Microchemical Journal xxx (xxxx) xxxx

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Microchemical Journal
journal homepage: www.elsevier.com/locate/microc

Spatial distribution of potentially toxic elements in urban soils of

Abbottabad city, (N Pakistan): Evaluation for potential risk
Sarib Jadoona,c, Said Muhammada,b, , Zakir Hilala, Muhammad Alia, Sardar Khand,
⁎

Nimat Ullah Khattakc

a
Department of Earth Sciences, COMSATS University, Abbottabad 22060, Pakistan
b
National Centre of Excellence in Geology, University of Peshawar, Peshawar 25130, Pakistan
c
Department of Geological Sciences, University of Manitoba, Winnipeg, MB R3T 2N2, Canada
d
Department of Environmental Sciences, University of Peshawar, Peshawar 25120, Pakistan

ARTICLE INFO ABSTRACT

Keywords: Potentially toxic elements (PTE) are one of the main sources of soil toxicity with detrimental impacts on the
Health index environment due to their persistence, perseverance, and potential health risks. This study investigated the PTE
Cancer risk such as nickel (Ni), lead (Pb), cadmium (Cd), cobalt (Co), iron (Fe), manganese (Mn), copper (Cu) and zinc (Zn)
Pollution quantification factor contaminations in urban soils of Abbottabad city, (N Pakistan). For this purpose, soils from different land types
Ecological risk index
were collected and assayed for PTE level using atomic absorption spectrometry. Results showed relatively higher
Pollution load index
Fe and lower Cd contamination. The contamination factor (Cf), pollution load index (PLI) and ecological risk
index (ERI) of pollution quantification factors were determined for PTE contamination. Results showed the
relatively high Cf values for Ni and low for Pb. The PLI crossed the threshold of 1 in 40% of sampling sites,
indicating significant PTE contamination at those sites. The ERI indicated low to considerable risk of PTE
contamination across all sampling sites. The PTE were evaluated for carcinogenic and non-carcinogenic risks via
ingestion, inhalation and dermal pathways. Health index (HI) values of 1.48E-02 and 1.18E-02 and cancer risk
(CR) values of 9.39E-09 and 2.03E-04 were found for adults and children, respectively. Potential sources of PTE
were quantitatively allocated by principal component analysis (PCA) along with geo-spatial analysis, indicating
natural and anthropogenic inputs.

1. Introduction
Soil has significant importance among various environmental
components because it acts as a natural sink and buffers contamination
by controlling their fate in the ecosystem [1,2]. The potentially toxic
elements (PTE) contamination has become a part of urban soil due to
rapid urbanization and industrialization [3]. The PTE were released
into the soil by various natural and anthropogenic sources including
denudation of bedrocks and mineral ores, industrial waste, vehicle
emissions, agrochemicals application, sedimentation of aerosols and
dust, wet and dry precipitation of contaminants and coal combustion
[4,5]. The continuous addition of PTE in soil resulted and increase in
sub-surface water contamination along with a reduced buffering capa-
city [1,6].
The PTE are also considered hazardous to the environment and
human health due to their perseverance, bioaccumulation and ubiquity.
The PTE has low threshold limits, with high toxicity and longer
residence times [6,7]. Soil PTE that are very toxic and hazardous in-
clude arsenic (As), cadmium (Cd), lead (Pb), cobalt (Co), chromium
(Cr) and nickel (Ni) [8]. The PTE intoxication in urban soils have grave
repercussion for human health because of their easy transfer to the
human body by several pathways [9]. The PTE detrimental effects in-
clude teratogenic, carcinogenic, mutagenic and neurotoxic effects de-
pending on the type and concentration [6,10]. Accumulation of Cd
leads to chronic health issues including fever, headache, nausea, hy-
pertension and bone fractures, while toxic exposure to Fe causes a
condition called hemochromatosis which further cause increased risk of
other diseases such as diabetes, heart diseases, cancer, liver problems
and arthritis, if left untreated for long time [11]. The excessive intake of
Co can lead to lung's problems, polycythemia, over-production of red
blood cells (RBCs) and thyroid artery malfunction [12]. Zinc toxicity
can cause lethargy, metal fume fever, anemia and nausea [13]. The
toxic effects of Pb include severe damages to the nervous, skeletal,
immune and circulatory system. Children are usually more susceptible

⁎
Corresponding author at: National Centre of Excellence in Geology, University of Peshawar, Peshawar 25130, Pakistan.
E-mail address: saidmuhammad1@gmail.com (S. Muhammad).

https://doi.org/10.1016/j.microc.2019.104489
Received 16 July 2019; Received in revised form 29 November 2019; Accepted 29 November 2019
0026-265X/ © 2019 Elsevier B.V. All rights reserved.

Please cite this article as: Sarib Jadoon, et al., Microchemical Journal, https://doi.org/10.1016/j.microc.2019.104489
S. Jadoon, et al.
to Pb toxicity and it causes various health and psychological issues
including behavior changes, memory degeneration and increased risk of
anemia [14,15]. People with toxic exposure to Mn and Cu are more
prone to mental diseases such as manganism and Alzheimer [16]. The
phytotoxicity and leaching of soil PTE into sub-surface water is con-
trolled by their soluble fraction, which also provides the assessment of
the mobilization potential of these PTE and their availability to various
organisms at contaminated sites [17].
Recently, the PTE contamination in urban soil has been focused in a
number of studies from various part of the world. However, very little
attention was paid to PTE contamination in urban soil and associated
health risk in developing countries like Pakistan due to poor economic
conditions, rapid industrialization and improper environmental man-
agement [18]. Therefore, this was first and baseline study with objec-
tives to evaluate the variation and distribution of the PTE (Zn, Cd, Pb,
Cu, Co, Fe, Mn, and Ni) in soils of various land types. Degree of pol-
lution in urban soils were gauged using pollution quantification factors
such as contamination factor (Cf), pollution load index (PLI) and eco-
logical risk index (ERI). Determined PTE concentrations were evaluated
for the potential risk assessment including chronic or non-carcinogenic
risk such as health index (HI) and cancer risk (CR). The PTE con-
centrations, PLI and health index (HI) values were interpolated using
geo-spatial and statistical analysis.
2. Materials and methods
2.1. Study area
The study area (Abbottabad city) is present in south-east region of
Hazara with an area of 54 km2 in the Khyber Pakhtunkhwa province,
Pakistan. The Orash valley contains Abbottabad city, with geographical
coordinates stretching from latitudes 34.12–34.23°N and longitudes
Fig. 1. Location map of study area, indicating the sampling sites in the Abbottabad city, (Khyber Pakhtunkhwa province, Pakistan).
2
Microchemical Journal xxx (xxxx) xxxx
73.15–73.28°E with elevation level at 4120 feet above sea level (Fig. 1).
The annual precipitation of city amounts to 1269 mm per year [19].
In geological terms, the study area was located to the west of
Jhelum fault, SW of Hazara Kashmir Syntaxes and the north of the main
boundary thrust (MBT) [20]. Several phases of deformation in the re-
gion had produced the intricate structures with intense folding and
faulting. The Abbottabad formation of the study area contains phases,
bands, lenses and nodules of phosphate rock deposits, which are dis-
tributed and mined on an area of about 30 km2 across Abbottabad [21].
High levels of Cu, Pb and Zn concentration are observed in phosphate
rock samples collected in the vicinity of Abbottabad city [21,22]. The
Pb mineralization in the form of small phases was reported in the Ab-
bottabad area, which is believed to represent hydrothermal fluid in-
jection along the fractures present in host rocks but local mining was
not possible as the ore concentrations are below the mining thresholds.
The galena (PbS) is the major constituent of the Pb ore that exists in the
aggregate form of small crystals, along with pyrite (FeS2), barite
(BaSO4) and irregularly shaped corroded quartz grain which are dis-
tributed within galena [23]. The small-scale deposits of Mn and Fe have
been observed in the ferromanganese ores, present within Hazira for-
mation in the vicinity of Abbottabad city. The bixbyite [(Mn,Fe)2O3] is
the major constituent of Mn-phase, while braunite, hollandite, pyr-
olusite and partridgeite occur in lesser amounts. However, the only Fe-
phase found in the ores was Hematite (Fe2O3) [24]. Extensive mining
activity in the vicinity of the Abbottabad city could have been the po-
tential source of PTE in soil and water ecosystem [25]. The optical
mineralogy indicated Fe ore hematite (Fe2O3) was the prominent mi-
neral present in soil samples after quartz and calcite. However, galena
(PbS) and bixbyite [(Mn,Fe)2O3] were present in relatively lesser
amounts. The most soil samples were assigned sandy loam and silt loam
soil types after they were classified using USDA classification system.
S. Jadoon, et al.
2.2. Soil sampling
Following the precedents set by previous studies [1,7], five land
types including waste dumping (WD) sites, agriculture lands (AL), road
sides (RS), residential areas (RE) and parks/play grounds (PG) were
selected for the evaluation of PTE concentration levels in soil. The 25
sampling zones (12 zones had 3 sub-sampling points and 13 zones 2
sub-sampling sites, and together 25 make 62 sub-sampling points) were
selected for soil collection and their even distribution was ensured in
the entire Abbottabad city. From each sampling site, topsoil (0–20 cm)
was taken in the polythene zip-lock bags, completely mixed, homo-
genized and then transported to laboratory. The sampling points were
evenly distributed at each sampling zone. The coordinates of sampling
zones were recorded using the global position system (GPS).
2.3. Sample preparation and analytical techniques
Representative soil samples were air dried for 10 days and then
passed through 2 mm mesh. The pH of soil sample was determined
using CONSORT 6030 in its water extract, which was prepared by
dissolving the 10 g of soil in deionized water of 25 ml, following
shaking and resting, the reside was separated from final extract by the
fine filter paper [18,26].
The acid extract of each oven dried soil sample was prepared by
adding 1 g of respective sample in the Teflon beaker containing (aqua
regia) mixture of nitric acid (HNO3, 9 ml) and hydrochloric acid (HCl,
3 ml) and digestion process was completed using the microwave system
[27]. After passing through the filtration process, each digestive sample
was made up to 50 ml using the deionized water and stored in the pre-
cleaned glass tubes in refrigerator.
The atomic spectrometry involves the recording of electromagnetic
radiations emitted or absorbed by free atoms when their valence elec-
trons change their atomic energy levels. As every atom has specific
electronic configuration so each element emits and absorbs light at a
characteristic wavelength. The amount of energy emitted or absorbed is
directly proportional to concentration of element in sample. It is mature
and widely used analytical technique to study the concentration of PTE
[28].
The acid extracts of each representative soil sample were further
assayed for PTE concentration in laboratory using atomic absorption
spectrometry (Perkin Elmer, AAnalyst 700) maintaining the optimum
analytical conditions. The delay and integration time of (AAnalyst 700)
was 5 s.
2.4. Data precaution and accuracy
Throughout the study, all standard solutions and reagents were
prepared using the analytical grade chemicals without any further
purification. The PTE standards were prepared using the certified stock
solutions (1000 mg/L) by suitable dilution. The quality control and
quality assurance were ensured using duplicate samples, blank control,
standard reference Fluka Kamica (Buchs, Switzerland) and standard
solutions of selected PTE. Analysis of representative soils samples were
measured in triplicates with a range of standard deviation within 3.5%.
The blank samples and three standard solutions of respective PTE were
also assayed after every 10 samples. Blank sample containing only acid
mixture and the reference soil (NIST 2709 San Joaquin soil sample)
were digested in each batch of experiment and results summarized
(Supporting Information Table S1). Relative standard deviations and
relative error percentage ranged between 0.04% and 11.96% and
0.91% to 8.90%, respectively.
2.5. Statistical analyses
The descriptive statistical parameters (ranges, mean and standard
deviation) were computed using the Microsoft Excel (2015) software.
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Microchemical Journal xxx (xxxx) xxxx
The normality tests were conducted to check the normalization of data,
they revealed that only Mn, Ni and Fe passed the Kolmogorov–Smirnov
(p>0.05) test of normality. The Pb and Zn data passed the
Kolmogorov–Smirnov (p>0.05) test of normality after the log-normal
distribution. However, using the two-step approach for normalization,
Cu, Co and Cd data passed the Kolmogorov–Smirnov (p>0.05) test of
normality as even log-normal transformation was not enough for their
normalization [29]. Statistical techniques like the ANOVA analysis,
correlation analysis and principal component analysis (PCA) were
carried in the SPSS ver. 25 (SPSS Inc., Chicago, IL, USA). The inverse
distance weightage (IDW) interpolation technique was used to prepare
the geo-spatial distribution maps exhibiting the PTE concentrations, HI
and PLI by Arc GIS ver. 10.5 (ESRI Inc., Redlands, CA).
2.6. Pollution quantification
Pollution levels in the study area were quantified and assessed using
various parameters. The extent of PTE contamination was gauged using
the Cf. For assessment of the Cf values, the relationship (Eq. (1)) sug-
gested by Hakanson [30] and Muhammad et al. [31], in which the Cf
values was obtained by the division of PTE concentration at examina-
tion site (Ci) by the background or pre-industrial concentration (Cn) of
that respective element. This research used those soils as reference or
background values, which are away from anthropogenic inputs. The
background values for Zn, Cd, Pb, Cu, Co, Fe, Mn, and Ni were de-
termined as 4.59, 0.07, 0.32, 0.38, 0.48, 118, 12.2 and 7.48 mg/kg,
respectively. There are 5 classification levels of soil according to value
of Cf; (1<) low or no contamination, (≥1>3) minimal to deficiency,
(≥3>6) considerate, (≥5>20) significant, (≥20>40) very high and
(<40) extremely high.
Ci
Cfi =
Cn (1)
Pollution load index provides the overall assessment of PTE intoxication
levels in the study area. The PLI was ith-root of the product of iCF,
where i was the total number of CF. Relatively higher polluted areas
had PLI values more than 1, while areas having no significant pollution
had the PLI value less than one Harikumar et al. [32]. It denoted by
Eq. (2):
PLI = [i] Cf 1 × Cf 2 × Cf 3 × …Cfi (2)
The other most readily used diagnostic tool in the ERI. It is denoted by
Eq. (3):
ERI = Tr × Cf (3)
where Tr indicates the toxic response factor of given PTE, respectively.
There are 5 classification levels of the soil according to value of ERI;
(>40) low or no contamination, (≥40>80) moderate, (≥80>150)
considerable, (≥150>300) high, (<300) very high.
2.7. Health risk assessment
The PTE were considered in health risk assessment due to their
established, dose-response relationship and relatively strong toxic ef-
fects on the human health (Supporting Information Table S2). For the
determination of average daily dose (ADD), three pathways were con-
sidered: (1) ingestion, (2) inhalation and (3) dermal contact or ab-
sorption of soil particles. ADD for each pathway can be determined
using the Eqs. (4–6), respectively US EPA [33]. Similarly, for cancer risk
analysis lifetime average daily dose (LADD) was also calculated for each
respective pathway using Eqs. (7–9) US EPA [33]. The quantitative
characterization of the non-carcinogenic and the carcinogenic risks of
exposure was done using the hazard quotient (HQ) and CR for in-
dividual PTE, respectively US EPA [33]. The HQ for each pathway was
calculated by the division of respective ADD by the reference dose (RfD)
S. Jadoon, et al. Microchemical Journal xxx (xxxx) xxxx

of that pathway of respective PTE and pathway as indicated in Eq. (10). et al. [7] in Jiangsu Province (China) and Muhammad et al. [40] in
Furthermore, HI, which was the summation of the HQ of each pathway, Kohistan (Pakistan).
PTE at particular sampling site, was determined to assess the non-car- Relatively high (10.9, 1.72 and 2.56 mg/kg) concentrations of Ni,
cinogenic hazard of more than one PTE by Eq. (11) based on the Co and Cu were recorded in the soil samples collected from RE, RS and
guidelines of US EPA [33]. Furthermore, lifetime average daily dose RE land types of Malikpura, Narian and Malikpura, respectively
(LADD) was multiplied with the cancer slope factor (SF) of respective (Supporting Information Fig. S1, Table 1). Upstream mining and
element to calculate the CR for each exposure pathway, respectively leaching from the geogenic sources might have been the cause of re-
(Eq. (12)) US EPA [33]. The total CR for all exposure pathways was latively high concentration levels of PTE [41,42]. The Mining of low-
calculated using Eq. (13) US EPA [33]: grade metal ore containing many metalloids always increases the PTE
C × IngR × EF × ED concentration in the surrounding areas. For example in south China, the
6
ADDingestion = × 10
(4) area in the vicinity of Dabaoshan mine is effected by PTE contamination
BW × AT
which decreases exponentially with the distance from mine wastewater,
ADDinhalation =
C × InR × EF × ED a similar effect is expected to be produced in the study area due to local
PEF × BW × AT (5) mining of phosphate rock [43]. Results indicate that Ni, Co and Cu
C × SA × ABS × AF × EF × ED concentrations in the soil samples passed the limits of CCME [34]. The
6
ADDdermal = × 10
(6) concentrations of Ni, Co and Cu were found lower when compared with
BW × AT
the results of Jiang et al. [7] in Jiangsu Province (China) and Mu-
LADDingestion =
C × IR × EF × ED
× 10 6 hammad et al. [40] in Kohistan (Pakistan).
BW × ATC (7) Relatively high concentrations (27.0 and 600 mg/kg) of Mn and Fe
C × InR × EF × ED were recorded in soil samples collected from RE and AL of Malikpura
LADDinhalation =
(8) and Banda Jalal Khan, respectively (Supporting Information Fig. S1,
PEF × BW × ATC
Table 1). The relatively high flux of these PTE at certain sites might be
LADDdermal =
C × SA × ABS × AF × EF × ED
× 10 6 due to weathering/erosions/leaching of minerals such as bixbyite
BW × ATC (9) [(Mn,Fe)2O3], apatite [Ca5(PO4)3(Cl/F/OH)] and hematite (Fe2O3)
from local bedrocks and mines drainage runoffs [24,44,45]. The Shah
ADDi
HQ = and Moon [24] discussed the formation of ferromanganese ores within
RfDi (10) in Hazara region comprising Abbottabad city. The study suggested that
ores are formed in a shallow-marine continental shelf environment. The
HI = HQy (11)
mineralogical and structural reconstitution is observed in ores after
CR = (LADDx × SFx ) subsequent deformation. The hydrogenous and hydrothermal source
(12)
material is responsible for the formation of these ores and they are
TotalCR = CRy formed in near shore shelf environment by upwelling deep-anoxic
(13)
ocean water into more oxygenated surface water. The understanding of
the formation, mineralogy and geochemistry of ores will help in the
3. Results and discussion formation of suitable remediation strategies. The observed results in-
dicate that Mn and Fe concentrations were within the safe soil Canadian
3.1. Potentially toxic elements contamination standards, although the concentrations were quite high at certain
sampling sites relative to background values [34]. The concentrations
Among soil samples, the highest pH value (7.9) was recorded for of Mn and Fe were found lower when compared with the results of
sample collected from the PG of Jail Park (Supporting Information Fig. Muhammad et al. [40] in Kohistan (Pakistan), while concentrations of
S1, Table 1). The pH values of all representative samples were within Fe were found higher compared with results of Jiang et al. [7] in
the limits of CCME [34]. The calcite content mostly calcium carbonate Jiangsu Province (China).
(CaCO3) increases the pH value as indicated by Aziz et al. [35] but also
increases the buffering capacity. The carbonate materials, leaching 3.2. Comparison of PTE in various studied sites
from the local geological formations might have been the reason of this
relatively high pH value. This indicates that a natural buffer in the form The concentrations of PTE were observed higher in the WD, RS, AL
of limestone is present in the geological formations of Abbottabad as it and RE as compared to PG land types. Higher PTE concentrations of
is considered a best agent for PTE remediation in contaminated soils. these land types could be attributed to long term deposition of solid
The relatively high (15.9, 0.35 and 5.80 mg/kg) concentrations of waste and vehicle emission, agrochemicals application and municipal
Zn, Cd and Pb were observed in soil samples taken from RE, AL and WD wastewater. The concentrations of PTE were observed to be lower when
land types of Malikpura, Banda Jalal Khan and Benzair hospital, re- compared with the global trend of urban soil contamination in major
spectively (Supporting Information Fig. S1, Table 1). These high values cities of the world and summarized in the Supporting Information Table
of Zn, Cd and Pb were mainly due to the enrichment of PTE in bedrocks S3. This may be due to the fact that Abbottabad city is not so old and
and geological formations [36,37]. For example in Norway, enrichment thus it has received low anthropogenic impact when compared with
of low-grade galena (PbS) deposit in bedrocks and downward move- very old cities such as Beijing, which was the heart of street smelting
ment of weathering material since last glaciation resulted in the for- and melting operations of metals contributing to its high PTE con-
mation of barren grounds within the forest [38]. The presence of galena centration levels.
(PbS) in surrounding bedrocks of Abbottabad can produce a similar
effect and can explain the high concentration of Pb in cities’ urban soils. 3.3. Statistical analyses
Precipitation of toxic aerosols from vehicle exhausts can also be re-
sponsible for the relatively high values of these PTE [39]. There is a Upon comparing PTE concentration levels of studied land types
need for further study to track seasonal variations in PTE concentra- using the one-way ANOVA, the significant statistical variation
tions to distinguish between localized and regional atmospheric con- (p<0.05) was determined. Results revealed that different land types
tributions. The Zn, Cd and Pb concentrations in soil samples were under were contributing differently or significantly in the mean metal con-
the admissible limit set by CCME [34]. The concentrations of Zn, Cd tamination of soil. The RS land type contributed significantly lower to
and Pb were found lower when compared with the results of the Jiang the PTE contamination as compared to other land types of the study

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Table 1.
The concentration of various PTE in selected land types of they study area (mg kg−1) (na=62).
Land Type Statistics Waste Dump Agriculture Roadside Residential Playground

pH Range 6.2–7.6 6.9–7.5 6.8–7.5 6.1–7.2 7.3–7.8

Mean 6.6 7.4 7.1 6.7 7.5
Std db 0.6 0.3 0.3 0.4 0.2
Cd Range <0.01–0.31 0.01–0.35 B.Dc-0.25 <0.01–0.21 0.01–0.02
Mean 0.08 0.15 0.07 0.06 0.02
Std d 0.13 0.14 0.10 0.09 0.01
Background 0.07
Co Range 0.34–0.55 0.36–0.68 0.51–1.72 0.35–0.61 0.43–0.60
Mean 0.43 0.52 0.99 0.52 0.55
Std d 0.08 0.14 0.45 0.10 0.07
Background 0.48
Cu Range 0.14–2.07 0.07–0.17 0.15–0.49 0.16–2.56 B.D −0.18
Mean 0.63 0.13 0.23 0.76 0.12
Std d 0.83 0.04 0.15 1.04 0.07
Background 0.38
Fe Range 169–266 235–600 79.3–175 194–537 125–336
Mean 211 348 132 335 239
Std d 35.1 146 34.3 135 89.1
Background 118
Mn Range 3.48–14.2 20.8–25.8 6.78–24.6 0.66–27.0 11.5–17.0
Mean 10.4 23.3 15.6 9.78 13.2
Std d 4.15 2.10 6.31 10.7 2.26
Background 12.2
Ni Range 7.19–8.89 8.07–8.50 6.84–7.96 7.08–10.9 4.64–8.03
Mean 7.86 8.27 7.52 8.74 7.06
Std d 0.63 0.18 0.47 1.42 1.40
Background 7.48
Pb Range 1.49–5.81 0.51–1.46 0.49–1.69 0.69–1.51 0.52–1.73
Mean 3.48 0.83 1.10 1.13 1.26
Std d 1.55 0.38 0.56 0.29 0.46
Background 0.32
Zn Range 2.49–10.9 4.71–9.49 3.17–7.259 2.86–15.9 3.13–5.83
Mean 6.08 6.19 4.78 6.89 4.38
Std d 3.07 1.94 1.64 5.25 1.05
Background 4.59

a
Number of soil samples.
b
Standard deviation.
c
Below detection limit.

area (Supporting Information Table S4). The Pb values were sig-
nificantly higher (p<0.05) in soil collected from the WD land types as
compared to other land types due to the excessive open dumping of
chemical waste and close to road side. The Fe values were significantly
lower (p<0.05) in the soil collected from the RS land types as com-
pared to other land types. These relatively low values of Fe might be
due to the fact that leaching from the bedrocks was the only source of
Fe contamination and it was more common in other sources as com-
pared to the RS land types. The Mn values were significantly higher
(p<0.05) in soil collected from the AL land types as compared to other
land types. These high values of Mn can be attributed to the excessive
use of fertilizers and leaching from the ferromanganese ore containing
bixbyite [(Mn,Fe)2O3].
The Inter-PTE correlation was summarized in the Supporting
Information Table S5. Upon analysis, a positive significant correlations
were observed in PTE pairs like Fe-Cu, Fe-Zn, Ni-Cu, Ni-Zn and Ni-Fe
(Supporting Information Table S5). This positive significant correlation
indicates that these PTE are closely associated with each other and tend
to thrive in similar environments. Their paleoenvironment and geolo-
gical sources may be the same, contributing to their close association.
The negative correlations were observed in some PTE pairs like Pb-Zn,
Co-Zn and Mn-Pb (Supporting Information Table S5). This negative
significant correlation indicate that these PTE are not closely associated
with each other and do not tend to thrive in similar environments. Their
paleoenvironment and geological sources may not be same, con-
tributing to their dissociation.
For source apportionment, a quantitative evaluation was conducted
using the PCA with varimax normalized rotation (PCA-V) and
summarized (Supporting Information Table S6). The PCA analyses in-
dicate their association and grouping with the three factors in soils of
studied land types. The three factors have indicated the cumulative
variance of 76.1%. Factor-1 contributed 32.9% to the total variance
with high loading on Zn, Cu, Fe and Ni (Supporting Information Table
S6). The sources of Zn, Cu, Fe and Ni could be the leaching and
weathering of hematite (Fe2O3) and bixbyite [(Mn,Fe)2O3] from bed-
rocks/ore deposits and mining/agriculture activities in the vicinity of
the Abbottabad city. Macronutrient fertilizersare a very prominent
source of PTE in agriculture soils around the world. The P rock deposit
that is mined in the vicinity of Abbottabad city and is used in the
preparation of fertilizers throughout the country is already reported to
have significant concentrations of PTE [21,22]. The use of livestock
manure as local fertilizer in the study area can explain the relatively
high concentration levels of Cu and Zn as it is reported to be high in
concentration of these PTE [46]. The high concentration levels of these
PTE in livestock manure is due to extensive use of Zn and Cu as growth
promoters in the poultry and cattle feed. The AROMIS project in Europe
and Luo et al. [47] in China reported that livestock manure was a
significant contributor for Zn (29–65% and 51%) and Cu (29–72% and
69%) in soils of Europe and China, respectively [46]. So, factor-1 can be
attributed to both anthropogenic and geogenic sources. Factor-2 was
accounted for 21.3% of the total variance with high loading on pH and
Mn in opposition to Pb (Supporting Information Table S6). The values
of pH and Mn are possibly manipulated by the plumbing and agri-
culture activity and leaching from Mn ore having bixbyite [(Mn,Fe)2O3]
in the vicinity of the Abbottabad city, indicating that factor-2 was
mostly associated with anthropogenic and geogenic sources. Factor-3

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S. Jadoon, et al. Microchemical Journal xxx (xxxx) xxxx

Table 2.
Calculation of non-carcinogenic risks (HQ) and carcinogenic risks (CR) from PTE in soils (na=62).
Adults (aged 18+) Children (aged 1–17)
Soil ingestion Inhalation Dermal contact Total Pathways Soil ingestion Inhalation Dermal contact Total Pathways

Hazard quotient
Cd 9.81E-05 1.44E-06 3.91E-03 4.01E-03 4.58E-04 3.37E-06 3.84E-04 8.46E-04
Co 2.64E-05 2.05E-05 1.58E-03 1.63E-03 1.23E-04 4.78E-05 1.56E-04 3.27E-04
Cu 1.67E-05 2.46E-09 2.22E-05 3.89E-05 7.80E-05 5.73E-09 2.18E-06 8.01E-05
Fe 4.99E-04 7.34E-08 1.99E-06 5.01E-04 2.33E-03 1.71E-07 1.96E-07 2.33E-03
Mn 4.95E-04 5.39E-05 1.59E-06 5.51E-04 2.31E-03 1.26E-04 1.56E-07 2.44E-03
Ni 5.49E-04 3.23E-05 2.84E-03 3.42E-03 2.56E-03 7.54E-05 2.79E-04 2.92E-03
Pb 3.68E-03 8.32E-08 9.03E-04 4.58E-03 2.64E-03 1.94E-07 8.87E-05 2.73E-03
Zn 2.44E-05 3.59E-09 9.74E-06 3.41E-05 1.14E-04 8.37E-09 9.56E-07 1.15E-04
Total 5.39E-03 1.08E-04 9.27E-03 1.48E-02 1.06E-02 2.53E-04 9.11E-04 1.18E-02
Cancer risk
Cd 3.89E-11 3.89E-11 9.09E-11 9.09E-11
Co 4.90E-10 4.90E-10 1.14E-09 1.14E-09
Cu 1.05E-09 1.05E-09 2.46E-09 2.46E-09
Ni 5.81E-10 5.81E-10 1.36E-09 1.36E-09
Pb 7.22E-09 5.24E-12 1.07E-11 7.23E-09 3.37E-08 1.22E-11 2.02E-04 2.03E-04
Total 7.22E-09 2.17E-09 1.07E-11 9.39E-09 3.37E-08 5.06E-09 2.02E-04 2.03E-04

a
Number of soil samples
b
Hazard Quotient
c
Cancer Risk.

was accounted for 12.9% of total variance with high loading on Cd
(Supporting Information Table S6). The Cd intoxication was probably
caused by the erosions/weathering/leaching of phosphate ore (apatite,
P2O5>40%) located in the vicinity of Abbottabad city as it is reported
to have a significantly high content of Cd in the form on gangue. The
relatively high Cd concentrations in phosphorus-based fertilizers are
cause of concern worldwide. For example, in Australia, fertilizers
manufactured from guano-derived phosphorites contained Cd more
than 300 mg/Kg and injected approximately 30–60 g Cd/ha to soils, so
use of phosphorus-based fertilizer in the study area can be considered a
possible source of Cd [48]. According to Hjortenkrans et al. [49] the
extensive emissions from the vehicle exhausts, tires and brake linings
can be considered a significant source of Cd. They reported that ve-
hicles on road in Stockholm, accounted for more than 50% of PTE
(mainly Cd) contamination in urban soils with tires being main con-
tributor of Zn and Cd. So vehicular sources can be associated with high
levels of Cd in urban soils. So, factor-3 can be attributed to both an-
thropogenic and geological sources
3.4. Pollution quantification
The WD land type had the highest mean Cf value of 11.4 for Pb,
while the lowest value observed for Cu in RS (Supporting Information
Fig. S2a). Results revealed that among PTE, the Cf values of Pb were
higher than other elements. Higher Cf values of Pb could be attributed
to high contamination level in soil of various land types due to both
natural and anthropogenic sources. The relatively higher CF values of
PTE were attributed to their higher contamination as compared to
background sites. The PLI index was calculated to assess cumulative
pollution load of selected PTE at every sampling site. The PLI surpassed
the threshold of 1 in 36% sampling sites indicating that significant PTE
contamination at those sites, which can be attributed to relatively high
PTE concentration levels as compared to their background or control
values (Supporting Information Fig. S2a).
The ERI was determined for each respective PTE, at every sampling
site (Supporting Information Fig. S2b). According to observed data, Cd
posed considerable ecological risk at 24% sampling sites, out of which
4% belong to WD land type of Salhad Chasma, 8% belong to AL land
types of Banda Jalal Khan and Nawanshehr and 4% belong to each RS,
RE and PG land types of Canteen store department, Jinnahbad and Jail
park, respectively. However, Pb posed a considerable ecological risk at
1 sampling site and moderate risk at 8% sampling sites of WD land
types of Benazir hospital, Nare and Salhad Chasma, respectively. These
relatively high ERI of respective PTE can be attributed to their high Tr
and relatively high concentration levels in soils when compared with
their background values. All other PTE posed a low ecological risk at
studied sites. In spatial distribution analysis, all the sites with high ERI
values appeared to be closer to the waste dumping sites downstream of
the city, which can be considered major source of PTE contamination
apart from the natural sources.
3.5. Health risk assessment
The ADD via various pathways indicated the disparity among the
different land types and summarized in the Supporting Information Fig.
S3 (a-f). Among recorded soil samples, maximum mean ADD value
through exposure pathways was observed for Fe and minimum for Cd in
WD, AL, RS, RE and PG. Among exposure pathways, the ingestion
showed the higher potential followed by dermal and the lowest via
inhalation in the Supporting Information Fig. S3 (a-f). Among age
group, children intake of studied PTE was higher than adults. Higher
intake of PTE in children could be attributed to hand to mouth prac-
tices. Higher exposure risk of the ingestion pathway was consistent with
those reported by Saddique et al. [8].
The non-carcinogenic risks and carcinogenic risks were determined
for each respective PTE for both adults and children via various path-
ways (Table 2). Lack of respective SF and RfD values produced the
missing values in the table for CR. The HI values via total pathways for
adults and children were 1.48E-02 and 1.18E-02, respectively. Both
values were less than 1, indicating no significant non-cancer risk to the
local population. The HI is also calculated on each sampling site and HI
value on every site was also less than 1 indicating no significant risk to
local population. The major exposure pathways for children and adults
were the ingestion and dermal contact. The HQ indices, besides de-
pending on the concentration they also depend on the RfD value and
toxicity of respective PTE. The WD had the relatively high mean HQ
values of 2.30E-02 for Pb and low of 3.88E-05 for Zn considering the
total pathways (Table 2). In WD land type, the relatively high HQ value
was recorded for the Pb in a soil taken from Salhad Chasma owing to its
relatively high intoxication, concentration, and respective RfD value.
The soil of AL and RS had relatively high mean HQ values of 8.63E-03
and 3.26E-03 for Cd and low of 8.44E-04 and 1.75E-05 for Co con-
sidering the total pathways (Table 2). In AL land type, the relatively
high HQ value was recorded for Cd in soil taken from Banda Jalal Khan

6
S. Jadoon, et al.
and canteen store department owing to its relatively high intoxication,
concentration, and the respective RfD value. Soils of RE and PG had
relatively high mean HQ values of 3.75E-03 and 3.37E-03 for Ni and the
low of 3.98E-05 and 2.89E-05for Zn considering the total pathways
(Table 2). In RE and PG soils, Pb and Ni showed the relatively high HQ
value in soil sample taken from the canteen store department owing to
its high intoxication, concentration, and respective RfD value. The re-
latively lower HI values were observed for northern sites i.e. Mirpur and
Nawanshehr and high for the downstream sites such as the Supply and
Salhad (Supporting Information Fig. S1). Higher HI values with
downstream could be attributed to the higher PTE contamination.
The total CR values for adults and children were 9.39E-09 and 2.03E-
04, respectively (Table 2). Children seemed more susceptible to cancer
due to the PTE intoxication via the total pathways. Only the CR value for
children via dermal contact exceeded the tolerable risk of 1.00E-04. The
CR values for all PTE were under the tolerable risk, except Pb in children.
The CR via dermal contact was much higher as compared to the other
pathways in children. The CR values increased in following order Cd <
Co < Ni < Cu < Pb for both adults and children. The proper re-
mediation methods should be adopted to reduce and mitigate CR. The
HQ and CR values were lower than those reported by the Jiang et al. [7]
in Jiangsu Province, China and higher than those reported by the Sad-
dique et al. [8] in Khyber Pakhtunkhwa province, Pakistan.
4. Conclusion
In the study soils, PTE contamination followed descending order of
Fe > Mn > Ni > Zn > Pb > Co > Cu > Cd. The observed accu-
mulation of PTE in soils of various land types of Abbottabad city, in-
dicate a potential hazard for the local population when compared with
the natural background values of PTE but the level of contamination is
not that significant when compared with the global trend. The one-way
ANOVA technique proposed that soil of different land types was con-
tributing significantly to the mean PTE concentration (p<0.05), RS
land type contributed significantly lower to PTE contamination as
compared to other land types of the study area. The PCA analysis as-
signed both geological (erosion/weathering/leaching) and anthro-
pogenic (agriculture/mining activities, traffic emissions, waste in-
cineration and dumping) sources to PTE intoxication. Health risk
assessment of non-carcinogenic risk via soil ingestion, inhalation and
dermal contact, revealed HI values of 1.48E-02 and 1.18E-02, for adults
and children, respectively. The CR values for PTE were under the tol-
erable risk, except Pb in children. Children seemed more susceptible to
cancer due to PTE intoxication via total pathways and only CR value for
children via dermal contact exceeded the tolerable risk of 1.00E-04.
This is a serious issue and demands more investigation related to Pb
contamination based on mineralogical studies as it can give us valuable
insights into the PTE behaviors at mineralogical scale and can also aide
in deducing mitigation measures. The carcinogenic risk via dermal
contact was much higher as compared to other pathways in children.
This study proposes that strong action should be taken by government
regulators, against anthropogenic sources of PTE to curtail con-
tamination footprint and health risks to the local population.
Declaration of Competing Interest
The authors declare that there are no conflicts of interest.
Acknowledgments
This research was supported by the Higher Education Commission
(HEC), Pakistan # 20–2828/NRPU/R&D/HEC/10/712. The
Department of Environmental Sciences, COMSATS University
Abbottabad is acknowledged for providing the instrumental support.
We also thanks to the anonymous reviewers for their comments which
improved the quality of the manuscript.
7
Microchemical Journal xxx (xxxx) xxxx
Supplementary materials
Supplementary material associated with this article can be found, in
the online version, at doi:10.1016/j.microc.2019.104489.
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