Abbasi 2021

Environmental Science and Pollution Research (2022) 29:27007–27025
https://doi.org/10.1007/s11356-021-17937-x
RESEARCH ARTICLE
Eutrophication and sediment–water exchange of total petroleum

hydrocarbons and heavy metals of Hashilan wetland, a national
heritage in NW Iran
Sajjad Abbasi1,2 · Sara Sheikh Fakhradini1 · Neamatollah Jaafarzadeh3 · Pooria Ebrahimi4 · Shirin Yavar Ashayeri1
Received: 1 September 2021 / Accepted: 30 November 2021 / Published online: 19 December 2021
© The Author(s) 2021
Abstract
The heavy metal(loid)s concentrations in water and sediments were analyzed in the Hashilan wetland to assess the spatial
distribution, pollution status, fate, partitioning, and ecological risk and also to identify the heavy metal(loid)s sources in
sediments using PMF (Positive Matrix Factorization) and APCs-MLR (absolute principal component score-multiple linear
regression) receptor models. According to the pollution indices, (Ni, Cu, Cr, Mo), and (Zn, Cr, and Cu) are considered the
most important pollutants in sediments and water, respectively. Ni, Cr, and Cu are the main contributors to ecological risks in
sediments of some stations. The potential ecological risk assessment proposed low ecological risk in water of the study area.
Higher distribution coefficient (Kp) values of Ni, Cr, Mn, Cu, Co, Pb, As, and Zn indicated the majority of these heavy metals
present in the sediments; whereas, the majority of Cd concentration occurs in water. PMF and APCs-MLR results indicated
the natural sources were the main factors affecting the concentrations of Ni, Cr, Zn, Al, Co, Fe, Pb, As, Cd and somewhat
Cu. Mixed natural and agricultural activities are the main sources of Mo, and somewhat Cu. According to the results, there
is low pollution of TPH (total petroleum hydrocarbons) in the sediment samples. Also, phosphate (PO42−) and nitrate (NO3−)
concentrations were below the recommended permissible limits at all sampling sites except the S8 station for NO3−.
Keywords Heavy metal · TPH · Eutrophication · Wetland · Hashilan · Iran
Introduction Tuboi et al. 2018). Nowadays, anthropogenic stressors such

as population growth, resources overexploitation, economic
Wetlands are recognized to be productive ecosystems due development, and agricultural encroachments and drainage
to water quality protection, sinks for nutrients and pollut- have affected and polluted the wetland environment (Tuboi
ants, water cycling maintenance, controlling floods and et al. 2018). Metal Pollutants enter the aquatic habitats not
flows, groundwater recharge, and so on (Andreu et al. 2016; only from natural sources including weathering, erosion, and
soil leaching but also from anthropogenic activities such as
urbanization, industrial and agricultural activities (Abbasi
Responsible Editor: Alexandros Stefanakis
et al. 2019; Strady et al. 2017) and endanger humans and
* Sajjad Abbasi animals health as a result of their toxicity, persistence, and
sajjad.abbasi.h@gmail.com; sajjad.abbasi@shirazu.ac.ir bioaccumulation via the food chain.
1
Total petroleum hydrocarbon (TPH) is a homogene-
Department of Earth Sciences, College of Science, Shiraz ous mixture including hundred chemical compounds
University, 71454 Shiraz, Iran
2
that originally come from crude oil. These compounds
Department of Radiochemistry and Environmental generally enter the aquatic environment through several
Chemistry, Faculty of Chemistry, Maria Curie-Skłodowska
University, 20‑031 Lublin, Poland anthropogenic activities such as contaminated lands,
3 pesticides, vehicle emissions, oil spillage, automobile
Environmental Technologies Research Center, Ahvaz
Jundishapur University of Medical Sciences, Ahvaz, Iran oils, or different harmful organic substances (Chen et al.
4 2020; Li et al. 2019). Several products of TPH contain
Department of Earth, Environmental and Resources
Sciences, University of Naples Federico II, 80126 Naples, heavy metals which are present in crude oil or may also
Italy be added as chemicals to these products (Defarge et al.
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27008 Environmental Science and Pollution Research (2022) 29:27007–27025
2018). However, numerous pesticides contain As, Co, Cr, Worth mentioning that the novelty of the current study is
Ni, and Pb elements and Cd, Co, Cu, Ni, Pb, and Zn metals to investigate organic and inorganic contaminants compre-
as impurities are found in different fertilizers. Moreover, hensively in the water and sediment of Hashilan Wetland
Fe, Mn, Zn, Pb, and Ni are present in some herbicides for the first time. The major purposes of this research are
(Gimeno-García et al. 1996). Eating, breathing, and direct 1) to specify the concentration, distribution, pollution rate
contact with contaminated soil, water, and sediments are and ecological risk of heavy metal(loid)s in water, and sedi-
considered the path of their entry into the human body ment the Hashilan wetland, 2) to determine the metal(loid)
(Quiñonez-Plaza et al. 2017). Also, these compounds can s source apportionment in the sediment, 3) to identify affec-
create negative effects on human and biota health, depend- tive factors on metal(loid)s partitioning between surface
ing on the different compounds values present in the TPH water and sediment, 4) to evaluate the trophic state of the
(Quiñonez-Plaza et al. 2017; Zhou et al. 2014). water samples, and 5) to investigate the pollution rate of
Sediments as a part of aquatic environments have a sig- TPH.
nificant role in biochemical cycling and food web protection
(Islam et al. 2018). Sediments provide a large capacity to
accumulate a large fraction of heavy metal(loid)s as a result Material and methods
of hydrolysis, co-precipitation, and adsorption processes
while a small portion of heavy metals remains in the water Study area
column (Hou et al. 2013; Wu et al. 2017). Also, sediments
could act as a secondary source due to environmental condi- Hashilan wetland, as a significant freshwater wetland in
tions change and releasing metals into the water, affecting a the Kermanshah Province, has been located at the Hashilan
health risk to aquatic biota due to their high bioavailability village, being 26 km northwest of Kermanshah city. It lies
(Cui et al. 2019). However, metal(loid) partitioning between between 46°, 51′ to 46°, 54′ eastern longitude and 34°, 34′ to
water and sediment is specified due to oxidation/reduction 35°, 34′ northern latitude (Fig. 1). This Wetland constitutes
and precipitation/dissolution reactions of heavy metal(loid) a unique feature in the Middle East which is called “karstic
s in sediments (Duarte et al. 2014). spring wetland,” an ecosystem mostly found in the Zagros
Water resources are essential in sustainable societal Mountains of Iran. Geologically, its catchment basin and
development and natural processes including erosion and the aquifers of its water sources are located in the limestone
climatic conditions, and anthropogenic activities, such as formations of the Triassic-Jurassic age. Hashilan Wetland
industrial and agricultural practices affect water resources is located in a syncline bordered by two anticlines in the
and a large amount of pollutants is discharged into the water northeast (Khorin anticline) and southwest (Biston anti-
reservoirs (Lyu et al. 2021). Eutrophication is considered cline). Surveying the wetland on a large scale is a part of
as an important environmental problem in the world. This the Miandarband plain which surrounds the two anticlines,
phenomenon occurs under the influence of natural factors contains several other wetlands and has two rivers namely
and human activities, which increase the amount of algae Razavar in the north and Gareso in the south (Abbasi et al.
and aquatic plants and decrease the dissolved oxygen of the 2021).
water (Lin et al. 2020, 2021). Thus, the evaluation of water The mean annual precipitation is about 450 mm, respec-
quality is a significant prerequisite for the conservation, tively. Also, the average temperature is 22 °C. The areal
control of water bodies, and safety guaranty of the regional coverage of wetland is about 450 ha. Sabz Ali spring, origi-
water environment. nating from the Khorein Mountains located on the northern
This study focuses on Hashilan wetland, which is one of border of the wetland supply the wetland water. This wetland
the most important agricultural areas in Kermanshah prov- consists of 110 islands ranging from 0.1 to 1 ha in size,
ince as a result of fertile soils, sufficient water resources and which causes the water to be distributed among the islands
suitable climate. Also, Hashilan wetland is one of the unique as the small and big channels. This wetland has been suf-
flora and fauna regions of this Province. Unfortunately, dis- fered from high-intensity agricultural activities, which is the
charge of agricultural runoff, containing different types of main occupation of the local inhabitants. It should be noted
contaminants such as microplastic particles (Abbasi 2021), the wetland supports a significant and unique population of
heavy metals, fertilizers, and herbicides into the wetland has flora and fauna.
affected human and biota health. Also, the presence of tour-
ists in this area can also be a threat to this wetland. Thus, Water and sediment sampling and analysis
decision-makers need to evaluate heavy metal(loid)s values
in water and sediment environments to specify the sources, Sixteen surface sediment samples and 6 water samples
fate, and ecological risk of pollutants and then eliminate were collected in September 2019 covering an area of
water and sediment pollution via urgent actions. about 450 ha. In each sampling location, about 2 kg surface
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Environmental Science and Pollution Research (2022) 29:27007–27025 27009
Fig. 1 Map of the study area

and sampling sites in Hashilan’s
wetland area
sediment (0–5 cm) was collected via a Van Veen stainless Usually, sites close to roads indicate higher TPH contents
steel grab and placed in a clear polyethylene bag. Then, the than other areas. Therefore, to evaluate the TPH concentra-
samples were transferred to the laboratory in an iced box. tions of Hashilan sediments, a total of 5 surface sediment
It should be mentioned that the water samples were only samples were collected from stations close to the roads and
taken from monitoring stations where the sediments were agricultural lands where agricultural machinery passes and
surrounded by water. The sampling stations information cov- immediately put in dark glass bottles which were already
ering the whole study area is illustrated in Table S1 (sup- washed with n-hexane and sealed by aluminum foil caps.
porting information). The collected samples were transported to the laboratory of
In the laboratory, the sediment samples were air-dried the Isfahan University of Technology in an ice-box at 4 °C
at room temperature. Agate Mortar and pestle were used and stored at -20 °C until analysis.
to crush the sediment. Larger debris such as plant leaves The surrogate standards (Pyrene-D10 lot:10,510 semi-
and pieces of glass were separated (2-mm sieve) after being volatile internal standards) and ultra-sonic bath (KUDOS
air-dried at room temperature. Finally, the samples were Modell SK3210LHC) were used during the extraction of
passed through a 220 mesh (63 μm) for elemental analysis approximately 5 g per dried sample. For the TPH calibration,
and then homogenized. Thus, the samples were measured the pyr-D10 was used as the internal standard. The samples
using inductively coupled plasma mass spectrometry (ICP- were then collected by means of a 30-ml organic solvent mix
MS) at Zarazma Mineral Studies Company, Iran. (DCM) of 1:1 v/v at room temperature (N-hexane and DCM)
13
for around 30 min. The solution is applied with amorphous wetland. In this study, potential ecological risk index (RI),
sulfate sodium and the next step is 2 mL of dried extracts. modified ecological risk index (MRI), sediment quality
The extract close to sediment samples was washed with a guidelines (SQGs), toxic units (TUs), and toxic risk index
silica gel column (Abbasi and Keshavarzi 2019; Sheikh (TRI) were applied to estimate the ecological risk in water
Fakhradini et al. 2019). Following the EPA 418 protocol, and sediments of the wetland. To recognize the potential
the samples for TPH were analyzed. The samples have then source of PTEs in sediments, Spearman correlation analy-
been analyzed using a High Leistung Fluorescence Detector sis, principal component analysis (PCA)/ absolute principal
(HP-1046) Hewlett-Packard (HP) 1090 in the laboratory of component scores (APCS) and positive matrix factorization
Isfahan University of Technology using a RIGOL L-3000 (PMF) model were utilized. Also, partition coefficient (Kp)
High-Performance Liquid Chromatographer (HPLC, RIGOL was calculated to determine the interaction of PTEs between
Technologies, Inc., Beijing, China) equipped with a RIGOL water and sediment phases. The details of the mentioned
L-3500 UV–vis detector (RIGOL Technologies, Inc., Bei- indices are described in the supporting information.
jing, China) and a Hewlett-Packard 1046 A fluorescence
detector (Agilent Technologies, California, USA). A rota-
tive vacuum evaporator concentrated the extracts to 1 ml. Results and discussion
The PAHs analysis was based on 20 μl of each extract. At a
rate of flux of 1 ml/min and temperature was set at 35 °C the Concentration of total petroleum hydrocarbons
mobile step was acetonitrile/water in gradient mode. (TPH) in sediments
The water samples were immediately purified in the field
by 0.45-μm Teflon filters. For PTEs analysis, the samples Total petroleum hydrocarbons (TPHs) values as the sum
were acidified to pH < 2 with ultrapure nitric acid (HNO3) of aliphatic and aromatic hydrocarbons ranged from 4.2 to
and kipped in dark polyethylene bottles at 4 ◦C prior to anal- 76 mg/kg averaging 30.44 ± 28 mg/kg in sediment samples.
ysis of PTEs concentration by inductively coupled plasma- The highest value of TPH was measured at the S2 site while
mass spectrometry (ICP-MS) at Zarazma Mineral Studies S1 represented the lowest TPH concentration. The TPH val-
Company, Iran. Temperature, pH, and salinity of water ues higher than 500 mg/kg in sediments indicate severely
samples were evaluated on-site using portable measuring polluted sediments, while their contents below 10 mg/kg
devices (Eutech Instruments, PCD650). show no pollution (Akhbarizadeh et al. 2016; Kucuksezgin
et al. 2012). Therefore, TPH concentrations in Hashilan sedi-
Quality assurance and quality control ment samples can be categorized as no polluted in site S1,
and low polluted for the other collected sediment samples.
Quality assurance and control (QA/QC) included the pro- Totally, the impact of human activities on the TPH concen-
cedural blank, analytical duplicates and use of certified trations in the Hashilan sediments was low.
reference material (OREAS reference materials) for water TPH values in the sediments of Hashilan wetland are
and sediment samples. The recovery percentages of the lower than those reported from Khark Island (80 to 618 mg/
investigated PTEs ranged from 80 to 110%, and the blank kg; Iran) (Akhbarizadeh et al. 2016), Yangtze estuary
was below the detection limit. Concentrations of heavy (50.05–428.50 mg/kg; China) (Li et al. 2019); Bohai Bay
metal(loid)s were recorded as mg/kg dry weight for sedi- (6.3–535 mg/kg; China) (Zhou et al. 2014), Barnegat-Bay-
ments, and μg/L for water in this study. Little Egg Harbor Estuary, USA (47–1003 mg/kg; USA)
Generally, the average recovery for TPH in sediment was (Vane et al. 2008), but higher than those from the Bay of
approximately 88–95%. Reagent blanks, analytical dupli- Bengal (1.8–40 mg/kg; India) (Venkatachalapathy et al.
cates/replicates, and analysis of the standard reference mate- 2010) Bizerte lagoon (0.05–20 mg/kg; Tunisia) (Mzoughi
rial (Dr. Ehrenstorfer GmbH Alkanes-Mix 10, and Sigma- et al. 2005); mangroves of the northern Persian Gulf (ND-
Aldrich Co. LLC EPA 525 PAH Mix A and EPA 525 PAH 1.7 mg/kg; Iran) (Mohebbi-Nozar et al. 2015) and Izmir Bay
Mix B) were processed. (0.43–7.8 mg/kg; Turkey) (Kucuksezgin et al. 2006).
Data analysis Concentration of heavy metal(loid)s in water

and sediments
In order to estimate the pollution rate of sediments and
water, this paper utilized different types of indices includ- The PTEs values and statistical parameters in the collected
ing enrichment factor (EF), geoaccumulation index (I geo), sediments and surface water of the Hashilan wetland are
contamination factor (Cf), Nemerow pollution index (NPI), summarized in Table 1. Regarding Levene’s test for equality
modified pollution index (MPI), and heavy metal toxic load of variances tests, all metal(loid)s concentrations in soil and
(HMTL) to specify the pollution degree of PTEs in Hashilan sediment zones had values of greater than 0.05, proposing
13
Table.1 Summary of statistical analysis of heavy metal(loid)s concentrations in surface water and sediments of the Hashilan wetland and comparison with water and sediment guidelines (WSA
are from Taylor and McLennan (1985) and water standards are given from: https://www.fao.org/3/T0234E/T0234E01.htm)
Pollutants Sediment (μg/g) n = 16 Water (μg/L) n = 6 Water Standards
Dla Min Max Mean STDb CVc TEL PEL WSAd Dl Min Max Mean STD CV EPAe AWPLf IWPLg TRVh
Ni 1 17 136 80.94 40.16 0.5 18 36 18 0.1 < 0.1 < 0.1 - - - - 20 - 87.71

Cr 1 17 210 111.13 62.05 0.56 37.3 90 42 1 0.67 1.37 0.98 0.34 0.35 100 5 8 117.3
Co 1 1.7 19.8 11.38 5.98 0.53 - - 6.9 1 < 1 < 1 - - - - - 50 23
Sc 0.5 1.9 16.3 9.69 4.8 0.5 - - 9.5 1 0.67 5.55 2.48 1.97 0.79 - - - -
Mn 5 117 915 460.44 251.77 0.55 - - 418 10 < 10 < 10 - - - 50* - 200 120
Fe 100 9011 41,089 25,926.8 10,840.04 0.42 - - 35,000 10 6.67 40 12.78 13.4 1.05 300** 300 5000 1000
Environmental Science and Pollution Research (2022) 29:27007–27025
Al 100 9805 63,889 39,383.7 17,473.26 0.44 - - 71,000 10 10 30 18.33 7.53 0.41 50* 100 5000 87
Mo 0.1 0.07 7 1.2 1.59 1.33 - - 1.8 0.1 0.85 4.35 2.74 1.3 0.47 - 73 - 370
Pb 1 2 21 10.56 5.4 0.51 35 91.3 25 0.1 0.67 4.4 2.9 1.35 0.47 15 7 200 9.05*
Zn 1 16 101 63.69 26.78 0.42 123 315 62 1 32.04 140.6 64.09 38.73 0.6 5000* 30 5000 212.5*
As 0.1 0.07 6.8 2.42 2.05 0.85 5.9 17 4.7 0.1 < 0.1 1.33 0.29 0.51 1.76 10 5 100 190
Cu 1 18 95 42.88 18.61 0.43 35.5 197 14 1 0.67 4.13 2.01 1.27 0.63 1300 4 200 23.8*
Cd 0.1 0.07 0.2 0.1 0.04 0.4 0.596 3.53 1.1 1 < 1 < 1 - - - 5 - 0.66
a
Detection limit
b
Standard deviation
c
Coefficient of variation
d
World soil average
e
Environmental Protection Agency
f
Aquatic Life Water Permissible Limits
g
Irrigation Life Water Permissible Limits
h
Toxicity Reference Value
13
27011
the assumption of equal variances is met (Table S2). There- Hashilan wetland in comparison with its mean contents in
fore, all soil and sediment samples were considered as a other investigated regions was high and also it was about
statistical population. 2.6-fold higher than that in the world-soil average.
Based on the results, Cu and Zn concentrations ranged Molybdenum concentration ranged from 0.07 to 1 mg/
from 18 to 95 mg/kg and 16 to 101 mg/kg, respectively. The kg in all sampling sites except S3 station with 7 mg/kg. The
elevated Cu contents were measured at stations S1 (95 mg/ maximum Mo value in the Hashilan wetland was about 3.8-
kg) and S2 (71 mg/kg). Also, the higher Zn concentrations fold higher than that in the world-soil average. Also, the
were belong to sites S7 (101 mg/kg), S1 (92 mg/kg) and range of Cd concentration was small, varying from 0.07 to
S2 (85 mg/kg). These stations have been located near the 0.2 mg/kg. The mean Cd content (0.1 mg/kg) in the study
road, where agricultural machinery passes. The mean con- area was below that of the world-soil average. However, its
centrations of these elements in the sediments of Hashilan mean value in the sediments was higher than those from
wetland are higher than those reported from Shadegan wet- Plateau lake wetland (China), Hengshuihu Wetland (China)
land (Iran), Tijuana Estuary (California, USA), Nile delta and Nile delta (Egypt), but lower than other studies.
(Egypt) and Sicily (Italy), but lower than those from Man- Totally, the average values of the investigated ele-
grove swamps (Hong Kong), Bellandur wetland (India), and ments decrease as follows (mg kg−1): Al (39,383.7) > Fe
Pearl River Estuary (China) (Table S3). The mean Cu value (25,926.8) > Mn (460.4) > Cr (111.12) > Ni (80.94) > Zn
in the Hashilan wetland was about 3.06-fold higher than that (63.7) > Cu (42.9) > Co (11.4) > Pb (9.7) > As (2.4) > Mo
in the world-soil average. (1.2) > Cd (0.1). The coefficient of variation (C.V) is defined
Nickel and Co concentrations varied from 17 to 136 mg/ as the standard deviation to the mean ratio, which could
kg and 1.7 to 19.8 mg/kg, respectively. The higher Ni and Co reflect the degree of humankind effects (Guan et al. 2019;
values were observed at S10 (136 and 19.2 mg/kg, respec- Wu et al. 2020). The coefficients of variation of As, Cr, Mn,
tively) and S7 (134 and 19.8 mg/kg, respectively) sites. Co, Ni, Pb, Sc, Al, Cu, Fe, Zn, and Cd were 85%, 56%, 55%,
These stations are farmlands which are located near the road. 52%, 50%, 50%,50%, 50%, 44%, 43%, 42%, 42%, and 40%,
The mean Ni and Co values (80.94 and 11.38 mg/kg, respec- respectively. The variation degree of these elements was
tively) in Hashilan wetland were about 4.5-fold and 1.7-fold between 0.1 and 1, indicating moderate variability (Jin et al.
higher than those in the world-soil average. 2019). While, the variation degree of Mo was greater than
The average Ni value in comparison with its mean con- 1, which is categorized as strong (Jin et al. 2019). The high
tents in other investigated regions was high. Also, the mean coefficient of variation of Mo proposed that human activities
Co concentration was lower than that from Anzali wetland could affect its value in the sediment of the wetland.
(Iran) and close to those of Sundarban (India) and Shadegan The elements of Ni, Mn, Co, and Cd were not detectable
(Iran) wetlands (Table S3). in the surface water of Hashilan wetland, which caused the
Pb, Mn and Al contents varied from 2 to 21 mg/kg, 117 portions of these heavy metals to be negligible for water pol-
to 915 mg/kg, and 9805 to 63,889 mg/kg, respectively. The lution. Cr and Fe elements were detectable at two or three
highest mean values of these elements belonged to the S7 sites. The elements of Cu and Mo contents ranged from 0.7
station. The mean Pb, Mn and Al contents (10.56, 460.44, to 4.13 µg/L, and 0.85 to 4.35 µg/L, respectively. The higher
and 39,383.7 mg/kg, respectively) in the study area were values of Cu and Mo were observed at S3, S8, and S12 sites
below those of the world-soil average. However, the mean where the pollutants values increase due to stagnant water.
value of Pb in the sediments was higher than those from Phosphate fertilizers, pesticides or fungicides contain Cu
the Nile delta (Egypt), Mighan Wetland (Iran) and Sicily and Mo elements which could be the source of these ele-
(Italia), but lower than other studies. Moreover, the mean ments at S8 (the outlet of agricultural wastewater into the
Mn concentration in the study area illustrated a higher value wetland) (Li et al. 2020). Also, wear dust from brake lin-
than Shadegan wetland (Iran) and Sicily (Italia), but a lower ings and tires of vehicles can be considered the source of
value than Sundarban (India) and Sicily (Italia). these elements at S3 (near the road) (Lin et al. 2015). Zinc
Arsenic concentration varied from 0.07 to 6.8 mg/kg with value varied from 32.04 to 59.13 µg/L in all sampling sites
mean value of 2.42 ± 2.05 mg/kg. The elevated values of this except the S8 station with 140.58 µg/L where agricultural
element were observed at S9 (6.8 mg/kg) and S7 (5.9 mg/ runoff entered the wetland. Lead concentration ranged from
kg) stations. The average value of As in the study area was 0.67 to 4.4 µg/L with a mean value of 2.9 µg/L. The higher
below those of the world-soil average and other investi- Pb contents were observed at S2 (4.4 µg/L), S8 (3.79 µg/L)
gated regions. Cr concentration varied from 17 to 210 mg/ and S1 (3.64 µg/L) sites. Aluminum and Sc concentrations
kg with mean value of 111.13 ± 62.05 mg/kg. The higher ranged from 10 to 30 µg/L and 0.67 to 5.55 µg/L, respec-
Cr contents were observed at S1 (210 mg/kg), S7 (195 mg/ tively. The highest contents of these elements were measured
kg) and S9 (190 mg/kg) sites which have been located near at stations S12 and S8, respectively. Also, As values were
the roads. Moreover, the average value of this element in only detected at S8 and S12 stations. Totally, the average
13
values of the investigated elements decrease as follows (µg particularly nickel, chromium, and cobalt. Therefore,
l−1): Zn (64.09) > Al (18.33) > Fe (12.78) > Pb (2.9) > Mo soils formed over them are polluted by the mentioned metals
(2.74) > Sc (2.48) > Cu (2.01) > Cr (0.98) > As (0.29). The were controlled by weathering processes of parent materials
concentrations of the investigated metal(loid)s were below (Allahyari et al. 2010; Namaghi et al. 2011).
the recommended drinking water standards by EPA (USEPA Mo showed significant and moderate enrichments at
2012) and WHO (2017). S3 and (S5 and S6) stations, respectively, while other sta-
tions were relatively unpolluted. Copper (Cu) revealed
significant and moderate enrichments at (S5, S6) and (S9,
Assessment of PTEs contamination S10 and S13) stations, respectively, while other stations
indicated deficiency to minor enrichments. Therefore,
Sediment quality assessment the anthropogenic sources are suggested for Cu, and Mo
at some stations. Totally, the mean EFs of trace elements
were ranked as follows: Ni (4.44) > Cu (3.8) > Cr (2.5) > Co
Geoaccumulation index (Igeo) The calculated Igeo values for (1.6) > Mn (1.14) > Zn (1.08) > Mo (1.04) > Fe (0.81) > Al
PTEs in sediments of the Hashilan wetland are presented in (0.57) > As (0.45) > Pb (0.44) > Cd (0.13), suggesting the
Fig. S1. Lead, Cd, As, Fe, and Al in the Hashilan sediments tested metal(loid)s except Ni, Cu, and Cr illustrated mini-
were classified as “unpolluted” status as a result of the I geo mum enrichment in general. While, the average contents of
index lower than Zero, while the Igeo values of Sc, Co, Mn, EFs for Ni, Cu, and Cr indicated moderate enrichment.
and Zn fluctuated from “unpolluted” to “unpolluted to mod-
erately polluted” status. Comparatively, the Igeo values for Cu Contamination factor (CF) The calculated CF values for
and Ni varied from -0.22 to 2.18 and -0.67 to 2.33, respec- PTEs in sediments of the Hashilan wetland are presented in
tively, suggesting “no contamination” to “moderate to strong Fig. S3. Contamination factor (CF) values calculated showed
contamination.” Chromium in sediments was classified as that all the sediment samples have been low contaminated
no pollution to moderate pollution. The Igeo values for Mo by Al, Cd, Pb, and Mo elements. Also, As revealed minor
showed an “unpolluted” status at all sampling sites except contamination for all sampling sites except S7 and S9 which
S3, which presented moderate pollution. Totally, the average were moderately polluted. Zinc and Co showed a moderate
Igeo values of the investigated metal(loid)s were as follows: degree of pollution at most stations. Chromium illustrated
Cd (-4.10), As (-2.64), Pb (-2.06), Mo (-1.99), Al (-1.63), low, moderate, and considerable contaminations at (S5, S6,
Fe (-1.16), Sc (-0.81), Zn (-0.72), Mn (-0.69), Co (-0.16), S8), (S3, S4, S11, S15, S16) and other stations, respectively.
Cr (0.48), Cu (0.92), and Ni (1.34), proposing the tested Moreover, serious contamination of Ni was observed at
metal(loid)s except Ni, Cr, and Cu indicated no pollution in S1, S7, S9, and S10 stations, also half of the stations were
general. Also, the average contents of I geo for Ni indicated considerably polluted by this heavy metal. Copper showed
moderate pollution, while those of Cr and Cu demonstrated serious contamination at the S1 station, while moderate to
uncontaminated to moderately contaminated conditions. considerable contaminations of Cu were observed for other
sampling sites. Manganese, Sc, and Fe showed low to mod-
Enrichment factor (EF) The calculated EF values for PTEs in erate contaminations in the Hashilan sediments. The mean
sediments of the Hashilan wetland are presented in Fig. S2 CFs of trace elements were ordered as follows: Ni (4.5) > Cu
(SI 2). The EFs values calculated revealed that Al, As, Cd, (3.1) > Cr (2.64) > Co (1.65) > Mn (1.1) > Zn (1.03) > Sc
Co, Mn, Pb, Sc, and Zn were minimal enriched at all sam- (1.02) > Fe (0.74) > Mo (0.67) > Al (0.55) > As (0.51) > Pb
pling sites, which indicate that the mentioned elements were (0.42) > Cd (0.09), suggesting the investigated metal(loid)
mainly originated from crustal materials or natural weather- s except Ni, Cu, Cr, Co, Mn, Zn, and Sc demonstrated low
ing. Also, the sediments were moderately enriched with Ni contamination in general. While, the mean contents of CFs
at all stations. Enrichment factors of Cr were also higher for (Ni, Cu), and (Cr, Co, Mn, Zn, Sc) showed considerable
or much closer to 2 in all the sampling sites, indicating the and moderate pollutions, respectively.
influence of anthropogenic pollution in sediments. Accord-
ing to studies conducted in Iran, the chromium and nickel Modified pollution index (MPI) and Nemerow pollution index
concentrations in the soil of Iran country (especially near (NPI) According to Table S4 and Fig. S4, MPI (modified
the Zagros mountains) are higher than those of the global pollution index) revealed that S5 and S6 sites have been
average of soil and upper crust (Abbasi et al. 2018, 2019). severely polluted, while other sampling stations except S14
Despite moderate EFs of Ni and Cr, these elements showed were moderately heavily polluted. Also, the site of S14 indi-
low and uniform EF ranges which illustrate a geogenic cated moderate pollution.
source. Ophiolite sequences of the Zagros fold-and-thrust NPI (pollution index) indicated S1, S2, S4, S7, S9, S10,
belt are associated with high levels of toxic trace elements, S12, S13, and S14 sites were heavily polluted, and the rest
13
sampling stations have been severe to moderately polluted. while other organic and inorganic pollutants listed in the
It seems that NPI has overestimated the pollution degree at ATSDR substance priority list could be considered to obtain
the sampling sites compared to MPI, which is computed by a better insight into the water quality of the study area.
the enrichment factor (Fig. S4).
Nemerow pollution index (NPI) To evaluate the Nemerow
pollution index, reference values were selected from AWPL,
Water quality assessment TRVs and EPA guidelines to provide more accurate informa-
tion about the pollution rate in the surface water.
Heavy metal toxicity load (HMTL) To evaluate the HMTL, The single factor index values of Zn at all stations, and Cr
the potentially toxic metal(loid)s including As, Cu, Pb, Zn, at S1, S2, S8 sites calculated by AWPL as a reference value
Cr, and Al were chosen from the ATSDR substance prior- exceeded 1 which caused NPI > 1 at all stations, representing
ity list (ATSDR 2017). Also, different guidelines includ- serious pollution of metal(loid)s at all monitoring sites (Fig.
ing aquatic life water permissible limits (AWPL) (CCME S5). The highest NPI value was 3.41, which was detected at
2007), toxicity reference values (TRVs) (WSRC 1999) and the S8 station. However, Zn and Cr were considered to be
recommended drinking water standards by the environmen- the significant factors for NPI > 1. In comparison, the sin-
tal protection agency (EPA) (USEPA 2012) were used to gle factor index values of the investigated PTEs calculated
assess different permissible toxicity loads. In the study area, by EPA and TRV guidelines as the reference values were
HMTL ranged from 55.35 to 153.56 mg/L with an aver- below 1 which caused NPI < 1 at all sampling sites, show-
age of 78.48 mg/L. The HTML calculated was less than ing no pollution threat at all stations (Fig. S5). The results
the permissible toxicity loads prepared by EPA and TRV indicated the pollution rate of water could be dependent on
guidelines (5774. 8 and 966.5 mg/L, respectively), suggest- the selected reference values. However, agricultural activi-
ing low pollution of PTEs at all sampling sites, while HTML ties have affected the aquatic environment of the Hashilan
of the S8 station (153.56 mg/L) was above the permissible wetland. Therefore, to protect the wetland environment, the
toxicity load prepared by AWPL guideline (119.1 mg/L) pollution rate is required to be controlled.
(Table 2). However, the pollution loads of Cu at S3, Cr at
S1, S2, S8 and Zn at all monitored stations were above their Mean‑PEL‑quotient The comparison between sediment
corresponding permissible toxicity loads prepared by AWPL quality guidelines and metal concentrations in sediment is
guideline, proposing the reduction of Zn, Cr, and Cu con- applied to evaluate the contamination effects on the biota
tents of the Hashilan water. However, this study has evalu- (Maanan et al. 2015). Copper values at most stations except
ated the water quality with respect to some heavy metals, S8 were above the respective TEL content; even though, its
Table.2 Heavy metal toxicity load of the surface water based on relative toxicity level of heavy metal(loid)s
Toxicity of heavy metals (mg/L)
Sampling sites Cu Pb Zn As Cr Al Heavy metal toxicity
load (HTML) (mg/L)
S1 1.30 5.57 53.99 0.11 1.13 6.85 68.96

S2 0.85 6.74 53.03 0.11 1.10 6.85 68.67
S3 3.32 1.03 43.33 0.11 0.60 13.70 62.09
S5 0.54 4.19 43.14 0.11 0.60 13.70 62.28
S8 2.25 5.80 128.35 2.23 1.22 13.70 153.56
S12 1.46 3.28 29.25 0.22 0.60 20.55 55.35
Total 9.72 26.61 351.09 2.89 5.24 75.35
Hazard Intensity Score* 805 1531 913 1676 893 685
Permissible toxicity load (EPA)a 1046.50 22.97 4565.00 16.76 89.30 34.25 5774.80
Permissible toxicity load (TRV)b 18.58 13.86 194.01 318.44 362.02 59.60 966.50
Permissible toxicity load (AWPL)c 3.22 10.72 27.39 8.38 0.89 68.50 119.10
*ATSDR 2017
a
Environmental Protection Agency
b
Toxicity Reference Value
c
Aquatic Life Water Permissible Limits
Ecological risk assessment for heavy metal(loid)s in sediments
13
concentrations were lower than the respective PEL value. from 10 to 15. Meanwhile, low toxic risk was measured at
Nickel concentrations were above the respective PEL value 4 stations with TRI values varying from 5 to 10. Three sta-
at all sampling sites except S5, S6, and S8 stations which tions also showed no toxic risk with TRI values lower than
could create potential adverse biological consequences 5. However, the areas with higher potential risk were mainly
at these sites. In the case of Cr, its contents exceeded the focused in the vicinity of roads.
respective PEL value at S1, S7, and S9 sites which could The mean contribution ratios of each metal(loid) to the
cause potential adverse ecological risk at the mentioned sta- TRI contents were 54.78 ± 6.43% for Ni, 19.44 ± 8.27% for
tions, while its maximum values at S5, S6, and S8 stations Cu, 15.24 ± 3.25% for Cr, 4.23 ± 0.56% for Zn, 2.7 ± 0.85%
were lower than the respective TEL content. Moreover, the for Pb, 2.18 ± 1.55% for As, and 1.44 ± 1.03% for Cd.
As, Cd, Pb, and Zn values in all sediment samples were Moreover, compared with the ratio of Cu, As, and Cd in
observed to be below the respective TEL contents, propos- the ΣTUs, the contributing ratio of the mentioned elements
ing that these elements in Hashilan wetland would not be was increased according to the TRI, proposing higher poten-
associated with adverse ecological risk. tial toxicity of the mentioned elements. Cu and Zn showed
However, the mean PEL quotients were between 0.11 and a lower toxicity contribution in the TRI compared to the
1.5 at all sampling sites, representing low to moderate eco- ΣTUs. In addition, according to ΣTU and TRI contents, the
logical risk for an aquatic organism, with a toxicity occur- highest contribution ratio has belonged to the Ni element.
rence of between 10 and 25%. According to the results, the ΣTUs method demonstrated
the lower potential toxicity risk compared to the TRI method
RI and MRI The highest and lowest values of E ri in sediments because the TRI index applied the TEL and PEL values,
of the Hashilan wetland were belong to Cu and As elements, providing more reference contents compared to the ΣTUs,
respectively. The rest of the heavy metals were observed which only consider high PEL values for toxicity risk esti-
in between the two extremes. Computed Er i with enrich- mation (Ji et al. 2019a).
ment factor indicated a moderate risk of Cu at the only S5 It is worthy to note that several methods of risk evalua-
site, while other elements exhibited low risk at all locations. tion utilize different toxicity parameters or values of PTEs,
Computed Eri with contamination factor in comparison with which cause different index contents or risk levels. Among
Eri with enrichment factor showed that the ecological risk of the MRI, RI, TRI, Mean-PEL-quotient, and TUs methods,
Cu has decreased to low risk at S5 station. Furthermore, all TRI equation better presented the toxicity risk of heavy met-
the heavy metal(loid)s presented low risk at all sites. als regarding the results of MPI and PI indices. However, the
MRI (modified ecological risk index), which is calculated risk level of Mean-PEL-quotient is higher than that of the
by enrichment factor, exhibited low ecological risk at all MRI and RI methods. Totally, TRI index is more suitable
sampling stations. Also, according to RI (potential ecologi- for the PTEs risk assessment in the sediments of Hashilan
cal risk index), which is calculated by contamination factor, wetland.
all stations caused low ecological risk for ecosystem (Fig.
S6 and Table S4).
Ecological risk assessment for heavy metals in water
ΣTUs and TRI The ΣTUs and TRI values for Hashilan
sampling sites are demonstrated in Fig. S7 and Fig. S8, Water quality guidelines of heavy metals for the protection
respectively. The ΣTUs values for all sediment samples of aquatic Life and agriculture proposed by the Canadian
varied from 0.8 to 5.52. Based on the ΣTUs results, five Council of Ministers of the Environment (CCME 2007)
sampling sites demonstrated moderate toxicity risk due to were used as the water quality reference values due to the
ΣTUs values greater than 4.0, while other sampling sites agricultural activities and existence of unique species in the
indicated low toxicity to the ecosystem. According to the Hashilan wetland. Also, another reference value called TRVs
contributing mean ratios of the metal/loids toxic units (TUs) (WSRC 1999) was used to evaluate the ecological risk of
in all sediment samples to ΣTUs, Ni (54.72 ± 5.20%), Cr Hashilan water.
(19.16 ± 3.73%), and Cu (13.66 ± 6.46%) presented higher The ecological risk index calculated by three refer-
potential toxicity compared to the Zn (7.16 ± 0.95%), Pb ence values including aquatic life water permissible limits
(2.85 ± 0.89%) As (1.5 ± 1.07%), and Cd (0.97 ± 0.74%). (AWPL), irrigation life water permissible limits (IWPL) and
Also, TRI values ranged from 2.45 to 15.95, with the high- aquatic toxicity reference values (TRVs) ranged from 5.8 to
est value at S1 and the lowest at S6, which was consistent 16.3 with a mean of 9.25, 0.27 to 0.67 with mean of 0.41,
with the ΣTUs contents. Compared with the ΣTU contents, and 1.4 to 3.4 with mean of 2.36, respectively (Fig. S9). The
2 stations (S1 and S7) indicated considerable toxicity risk RI results indicated a low ecological risk for all sampling
with the TRI values greater than 15. Also, seven stations sites. With respect to the single metal risk index, the ecologi-
exhibited moderate toxicity risk with the TRI values varying cal risk of all the investigated PTEs in surface water was low.
13
Source identification of heavy metals positive correlation with Cu, while no correlation was found
in the sediments between Mo and other elements, suggesting their concentra-
tions may be controlled via different sources which cause
Correlation analysis the distributional difference between them (Suresh et al.
2012; Yuanan et al. 2020). A significant correlation was not
The Spearman correlation coefficients among trace metal/ found among cation exchange capacity (CEC) and other ele-
metalloids and those between metals and physiochemi- ments and parameters, and only a weakly positive correla-
cal parameters in the sediment system are illustrated in tion was observed between CEC and clay particles. Most
Table S5. These relationships could be applied to determine studies emphasize the CEC value depends on clay particles
PTEs sources (Ji et al. 2019b; Xiao et al. 2019). Also, the and organic matter, while the elemental composition of clay
mobility and bioavailability of heavy metals in sediments particles must be mentioned (Malcolm and Kennedy 1970).
could be affected by sediment properties like organic matter, Also, CEC values of greater particles size could be higher
particle composition, EC and pH (Gao et al. 2016). than clay particles, depending on parent material, age and
Particle size can modify the distribution and adsorp- degree of weathering, type of clay minerals, climatic factors,
tion behavior, erosion and remobilization of heavy metals and physical and chemical dispersion (Malcolm and Ken-
(Huang et al. 2020). Among different particles, fine grains nedy 1970). Therefore, in order to understand the controlling
tend to absorb more heavy metals by providing a high spe- factors of CEC parameters, the mineralogy of particles, type
cific surface area and binding sites (Gao et al. 2016; Hu of organic matter and other effective parameters should be
et al. 2018). According to the correlation coefficients, silt studied.
particles were weakly correlated with the studied elements, Spatial distribution patterns, transfer and mobility of
while clay particles illustrated positive correlation with Ni, PTEs could be affected by Fe/Mn oxides (Ji et al. 2019b).
Al, Fe, Sc (p < 0.01, r = 0.7); Co (p < 0.01, r = 0.6); Cr, Pb, However, Fe and Mn were significantly correlated with the
Zn (p < 0.05, r = 0.5) which indicate the mentioned metals studies elements except As, Cd and Mo in sediments. Nickel,
tend to accompany with the proportion of clay. However, Pb, Zn, Cr, Co, As, and Sc revealed a significant positive
only a negative correlation was found between clay particles correlation with each other (r > 0.6). Copper also showed a
and Mo (p < 0.05, r = -0.5). Also, sand particles were nega- positive correlation with As, while this heavy metal was sig-
tively correlated with the investigated PTEs except for Mo, nificantly and positively correlated with the mentioned ele-
suggesting these heavy metal(loid)s could be easily released ments, which indicate the same source probably and/or simi-
from the sand grains (Yavar Ashayeri and Keshavarzi 2019; lar geochemical behaviors for the mentioned PTEs (Suresh
Khalil and El-Gharabawy 2016). et al. 2012; Xiao et al. 2019; Zhu et al. 2017). However, Sc
Organic matter as a significant sink tends to create com- is an immobile metal that originated from lithologic sources
plexes with metals via providing certain ligands (Gao et al. (Li et al. 2020), showing the parent rock has impressed
2016; Zhu et al. 2017). However, OM was negatively cor- the contents of metal(loid)s associated with Sc. Cadmium
related with Co, Fe (p < 0.01; r = -0.8); As, Ni, Al, Cr, Sc illustrated no significant relationship with metal(loid)s and
(p < 0.01; r = -0.7), and Pb, Zn (p < 0.01; r = -0.6), indicat- parameters, and only a weakly positive correlation was
ing distribution and adsorption of the investigated elements observed among this heavy metal and Cu, Pb, Zn, Ni, and
has been less affected by organic matter compared to the Cr (P > 0.05; r = 0.3). These results may be due to the similar
other influential factors and adsorbents. Organic matter values and limited fluctuations of Cd concentrations at most
(OM) showed a significant positive correlation with sand sampling sites.
(p < 0.05; r = 0.5). The higher contents of organic matter The mobility of elements could also be controlled by
were found at the stations in which agricultural wastewa- sediment pH (Fei et al. 2019; Ustaoğlu and Islam 2020). In
ter enters the wetland because not only agricultural runoff the study area, sediment’s pH was weakly correlated with
contains high values of organic matter (Zhu et al. 2017) but the investigated metals as a result of the limited variability
also dense vegetation is observed at these situations. At the and alkaline status of pH values.
mentioned stations, as the runoff enters the wetland, the flow
velocity of agricultural runoff decreases which causes the Principal component analysis (PCA)
coarse particles to be firstly deposited in these positions.
Therefore, the association of sand particles and organic Principal component analysis was firstly employed for iden-
matter is observed in these stations which causes a strong tifying the potential contamination sources of PTEs. The
correlation between them. Molybdenum also had a positive measured KMO value and significance level of Bartlett's
correlation with OM and sand particles. Such correlations Sphericity test were 0.7 and 0 (< 0.05), respectively, indicat-
could be related to the same origin or transport path for them ing the suitability of data for performing PCA analysis. Kai-
(Liu et al. 2019). Also, this heavy metal indicated a weakly ser's rule was utilized to specify the components extracted
13
from the variables. The factor loadings > 0.75, 0.75–0.5 and (Azzi et al. 2017; Gupta et al. 2014). Also, Cu is extensively
0.5–0.3 are defined as “strong”, “moderate” and “weak”, utilized as a significant metal for pesticides or fungicides
respectively (Zeng et al. 2019; Zhang et al. 2020). Table 3 (Li et al. 2020; Liang et al. 2017). On the other hand, wear
illustrated the factor loadings of the studied PTEs at the dust from brake linings and tires of vehicles and agricultural
extracted components. machinery can be a source for the release of these elements
The PCA performance identified two varimax rotated into the environment (Lin et al. 2015). Thus, this factor is
factors with eigenvalues greater than 1 and accounting for related to both natural sources and agricultural activities.
81.62% of the total variance. The first principal component Copper on two principal components showed moderate
(PC1) accounted for 69.75% of the total contribution with loading, which suggested two sources of principal compo-
high Pb, Zn, Ni, Co, As, Mn, Cr, Al Sc, Fe loadings and nents (natural, and mixed sources) could be considered for
moderate Cu and weak Cd weights, which is in agreement this metal. Moreover, Cd metal showed ambiguous attribu-
with the results of the correlation analysis. tion and weak load on two principal components. The cor-
Based on the EF assessment, the mentioned elements relation analysis illustrated this element has no significant
except Ni and Cr exhibited depletion or minor enrichment in correlation with other elements. Also, the Cd concentrations
the sediments. Since the Ni and Cr contents in soils mainly were evaluated low and uniform, suggesting this heavy metal
depend on their concentrations in parent rocks, and human was derived from lithogenic origins.
inputs of Ni and Cr from manure, limestone, and fertilizers Then, the percent contribution of each component was
are generally less than their background values in soils (Lv assessed by multiple linear regression via performing a step-
2019), these heavy metals have been moderately enriched wise procedure. Two principal component scores including
due to the geogenic source. Totally, a natural source (parent natural and mixed sources were regressed against the inves-
rock materials) could be attributed to this component due to tigated metal(loid)s. The obtained equation is presented as:
the presence of lithogenic elements such as Fe, Sc, Mn, and
Al in PC1 (Qiutong and Mingkui 2017; Zhu et al. 2019). Z = 0.981PC1 + 0.057PC2(R2 = 0.96) (1)
PC2, with 10.25% of the total variance and 1.18 of the Then, the regression coefficients detected were applied to
Eigen value, indicated a high weight of Mo, moderate Cu estimate the portion of each source, presented by principal
loading and weak Cd weight. According to the EF values, components. Based on the results, the contribution of natu-
Mo and Cu demonstrated middle to extreme enrichments ral sources was 94.51% of the total portions and the mixed
at some stations. Also, wide and skewness EF values were sources containing geological origin and agricultural activi-
observed for Mo and Cu. Phosphate fertilizers, which are ties (fertilizers and agricultural equipment) contributed 5.5%
used in croplands, contain some metals such as Cu, and Mo of the total shares.
Although the contribution rates of two sources were spec-
ified, the PTEs portions in each source could not be achieved
Table.3 The rotated factor Principal component due to negative values detected in component scores derived
pattern derived from PCA
for the contents of heavy 1 2 from the APCS-MLR model (Dong et al. 2019).
metal(loid)s in the sediments of
Hashilan wetland Mo -0.28 0.85
Cu 0.57 0.54 Positive matrix factorization model
Pb 0.90 0.20
Zn 0.93 0.28 To verify the extracted sources of PCA analysis, the PMF
Ni 0.97 0.06 model was employed not only to recognize the sources of
Co 0.98 0.08 heavy metals but also to quantify the metal(loid)s contribu-
Mn 0.90 0.04 tions in sediments (Dong et al. 2019; Yuanan et al. 2020).
As 0.79 0.07 The PMF model run was 20 times and the seed num-
Cd 0.32 0.33 ber was randomly selected. To detect the minimum Q value
Cr 0.95 0.24 and the optimal number of origins, two to five factors were
Al 0.98 0.09 tested. The lowest and stable amount of Q was achieved
Sc 0.97 0.07 when the factors extracted were three (Fig. 2). Also, the
Fe 0.98 0.01 signal-to-noise ratios (S/N) of the investigated metal(loid)s
Eigenvalue 9.40 1.18 were higher than 1, indicating the data qualities are strong
% of variance 71.40 10.20 (Mao et al. 2020; Wu et al. 2020).
Also, the scaled residuals of sediment samples illus-
Bold figures indicating high
positive correlation of initial trated a normal distribution between -3.0 and 3.0. Moreover,
variables to rotated fact Qrobust /Qtrue ratio was 0.96 and R2 between the predicted
13
Fig. 2 Results of PMF source

apportionment modeling for
heavy metal(loid)s in the sedi-
ments of Hashilan wetland
and measured values of all metal(loid)s was greater than these elements in F2 compared to the F1 may be related
0.6, proposing the factors extracted by the PMF model are to a high CV of their concentrations. According to various
reliable (Fig. 2). The validity of PMF results was estimated researches, the concentrations of Fe, Al, Sc, Mn, Cr, and
via the performance of 80 bootstrap runs with a minimum Ni are controlled by parent materials (Dong et al. 2019;
R2 value of 0.6. Liang et al. 2017; Lu et al. 2020). These two factors, simi-
According to Fig. 3, Factor 1 (F1) was dominated by lar to factor 1 of the PCA model, propose the mentioned
Sc (42%), Fe (41%), Co (41%), Ni (40%), Zn (40%), Al metal(loid)s were released from natural weathering of rock
(39%), Pb (36%), Cr (35%), Cu (32%), followed by Mn materials (Harikrishnan et al. 2017).
(15%), Cd (12%), Mo (6%) and As (1%). The metal(loid) Factor 3 indicated high weights of Mo (94%), Cd (46%),
s in Factor 1 were again categorized into a group (Factor and Cu (27%), while its contributions to Mn (17%), Pb
2) for PMF, which was presented by As (80%), Mn (68%), (12%), As (9%), Zn (8%), Al (6%), Cr = Fe (4%), Ni (3%),
Ni (67%), Cr (61%), Co (59%), Sc (56%), Al = Fe (55%), and Sc (2%) were relatively low. As mentioned, EF values
Pb = Zn (52%), Cu (41%), and Cd (32%). As mentioned, of Mo and Cu were middle to extreme at some stations.
As and Mn elements showed natural sources based on the Also, Mo and Cu are found in fertilizers, manures and
EF and I geo equations. However, higher percentages of other agricultural activities (Azzi et al. 2017). Thus, this
13
Fig. 3 Contribution of the
heavy metal(loid)s according to
factor profiles obtained by PMF
model
factor would describe the same pollution source (mixed Nickel, Cr, Mn, Cu, Co, and Pb indicated higher con-
natural and agricultural origins) as PC2 of PCA analysis. tents of Kp (log Kp > 2.9) relative to other elements, propos-
Similar to PCA analysis, which indicated analogous and ing their lower solubility in water and higher affinity to be
weak weights of Cd in two PCs, the cadmium contribu- adsorbed to sediment samples. The relatively higher Kp (log
tions between F3 and (F1 and F2) of the PMF model were Kp > 2.9) of As and Zn were recognized at most stations,
almost similar. However, the EF and Igeo of Cd illustrated suggesting these elements prefer to be adsorbed in solid-
the weathering of parent rock has controlled its concentra- phase compared to soluble phase. However, As and Zn were
tions in soil and sediment of Hashilan wetland. Copper also present in the water phase at (S8, S12) and (S5, S8) stations,
showed a similar load on two principal components in the respectively.
PCA analysis, while Cu in the PMF model accounted for In contrast, relatively lower K p of Cd (log K p < 2.9) pro-
27% of factor 3 and 73% of F1 and F2, proposing the natural posed the lower affinity of solid phase to adsorb this ele-
sources include a larger contribution of Cu compared to the ment. The distribution coefficient of Mo indicated that this
agricultural activities. element is more present in soluble phase relative to solid-
Due to the different algorithms used by PCA and PMF phase except for S3, and S8 sites due to high mobility of Mo
models, the results of source contributions illustrate differ- at natural to alkaline conditions (Smedley and Kinniburgh
ences. Thus, the comparison of models helps to obtain more 2017).
detailed information of metal(loid)s sources. In the Hashilan wetland, the median log K p contents for
As, Co, Cr, Cu, Mo, and Ni were, 3.7 L/kg,4.2 L/kg, 5.13
Sediment–water distributions L/kg, 4.6 L/kg, 2.7 L/kg, and 6.02 L/kg respectively, which
presented the higher values relative to the respective median
Some agents such as pH, metal contents in soluble and solid contents for the EPA (Allison et al. 2005).
phases, the values of metal complexing agents, and the
physio-chemical properties of water and sediments affect the Correlation of phase partition with influential factors
partition coefficient of elements in the water–sediment sys-
tem (Allison et al. 2005). High contents of Kp (log Kp > 2.9) Clay particles tend to adsorb heavy metals due to the nega-
indicate that PTEs prefer to be available in the sediment tive charge and high surface area (Zhao et al. 2013). In this
phase; whereas, low contents (log Kp < 2.9) show that the study, clay particles indicated the weakly positive trend with
solution has preferentially preserved the dominant portion partition coefficients of Cu, Zn, Ni, Co, Cd, Fe, Al (r < 0.5)
of metal(loid)s (Jung et al. 2005). and a significant opposite trend with Mo (r = -0.8). Also,
Among the PTEs, Ni presented the highest K p with 6.25 silt particles showed a negative correlation with partition
L/kg (S1 site); whereas, the lowest K p content belonged coefficients of Fe, Sc (r = -0.9), and Cu, Zn, Ni, Co, Cr,
to the Cd with 2 L/kg (S5 site). The mean values of Kp As, Al (r = -0.7) (Table S7). However, smaller grains are
decreased as (L/kg): Ni (5.92) > Cr (4.92) > Mn (4.67) > Cu favorable to desorb or adsorb the metals (Feng et al. 2017).
(4.43) > Co (4.05) > Pb (3.54) > As (3.53) > Zn (2.96) > Mo The positive correlation of OM with partition coefficients
(2.76) > Cd (2.20) (Table S6). of Pb and Mo (r = 0.4) showed that these particles create
bonds to prevent Pb and Mo liberation. However, a negative
13
correlation of OM with partition coefficients of Cu, Ni, Co, O3− input enters wetland water, which can pose a threat to
N
As, Cd, Fe, Sc, Al, and Mn (r = (-0.3)-(-0.7)) was observed. increase the risk of water eutrophication. This is of particu-
In the investigated stations, pH values showed opposite trend lar importance in wetland ecosystems with a high propor-
with Mo and As (r = -0.9 and -0.5, respectively), while this tion of agricultural use because their effluents are mostly
parameter did not affect the distribution coefficients of the enriched by N, mainly in form of NO3− derived from ferti-
other mentioned elements (Table S7). However, although lizers that are not fixed to the exchangeable soil complex. In
the range of pH fluctuations is small, varying from 6.50 to fact, wetlands have been highlighted as valuable ecosystems
6.88, this factor could influence the Mo and As desorption to mitigate the negative impacts of NO3− excess because of
from sediments. In this study, the effect of other influential their capacity to act as green filters (Álvarez-Rogel et al.
factors like Fe–Mn oxides concentrations in sediments, and 2016). On the other hand, low depth and standing water at
the sorbents nature and their values in water on the metal S8 and S12 stations can also promote evaporate process,
partitioning must be examined. causing an increase in the concentration of pollutants. Also,
all samples had nitrite (NO2−) and ammonia (NH3) values
Agricultural nutrient pollutants and eutrophication well below the FAO (1973), as shown in Table S8. The max-
imum NO2− (0.038 mg/l) and N H3 (1.58 mg/l) value was
In wetland ecosystems, the fate of nutrients (N and P) is also measured at the S8 station. Environmental and health
determined by a combination of natural processes and concerns associated with different forms of nitrogen in water
human activities such as agriculture (Uwimana et al. 2018). can be classified as human health, aquatic life toxicity, and
Due to the unreasonable and excessive application of pesti- eutrophication. Exposure to nitrate and in some cases nitrite
cides and fertilizers, and agricultural non-point source con- polluted water has notably contributed to methemoglobine-
tamination has led to severe eutrophication in downstream mia in infants. According to the Safe Drinking Water Act
wetlands (Yu et al. 2018). The increase in nitrate and phos- standard, known as a maximum contaminant level (MCL),
phate contamination in surface water and groundwater of established by the US Environmental Protection Agency
the study area is associated with intensive agriculture activi- (EPA), the nitrate and nitrite concentrations in the wetland
ties that are lead to an increased load of nutrient pollutants water (except at S8 station for nitrate) were below 10 mg/l
through the use of nitrogen and phosphate fertilizers. On and 1 mg/l, respectively.
the other hand, high N and P concentrations are the main The highest concentration TP (0.2 mg/1) was found in the
cause of the eutrophication of wetland water. Not only do water of the S12 station due to receiving effluents from agri-
these impact the ecological character of wetlands, but they cultural lands, and the lowest value was measured 0.02 mg/l
also have effects on human health and the quality of drink- in the water of S1 station, which is located close to Sabz Ali
ing water supplied from wetlands (Ramsar 2014). Therefore, spring. Both total phosphorus (TP) and phosphate ( PO43−)
in this study, the contamination of N and P compounds as values did not differ significantly between the different sta-
nutrient pollutants in the water is compared with drinking tions although TP concentration at all stations was twice
and agricultural water standards. As shown in the Table S8, high as that in the P O43− concentration, as shown in Fig.
3−
the total nitrogen (TN) concentration in water samples was S11. The PO4 concentration ranged between 0.01 mg/l
varied between 8.63 mg/l and 48.16 mg/l. Exceptionally and 0.14 mg/l with a mean value of 0.05 mg/1 (Table S8).
high TN concentration were observed at S8 site which could Moreover, the PO43− concentration at all sampling points
be related to agricultural activities which has likely mostly was below the recommended limit of 2 mg/l (FAO 1973).
increased the concentration of TN in the station due to the Increasing the P O43− concentration in water can cause accel-
use of chemical fertilizers. erated growth of phytoplankton (algal blooms) and pose
Nitrate (NO3−) is typically the dominant form of N in a threat to water eutrophication in the wetland. Nuisance
natural waters and polluted water. Nitrate and other forms of algal growths are not uncommon in surface waters below
nitrogen in an aquatic ecosystem can originate from natural the low reference level (0.1 mg/l) for P by recommended
sources, but when N values are elevated, the sources are water quality criteria (US EPA 2002), however, the results of
commonly related to anthropogenic sources (MPCA 2013). this study suggested that the P concentration at the S12 sta-
In Fig. S10 and Table S8, the values of nitrate ( NO3−) in tion is more than the reference level and can cause negative
water sampling stations are observed. NO3− values in all impacts in a long time on the wetland health. Zhang et al.
stations (except S8) were lower than the value reported by (2003) found that in TP value between 0.16 and 0.25 mg/l,
FAO (1973). In the S8 station, the NO3− concentration was the water state changes from fresh to turbid resulting in a
37.08 mg/l, due to water samples being taken near the farms. significant decrease in the submerged vegetation. There
However, the mean N O3− concentration was relatively are various sources of P, both natural (such as soils, rocks
higher in wetland water (10.39 mg/l), which showed the use and atmospheric precipitation) and human (including agri-
of massive anthropogenic fertilizers has caused an additional cultural fertilizers, municipal and industrial wastewater)
13
origins. Apatite [Ca5(PO4)3(F,Cl,OH)] is the most abun- in all the water samples was higher than the Redfield ratio
dant naturally occurring P containing mineral in the Earth’s of 16, and was thus P limited. This coincided with the high
crust. The world’s main source of phosphatic fertilizer is inputs of N at this wetland (Fig. S12). Also, the N:P ratio
rock phosphate, a naturally occurring P-rich sedimentary or shows that in Hashilan wetland, like most other freshwa-
igneous rock containing about 5–13% P (Nieder et al. 2018). ter ecosystems, is commonly P limited. In fact, phosphorus
The major external source of P in the water of Hashilan is the main limiting nutrient for the primary production of
wetland is agricultural runoff. phytoplankton in many freshwater systems, while nitrogen
To evaluate the trophic status of a water column there are is generally limiting in marine environments (Howarth and
no fixed or perfect assessment criteria. However, the general Marino 2006). Although excessive TP and TN in water are
parameters to evaluate the trophic stage or eutrophication considered as the only factors inducing water eutrophication,
include dissolved oxygen concentration, water transpar- nutrient enrichment is only necessary but not an adequate
ency, algal chlorophyll, and total nutrient concentration (P condition for the algal bloom. Water eutrophication can
and N). In general, it is convenient to associate the trophic occur quickly when all of the influencing factors involving
status in terms of nutrient concentration as this is the key slow current velocity, excessive TP and TN, biodiversity and
factor controlling the eutrophication process (Bhagowati and microbial activity, and temperature and other environmental
Ahamad 2019). The general guideline for N and P concen- factors are favorable (Yang et al. 2008).
trations indicating the different trophic states of the water
column are given in Table S9. The eutrophication or red
tide occurs when total nitrogen and phosphorus concentra- Conclusion
tions exceed 300 μg/l and 20 μg/l, respectively (Yang et al.
2008). According to the finding of Richardson et al. (2007), This study focused on the distribution, fate, ecological risk
threshold protective of total phosphorus for all trophic levels assessment, and source apportionments of heavy metal(loid)
would best be defined as a threshold zone at 12–15 μg/l, s in sediments of Hashilan wetland. In this research, several
and exceeding surface water TP threshold value of 15 μg/l methods for pollution and risk assessment were used, in order
can cause an ecological imbalance of algal, macrophytes to best interpret the pollution state of water and sediments of
and other aquatic organisms. For data evaluation purposes the wetland. The results showed that the highest values of the
nutrient levels in the Hashilan wetland are compared to investigated elements belonged to farmlands that are located
the trophic status guidelines (Table S9). According to the near the road. However, only the mean concentrations of Ni,
trophic status classification scheme, based on the TP levels, Cr, and Cu in sediment samples were higher than those in
the S2, S3, and S8 stations were at a eutrophic state. In the the world-soil average. However, Ni and Cr were moderately
S1 station, the TP content was 0.02 mg/l and was at a meso- enriched at most stations. The moderate and significant enrich-
trophic state and the water quality of the S5 and S12 stations ments of Mo and Cu in sediments were measured at some sam-
was hypertrophic level. Based on the mean TP concentration pling sites where agricultural runoff enters the wetland. Due
(0.08 mg/l), the water quality of the Hashilan wetland was to the moderate and significant enrichments of the mentioned
at a eutrophic state. Concentrations of TP higher than 30 µg elements, all stations were moderately and severely polluted.
/l are generally considered favorable for eutrophication in Among the several methods of risk assessment, the TRI equa-
freshwater ecosystems, provided that inorganic nitrogen or tion better presented the toxicity risk of heavy metals regarding
other nutrients are not limiting (De Villiers 2007). In addi- the results of the MPI index which shows more than half of the
tion, minimum and maximum TN concentrations indicate stations pose considerable to moderate environmental risk. The
that all of the Hashilan wetland monitoring stations have highest risk contribution belonged to the Ni element.
come into hypertrophic conditions, i.e., TN values exceed- According to the EF and two multivariate receptor models,
ing 2000 µg/l according to the trophic status classification Pb, Zn, Ni, Co, As, Mn, Cr, Al Sc, and Cd were mainly origi-
scheme (Table S8 and S9). Our results indicated that TP nated from natural sources while Mo and Cu were derived from
and TN concentrations in Hashilan wetland exceeded the mixed natural and agricultural activities. High concentrations of
thresholds for algae blooms. On the other hand, increased Ni and Cr are related to the Ophiolite sequences of the Zagros
levels of the nutrient towards the downstream of the wetland fold-and-thrust belt which along with Cu and Mo have con-
possibly reflect the intensity of human activities within the taminated the sediments of most stations. Also, low pollution
reaches of the catchment. of TPH was observed in Hashilan sediment samples, propos-
The ratio of N:P in the water body (referred to as the ing the impact of anthropogenic sources on the TPH values
“Redfield ratio”) is an important indicator of which nutri- is low. The results indicated that the surface water of a few
ent is limiting eutrophication. The high ratio of N:P which stations are contaminated with Zn, Cu, and Cd. However, the
is greater than 16 indicates that P is most likely a limiting ecological risks of these elements to the aquatic biota were neg-
nutrient to plant growth (Zheng et al. 2019). The N:P ratio ligible. Also, downstream stations indicated higher phosphate
13
and nitrate concentrations compared to the other sites due to Abbasi S, Keshavarzi B (2019) Source identification of total petroleum
the entrance of agricultural effluents in this part of the wetland. hydrocarbons and polycyclic aromatic hydrocarbons in PM10 and
street dust of a hot spot for petrochemical production: Asaluyeh
According to the mean TP and TN concentrations, the water County, Iran. Sustain Cities Soc 45:214–230
quality of the wetland was at eutrophic and hypertrophic status, Abbasi S, Keshavarzi B, Moore F, Mahmoudi MR (2018) Fractiona-
respectively. Totally, monitoring and urgent actions must be tion, source identification and risk assessment of potentially
done to reduce the input of nutrients into the water body. toxic elements in street dust of the most important center for
petrochemical products, Asaluyeh County, Iran. Environ Earth
Sci 77:673
Supplementary Information The online version contains supplemen- Abbasi S, Keshavarzi B, Moore F, Shojaei N, Sorooshian A, Soltani
tary material available at https://d oi.o rg/1 0.1 007/s 11356-0 21-1 7937-x. N, Delshab H (2019) Geochemistry and environmental effects of
potentially toxic elements, polycyclic aromatic hydrocarbons and
Acknowledgements This study was funded by the Cultural Heritage, microplastics in coastal sediments of the Persian Gulf. Environ
Handicrafts and Tourism Organization of Iran (Natural Heritage) and Earth Sci 78:492
the authors wish to express their gratitude to Shiraz University for Abbasi S, Ashayeri SY, Jafarzadeh N, Fakhradini SS, Alirezazadeh
logistic and technical assistance. M, Ebrahimi P, Peely AB, Rezaei N, Mokhtarzadeh Z, Naraki H
(2021) Hydrological and hydrogeological characteristics and envi-
Author contribution Sajjad Abbasi: Initial idea, Sampling, Project ronmental assessment of Hashilan Wetland, a national heritage in
manager, Project leader, Laboratory activity, Conceptualization, Meth- NW Iran. Ecohydrology Hydrobiology. https://doi.org/10.1016/j.
odology, Investigation, Interpretation, Writing, Review and Editing. ecohyd.2021.08.014
Sara Sheikh Fakhradini: Conceptualization, Investigation, Inter- Akhbarizadeh R, Moore F, Keshavarzi B, Moeinpour A (2016) Ali-
pretation, Writing, Review and Editing. phatic and polycyclic aromatic hydrocarbons risk assessment
Nematollah Jafarzadeh: Review and Editing. in coastal water and sediments of Khark Island, SW Iran. Mar
Pooria Ebrahimi: Review and Editing. Pollut Bull 108:33–45
Shirin Yavar Ashayeri: Interpretation, Writing, Review and Allahyari K, Saccani E, Pourmoafi M, Beccaluva L, Masoudi F
Editing. (2010) Petrology of mantle peridotites and intrusive mafic
rocks from the Kermanshah ophiolitic complex (Zagros belt,
Funding This study was funded by the Cultural Heritage, Handicrafts Iran): implications for the geodynamic evolution of the Neo-
and Tourism Organization of Iran (Natural Heritage). Tethyan oceanic branch between Arabia and Iran. Ofioliti
35:71–90
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(2016) Presence of pharmaceuticals and heavy metals in the
Consent for publication Not applicable. waters of a Mediterranean coastal wetland: potential interac-
tions and the influence of the environment. Sci Total Environ
Competing interests The authors declare no competing interests. 540:278–286
ATSDR (Agency for Toxic Substances and Disease Registry) (2017)
Agency for toxic substances and disease registry, substance
Open Access This article is licensed under a Creative Commons Attri- priority list. Available at https://www.atsdr.cdc.gov/spl.index.
bution 4.0 International License, which permits use, sharing, adapta- html#2019spl
tion, distribution and reproduction in any medium or format, as long Azzi V, Kazpard V, Lartiges B, Kobeissi A, Kanso A, El Samrani
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included in the article's Creative Commons licence, unless indicated dynamics and recent developments in lake modeling. Ecohydrol
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the article's Creative Commons licence and your intended use is not CCME (Canadian Council of Ministers of the Environment) (2007)
permitted by statutory regulation or exceeds the permitted use, you will Canadian Water Quality Guidelines for the Protection of
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Abbasi 2021

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Environmental Science and Pollution Research (2022) 29:27007–27025

Eutrophication and sediment–water exchange of total petroleum

Keywords Heavy metal · TPH · Eutrophication · Wetland · Hashilan · Iran

Introduction Tuboi et al. 2018). Nowadays, anthropogenic stressors such

Fig. 1 Map of the study area

Data analysis Concentration of heavy metal(loid)s in water

Ni 1 17 136 80.94 40.16 0.5 18 36 18 0.1 < 0.1 < 0.1 - - - - 20 - 87.71

S1 1.30 5.57 53.99 0.11 1.13 6.85 68.96

Fig. 2 Results of PMF source

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Abbasi 2021

Uploaded by

Copyright:

Available Formats

Abbasi 2021

Uploaded by

Document Information

Original Title

Copyright

Available Formats

Share this document

Share or Embed Document

Sharing Options

Did you find this document useful?

Is this content inappropriate?

Copyright:

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Abbasi 2021

Uploaded by

Copyright:

Available Formats

Environmental Science and Pollution Research (2022) 29:27007–27025

Eutrophication and sediment–water exchange of total petroleum

Keywords Heavy metal · TPH · Eutrophication · Wetland · Hashilan · Iran

Introduction Tuboi et al. 2018). Nowadays, anthropogenic stressors such

Fig. 1 Map of the study area

Data analysis Concentration of heavy metal(loid)s in water

Ni 1 17 136 80.94 40.16 0.5 18 36 18 0.1 < 0.1 < 0.1 - - - - 20 - 87.71

S1 1.30 5.57 53.99 0.11 1.13 6.85 68.96

Fig. 2 Results of PMF source

You might also like

Fig. 1 Map of the study area

Fig. 2 Results of PMF source