e.g., AET and NDVI) were identified as the
most important variables (Fig. S8b), being quite similar to other studies
(Ayotte et al., 2017; Fu et al., 2022; Nath et al., 2022; Podgorski and
Berg, 2020). The Model II, which considered sedimentary characteristics
relative to the Model III, showed a higher AUC value than that in the
Model III (Table 2). This suggests that the performance of the Model II
was significantly improved relative to that of Model III. In the Model II, sed-
imentary characteristics (e.g., well depth, overlying sand thickness, and
overlying clay thickness) were also identified as important predictors
(Fig. S8a). However, when considering groundwater geochemicals in the
Model I, a much higher AUC value (0.84) was achieved compared to that
in the Model II with 0.74. This suggests that even better prediction results
were achieved when both groundwater geochemicals and sedimentary
characteristics were included in the model (Fig. 3). Groundwater
W. Guo et al. Science of the Total Environment 897 (2023) 165511

Fig. 5. Boxplots showing (a) the thickness of overlying clay and sand layers and (b) the proportion of overlying clay and sand layers to total thickness of sediments
corresponding to aquifers with low- and high-As groundwater. Red points show average values.

geochemicals, especially groundwater Fe(II) concentrations, were much
more important in predicting groundwater As concentrations than climate
parameters (Figs. 4 and S8). This suggests that sedimentary characteristics
and groundwater geochemicals should be considered in better predicting
groundwater As distributions, which can significantly improve the accu-
racy of the model.
3.4. Model limitation and implications
By utilizing random forest predicting models, we evaluated the impor-
tance of sediment characteristics and groundwater geochemicals in
predicting groundwater As distributions. In comparison with the existing
As prediction models with an AUC value of 0.784 (e.g., Fu et al., 2022),

Fig. 6. Probability distribution map of high As groundwater in (a) Model II, and (b) Model III, and the AUC values in (c) Model II, and (d) Model III.

8
W. Guo et al.
the prediction results showed significant improvement when considering
both groundwater geochemicals and sediment characteristics with an
AUC value of 0.84 (Fig. 2). We found that groundwater geochemicals, espe-
cially groundwater Fe(II) concentrations representing the extent of Fe(III)
oxide reduction, showed higher relative importance in predicting ground-
water As concentrations than that of climate parameters. The latter one
has been recognized as the most important predictors in previous modeling
studies (Ayotte et al., 2017; Fu et al., 2022; Nath et al., 2022; Podgorski and
Berg, 2020). The As predicting maps can be used by authorities to identify
areas potentially threatened by high-As groundwater, and provide the guid-
ance on locating safe drinking groundwater for local residents.
The study highlights the importance of groundwater geochemicals and
sediment characteristics in improving the model prediction. However, the
limitation of the model is that it requires a large number of datasets
which would be unavailable in rural/developing areas. Future studies
should find a way to construct prediction models precisely with limited
datasets of both groundwater and sediments.
4. Conclusion
The random forest model was applied to predict the spatial distribution
of geogenic As concentration in the Hetao Basin, using 22 variables cover-
ing climate, topographic features, soil properties, sediment characteristics,
groundwater geochemicals, and hydraulic gradients. The established
Model I precisely captured the patchy distributions of groundwater As con-
centrations with OOB score, ACC, PPV, and AUC values of 0.84, 0.79, 0.81,
and 0.84, respectively. The prediction results show that the high-As areas
were concentrated in the depositional center of the Hetao Basin, especially
in the east of the basin. Among the all considered predictors, the model
identified that Fe(II) was the most prominent variable predicting high-As
groundwater, indicating that the enrichment of As in groundwater was re-
lated to the reductive dissolution of Fe(III) oxides. The high relative impor-
tance of SO2− 4 indicated that sulfate reduction was also conducive to
groundwater As enrichment in inland basins. Climate data, which were pre-
viously ranked as the predominant predictor, were less important than
groundwater geochemicals (including Fe(II) and SO2− 4 ). By comparing
the three different prediction models (e.g., Models I, II, and III), we sug-
gested that introduction of groundwater geochemicals and sediment char-
acteristics as variables significantly improved the precision and accuracy
of the prediction model. Future studies should find a way to construct a pre-
cise prediction model with limited datasets of groundwater samples and
sediment samples.
CRediT authorship contribution statement
Wenjing Guo: Writing – original draft, Data curation, Formal analysis,
Visualization, Methodology, Software. Zhipeng Gao: Writing – review &
editing, Project administration, Resources, Supervision, Validation,
Funding acquisition. Huaming Guo: Writing – review & editing, Project
administration, Resources, Supervision, Validation, Funding acquisition.
Wengeng Cao: Resources, Data curation.
Data availability
Data will be made available on request.
Declaration of competing interest
The authors declare that they have no known competing financial inter-
ests or personal relationships that could have appeared to influence the
work reported in this paper.
Acknowledgements
The authors declare no conflict of interest. The study was financially
supported by the National Key Research and Development Program of
9
Science of the Total Environment 897 (2023) 165511
China (grant No. 2021YFA0715902), and National Natural Science
Foundation of China (grant No. 42102285).
Appendix A. Supplementary data
Supplementary data to this article can be found online at https://doi.
org/10.1016/j.scitotenv.2023.165511.
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