land

Article
Assessment of the Ecological and Health Risks of Potentially
Toxic Metals in Agricultural Soils from the Drosh-Shishi
Valley, Pakistan
Muhammad Sarim 1 , Tayyab Jan 2 , Seema Anjum Khattak 2 , Adil Mihoub 3 , Aftab Jamal 4, * ,
Muhammad Farhan Saeed 5 , Somayeh Soltani-Gerdefaramarzi 6 , Saadia Rashid Tariq 7 ,
Manuel Pulido Fernández 8 , Roberto Mancinelli 9, * and Emanuele Radicetti 10, *

1 State Key Laboratory of Continental Dynamics, Department of Geology, Northwest University,

Xi’an 710069, China
2 National Centre of Excellence in Geology, University of Peshawar, Peshawar 25130, Pakistan
3 Center for Scientific and Technical Research on Arid Regions, Biophysical Environment Station,
Touggourt 30240, Algeria
4 Key Laboratory of Arable Land Conservation (Middle and Lower Reaches of the Yangtze River), Ministry of
Agriculture, College of Resources and Environment, Huazhong Agricultural University, Wuhan 430070, China
5 Department of Environmental Sciences, COMSATS University Islamabad, Vehari Campus,
Vehari 61100, Pakistan
6 Department of Water Sciences and Engineering, Collage of Agriculture and Natural Resource Ardakan
University, Ardakan 95491-89518, Iran
7 Department of Chemistry, Lahore College for Women University, Lahore 54000, Pakistan
8 Grupo de Investigación Geo Ambiental, Universidad de Extremadura, 10071 Cáceres, Spain
Citation: Sarim, M.; Jan, T.; Khattak,
9 Department of Agricultural and Forestry Sciences (DAFNE), University of Tuscia, 01011 Viterbo, Italy
S.A.; Mihoub, A.; Jamal, A.; Saeed,
10 Department of Chemical, Pharmaceutical and Agricultural Sciences (DOCPAS),
M.F.; Soltani-Gerdefaramarzi, S.;
University of Ferrara, 44121 Ferrara, Italy
Tariq, S.R.; Fernández, M.P.;
* Correspondence: [email protected] (A.J.); [email protected] (R.M.); [email protected] (E.R.)
Mancinelli, R.; et al. Assessment of
the Ecological and Health Risks of
Potentially Toxic Metals in
Abstract: Soil pollution is a highlighted concern of modern society, particularly in developing
Agricultural Soils from the countries. The Drosh-Shishi valley, which is a hilly region near Afghanistan with a land area of
Drosh-Shishi Valley, Pakistan. Land around 15,000 km2 , is situated in the south of Chitral District (Pakistan) and has a population of
2022, 11, 1663. https://doi.org/ approximately 450,000. Nowadays, this region is being explored for soil pollution, specifically heavy
10.3390/land11101663 metals which pose a potential risk to human health. Therefore, our main goal was to investigate
possible sources of heavy metals’ spread and to assess the content levels in soil and the associated
Academic Editors: Gregorio García,
Rocio Millan and Araceli
risks for human. We collected 34 representative samples from transported sediments and 31 from
Pérez-Sanz agricultural crops. We analyzed the soil samples for the contents of Cd, Co, Cr, Cu, Mn, Ni, Pb, and
Zn using ICP-OES analyzers. These values were used to obtain the contamination factor (CF) and to
Received: 25 August 2022
estimate the potential health risk caused by heavy metals according to the USEPA dose–response
Accepted: 20 September 2022
model. Our results suggest that the heavy metal pollution has a geogenic source, but it is also
Published: 27 September 2022
aggregated by chemical fertilizers used in farming. Regarding levels, most of the metals except Pb
Publisher’s Note: MDPI stays neutral showed contents above the permissible level, with CF values from moderate to high. Overall, Cu
with regard to jurisdictional claims in and Ni showed a significant total cancer risk (TCR > 1 × 10−4 ) in children. Therefore, we conclude
published maps and institutional affil- that heavy metal pollution is causing a serious threat to humans in this area, and we recommend
iations.
that authorities should make more efforts in monitoring the heavy metals content in soils to reduce
potential health risks.

Keywords: environmental pollution; agricultural land; toxicity; atomic spectroscopy; human welfare;
Copyright: © 2022 by the authors.
Licensee MDPI, Basel, Switzerland.
Chitral District
This article is an open access article
distributed under the terms and
conditions of the Creative Commons
Attribution (CC BY) license (https://
1. Introduction
creativecommons.org/licenses/by/ The expansion of industrial activities [1] and agricultural intensification [2] in the
4.0/). world have provoked severe land degradation. Soil contamination by heavy metals is

Land 2022, 11, 1663. https://doi.org/10.3390/land11101663 https://www.mdpi.com/journal/land

Land 2022, 11, 1663 2 of 12

considered a serious threat in such areas [3]. Specifically, it increases toxicity in plants [4];
reduces water quality [5,6]; decreases soil health, crop yields [7], and food quality [8]; and
threatens the health and well-being of humans and animals by the pollution of the food
chain [9,10].
Heavy metals dispersed in soils, water, and the atmosphere and their levels in the
biosphere increase due to anthropogenic activity [11]. Heavy metal sources might be
natural, such as parent materials (rocks), or anthropogenic, such as industry, transportation,
and household emissions [11,12].
Heavy metals may be released into the environment from industrial activities, fertil-
izers, pesticides, solid waste disposal, irrigation with effluents, sludge application, and
automobile exhausts [13,14]. The soil environment is continually deteriorating due to
improper waste disposal, chemical fertilizers, pesticides, industrial production, mineral
exploitation, and food processing [15]. Due to heavy metals’ non-biodegradability, these
pollutants are accumulating in the soil environment to a considerable extent, where these
pollutants can be bio-accumulated, bio-transferred, and biomagnified in food chains.
Vegetables grown on soils contaminated with heavy metals have been a major food
chain channel for human exposure, posing a substantial health risk. Soil is the first route of
accumulation of heavy metals in plant edible parts, and the second is through air deposition
on exposed plant surfaces [16]. The health risk posed by a polluted food may be assessed
by calculating daily metal intake, using a daily dietary index, and using a health risk
index [17].
Heavy metal contamination has been increased in soils, urban road dusts, surface
water, groundwater, wastewater, and air in Pakistan because of the fast population growth,
industrialization, and urbanization [18]. Pakistan produces thousands of tons of different
vegetables, but some of these products are seriously contaminated with heavy metals [19].
The lack of strict environmental controls in emerging nations such as Pakistan has led to an
increase in the amount of heavy metals released into the environment [20].
Due to low socioeconomic status, vegetables are the most consumed food in these
countries because of easy access; therefore, they could be the primary source of human
exposure to heavy metals. In general, vegetable production has increased because of easily
available resources such as wastewater irrigation, agrochemical fertilizers, and pesticides.
In order to avoid or reduce hazards to human health, it is essential to recognize heavy
metal primary sources, their dispersal, and exposure routes, as well as to establish safe
threshold limits [21].
In the Drosh-Shishi valley (Pakistan), vein-type copper and lead have been reported
in two sites along the Shishi fault in the eastern part [22]. In addition, a high mineral
potential of copper, lead, and antimony was also reported [23]. Some rock units, such as
talc carbonates associated with serpentine blocks in the northern suture zone along the
Shishi and Mir Khani-Arandu valleys, are good host rocks for emeralds [24].
The mineral and agricultural resources of Pakistan have been exploited for economic
growth. This exploitation has resulted in huge stress on the mining and agricultural sectors
of the country and in environmental degradation [25]. Various studies have focused on the
potentially toxic elements (PTEs) contamination along with the mining [26,27] and agricultural
activities in Pakistan. Most recently, Ishaq et al. [28] reported the PTEs in the water and soil of
Chitral city (Pakistan). It was reported that the mean concentration of heavy metals exceeded
the permissible limits and was found to be much higher than their natural background values.
These findings indicate that these zones are accumulating heavy metal pollution in soils,
which poses potential risks to human health as the soil contamination ends up polluting
food and water. A research gap exists about the spatial distribution, levels, and risk for
humans. Therefore, this study has been conducted in the Shishi valley, which is located near
the mineral-rich zone of Chitral District (northern Pakistan). To prevent the bioaccumulation
of pollutants in plants and humans, agricultural soils must have their quality evaluated prior
to crop cultivation. The main objectives of our present investigation were to assess the heavy
 potential risks to humans.

2. Materials and Methods

2.1. Study Area
This research was carried out in the Drosh-Shishi valley, located in the south of
Land 2022, 11, 1663 3 of 12
Chitral District (35°35’N, 71°49’E - Pakistan), in 2018. The majority of soil samples were
taken along the Shishi River, in the village of Shishi, which lends its name to the nearby
valley and river. This river is located in the district of Chitral, which is bordered to the
metal
east bycontamination
Gilgit-Baltistan,in the
tosoil
the of the studyby
northwest area and evaluate
Afghanistan, theto
and soil
thecontamination
south by Dir level as
District
well as to assess potential risks to humans.
(Fig. 1). The total population of Chitral District is 447,362 inhabitants, covering a surface
area of 14,850 km2 (District Census Report 2017). The total cultivated area is about 23,000
2. Materials and Methods
ha, with wheat, maize, barley, and rice and vegetables crops. The major water source is
2.1. Study Area
surface water, including irrigation channels, streams, and perennial springs used for
This research
drinking as well as was carried purposes.
irrigation out in the Drosh-Shishi valley,point
From a geological located in thethe
of view, south of Chitral
Drosh-Shishi
District (35 ◦ 350 N, 71◦ 490 E—Pakistan), in 2018. The majority of soil samples were taken
valley is dominated by greenstones and amphibolites that present a high content of
along
copper the(Cu)
Shishi River, in with
associated the village of Shishi,[29].
chalcopyrites which lends
Their its name to the
mineralization is nearby valley
generally re-
and river. This river is located in the district of Chitral,
stricted along the shear zones and fractures of the Shishi fault [22].which is bordered to the east by
Gilgit-Baltistan, to the northwest by Afghanistan, and to the south by Dir District (Figure 1).
The
2.2. total populationand
Soil Sampling of Chitral
Analysis District is 447,362 inhabitants, covering a surface area of
2
14,850 km (District Census Report 2017). The total cultivated area is about 23,000 ha, with
wheat, Two sampling
maize, barley,plots
and were selected:
rice and transported
vegetables crops. sediments
The major(n = 34 source
water samples) and ag-
is surface
ricultural
water, soils (n
including = 31 samples),
irrigation channels,in streams,
which random topsoil springs
and perennial samplesused (0–30forcm in depth)
drinking as
were collected. Moreover, soil samples from different crops fields
well as irrigation purposes. From a geological point of view, the Drosh-Shishi valleywere collected, such is as
maize, wheat, beans, and vegetables, and transported sediments
dominated by greenstones and amphibolites that present a high content of copper (Cu)were collected from the
main channel
associated withofchalcopyrites
mineralized zones in themineralization
[29]. Their area. Each sampling pointrestricted
is generally was recorded
alongwiththe
an accurate GPS (Figure 1).
shear zones and fractures of the Shishi fault [22].

Figure 1. Map of study area showing location of sampling points.

2.2. Soil Sampling and Analysis

Two sampling plots were selected: transported sediments (n = 34 samples) and agri-
cultural soils (n = 31 samples), in which random topsoil samples (0–30 cm in depth) were
collected. Moreover, soil samples from different crops fields were collected, such as maize,
wheat, beans, and vegetables, and transported sediments were collected from the main
channel of mineralized zones in the area. Each sampling point was recorded with an
accurate GPS (Figure 1).
After preparation of the samples in a laboratory, 0.10 g of each sample was used to
estimate the total contents of metals by wet digestion (Anton Paar GmbH–Multiwave 3000).
Nitric acid (65%), hydrochloric acid (36.5%), and hydrofluoric acid (48%) were utilized for
digestion purposes. The concentrations of eight heavy metals (chromium (Cr), cadmium
(Cd), lead (Pb), nickel (Ni), zinc (Zn), manganese (Mn), copper (Cu), and cobalt (Co)) were
determined by the CISRI laboratory (China Iron & Steel Research Institute Group) through
inductively coupled plasma emission spectrometry (ICP-OES) methods (Agilent, 5110,
Land 2022, 11, 1663 4 of 12

USA) [30]. Each sample was analyzed three times, and the mean values were obtained. In
this study, quality assurance and quality control (QA/QC) were rigorously maintained
throughout the experiment by analyzing blanks and duplicates. Recovery rates for the
heavy metals varied between 80 and 100%, indicating a high accuracy of the method used
in this study, and the results are consistent with the quality control standard.

2.3. Contamination Factor and Assessment Model

Potential effects on the environment and humans were estimated from the calculation
of the contamination factor (CF) and the human exposure and health risk assessment model,
respectively. This model is based on the calculation of 12 equations that are shown and
described below.
The contamination factor is considered a typical tool to assess heavy metal pollution
in different environments. The CF was calculated using Equation (1) and interpreted
according to the classes proposed by Hakanson [31]: CFi < 1, low contamination factor
(indicating low sediment contamination of the substance in question); 1 ≤ CFi < 3, moderate
contamination factor; 3 ≤ Cfi < 6, considerable contamination factor; CFi ≥ 6, very high
contamination factor.
Cm sample
CFi = (1)
Cm background
where CFi is the environmental contamination, Cm sample is the concentration of the
element in the soil samples, and Cm background is the concentration of the metal in the
upper continental crust. In Pakistan, there are still no local background concentrations
or reference values for HMs in soils; for these reasons, as reference values (background),
standard concentrations of the investigated metals in the Earth’s crust were adopted as
background concentrations [30]. The risk model was used to determine the total exposure
of humans to the trace elements. In this model, the receptors are children and adults [32]. It
enabled us to evaluate both non-carcinogenic (Equations (2)–(6)) and carcinogenic risks
(Equations (7)–(11)) by three exposure pathways: ingestion (Equation (2)), dermal contact
(Equation (3)), and inhalation (Equation (4)) [33]. For non-carcinogenic risk, the average
daily intake (ADD) of heavy metals through each exposure pathway, namely oral inges-
tion (Equation (2)), dermal contact (Equation (3)), and air inhalation (Equation (4)), was
calculated. The following equations were used:

(C × IRS × EF × ED)
ADD_ing = × 10−6 (2)
(BW × AT)

(C × SA × AF × ABS × EF × ED)
ADD_dermal = (3)
(BW × AT)
(C × IRi × EF × ED)
ADD_inh = (4)
(PEF × BW × AT)
where ADD_ing, ADD_dermal, and ADD_inh represent the average daily exposure dose
through the ingestion, dermal contact, and inhalation pathways (mg kg−1 day−1 ), respec-
tively; IR_s is the soil uptake rate (mg day−1 ); IR_i is the soil suction rate (m3 day−1 ); EF is
the frequency of contact (days per year); ED is the exposure duration (years); BW is the body
weight (kg); AT is the time period of average doses (days); PEF is the emission factor (m3
kg−1 ); SA is the skin exposure surface area (cm2 ); AF is the adhesion factor (kg cm−2 day−1 );
ABS is the skin absorption factor; RfD is the reference dose (mg kg−1 day−1 ); and LT is the
average lifetime (days).
The total non-carcinogenic risk (THI) is therefore a sum of the hazard quotients (HQs,
Equation (5)) that were estimated from the division of each ADD by its RfD, i.e., every
metal × 3 pathways (Equation (6)).

THI = ∑ HQ (5)
Land 2022, 11, 1663 5 of 12

∑ ADD
HQ = (6)
Rfd
Regarding the carcinogenic risk (CR), the average potential lifetime daily dose (LDD)
was calculated for each exposure pathway by using Equation (7) (oral ingestion), (8) (dermal
contact) and (9) (air inhalation). Subsequently, the CR for each case and the total CR (TCR)
were calculated by using Equations (10) and (11), respectively.

(C × IRs × EF × ED)
LADD_ing = × 10−6 (7)
(BW × LT)

(C × SA × AF × ABS × EF × ED)
LADD_dermal = (8)
(BW × LT)
(C × IRi × EF × ED)
LADD_inh = (9)
(PEF × BW × LT)
CR = ∑(LADD × SF) (10)
TCR = ∑ CR (11)
where LADD_ing, LADD_dermal, and LADD_inh represent the average daily carcinogenic
risk exposure dose of the oral ingestion, dermal contact, and air inhalation pathways
(mg kg−1 day−1 ), respectively; IR_s is the soil uptake rate (mg day−1 ); IR_i is the soil
suction rate (m3 day−1 ); EF is the frequency contact (days per year); ED is the exposure
duration (years); BW is the body weight (kg); AT is the time period of average doses
(days); PEF is the emission factor (m3 kg−1 ); SA is the skin exposure surface area (cm2 );
AF is the adhesion factor (kg cm−2 day−1 ); ABS is the skin absorption factor; RfD is the
reference dose (mg kg−1 day−1 ); SF is the carcinogenic factor (mg kg−1 day−1 ); and LT is
the average lifetime (days). The RfD and SF values of each metal are shown in Table 1. The
other parameters used in this model specifically for children and adults are summarized in
Table 2.

Table 1. Reference values used for calculating the health risk assessment model for each heavy metal.
RfD: reference dose; SF: carcinogenic factor. Both parameters are expressed in mg kg−1 day−1 [34].

RfD SF
Metals
Ingestion Dermal Inhalation Ingestion Dermal Inhalation
Cd 1.0 ×10−3 2.5 × 10−5 5.71 ×10−5 6.1 6.1 6.3
Pb 3.5 × 10−3 5.25 × 10−4 3.52 × 10−3 - - -
Cu 0.04 0.012 0.0402 - - -
Cr 3.0 × 10−3 6.0 × 10−5 2.86 × 10−5 0.5 20 42
Zn 0.3 0.06 0.3 - - -
Ni 0.02 8 × 10−4 0.026 - - -

Table 2. Parameters utilized for the health risk assessment model and their values for children and
adults [34].

Parameter Description Unit Children Adults

IRs Ingestion rate of soil mg day−1 50 20
IRi Inhalation rate m3 day−1 7.6 16
EF Exposure frequency days y−1 350 350
ED Exposure duration years 6 24
BW Average body weight kg 24.7 57
AT Average exposure time days ED × 365 ED × 365
SA Surface area of skin cm2 2.800 5.700
AF Adherence factor kg cm−2 day−1 2 × 10−6 2 × 10−7
ABS Skin absorption factor unit less 0.001 0.001
PEF Emission factor m3 kg−1 1.36 × 109 1.36 × 109
LT Lifetime days 76.49 × 365 76.49 × 365
Land 2022, 11, 1663 6 of 12

2.4. Data Analysis

Most of the properties (heavy metals) were firstly described by using basic descriptive
statistics parameters. Secondly, we explored sources by means of bi- and multivariate
techniques such as correlation and principal component analysis (PCA) [35]. A corre-
lation analysis was conducted to understand how the metals are related to each other
and with other parameters studied. PCA was performed to identify those factors that
explain the data variance of our dataset [36]. The effectiveness of the combination of both
techniques for identifying potential sources of heavy metals has been already proven in
other environments [37]. The statistical procedure was carried out using SPSS Statistics
20.0 (IBM).

3. Results
3.1. Heavy Metals
The descriptive statistical values of our dataset composed of 31 soil samples collected
in agricultural soils and 34 in transported sediments are shown in Table 3. The mean
concentration of every metal except Cr, Pb, Ni, Zn, and Mn was higher in the agricul-
tural lands than their corresponding background values (crust value). Nonetheless, their
high data variability showed fluctuating concentration levels in this context. Regarding
transported sediments, their mean values were mostly lower than those in the agricultural
areas but were also lower than those of the Earth crust except for Cd, Cu, and Co. Both
environments showed a similar statistical pattern concerning data variability, pointing both
to fluctuating conditions and to the possibility of random infiltrations from anthropogenic
sources. Nevertheless, except for Pb, the rest of the parameters generally returned values
of CV below 50%, which can be considered low or intermediate variability.

Table 3. Values of heavy metals’ concentration (mg kg−1 ) in agricultural soils and transported sediments.
SE: standard error; SD: standard deviation; CV: coefficient of variation; BG: background value.

Agricultural Soils
Metal Mean Median Min Max SE SD CV Skewness Kurtosis BG
Cr 55.48 55.50 30.89 92.53 2.98 16.85 30.38 0.29 −0.78 83
Cd 3.49 3.77 0.00 6.12 0.21 1.18 33.68 −0.47 0.96 0.098
Pb 9.13 8.94 0.00 21.65 1.08 6.12 67.03 0.34 −0.95 17
Ni 38.60 36.89 22.96 62.00 1.82 10.29 26.63 0.92 0.52 44
Zn 68.60 69.84 21.95 123.00 4.47 25.27 36.81 0.33 −0.26 71
Mn 568.00 555.20 246.77 830.40 28.43 160.82 28.28 −0.27 −0.64 600
Cu 69.30 64.33 38.90 123.40 4.27 24.18 34.88 0.73 −0.36 25
Co 34.00 34.85 22.23 41.00 0.89 5.04 14.80 −0.71 −0.05 17
Transported sediments
Metal Mean Median Min Max SE SD CV Skewness Kurtosis BG
Cr 52.70 53.74 32.00 69.70 1.70 10.00 18.90 −0.30 −0.70 83
Cd 5.50 5.25 2.20 11.00 0.40 2.10 37.60 0.80 0.50 0.098
Pb 4.80 3.34 0.00 22.20 0.80 4.60 94.60 1.70 4.80 17
Ni 35.60 35.16 20.90 59.30 1.90 11.20 31.40 0.50 −0.40 44
Zn 40.50 39.50 29.00 61.00 1.50 8.50 21.00 0.70 −0.10 71
Mn 453.00 457.50 336.00 521.00 7.40 43.00 9.50 −1.00 1.30 600
Cu 35.40 32.00 13.00 80.00 2.80 16.20 45.80 1.10 1.50 25
Co 26.70 26.40 12.20 45.60 1.60 9.40 35.10 0.20 −0.80 17

3.2. Contamination Factor

The CF values obtained for each heavy metal are shown in Table 4. The degree
of contamination ranged from no to moderate pollution, except for Cd which reached
levels of very high as both agricultural soils and transported sediments were very highly
Land 2022, 11, 1663 7 of 12

contaminated with Cd. Curiously, Pb recorded the lowest degree of contamination in spite
of its high values of concentration that were recorded (see Table 3 above).

Table 4. Contamination factors for agricultural soils and transported sediments.

Metal Agricultural Soils Contamination Degree Transported Sediments Contamination Degree

Cr 0.67 Low 0.63 Low
Cd 35.61 Very high 56.12 Very high
Pb 0.54 Low 0.28 Low
Ni 0.88 Low 0.81 Low
Zn 0.97 Low 0.57 Low
Mn 0.95 Low 0.76 Low
Cu 2.77 Moderate 1.42 Moderate
Co 2.00 Moderate 1.57 Moderate

3.3. Sources of Contamination

In order to identify potential sources, a correlation analysis between every heavy metal
was performed (Table 5). Zn was positively correlated with Cd and Cr in agricultural soils,
pointing towards their probable common source. In addition, strong positive correlations
were found among various metal pairs from transportation sources, including Pb–Ni, Mn–
Ni, etc. (p < 0.05). The results indicated a mixture of positive and negative correlations.
Thus, it means the sources of contamination are not similar in all the cases.

Table 5. Coefficients of correlation between every metal in agricultural soils and transported sediments.

Agricultural Soils
Cr Cd Pb Ni Zn Mn Cu
Cd 0.353
Pb −0.178 −0.102
Ni 0.064 −0.077 −0.282
Zn 0.411 0.472 −0.136 0.188
Mn 0.128 0.260 0.026 −0.058 0.316
Cu 0.020 0.262 0.226 −0.183 −0.066 −0.163
Co 0.043 0.213 −0.019 −0.056 0.117 0.348 0.137
Transported Sediments
Cr Cd Pb Ni Zn Mn Cu
Cd 0.274
Pb −0.463 −0.177
Ni −0.104 0.022 0.345
Zn −0.180 0.031 0.323 0.270
Mn 0.234 0.161 −0.166 0.340 −0.147
Cu −0.043 −0.114 0.018 −0.256 −0.227 0.026
Co 0.014 −0.278 0.031 −0.032 0.090 −0.277 0.005

Principal component analysis (PCA) was employed to understand the factors behind
and trace the most probable sources of metals as well as their mutual relationships and
variation in agricultural soils. The coefficients of correlation or loadings among the metals
and the most important PCs are shown in Table 6. They are in consonance with the results
obtained in the previous correlation analysis (Table 5). A total of 60% of variance was
explained by the first three components in both environments: PC1 ≈ 25%, PC2 ≈ 20%,
and PC3 ≈ 15%. In PC1, Cr, Cd, and Zn showed the highest loadings; meanwhile, Pb and
Cu in PC2 and Co and Mn in PC3 showed a likely common source.
Land 2022, 11, 1663 8 of 12

Table 6. Coefficients of correlation among metals and the three principal components.

Agricultural Soils Transported Sediments

Metals
PC1 PC2 PC3 PC1 PC2 PC3
Cr 0.761 −0.108 −0.079 −0.794 0.008 0.086
Cd 0.752 0.307 0.170 −0.497 0.253 0.360
Pb −0.219 0.615 0.125 0.798 0.262 0.034
Ni −0.017 −0.698 −0.191 0.324 0.581 0.483
Zn 0.746 −0.222 0.231 0.273 0.696 −0.154
Mn 0.148 −0.087 0.855 −0.169 −0.020 0.800
Cu 0.108 0.765 −0.261 0.237 −0.754 0.068
Co 0.046 0.172 0.694 0.020 0.119 −0.692
Eigenvalues 1.994 1.658 1.195 2.008 1.651 1.179
% of variance 24.925 20.725 14.933 22.249 19.241 18.981
Cumulative % 24.995 45.650 60.583 22.249 41.491 60.472

3.4. Health Risk

We also analyzed both non-carcinogenic and carcinogenic risk. In the first case,
the total contents of heavy metals in agricultural soils were not absolutely bioaccessible
(bioaccessibility < 1.0). Therefore, we suspect our results could suppose an overestimation
of the health risk. Table 7 shows the adjusted values of bioaccessibility and exposure for
the calculations.

Table 7. Values of non-carcinogenic and carcinogenic risk for children and adults by different pathways.

Non-Carcinogenic Risk
Children Adults
HQingestion HQdermal HQinhalation THI HQingestion HQdermal HQinhalation THI
Cd 6.97 × 10−6 7.81 × 10−8 7.79 × 10−10 0.01 1.21 × 10−6 6.89 × 10−8 7.11 × 10−10 4.0 × 10−3
Pb 1.73 × 10−5 8.0 × 10−7 1.94 × 10−9 6 × 10−3 3.01 × 10−6 1.71 × 10−7 1.77 × 10−9 1.0 × 10−3
Cr 1.0 × 10−4 1.22 × 10−6 1.21 × 10−8 0.06 1.88 × 10−5 1.07 × 10−6 1.11 × 10−8 0.024
Cu 1.73 × 10−5 1.94 × 10−7 1.94 × 10−9 5 × 10−4 3.01 × 10−6 1.71 × 10−6 1.77 × 10−9 8.96 × 10−5
Ni 1.74 × 10−5 1.94 × 10−7 1.94 × 10−9 4 × 10−4 1.31 × 10−5 7.49 × 10−7 7.74 × 10−9 2.0 × 10−3
Zn 1.74 × 10−5 1.94 × 10−7 1.94 × 10−9 6.11 × 10−5 2.34 × 10−5 1.33 × 10−6 1.37 × 10−8 1.0 × 10−4
Carcinogenic Risk
Children Adults
CRingestion CRdermal CRinhalation TCR CRingestion CRdermal CRinhalation TCR
Cd 5.47 ×10−7 6.13 ×10−9 6.11 × 10−11 3.3 × 10−6 3.79 ×10−7 2.16 × 10−8 2.23 × 10−10 2.44 × 10−6
Pb 1.36 × 10−6 1.53 × 10−8 1.52 × 10−10 8.40 × 10−6 9.44 × 10−7 5.38 × 10−8 5.55 × 10−10 6.09 × 10−6
Cr 8.52 × 10−6 9.55 × 10−8 9.53 × 10−10 6.21 × 10−6 5.91 × 10−6 3.37 × 10−7 3.48 × 10−9 9.84 × 10−6
Cu 2.36 × 10−5 1.35 × 10−6 1.39 × 10−8 7.04 × 10−4 7.42 × 10−6 4.23 × 10−7 4.36 × 10−9 4.79 × 10−5
Ni 3.01 × 10−6 1.72 × 10−7 1.77 × 10−9 3.0 × 10−4 4.13 × 10−6 2.357 × 10−7 2.43 × 10−9 6.87 × 10−6
Zn 1.36 × 10−6 1.53 × 10−8 1.52 × 10−10 9.92 × 10−7 7.35 × 10−6 4.186 × 10−7 4.32 × 10−9 1.22 × 10−5

For children, ingestion HQ values ranged from 6.97×10−6 (Cd) to 0.00001 (Cr), while
these values were lower for dermal contact and air inhalation. The values in adults were
also relatively lower than those in children. The HQ values of all exposure pathways in
agricultural soils were lower than one.
Regarding carcinogenic risk, the values showed some risk for heavy metals such as
Cu and Ni, particularly in children (TCR > 1 × 10−4 ). In adults, the highest risk was
observed from the contents of Cu and Zn, usually provided from agriculture through the
application of manures. The significant difference found between the values of TCR for
Zn in children and adults is also remarkable, particularly due to the low impact of air
inhalation in children in comparison to adults.

4. Discussion
Our investigation depicts that the average HM concentrations are relatively high,
particularly in the agricultural lands. Nonetheless, their data patterns revealed a varying
Land 2022, 11, 1663 9 of 12

pattern that may prompt us to consider punctual sources of contamination associated with
anthropogenic sources. This finding would be in consonance with the ideas expressed by
Wang et al. [38] in their work conducted in apple orchards. Of course, the concentrations
of heavy metals recorded here are above background values. In addition, their variability
suggests their being a consequence of anthropogenic activities since low variability should
be interpreted as an adequate content to be considered a natural resource. In other words,
only humans can alter the natural spatial homogeneity of these properties in soils and
sediments.
The sources of these metals are often identified through a correlation analysis be-
tween them that shows identical behaviors and/or mutual dependence [39]. According
to Wang et al. [40], a significant positive correlation between metals can be interpreted as
them coming from a similar source, having comparable behavior, and transferring under
physico-chemical environments. For instance, we suspect that industrial seepages can be
an important source since some industries, such as food processing and paint factories as
well as leather tanning, electroplating, plastic, etc., are located nearby in the study area.
Another plausible hypothesis is the use of pesticides and fertilizers since agricultural lands
recorded higher concentrations on average.
Some sources appeared to be identified by the PCA, with conclusions that are compa-
rable to those from the correlation analysis. PC1 is probably associated with anthropogenic
factors because the average contents of some metals were relatively high.
The influence of human activities on the content of cadmium in soil has already been
proven by Loganathan et al. [41]. Thus, in this case, the possibility of industrial and
chemical activities being the main source for transported sediments and intensive farming
being the main source for agricultural soils can be assumed [42]. In fact, heavy metals such
as Zn and Cd are commonly found in organic fertilizers, particularly phosphates, and also
chemical pesticides [43]. In this line, Atafar et al. [44] also identified overuse of chemical
fertilizers and pesticides as the most plausible source. Concerns about the accumulation
of Cd in soils have led some producers of fertilizers, following the suggestions of the
European Union (EU), to change fertilization methods [45] and sources [46].
In PC2, the average content of Pb was very similar to the background value, i.e.,
from a geogenic source. For instance, Navarro-Pedreño et al. [47] suggested that metals
such as Cu are controlled by the geochemical composition of the parent material and
geogenic processes. Potentially, it can be a consequence of specific agronomic practices
(e.g., manure) [36].
Livestock manures are important sources of soil pollution due to excesses of Zn and
Cu. High levels of Cu can be due to some specific agrochemicals and also traffic density
due to proximity between roads and plots. This finding is consistent with Chen et al. [37],
who reported that Cu and Pb are the main heavy metals derived from anthropogenic
sources in agricultural soils. Additionally, Tahirkheli et al. [22] noticed vein-type copper
and lead along the Shishi valley, so it can be considered that PC2 could be a nature–human
compound source factor.
Co and Mn dominated PC3, and Mn showed values much higher than its background
values. It can be speculated that the origin of these could be the regular weathering of the
parent material. In fact, Micó et al. [46] found high levels of Co, Cr, and Ni in calcareous
and alluvial areas. In this regard, PC3 can be interpreted as a lithological influence factor.
The association of Co with the cluster composed of Cr, Cd, and Zn as well as the positive
correlations between them can point out that it can be a geogenic source. The results
obtained in the transported sediments and agricultural soils show prevailing similarities.
However, confirmation of the identity of the exact source of changes in this region needs
further in-depth studies.
Regarding human health, the values obtained here did not indicate a serious risk
of cancer and diseases in spite of having recorded values much higher than the usual
background values for every HM. According to the USEPA [33], HQ values lower than one
for a given metal should be interpreted as a safe level. Our results suggest that ingestion
Land 2022, 11, 1663 10 of 12

and dermal contact are the main ways of entrance. This result is consistent with comparable
findings from earlier research [9]. Our concerns, however, stem from the fact that all of
these exposure paths could result in non-carcinogenic risk because of the area’s growing
urbanization and agricultural practices for economic expansion.
The cancer risk associated with Cu and Ni in children is the most concerning finding
from our research. According to the USEPA [33], TCR values below 1 × 10−6 should be
regarded as inconsequential and show that the relevant element is non-carcinogenic. The
measured TCR levels exceeded 1 × 10−4 . It can be considered that the model utilized in
this work is an effective tool for risk assessment. Nonetheless, the calculation of these
risks (carcinogenic and non-carcinogenic) is influenced by several uncertainty factors.
Additionally, Pakistan and/or other countries may not be able to fully utilize the USEPA [33]
values. As a result, we support performing this kind of research in many more study
scenarios. This study draws the attention of local farmers and policymakers about the
convenience of maintaining and supporting a sustainable food production system in which
the use of fertilizers is progressively reduced through precision farming and/or other
techniques [48]. Therefore, this research could help policymakers sustainably regulate
agricultural activities and adopt measures for improving crop production and protecting
agricultural lands from environmental pollution.

5. Conclusions
This study analyzed the HM concentrations (levels, sources, and health risk) in a
developing area of Pakistan. Their contents were sorted as Mn > Cu > Zn > Cr > Ni >
Co > Pb > Cd in agricultural soils and as Mn > Cr > Zn > Ni > Cu > Co > Cd > Pb in
transported sediments. Our results suggest that this area has three sources of heavy metals:
anthropogenic (PC1), mixed (PC2), and geogenic (PC3). Regarding human influence, apart
from industrial activities nearby, agriculture should perhaps reduce the consumption of
chemical fertilizers and pesticides, and a rethinking of the current application of manure
could also be useful. Concerning health hazards, the values obtained here showed con-
cerning levels of Cu and Ni for childhood cancer rather than non-carcinogenic risk. The
rapid urban growth of this area and the consequently higher demand for food products
can cause agricultural intensification, and cancer risk could perhaps start to be a serious
problem for local authorities. Nevertheless, further in-depth research in this area and
many others abroad is still needed. Several soil remediation strategies and management
approaches, including physical remediation, chemical remediation, bioremediation, and
agro-ecological engineering techniques, are being explored with the potential to reduce
heavy metal contents in soils. However, the implications of these sustainable solutions
which are both technically and economically feasible are needed to bring in practices at the
field level by enforcing the execution of policies.

Author Contributions: Conceptualization, M.S., A.M. and A.J.; methodology, A.J., A.M. and M.F.S.;
software, T.J., S.A.K. and S.S.-G.; validation, R.M., E.R., S.R.T. and A.M.; formal analysis, A.M., A.J.,
S.R.T. and S.S.-G.; investigation, M.S., T.J. and A.J.; resources, M.F.S.; data curation, A.J., A.M. and
M.P.F.; writing—original draft preparation, M.S., A.M. and A.J.; writing—review and editing, M.P.F.,
A.J., A.M., E.R., R.M., S.S.-G. and S.R.T.; visualization, M.P.F., A.M. and A.J.; supervision, A.J. and
A.M.; project administration, M.F.S.; funding acquisition, M.F.S. and A.J. All authors have read and
agreed to the published version of the manuscript.
Funding: This research received no external funding.
Data Availability Statement: Not applicable.
Acknowledgments: We gratefully acknowledge Muhammad Fawad (Department of Weed Science
and Botany, Faculty of Crop Protection Sciences, The University of Agriculture, Peshawar 25130,
Pakistan) for his technical help throughout the writing of this manuscript. The authors thank
the Higher Education Commission (HEC) of Pakistan for financial support. This study was also
financially assisted by HEC, Pakistan, under HEC Project. Ref No. 20-15833/NRPU/R&D/HEC.
Land 2022, 11, 1663 11 of 12

Conflicts of Interest: The authors declare no conflict of interest.

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