1 s2.0 S2352186419306169 Main

Environmental Technology & Innovation 17 (2020) 100554
Contents lists available at ScienceDirect
Environmental Technology & Innovation

journal homepage: www.elsevier.com/locate/eti
Contamination features, geo-accumulation, enrichments and

human health risks of toxic heavy metal(loids) from fish
consumption collected along Swat river, Pakistan
∗ ∗
Miao Liu a,b , Yuxin Xu a,b , , Javed Nawab c , , Ziaur Rahman d , Sardar Khan e ,
Muhammad Idress c , Zia Ud din c , Abid Ali f , Riaz Ahmad g , Said Akbar Khan h ,
Asad Khan i , Muhammad Qayash Khan f , Yu-Ting Tang j , Gang Li k
a
College of Resource and Environment, Shandong Agricultural University, Taian, Shandong, 271018, China
b
Key Laboratory of Agricultural Environment in Shandong University Taian, Shandong, 271000, China
c
Department of Environmental Sciences, Abdul Wali Khan University Mardan, Pakistan
d
Department of Microbiology, Abdul Wali Khan University Mardan, Pakistan
e
Department of Environmental Sciences, University of Peshawar, Peshawar 25120, Pakistan
f
Department of Zoology, Abdul Wali Khan University Mardan, Pakistan
g
State Key Joint Laboratory of Environment Simulation and Pollution Control, School of Environment, Beijing Normal
University, Beijing 100875, China
h
Department of Earth & Environmental Sciences, Bahria University Islamabad, Pakistan
i
Department of Geology, FATA University, F.R. Kohat, Darra Adam Khel, Pakistan
j
School of Geographical Sciences, University of Nottingham Ningbo China, Ningbo, 315100, China
k
CAS Key Lab of Urban Environment and Health, Fujian Key Lab of Watershed Ecology, Institute of Urban Environment Chinese
Academy of Sciences, Xiamen 361021, China
article info a b s t r a c t
Article history: Toxic heavy metal(loids) (THMs) are released into natural water systems from geological
Received 24 September 2019 and anthropogenic sources, and easily accumulated via water and sediments in aquatic
Received in revised form 14 November 2019 fish species. The monitoring of THM concentrations in river water, sediments and fish
Accepted 23 November 2019
muscles is therefore, essential to make sure acquiescence with food security guidelines
Available online 27 November 2019
and resulting end user safety. The present study aimed to investigate the concentrations
Keywords: of arsenic (As), cadmium (Cd), lead (Pb), chromium (Cr), copper (Cu), nickel (Ni) and
Freshwater ecosystem zinc (Zn) in water, bed sediments and their bioaccumulation in freshwater fish tissues
Toxic heavy metalloids collected from five locations along Swat River, Pakistan. Results indicated that Cd
Contamination concentration in the downstream (30%) water samples exceeded the safety guideline
Bioaccumulation
values of World Health Organization (WHO), while the other selected THMs were
Food chain
within the safety limits. The ecological risk (Eri ) for sediments showed considerable
Health risk
ecological risk (80≤Eri<160) to excessive ecological risk (Eri >320) for Pb, As and Cd, while
the potential ecological risk (RI) showed considerable level ((190≤RI<380) of risk at
downstream. Moreover, downstream portion showed multifold potential ecological risk
index enrichment as compared to upstream portion of the river. Likewise in fish tissues
the THMs were found in order of Zn >Cd >Pb >Cr >As >Cu >Ni. In the study area, the
selected THMs were within the permissible limits all the fish tissue samples showing no
potential health risk (carcinogenic and non-carcinogenic <1) for the local inhabitants and
fishermen. But in near future due to the continuous flow of wastewater from (industrial,
agriculture and hotels) without treatment and open dumping and throwing of municipal
wastes directly into the river as it passes through downstream may deteriorate river
∗ Corresponding authors.
E-mail addresses: yuxinxu@sadu.edu.cn (Y. Xu), javednawab11@yahoo.com (J. Nawab).
https://doi.org/10.1016/j.eti.2019.100554
2352-1864/© 2019 Published by Elsevier B.V.
2 M. Liu, Y. Xu, J. Nawab et al. / Environmental Technology & Innovation 17 (2020) 100554
ecosystem. As a whole the downstream of the river was more polluted as compared
to the upstream. So appropriate implementation of management policies beside THMs
contamination their accumulation in freshwater ecologies and management of aquatic
life should be the prime priorities of the state worldwide to protect fragile environment.
© 2019 Published by Elsevier B.V.
1. Introduction
In developing countries the rapid development in terms of industrial and agricultural activities have raised severe
concerns about the release of toxic heavy metal(loids) (THMs) to the aquatic ecosystem (Rai, 2008; Wang et al., 2010).
THMs such as arsenic (As), cadmium (Cd), lead (Pb), chromium (Cr), copper (Cu), nickel (Ni) and zinc (Zn) released from
natural components (weathering of parent’s rocks, volcanic eruption) to the environment and as well from various human
activities (e.g. industries, intensive agriculture practices, sewage sludge, municipal waste, landfills, smelting and mining)
have been reported previously (Zhong et al., 2012; Nawab et al., 2015; Sun et al., 2015; Nawab et al., 2017, 2019). The
distribution of THMs in water, sediments, and their bioaccumulation in aquatic fish species plays a vital role in forming
sources of metal contamination in the aquatic ecosystem (Maurya and Malik, 2019; Sarah et al., 2019). Sediments can act
as a sink or source of nutrient to micro-biome and play important role in the aquatic ecosystem by providing support to
the living organisms (Jain et al., 2004; Gu et al., 2014). Furthermore, limited studies have documented that sediments can
act as an indicator for current and chronological contamination in the surrounding environment (Li et al., 2000; Hu, 2014;
Nawab et al., 2018). Higher concentrations of THMs in freshwater sediments may cause health related issues to human
due to the biotransformation of contaminants in the food chain (Yi et al., 2011; Alamdar et al., 2016).
Fish play an important role in a balanced diet of human due to the presence of macronutrient like vitamins, good quality
protein, carbohydrates, omega-3 and omega-6 fatty acids and polyunsaturated fatty acids and as well as micro nutrients
including zinc (Zn), copper (Cu), selenium (Se) and iron (Fe) (Mishra et al., 2007; Tacon and Metian, 2013; Domingo, 2016).
The consumption of fish have many advantages related to health and might reduce the risk of acquiring cardiovascular
and neurological diseases (Raatz et al., 2013; Oliveri Conti et al., 2015). But due to the natural and anthropogenic activities,
the accumulation of THMs in fish tissues has been increased globally and created serious risk for public health (Olmedo
et al., 2013; Malik et al., 2014). In aquatic ecosystem, the metals are released and further dissolved in water and the
fish bio-accumulate these THMs after absorbing them from body parts such as gills, alimentary canal and skin. Fish
can also be exposed to THMs via metals contamination including point and non point food sources (Squadrone et al.,
2013; Negi and Maurya, 2015). In addition the biotic and abiotic features of the ecosystem, such as age, sex, size, history
and life cycle, nourishing habits, water quality parameters (e.g. acidity), and exposure duration to THMs are the key
factor responsible for the accumulation of toxic metals in fish organs and muscles (Velusamy et al., 2014; Farahani et al.,
2015; Maktabi et al., 2015). Moreover, seasonal and biological variations cause fluxes in the levels of THMs within fish
organs (Dadar et al., 2016). Globally, fish is a preferred dietary option because of its nutritional value and availability,
so it is essential to investigate the THMs concentrations in water, sediments and their bioaccumulation in economically
and commercially important fish species. In developing countries like Pakistan, THMs are released to the water bodies
without proper screening and treatment which can be hazardous to aquatic ecosystem and human beings are consuming
the aquatic species nearby as food sources. Therefore, it is of vital importance to monitor the contaminants in fish and
fishery foodstuffs in aquatic environment for consumers. To date, no scientific research has been conducted so far covering,
the rural and urban areas along the whole Swat River basin in terms of investigating simultaneously the drinking water
quality, sediment quality and the bioaccumulation potential of THMs (Cd, As, Pb, Cr, Ni, Cu and Zn) in the tissues of five
important both ecologically (key species of the river) and economically (potential source of human diet) freshwater fish
species. Furthermore the sediments pollution risk indices and health risk (carcinogenic and non-carcinogenic) associated
with drinking water from the river and consuming fish tissues were also investigated in this research work. This research
work could help us to understand the enrichment behavior of THMs variation in river ecosystems and how we can protect
this fragile environment from further contamination.
2. Material and methods
2.1. Study area
Swat is considered to be a mini Switzerland on Earth. Swat River is in the northern parts of Khyber–Pakhtunkhwa
province, Pakistan. Its main sources lie in the Hindukush Mountains fed mainly by glacier water throughout the year. In
Kalam valley the Swat River joined Utror River and Ushu River. The river than flows in the direction of the south and
further it joins the Gabral, Daral and Bashigram streams respectively. It then passes through the entire District Swat and
enters District Dir at Chakdara and then joins River Panjkora at lower Dir and passes through Malakand Agency, District
Charsadda and finally enters into the mouth of River Kabul at Nissata point. The total length of Swat River is 240 kilometers
M. Liu, Y. Xu, J. Nawab et al. / Environmental Technology & Innovation 17 (2020) 100554 3
Fig. 1. Swat River location map showing the sampling location.
(149 miles) and Basin 14,000 km2 (5405 square miles). Numerous micro hydro-electric power (MHP) projects are operated
along the Swat River which produces power for local usage. The upper, central and lower Swat valleys lie towards the
south of the Swat Kohistan. The upper stream portion of the river is narrow while the central and lower portions are
wide open and passes through densely inhabited towns and farming fields irrigating large areas of District Swat and
District Charsadda (Fig. 1). Swat River serves as a tourist spot and permanent fishery hotspot throughout the year, from
which the majority of the local people generate income for their livelihood. The upstream portion of the river (Kalam and
Behrain), a world famous tourist spot and attracts tourists not only from Pakistan but also from different parts of the globe.
Nowadays, water pollution is a serious problem in Swat River due to unplanned urbanization, industrialization, intensive
agricultural practices, tourism, emission and discharge of the waste from the municipality and hotels built on river banks.
The developments result the contamination of drinking water, sediment quality and also the aquatic ecosystem that is
considered food sources of the community. So it is necessary to highlight this serious issue on local level as well as through
scientific research to the international community and readers worldwide.
2.2. Sampling, extraction and analysis
Samples of river water, bed sediment and fish were collected from the five locations of the study area in June 2016,
including S1 (Upstream Bahrain), S2 (Upstream Mingora), S3 (Downstream Landakey), S4 (Downstream Batkhela) and S5
(Downstream Charsadda) as shown in Fig. 1. The water samples were filtered using Cellulose Acetate (CA) Syringe Filters,
(0.45 µm) on the spot and stored at 4 ◦ C. Bed sediments (0–20 cm) were collected by galvanized steel soil sampler with
a 0.5′′ core diameter. After being transported to the laboratory, the samples were air-dried in the dark to reduce water
content. Further, they were powdered using round ball mill and then sieved through a 2 mm Nylon mesh. The sieved
samples were then stored in zip bags at room temperature before further analysis. The bed sediment samples of (0.5 g)
were microwave digested with a mixture of different acids including hydro fluoric acid (HF), nitric acid (HNO3 ) and per
chloric acid (HClO4 ) according to the standard procedure adopted by Nawab et al. (2016b).
Fish samples such as Tor macrolepis, Glyptothorax stocki, Cyprinus carpio, Cirrhinus mrigala, Schizothorax plagiostomus
were purchased from native fishermen at each sampling spot (S1 to S5) and were directly transported from the field to
laboratory and stored at −18 ◦ C. Normally people prefer to intake fish tissues for nutritional value thus, round about
50–100 g of dorsal muscles were taken from each fish and were freeze-dried for further processing. Fish tissue samples
(1.0 ± 0.02 g) were acid digested using Teflon digestion beakers to which, 10 ml of ultra-pure HNO3 were added before
being heated up to 100 ◦ C, and further a solution mixture of 4 mL (HNO3 :HF) at 1:1 (v/v) was added for microwave
digestion. Three steps are necessary for microwave digestion: 0.5 MPa for 1 min, 1.0 MPa for 2 min, and 1.5 MPa for 3
min. After the digestion procedure, the digested samples were filtered and moved to volumetric flasks and Milli-Q water
were added up to 50 mL (Yi et al., 2011).
2.3. Instrumental analysis and quality assurance
For instrumental analysis the Pb and Cd in all sediments and water samples were analyzed through Inductively Coupled
Plasma Mass Spectrometer ICP-MS (Agilent Technologies, 7500 CX, USA). While Cr, Cu, Ni and Zn concentrations were
measured by Inductively Coupled Plasma Atomic Emission Spectroscopy ICP-AES (Model Plasma AtomCom MK II from
Jarrell-Ash, Franklin, MA, USA). As concentrations in water, sediments and fish tissues were determined using Atomic
Fluorescence Spectrometry (AFS, 610A, Beijing Ruili Analytical Instrument Company, China). In fish tissue, Zn, Ni and Cu
were measured completely by ICP-AES, whereas Cd, Cr and Pb were determined through ICP-MS. In sediments samples,
dilutions (up to 10,000) were essential for some analytes due to its originally high concentrations. The investigative quality
control comprised analyzing the reagent blank, parallel sample and standard reference material for soil (GSS-8, GSS- 9,
GSS-14, and GSS-15) to verify the stability of the equipment. All the analyses were performed in triplicate in the Institute
of Urban Environment Chinese Academy of Sciences (CAS), Xiamen China.
2.4. Sediment risk assessment
Worldwide various indices are used to assess and measure THMs pollutions in soil and sediments (Haris et al., 2017).
Pollution indices are considered as a tool regarding THMs pollution in sediments (Dung et al., 2013; Mazurek et al.,
2017). Pollution indices identify environmental risks along with soil and sediments quality degradations (Caeiro et al.,
2005) and whether these THMs accumulated in environment either from natural or anthropogenic sources (Caeiro et al.,
2005). Pollution indices further require geochemical reference data to tell the difference between natural and abnormal
concentrations (Reimann and Garrett, 2005). In this study, pollution indices used for assessing level of pollutants were
contamination factor (CF), geo-accumulation index (Igeo), enrichment factor (EF), ecological risk index (Eri), contamination
degree (CD) and potential ecological risk index (RI).
2.5. Contamination factor (CF)
The CF index was developed for sediments quality assessment by Hakanson (1980). CF can be calculated by the
following Eq. (1):
Csm
CF = (1)
Cbm
Where ‘Csm ’ represents mean concentrations of observed THMs in contaminated site and ‘Cbm ’ mean concentrations in
background site. The different categories of classifications are: low level (CF < 1), normal level (1 ≤ C < 3), considerable
level (3 ≤ CF < 6) and excessive level CF > 6 (Mmolawa et al., 2011; Chen et al., 2005; Hakanson, 1980).
2.6. Geo-accumulation index (Igeo)
Igeo is used to evaluate THMs concentrations quantitatively in sediments and also used to assess THMs risk in aquatic
environment (Muller, 1969). Igeo is calculated according to the following Eq. (2):
Cn
Igeo = log2 ( ) (2)
1.5Gb
Where ‘Cn’ is the concentrations of each THMs in contaminated site and ‘Gb’ is the concentrations in background site.
The factor 1.5 is the background matrix factor due to lithogenic effects. The Igeo can be used as a tool to separate sediments
quality in different classes: safe level (Igeo < 0), safe to normal level (0≤ Igeo < 1), normal level (1≤ Igeo < 2), normal to high
level (2≤ Igeo < 3), high level (3≤ Igeo < 4), high to excessive level (4≤ Igeo < 5), excessive level Igeo > 5 (Hu et al., 2019;
Muller, 1969).
2.7. Contamination degree
The THMs contamination degree in soil was considered according to Hakanson (1980). The contamination degree was
calculated using the following Eq. (3).
n
∑
CD = CFi (3)
i=1
Where n represents the types of THMs analyzed and CFi is the contamination factor for each metal in the study area.
2.8. Enrichment factor (EF)
EF measured the possible impacts of anthropogenic activities on sediments quality. Some metals tend to have lower
anthropogenic origin such as Fe, Al, Ca, Ti, Sc and Mn. They are used as conservative elements. EF can be calculated
according to Eq. (4):
( Metal )
sample
EF = ( MetalFe) (4)
Fe
Background
Where ‘ Metal sample’ in contaminated site and ‘ Metal

( ) ( )
Fe Fe
Background’ means the ratio between specific metal of interest
concentration and Fe concentration. EF have four classes; low level enrichment (EF < 2), moderate enrichment (2 ≤ EF
< 5), significant enrichment (5 ≤ EF < 20), Excessive enrichment 20 ≤ EF < 40 (Sutherland, 2000; Zoller et al., 1974).
Whenever, the EF values between 0.5–1.5 indicates the metal detected is from natural origin, if the values are above 1.5,
then it is possible that the metals in the sediments is from anthropogenic origin Elias and Gbadeges in 2011.
2.9. Ecological risk indices
The Eri and RI help to assess ecological risks caused by THMs concentrations in sediments and are expressed as follows:
Eri = Tri × CF (5)
n
∑
RI = Eri (6)
i=1
Where ‘Tri ’ means toxic response coefficient for each THMs; ‘CF ’ contamination factor. There are five classes for sediment
quality: low ecological risk (Eri < 40), normal ecological risk (40≤Eri < 80), considerable ecological risk (80≤Eri < 160),
high ecological risk (160≤Eri < 320) and excessive ecological risk Eri > 320 (Brady et al., 2015; Soliman et al., 2015). The
toxic response coefficients were 5, 30, 10, 2, 5, 5, and 1 for Pb, Cd, As, Cr, Ni, Cu and Zn respectively (Hu et al., 2019;
Maanan et al., 2015). RI is the sum of individual potential ecological risks caused by THMs based on which, the risk level
can be evaluated: low ecological risk (RI < 95), normal ecological risk (95 ≤ RI < 190), considerable ecological risk (190
≤ RI < 380), excessive ecological risk RI > 380 (Lin et al., 2017; Malvandi, 2017).
2.10. Health risk assessment
To assess the human health risk due to fish and water consumption, the Target Hazard Quotient (THQ) concept was
followed according to (Yi et al., 2011). The detail formulas and equations regarding HQ and THQ for water are provided
in supporting information (S1). Non-carcinogenic risks to human health via consumption of fish were evaluated on the
basis of non-carcinogenic risk index THQ was calculated as the ratio between exposure and the reference dose (Copat
et al., 2012), using the formula reported by Ahmed et al. (2015)
THQ = [(EFr×ED×FIR×CM)/(RfoD×BW×AT)]×10−3 (7)
Where exposure frequency (EF) (365 days/year), exposure duration (ED) (60 years), concentration of metal (CM) in fish
(mg/kg, ww), oral reference dose (RfoD) (mg kg−1 day−1 ) is based on USEPA (2010), average time (AT) for non-carcinogenic
(365 days/year × number of contact years, supposing 60 years, Fish ingestion (FIR) (100 g person−1 day−1 ) for fisherman
and (10 g person−1 day−1 ) for local people, average body weight (BW) for adult consumer was 60 kg (Eqani et al., 2013).
The total TTHQ (Total Target Hazard Quotient) was adopted to assess the combined influence of two or more THMs. TTHQ
values were designed according to Eq. (8).
TTHQ = THQCd + THQNi + THQCr + THQAs + THQZn + THQCu + THQPb (8)
The carcinogenic risk for As, Cr and Pb can be calculated by using their cancer slope factor (CSF) from Integrated Risk
Information System (USEPA, 2010), while for other THMs the CSF is not available.
[(EFr×ED×FIR×C×CSF)]
Carcinogenic risk = ×10−6 (9)
BW × AT
Carcinogenic risks were measured as the incremental probability of an individual to develop cancer over a lifetime
exposure and acceptable risk levels for carcinogens range from 10−4 (risk of developing cancer over a human lifetime
is (1 in 10,000) to 10−6 (1 in 1,000,000).
2.11. Statistical analysis
Statistical Package for the Social Sciences (SPSS) version 21 and Microsoft Excel, version 2010 were used for calculation,
whereas the study area location map was prepared via Arc-GIS computer software. The graphs were prepared in Origin
lab (16).
3. Results and discussion
3.1. Heavy metal(loids) concentration in surface water
Freshwater resources contamination pose threat to local people consuming that water on daily basis, meanwhile the
drinking water is considered as the main route of human exposure to THMs. Among the THMs in Swat River the average
concentration of Pb in water was observed in upstream (0.45 and 0.71 µg L−1 ) and downstream (5.90, 8.32 and 49.0 µg
L−1 ), for Cd upstream (0.90 and 0.41 µg L−1 ) and downstream (2.82, 3.90 and 9.12 µg L−1 ), for As upstream (0.02 and
0.39 µg L−1 ) and downstream (0.83, 0.97 and 1.10 µg L−1 ), for Cr upstream (6.62 and 8.21 µg L−1 ) and downstream
(9.91, 15.2, 34.0 µg L−1 ), for Ni upstream (5.93 and 6.80 µg L−1 ) and downstream (7.82, 9.70 and 10.1 µg L−1 ), for Cu
upstream (0.98 and 2.40 µg L−1 ) and downstream (5.22, 8.92, and 9.70 µg L−1 ) and for Zn upstream (14.2 and 38.1) and
downstream (57.3, 71.0 and 94.4 µg L−1 ) respectively as shown in Table 1. In the study area, the THMs concentrations
in upstream were found in the direction of Zn > Cr > Ni > Cu > Cd > Pb > As while, in downstream, the direction was
Zn > Pb > Cr > Ni > Cu > Cd > As. Comparatively the concentrations of THMs such Pb, Cd, As, Cr, Ni, Cu and Zn was
recorded lower in the upstream portion, while highest in the downstream portion of Swat River. The overall average
loads of THMs in both upstream and downstream water are summarized in Fig. 2A. Among the THMs in Swat River the
Cd concentration at downstream portion (30%) exceeded the safety guideline values of WHO, while the remaining were
within the safety guideline values. The people consuming river water in the downstream portion were facing some kidney
problems and as well as some birth defects. High concentrations and exposure to Cd in drinking water was associated with
prolonged renal failure (Gobe and Crane, 2010). Henson and Chedrese (2004) described the relationship of Cd exposure
through gestation with early birth and reduced natal weights. Furthermore the diseases such as cardiovascular, anemia,
osteoporosis, anosmia (loss smell senses), kidneys complications and hypertension may also lead to prolonged exposure
to Cd (Yoshida et al., 1999; ATSDR, 2015).
Furthermore all the THMs such as (Ni, As, Cu, Zn, Pb and Cr) were within the safety limits of WHO and Pak-EPA in
both upstream and downstream portion of Swat River. The pollution in the downstream might be due to geogenic (mafic
and ultramafic rocks) and anthropogenic activities including industrialization, municipal water, pesticides application,
wastewater from farm fields, sewage sludge, automobile workshops, mining effluents, hotels effluents and urban districts
including (Charsadda, Malakand Agency and Swat) located near Swat River. The drinking water sources (surface water and
groundwater) have the potential to be contaminated by THMs (Nawab et al., 2016a; Bryan and Langston, 1992). Previous
studies have documented the THMs contamination in drinking water sources and its associated effects (Liu et al., 2009,
2011; Nawab et al., 2016a; Montuori et al., 2013; Volety, 2008). The trace elements such as Cd, As, Pb, Cu, Cr, Ni, and
Hg are of main concern as compared to other metals, mostly due to their existence at moderately high levels in drinking
water and their effects on public health (ATSDR, 2015). Among the trace elements Cd can cause damage to kidney and also
carcinogenic whereas, arsenic is related to skin damage and cancer risk. Further blood cholesterol, heart diseases, liver
and kidney damages can be related to Ni and Cr, anemia is linked with Pb and excess of Zn was related to dehydration,
vomiting and dizziness, while intestinal disorder and hypotension was related to Cu (ATSDR, 2015; USEPA, 2015)
3.2. Health risk assessment from THMs
3.2.1. Average daily intake

The average daily intakes (ADIs) of drinking water consumption of the selected THMs such as Pb, Cd, As, Cr, Ni,
Cu, Zn in upstream (S1) for children the values were 1.3×10−2 , 2.7×10−2 , 6.1×10−4 , 2.0×10−1 , 1.8×10−1 , 2.9×10−2 ,
4.2×10−1 µg kg−1 -day respectively. For adults the values were 1.2×10−2 , 2.5×10−2 , 5.5×10−4 , 1.8×10−1 , 1.6×10−1 ,
2.7×10−2 , 3.8×10−1 µg kg−1 -day respectively as shown in Table 1. In upstream (S2) the values of ADIs via drinking
water consumption of the same THMs for children were 2.1×10−2 , 1.2×10−2 , 1.1×10−2 , 2.5×10−1 , 2.×10−1 , 7.3×10−2 ,
1.6×10−1 µg kg−1 -day similarly, for adults were 9×10−2 , 1.1×10−2 , 1×10−2 , 2.2×10−1 , 1.8×10−1 , 6.6×10−2 , 5.5×10−2
µg kg−1 -day respectively. In downstream (S3) the ADI values for children via drinking water consumption of the same
THMs were 1.8×10−1 , 8.5×10−2 , 2.5×10−2 , 3.0×10−1 , 2.3×10−1 , 1.5×10−1 , 1.7×101 µg kg−1 -day. Similarly for adults,
the values were 1.6×10−1 , 7.7×10−2 , 2.3×10−2 , 2.7×10−1 , 2.1×10−1 , 1.4×10−1 , 1.5×101 µg kg−1 -day as shown in
Table 1. In downstream (S4) for children the ADI values via drinking water consumption for Pb, Cd, As, Cr, Ni, Cu, Zn were
2.5×10−1 , 1.1×10−1 , 2.9×10−2 , 4.5×10−1 , 2.9×10−1 , 2.7×10−1 , 2.1×101 µg kg−1 -day. Moreover, for adults the values
Table 1
Toxic heavy metal(loids) average concentrations in water (ug L−1 ) and its associated health risk in Swat River, Pakistan.
Study area Parameters Average (ug/L) ADI RFD HQ
Children Adults Children Adults
−2 −2 −4
S1 (Upstream) Pb 0.45 1.3 × 10 1.2 × 10 36.0 3.8 × 10 3.4×10−4
Cd 0.90 2.7 × 10−2 2.5 × 10−2 0.50 5.5 × 10−2 5.1×10−2
As 0.02 6.1 × 10−4 5.5 × 10−4 0.30 2.0 × 10−3 1.8×10−3
Cr 6.62 2.0 × 10−1 1.8 × 10−1 1500 1.3 × 10−4 1.2×10−4
Ni 5.93 1.8 × 10−1 1.6 × 10−1 20.0 9.0 × 10−3 8.1×10−3
Cu 0.98 2.9 × 10−2 2.7 × 10−2 37.0 8.0 × 10−4 7.3×10−4
Zn 14.2 4.2 × 10−1 3.8 × 10−1 300 1.4 × 10−3 1.2×10−3
THQ = 6.8 × 10−2 THQ = 6.2 × 10−2
S2 (Upstream) Pb 0.70 2.1 × 10−2 9.0 × 10−2 36.0 5.9 × 10−4 5.4×10−4
Cd 0.41 1.2 × 10−2 1.1 × 10−2 0.50 2.4 × 10−2 2.2×10−2
As 0.39 1.1 × 10−2 1.o × 10−2 0.30 3.9 × 10−2 3.6×10−2
Cr 8.21 2.5 × 10−1 2.2 × 10−1 1500 1.6 × 10−4 1.5×10−4
Ni 6.80 2. × 10−1 1.8 × 10−1 20.0 1.0 × 10−2 9.4×10−3
Cu 2.40 7.3 × 10−2 6.6 × 10−2 37.0 1.9 × 10−3 1.8×10−3
Zn 38.1 1.6 × 10−1 5.5 × 10−2 300 3.8 × 10−3 3.5×10−3
THQ = 8.1 × 10−2 THQ = 7.3 × 10−2
S3 (Downstream) Pb 5.91 1.8 × 10−1 1.6 × 10−1 36.0 5.0 × 10−3 4.5×10−3
Cd 2.82 8.5 × 10−2 7.7 × 10−2 0.50 1.7 × 10−1 1.5×10−1
As 0.83 2.5 × 10−2 2.3 × 10−2 0.30 8.4 × 10−2 7.6×10−2
Cr 9.91 3.0 × 10−1 2.7 × 10−1 1500 2.0 × 10−4 1.8×10−4
Ni 7.82 2.3 × 10−1 2.1 × 10−1 20.0 1.1 × 10−2 1.13×10−2
Cu 5.22 1.5 × 10−1 1.4 × 10−1 37.0 4.2 × 10−3 3.9×10−3
Zn 57.3 1.7 × 101 1.5 × 101 300 5.8 × 10−3 5.2×10−3
THQ = 2.8 × 10−1 THQ = 2.5 × 10−1
S4 (Downstream) Pb 8.32 2.5 × 10−1 3.0 × 10−1 36.0 7.0 × 10−3 6.4×10−3
Cd 3.90 1.1 × 10−1 1.0 × 10−1 0.50 2.3 × 10−1 2.1×10−1
As 0.97 2.9 × 10−2 2.6 × 10−2 0.30 9.8 × 10−2 8.9×10−2
Cr 15.1 4.5 × 10−1 4.1 × 10−1 1500 3.0 × 10−4 2.7×10−4
Ni 9.70 2.9 × 10−1 2.6 × 10−1 20.0 1.4 × 10−2 1.3×10−2
Cu 8.92 2.7 × 10−1 2.4 × 10−1 37.0 7.3 × 10−3 6.6×10−3
Zn 71.0 2.1 × 101 1.9 × 101 300 7.2 × 10−3 6.5×10−3
THQ = 3.7 × 10−1 THQ = 3.3 × 10−1
S5 (Downstream) Pb 49.0 1.4 × 101 3.6 × 10−1 36.0 4.1 × 10−2 3.7×10−2
Cd 9.12 2.7 × 10−1 2.5 × 10−1 0.50 5.5 × 10−1 5.1×10−1
As 1.10 3.3 × 10−2 3.0 × 10−2 0.30 1.1 × 10−1 1.0×10−1
Cr 34.0 1.0 × 101 9.4 × 10−1 1500 6.9 × 10−4 6.2×10−4
Ni 10.1 3.0 × 10−1 2.7 × 10−1 20.0 1.5 × 10−2 1.3×10−2
Cu 9.70 2.9 × 10−1 2.6 × 10−1 37.0 8.0 × 10−3 7.2×10−3
Zn 94.4 2.8 × 101 2.6 × 101 300 9.5 × 10−3 8.7×10−3
THQ = 7.3 × 10−1 THQ = 6.7 × 10−1
were 3×10−1 , 1.0×10−1 , 2.6×10−2 , 4.1×10−1 , 2.6×10−1 , 2.4×10−1 , 1.9×101 µg kg−1 -day. In downstream (S5) area for
children the ADI values via drinking water consumption of Pb, Cd, As, Cr, Ni, Cu, Zn were 1.4×101 , 2.7×10−1 , 3.3×10−2 ,
1.0×101 , 3.0×10−1 , 2.9×10−1 , 2.8×101 µg kg−1 -day, while for adults the values were 3.6×10−1 , 2.5×10−1 , 3.0×10−2 ,
9.4×10−1 , 2.7×10−1 , 2.6×10−1 , 2.6×101 µg kg−1 -day respectively presented in Table 1. Among the THMs (Pb, Cd, As, Cr,
Ni, Cu and Zn) the highest ADI values were recorded at downstream portion for both children and adults due to higher
concentrations of THMs than upstream portion.
3.2.2. Hazard quotient (HQ) and total hazard quotient (THQ)

Table 1 summarizes the HQ and THQ values of As and THMs via drinking water consumption in Swat River. In
upstream (S1), the lowest HQ values for Pb, Cd, As, Cr, Ni, Cu, Zn were observed for children via surface water
consumption 3.8×10−4 , 5.5×10−2 , 2.0×10−3 , 1.3×10−4 , 9.0×10−3 , 8.0×10−4 , 1.4×10−3 . For adults, the values were
3.4×10−4 , 5.1×10−2 , 1.8×10−3 , 1.2×10−4 , 8.1×10−3 , 7.3×10−4 , 1.2×10−3 respectively. Similarly in downstream (S5), the
highest HQ values for the same THMs were observed for children via surface water consumption 4.1×10−2 , 5.5×10−1 ,
1.1×10−1 , 6.9×10−4 , 1.5×10−2 , 8.0×10−3 , 9.5×10−3 and for adults, the values were 3.7 ×10−2 , 5.1×10−1 , 1.0×10−1 ,
6.2×10−4 , 1.3×10−3 , 7.2×10−3 , 8.7×10−3 respectively as shown in Table 1. Moreover the THQ values in upstream portion
for children were (6.8×10−2 and 8.1×10−2 ) and for downstream were (2.8×10−1 , 3.7×10−1 and 7.3×10−1 ) while for
adults, the values for upstream and downstream were (6.2×10−2 and 7.3×10−2 ) and (2.5×10−1 , 3.3×10−1 and 6.7×10−1 )
respectively. The HQ values of THMs in the study area for both children and adults were found in the direction of Cd >As >
Ni > Pb > Cu > Zn > Cr. Moreover the THQ values for both adults and children showed that downstream portion represent
greater risk as compared to upstream portion of Swat River as shown in Table 1.
Fig. 2. Average load of THMs in Swat River (A) water (ug L−1 ) (B) sediments (mg kg−1 ) and (C) fish tissues (mg kg−1 ).
In the study area both the HQ and THQ values were lowest for both children and adults in the upstream area, while
highest in the downstream area of Swat River. These high values of HQ and THQ is mainly due to the high concentrations of
THMs in downstream area which is mainly due to domestic discharge from urban population, municipal wastes, intensive
agricultural practices, mining, smelting and industrial waste discharge directly to the river. The HQ and THQ values were
observed to be lower than 1 indicating no health risk from the consumption of surface water in the study area (USEPA,
1999; Nawab et al., 2016a). Moreover, the HQ values for Cd was observed higher while for Pb, Cr, Ni, Cu and Zn was lower
when compared with Mohammed et al. (2011) surface and groundwater of Kohistan region. While the HQ values for all
the THMs were observed higher when compared with that in Kavcar et al. (2009).
3.3. Sediment risk assessment and pollution indices
The basic descriptive statistical values and distribution patterns of the studied THMs in upstream and downstream
portion along with the reference values of USEPA (1999), WHO (2004) and CCME (1999) are presented in Table 2. The
overall average loads of THMs in the sediments of both upstream and downstream are presented in Fig. 2B. The sediment of
Swat River is sandy loam (sand: 82.04 ± 1.15%, silt: 8.10 ± 0.61%, clay: 7.07 ± 1.08%) with low organic matter percentage
of (2.91 ± 1.04%). Arsenic (As) is a non-essential and toxic element released from different sources including manmade and
natural. In Swat River the mean concentration of As in upstream were 0.00036 and 0.0085 mg kg−1 and in downstream
were 0.017, 0.055 and 0.086 mg kg−1 . The highest concentration value of As (0.18 mg kg−1 ) was observed in downstream
and the lowest (0.00009 mg kg−1 ) was observed in upstream. In case of As, no safety limits has been set for sediments
by USEPA (1999), WHO (2004) and CCME (1999). Cd is also a non-essential and toxic element which is released into
the environment through metals industries, power plants, atmospheric deposition, weathering of parent rocks, phosphate
fertilizers usage, municipal solid waste burning, treatment plants and toxic wastes released from industrial sectors (WHO,
2010; Ghrefat et al., 2011; ATSDR, 2012; Abdullah et al., 2015). The mean concentrations of Cd in the upstream of the
river were 0.0062 and 0.0093 mg kg−1 and downstream were 0.023, 0.14 and 0.27 mg kg−1 respectively. Maximum
concentration of Cd (0.38 mg kg−1 ) was observed in downstream, which was almost near to USEPA (1999), WHO (2004)
and CCME (1999) safety limits. This high concentration may be due to the discharge from numerous industries in Dragai,
Table 2
Toxic heavy metal(loids) range and mean concentrations (mg kg−1 ) in sediments of Swat River, Pakistan.
River Swat Statistics As Cd Pb Ni Cr Cu Zn
Mean 0.00036 0.0062 0.0039 0.0049 0.0082 0.0019 0.019
S1 (Upstream n = 8) Max 0.0057 0.017 0.0096 0.037 0.016 0.028 0.077
Min 0.00009 0.00015 0.00084 0.00071 0.00054 0.00047 0.0013
Mean 0.0085 0.0093 0.0067 0.0081 0.016 0.0058 0.037
S2 (Upstream n = 7) Max 0.017 0.066 0.049 0.074 0.057 0.060 0.099
Min 0.00041 0.00056 0.0018 0.00096 0.0071 0.0009 0.0068
Mean 0.017 0.023 0.0088 0.025 0.058 0.0069 0.076
S3 (Downstream n = 9) Max 0.052 0.088 0.073 0.081 0.073 0.084 0.12
Min 0.0029 0.0017 0.0039 0.0054 0.008 0.0015 0.0091
Mean 0.055 0.089 0.081 0.048 0.079 0.0094 0.094
Min 0.0064 0.0058 0.0066 0.0072 0.009 0.0035 0.048
Mean 0.086 0.27 0.23 0.066 0.095 0.018 0.12
Min 0.042 0.061 0.029 0.011 0.037 0.0092 0.087
USEPA (1999) – 0.6 40 16 25 16 110
WHO (2004) – 0.6 – 20 25 25 123
CCME (1999) – 0.6 35 – 37.3 37.7 123
Charsadda and Batkhela. Phosphate fertilizers usage, mafic and ultramafic rocks might also be the possible sources of Cd
contamination in the Swat River.
Similarly, Pb also originates from natural and anthropogenic sources. Most important sources consist of automobile
emissions, volcanic eruption, timberland fires, incineration of waste, industrial waste, pesticides and paint industries
containing Pb (ATSDR, 2007; Abdullah et al., 2015). In the current study, the mean Pb concentration values in upstream and
downstream were 0.0039 and 0.0067 mg kg−1 and 0.0088, 0.081 and 0.23 mg kg−1 , respectively. Highest concentration
of Pb (0.30 mg kg−1 ) was found in downstream of the river. Moreover the concentration of Pb at each sampling sites
were within USEPA (1999) and CCME (1999) safety guideline values. Similarly the total mean concentration of Ni in
the upstream was 0.0049 and 0.0081 mg kg−1 and in downstream was 0.025, 00048 and 0.066 mg kg−1 . The highest
concentration value of Ni (0.15 mg kg−1 ) was again observed in downstream of the river. However, all the Ni values were
within the USEPA (1999) and WHO (2004) safety limits. The Ni concentration in Swat River may be due to the effluents
released without treatment from Ghee industries located in Dargai and Charsadda area. The mean concentration of Cr
in Swat River sediments in upstream were 0.0082 and 0.0058 (mg kg−1 ) and in downstream were 0.0069, 0.0094 and
0.018 (mg kg−1 ) respectively, as shown in Table 2. The maximum Cr concentration value (0.24 mg kg−1 ) was found in
downstream and the lowest (0.00054 mg kg−1 ) in upstream of the river. All the Cr values were within the permissible
limits of USEPA (1999), WHO (2004) and CCME (1999).
For aquatic life Cu is an essential micronutrient, but the concentration higher than background makes the metal toxic.
It also originates from natural (forest fire, volcanoes and plants decomposition) and manmade (fertilizers, pesticides,
municipal and industrial wastewater) activities (Eisler, 2000; ATSDR, 2004; Nordberg et al., 2007). In aqueous solution,
the solubility of Cu is low and easily to be adsorbed on water-borne suspended units. Subsequently, a series of natural
processes take place and the water-borne Cu lastly adds in the sediment which finally reflects the degree of pollution in
aquatic ecosystem. The average concentration of Cu in upstream was 0.0094 and 0.0058 (mg kg−1 ) and in downstream
was 0.0069, 0.0094 and 0.18 (mg kg−1 ). Highest concentration of Cu (0.0094 mg kg−1 ) was observed in the downstream
which also did not exceeded the USEPA (1999), WHO (2004) and CCME (1999) safety limits. On the other hand, potential
sources of Cu in the sediments of Swat River may be due municipal solid waste dumping, fossil fuels combustion, steel
and welding industry and local wastewater release without proper treatment from different populated areas of Khyber
Pakhtunkhwa, Pakistan.
The mean concentration of Zn in the upstream and downstream portions were 0.019 and 0.037 (mg kg−1 ) and 0.076,
0.094 and 0.12 (mg kg−1 ) respectively, as shown in Table 2. Highest concentration of Zn (0.26 mg kg−1 ) was observed in
downstream which was considerably lower than USEPA (1999), WHO (2004) and CCME (1999) permissible limits. The Zn
also originates from natural and human activities. Fertilizer application to farmland crops in the catchment area of Swat
River is a common practice, which could contribute to the Zn concentrations in the sediments throughout the Swat River,
Pakistan. The total concentrations of all the THMs in Swat River sediments, at each sampling locations, were within the
safe limits set by USEPA (1999), WHO (2004) and CCME (1999).
Table 3 represents the contamination factor (CF), geo-accumulation index (Igeo ), contamination degree (CD), enrichment
factor (EF), ecological risk index (Eri) and potential ecological risk (RI) for THMs in Swat River, Pakistan. In this study
upstream (S1) site is considered as reference site due to their safe/low level metals concentrations. The minimum CF value
0.4 was observed for Cd and highest 109 was observed for Pb in Swat River. Moreover, CF values in terms of THMs were in
order of Pb > As > Cu > Zn > Cd > Cr > Ni, respectively as shown in Table 3. CF values showed higher contamination level as
compared to other studies conducted by Alahabadi and Malvandi (2018) and Chetty and Pillay (2019). The anthropogenic
Table 3
Potential toxicity and sediment pollution indices of Swat River, Pakistan.
CFa Pb Cd As Cr Ni Cu Zn CDe
S2 (Upstream) 1.5 0.4 19.5 1.2 1.1 2.4 2.7 29.0
S3 (Downstream) 13.1 3.1 41.5 1.5 1.3 5.3 4.07 69.9
S4 (Downstream) 18.4 4.3 48.5 2.3 1.6 9.08 5.07 89.3
S5 (Downstream) 109 10 55 5.1 1.7 9.9 6.71 197
Ibgeo RIf
S2 (Upstream) 0.7 0.2 8.8 0.5 0.5 1.1 1.20 13.1
S3 (Downstream) 19.6 4.6 62.2 2.2 2.0 8.0 6.10 105
S4 (Downstream) 8.3 1.9 21.9 1.02 0.7 4.1 2.30 40.3
S5 (Downstream) 163.3 15 82.5 7.7 2.5 14.8 10.1 296
Efc
S2 (Upstream) 1.04 0.3 13 0.8 0.8 1.6 1.8
S3 (Downstream) 10.5 2.5 33.2 1.2 1.05 4.2 3.2
S4 (Downstream) 24.6 5.7 64.6 3.03 2.2 12.1 6.8
S5 (Downstream) 54.4 5 27.5 2.6 0.8 4.9 3.3
Eri
S2 (Upstream) 3.5 6.02 88.0 1.1 2.6 5.5 1.2
S3 (Downstream) 98.3 140 622 4.5 9.9 39.8 6.1
S4 (Downstream) 41.6 58.7 219 2.05 3.71 20.5 2.3
S5 (Downstream) 817 450 825 15.4 12.7 74.2 10.1
Where Cfa (Contamination factor), Igeo b (Geo-accumulation Index), Efc (Enrichment factor), Erid (Potential ecological risk index for single metal), CDe
(Contamination degree), RIf (Potential ecological risk index).
activities such as industrial wastewater, mining and agriculture activities are responsible for river water and sediments
contamination (Alahabadi and Malvandi, 2018).
The Igeo results were interpreted according to the classification established by Muller (1969). The results indicated that
upstream of the river for Pb, Cd, Cr and Ni shows safe to normal level, Cu and Zn shows normal level and for As shows
excessive level of contamination. While on the other hand the downstream of the river for Pb, Cd, As, Cu and Zn shows
excessive level of contamination, for Cr shows high level of contamination and for Ni shows normal level of contamination.
The geo-accumulation index for THMs in upstream portion were found in order of As > Zn > Cu > Pb > Cr > Ni > Cd, while
for downstream portion the order were Pb > As > Cu > Cd > Zn > Cr > Ni. The studied river showed higher Igeo values
when compared with other studies conducted by Chabukdhara and Nema (2012) and Zahra et al. (2014). Furthermore
the results of Igeo values showed that Swat River is contaminated in terms of THMs (Chabukdhara and Nema, 2012). The
downstream portion showed multifold geo-accumulations indices as compared upstream portion and as well as the study
carried out by Pandey et al. (2019).
The levels of THMs contamination in particular locations and their source of contamination can be reflected from EF
values (Feng et al., 2004; Chen et al., 2007). The EF values varied from low (0.3; Cd) to high (64.6; As) enrichments.
Upstream of the river shows low to significant enrichment whether downstream shows low to excessive enrichment. The
EF values in upstream portion follow the order As > Zn > Cu > Pb > Cr >Ni > Cd in terms of THMs, while the downstream
portion follow the order As >Pb > Cu > Zn > Cd > Cr > Ni. The EF values in some other rivers also showed the level of
no pollution to moderate pollution as the study conducted in South Korea (Pandey et al., 2019). Chemical manufacturing
industries, plastic, and metals processing industries are responsible for THMs pollution (Tchounwou et al., 2012).
In Swat River, minimum CD value was observed for upstream of the river (29.05) and highest (296.02) for downstream
of the river. However, all the sites have excessive levels of contaminations. Further, CD values in downstream portion show
higher level of contamination when compared with other studies carried out by Laxmi Mohanta et al. (2019) and Nawab
et al. (2018).
3.4. Ecological risk assessments of sediments
The Eri value was calculated for seven THMs (As, Pb, Cd, Zn, Ni, Cr and Cu) and the details are listed in Table 3.
In the studied river, the lowest Eri value (1.1) was observed for Cr in upstream and highest (825) was observed for
As in downstream of the river. Generally, Eri for each observed THMs varied from low to considerable ecological risk
at upstream, while downstream shows low to excessive level of ecological risk. The Eri indicated that the severity of
contamination of the seven THMs were found in order of As > Cd >Pb > Cu > Ni > Zn > Cr for upstream, while for
downstream the order was As > Pb > Cd > Cu > Ni > Cr >Zn as shown in Table 3. Moreover Cd, As and Pb shows excessive
high level of ecological risk in the downstream (S5) site, while the rest of THMs shows low level Eri. The high level
ecological risk of As, Cd and Pb in sediments may be due to geogenic sources, industries and excessive uses of phosphate
fertilizers (Onoyima et al., 2011).
Table 4
Comparison of toxic heavy metal(loids) sediments load with other parts of the world.
Location As Cd Pb Ni Cr Cu Zn References
India – 1.7 26.7 26.7 69.9 29.8 67.8 Pandey and Singh (2017)
Iraq – 1.87 22.56 67.08 58.40 18.91 48.00 Salah et al. (2012)
South Africa – 0.0011 0.013 – 0.295 0.092 0.138 Edokpayi et al. (2016)
China – 3.78 23.1 20.5 74.7 – 238 Li (2014)
Bangladesh – 0.8 79.8 – 101.2 184.4 502.3 Saha and Hossain (2010)
Greece 1.4 <0.005 11.8 <8 – 70.0 185.2 Giouri et al. (2010)
Hungary ND 1.2 46.3 – 64.0 65.7 187 Woitke et al. (2003)
North Africa – 6.53 98.15 13.61 – 13.94 2252 Salem and Ayadi (2016)
Iran ND 6.85 162.0 ND ND 9.17 – Karbassi et al. (2008)
Pakistan 0.0333 0.0897 0.0660 0.0304 0.0096 0.0423 0.0692 Present study
The potential ecological risk index (RI) shows the risk produce by the THMs and their toxicity on aquatic communities.
In Swat River, the lowest RI value (13.1) was found for upstream and highest (296) was observed for downstream. RI
values range from low to moderate ecological risk in both upstream and downstream of the river, respectively as shown
in Table 4. The ecological risk for all the factors (RI) showed moderate risk for the downstream (S5) site, while low risk
for the remaining sites. Most of the populated and industrial sites of Swat River posed ecological risk. The downstream
(S5) of the river showed multifold ecological risk when compared with other sites and studies carried out by Shen et al.
(2019) and Looi et al. (2019).
3.5. Sediments comparison around the globe
Rivers sediments are the most important sinks for THMs adsorption (Diop et al., 2015). Metals are released into river
bodies through natural and anthropogenic process like erosion, weathering industrial release, domestic waste, municipal
waste and agricultural products uses (Rzetala, 2015; Pandey et al., 2013). Sediments contamination is one of the serious
environmental issues in Pakistan. In the present study the THMs concentration values were different at each sampling site.
The mean concentration value of As 0.0333 (mg kg−1 ) were below as compared to the study carried out by Giouri et al.
(2010). Cd concentration level with a mean value of 0.0897 (mg kg−1 ) was higher than the value in the study conducted
by Edokpayi et al. (2016) and Giouri et al. (2010) as shown in Table 4. Cd concentration in Swat River was lower than the
studies conducted by Pandey and Singh (2017), Salah et al. (2012), Li (2014), Saha and Hossain (2010), Woitke et al. (2003),
Salem and Ayadi (2016) and Karbassi et al. (2008). The concentration of Pb with a mean value of 0.0660 (mg kg−1 ) were
also higher than that documented in Edokpayi et al. (2016). Pb concentration remain lower than reported by Pandey and
Singh (2017), Salah et al. (2012), Li (2014), Saha and Hossain (2010), Giouri et al. (2010), Woitke et al. (2003), Salem and
Ayadi (2016) and Karbassi et al. (2008). Ni concentration level 0.0304 (mg kg−1 ) was considerably lower than Pandey and
Singh (2017), Salah et al. (2012), Li (2014), Giouri et al. (2010) and Salem and Ayadi (2016). Swat River was below from
the reference values. Cu concentrations with a mean value of 0.0423 (mg kg−1 ) were also lower than the given references
values. The highest Cu concentration value at downstream (S4) site was only higher than that in Edokpayi et al. (2016).
Zn concentration level 0.0692 (mg kg−1 ) was considerably lower than Pandey and Singh (2017), Salah et al. (2012), Saha
and Hossain (2010), Giouri et al. (2010), Woitke et al. (2003) and Salem and Ayadi (2016). Zn concentration level (0.26 mg
kg−1 ) in downstream (S5) site was only higher than that reported by Edokpayi et al. (2016). In the studied river, almost
all the THMs concentration levels were comparatively lower than the other parts of the world as shown in Table 4.
3.6. Toxic heavy metal(loids) concentrations in fish species
In human diet, fish plays an important role and intense interest has been shown by researchers in both quality and
safety aspects for human health (Murtala et al., 2012; Nawab et al., 2018). The THMs concentration in fish muscles is
usually lower as compared to other parts (Demirak et al., 2006). In aquatic ecosystem high concentrations of THMs
have caused severe community concerns worldwide, due to their bioaccumulation and transfer in food chains, as well
as adverse health problems in human (Baby et al., 2010; Yi and Zhang, 2012). Recently, significant attention has been
paid to widespread variety of chemical contaminants, comprising the THMs (EI-Demerdash and Elegamy, 1996; Olmedo
et al., 2013; Alamdar et al., 2016; Nawab et al., 2018). In present study the mean concentrations of Pb, Cd, As, Cr, Ni, Cu
and Zn in the fish muscles ranged from 0.004 to 0.083, 0.007 to 0.097, 0.002 to 0.018, 0.003 to 0.072, 0.0008 to 0.013,
0.003 to 0.009 and 0.01 to 0.07 mg kg−1 while the mean concentrations were 0.032, 0.036, 0.008, 0.024, 0.006, 0.0062
and 0.04 mg kg−1 respectively as shown in Table 5 and Fig. 2C. Among the THMs, the lowest concentration was observed
for Ni (0.006 mg kg−1 ) and Zn (0.04 mg kg−1 ) respectively as shown in Fig. 2C.
The mean concentration of THMs in fish muscles were followed in order of Zn > Cd > Pb > Cr > As > Cu > Ni. The
highest mean Pb concentration (0.083 mg kg−1 ) was observed in Cyprinus carpio and the lowest concentration (0.0041
mg kg−1 ) was observed in Glyptothorax stocki as shown in Table 5. Different regulatory authorities has set standards such
as Australian National Health and Medical Research Council (ANHMRC) allowed Pb concentration of 2.0 (mg kg−1 ) or
12
M. Liu, Y. Xu, J. Nawab et al. / Environmental Technology & Innovation 17 (2020) 100554
Table 5
Bioaccumulation of toxic heavy metal(loids) (mg kg−1 ) in important native fish species collected from Swat River, Pakistan.
Fish species Statistics Pb Cd As Cr Ni Cu Zn
Tor macrolepis (n = 7) Range 0.0027–0.043 0.0032–0.062 0.0073–0.018 0.0059–0.036 0.0015–0.0068 0.002–0.0051 0.006–0.068
Mean 0.0282 0.019 0.0091 0.011 0.0043 0.0035 0.015
Glyptothorax stocki (n = 5) Range 0.0013–0.0076 0.0063–0.012 0.00081–0.0069 0.0019–0.0048 0.00057–0.0019 0.003–0.0074 0.004–0.052
Mean 0.0041 0.0076 0.0025 0.0031 0.00083 0.005 0.01
Cyprinus carpio (n = 6) Range 0.0102–0.136 0.039–0.142 0.054–0.073 0.0124–0.055 0.0072–0.031 0.0066–0.017 0.009–0.114
Mean 0.083 0.097 0.018 0.020 0.009 0.0083 0.078
Cirrhinus mrigala (n = 5) Range 0.0078–0.039 0.0041–0.017 0.0026–0.0061 0.0082–0.064 0.009–0.047 0.004–0.007 0.061–0.095
Mean 0.015 0.008 0.0043 0.017 0.013 0.0052 0.076
Schizothorax plagiostomus (n = 7) Range 0.0087–0.061 0.0073–0.086 0.0013–0.027 0.004–0.009 0.002–0.0063 0.008–0.015 0.0072–0.039
Mean 0.034 0.051 0.0098 0.072 0.0039 0.0094 0.022
below on wet weight basis (wwb) and of 9.6 (mg kg−1 ) or below on dry weight basis (dwb) supposing the moisture
content of the fish meat up to 79% (Plaskett and Potter, 1979). While in Spanish and UK regulation, the maximum level of
Pb in fish should not exceed (9.6 mg kg−1 ) on (dry weight basis) (Demirak et al., 2006). The existent examination revealed
that Pb level were within the safety guideline for human consumption in all the investigated fish species.
Similarly, the highest mean Cd concentration (0.097 mg kg−1 ) was recorded in Cyprinus carpio and the lowest concen-
tration (0.007 mg kg−1 ) was recorded in Glyptothorax stocki. Cd concentration was compared with Spanish legislation
is (1.0 mg kg−1 ). The maximum allowable Cd level set by Australian National Health and Medical Research Council
(ANHMRC) in aquatic food is 2.0 (mg kg−1 ) However, Western Australian Authorities has suggested the level of 5.5 (mg
kg−1 ) for Cd (Plaskett and Potter, 1979). In Swat River the Cd concentration in all the fish muscles were within permissible
limits when compared with various regulatory authorities. Moreover, the highest As mean concentration (0.018 mg kg−1 )
was observed in Cyprinus carpio and the lowest concentration (0.002 mg kg−1 ) was recorded in Glyptothorax stocki. The
maximum allowable limit of As set by Australia New Zealand Food Agency (ANZFA) Standards Code is 2.0 (µg g−1 ) on
a wet weight basis, i.e., 9.6 (µg g−1 ) on a dry weight basis supposing moisture content of 79% in fish muscles (ANZFA,
2011). For human health protection, US-EPA has allowed arsenic concentration of 1.3 (µg g−1 ) on a wet weight basis in
muscle, i.e., (6.24 µg g−1 ) on a dry wet basis (Burger and Gochfeld, 2005). Thus, the concentrations of As recorded in this
study were well below the recommended values by ANZFA and US-EPA. In terms of Cr, the highest mean concentration
(0.072 mg kg−1 ) was observed in Schizothorax plagiostomus and the lowest concentration (0.003 mg kg−1 ) was recorded
in Glyptothorax stocki. The maximum allowable limit of Cr in fish muscles according to Western Australian Food and Drug
regulations is 5.5 (µg g−1 ) (Plaskett and Potter, 1979). Moreover, the highest mean Ni concentration (0.013 mg kg−1 ) was
observed in Cirrhinus mrigala and the lowest concentration (0.0008 mg kg−1 ) was observed in Glyptothorax stocki. The
results reveals that our values were lower than the safety guidelines value of 5.5 (µg g−1 ) on a wet weight basis i.e. 26.4
(µg g−1 ) on a dry weight basis by Western Australian Food and Drug Regulations (Plaskett and Potter, 1979) assuming
79% moisture content in fish muscles.
In the studied river maximum Cu average concentration (0.009 mg kg−1 ) was recorded in Schizothorax plagiostomus
and the lowest concentration (0.003 mg kg−1 ) was recorded in Tor macrolepis. Different authorities set safety limits for
Cu in fish muscles such as Australian National Health and Medical Research Council (ANHMRC) and Food and Agricultural
Organization (FAO) allowed permissible limit of 30 (µg g−1 ) on a wet weight basis (Bebbington et al., 1977). Agreeing with
UK Food Standards Committee Report, the level of Cu in food on a wet weight basis should not exceed 20 (µg g−1 ) (Cronin
et al., 1998). Australian Food Standard Code allowed Cu concentration up to 10 (µg g−1 ) (wet weight basis). Moreover, the
Spanish legislation permitted Cu level in fish muscle up to 20 µg g−1 (wet weight basis). Furthermore, highest mean Zn
concentration (0.078 mg kg−1 ) was observed in Cyprinus carpio and the lowest concentration (0.01 mg kg−1 ) was observed
in Glyptothorax stocki as presented in Table 5. Zinc is an essential trace element present in all living thing and help in
metabolic processes. However, prolonged Zn excessive intake can lead to iron and copper deficiencies and can cause
nausea, vomiting, nausea, fever, tiredness, abdominal pain, human skin irritation and headache. The regularity authorities
such as WHO and ANHMRC (Bebbington et al., 1977) permitted safe level of (1000 mg kg−1 ) for Zn, which is much higher
than our observed values, indicating no adverse health effects.
3.7. Risk assessment via consumption of fish
In this study, the THQ of THMs through consumption of fish were found in order of Cd > As > Pb > Ni > Cu > Zn
> Cr and Cd > As > Pb > Ni > Cu > Zn > Cr for general population and fishermen, respectively. The THQ of Pb, Cd, As,
Cr, Ni, Cu and Zn were 1.60×10−03 , 7.10×10−03 , 5.66×10−03 , 3.19×10−06 , 6.03×10−05 , 3.05×10−05 and 2.61×10−05 for
general population while 1.60×10−02 , 7.10 ×10−02 , 5.66×10−02 , 3.19×10−05 , 6.03×10−04 , 3.05×10−04 and 2.61×10−04 for
fishermen, respectively. The total THQ of THMs via consumption of fish was 1.45×10−02 and 1.45×10−01 for general
population and fishermen, respectively. In short, our results indicated up to some extent fish muscles might be a significant
nutritional source of Cd, As and Pb exposure for fishermen community, particularly for those residing in locality of the
river bank side. On the other hand, all the studied THMs concentrations in all the fish species collected from Swat River
were within the health safety limits and do not pose any considerable health threat to the consumers especially the
population with low and high fish daily intake. Similarly, it can be seen that the carcinogenic risk values for Pb, As
and Cr via consumption of fish were 3.71×10−11 , 2.55×10−09 and 2.39×10−09 for general population while 3.71×10−10 ,
2.55×10−08 and 2.39×10−08 for fishermen respectively were within the acceptable range (1.0 × 10−04 to 1.0 × 10−06 ) of
USEPA (1989). Aquatic ecosystem exposure to THMs might pose potential health risk to human due to the well-known
process of food chain contamination and accumulation (Hao et al., 2013). Earlier researchers comprehensively stated that
As poses a number of possible risks to human health from either food consumption, potable water, inhalation and can
create several health irregularities e.g., spotted melanosis, skin pigmentation, hyperkeratosis, infertility, lung cancer and
heart diseases (Shen et al., 2013; Alamdar et al., 2016).
4. Conclusion
In general, the concentrations of THMs in water, sediments and fish species along with human health risk assessment,
it can be concluded that the THMs contamination of sediments and fish muscles in the Swat River were observed below
the safety limits when compared with international safety guideline values of other countries. While Cd concentration in
the 30% of the downstream water samples exceeded the safety guideline values of World Health Organization (WHO), the
remaining THMs were within the safety limits. Highest mean concentrations of Cd, As, Pb, Cr, Zn, Ni and Cu in water,
sediments and fish muscles were observed in the downstream (S5) site of the Swat River as compared to the other
sites. Local inhabitant and fishermen would not experience health risks (carcinogenic and non-carcinogenic < 1) from
the consumption of THMs via fish ingestion in the studied river. Therefore, we can conclude that these THMs should
not pose any health threat to the consumers resulting from the consumption of studied fish. The downstream section
of the river was more contaminated as compared to the upstream section. The main reason of the downstream section
pollution may be due to unplanned urbanization, intensive agricultural practices, open dumping of wastes near river side’s,
municipal wastewater discharge, industrial effluents, stream discharge form sides villages and hotel effluents. Therefore it
is necessary to give prime importance to Swat River to make sure appropriate management and monitoring of wastewater
before releasing the contaminated wastes into nearby tributaries. Administrative authorities and local bodies must confirm
strict implementation of the National Environmental Quality (NEQs) and International Environmental Quality (INEQs)
standards of agricultural, municipal, hotels and industrial effluents to save this fragile environment of the river.
Declaration of competing interest
The authors declare that they have no known competing financial interests or personal relationships that could have
appeared to influence the work reported in this paper.
Acknowledgments
This paper is based upon the fund supports provided by Ministry of Science and Technology of China (MSTC) with
National Key Research and Development Program (2017YFE0119000).
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Environmental Technology & Innovation 17 (2020) 100554

Contents lists available at ScienceDirect

Environmental Technology & Innovation

Contamination features, geo-accumulation, enrichments and

2. Material and methods

2.1. Study area

Fig. 1. Swat River location map showing the sampling location.

2.2. Sampling, extraction and analysis

2.3. Instrumental analysis and quality assurance

2.4. Sediment risk assessment

2.5. Contamination factor (CF)

2.6. Geo-accumulation index (Igeo)

2.7. Contamination degree

2.8. Enrichment factor (EF)

Where ‘ Metal sample’ in contaminated site and ‘ Metal

2.9. Ecological risk indices

2.10. Health risk assessment

2.11. Statistical analysis

3. Results and discussion

3.1. Heavy metal(loids) concentration in surface water

3.2. Health risk assessment from THMs

3.2.1. Average daily intake

3.2.2. Hazard quotient (HQ) and total hazard quotient (THQ)

3.3. Sediment risk assessment and pollution indices

3.4. Ecological risk assessments of sediments

3.5. Sediments comparison around the globe

3.6. Toxic heavy metal(loids) concentrations in fish species

3.7. Risk assessment via consumption of fish

Declaration of competing interest

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