Bisphenol A (BPA) and polycyclic aromatic hydrocarbons (PAHs) in the surface sediment and bivalves from Hormozgan Province coastline in the Northern Persian Gulf: A focus on source apportionment

Marine Pollution Bulletin 152 (2020) 110941

Contents lists available at ScienceDirect

Marine Pollution Bulletin journal homepage: www.elsevier.com/locate/marpolbul

Bisphenol A (BPA) and polycyclic aromatic hydrocarbons (PAHs) in the surface sediment and bivalves from Hormozgan Province coastline in the Northern Persian Gulf: A focus on source apportionment

T

⁎

Fatemeh Abootalebi Jahromia, Farid Moorea, Behnam Keshavarzia, , Seyedeh Laili Mohebbi-Nozarb, Zargham Mohammadia, Armin Sorooshianc,d, Sajjad Abbasia a

Department of Earth Sciences, College of Sciences, Shiraz University, Shiraz, 71454, Iran Persian Gulf and Oman Sea Ecological Research Institute (PGOSERI), Iranian Fisheries Science Research Institute (IFSRI), Agricultural Research Education & Extension Organization (AREEO), Bandar Abbas 79145-1597, Iran c Department of Chemical and Environmental Engineering, University of Arizona, Tucson, AZ 85721, USA d Department of Hydrology and Atmospheric Sciences, University of Arizona, Tucson, AZ 85721, USA b

A R T I C LE I N FO

A B S T R A C T

Keywords: Coastal sediments Bivalve SOM PMF Risk assessment Human health risk

This study investigates Polycyclic Aromatic Hydrocarbons (PAHs) and Bisphenol-A (BPA) pollution in coastal sediments and bivalves of Hormozgan Province coastline. The results indicated that the BPA concentration in some bivalves reached up to 340.16 ng g−1. The mean BPA concentration in the sediment samples was also 787.01 ng g−1. The ∑PAHs content in sediments ranged from 14.54 to 85.00 ng g−1, while values for bivalves ranged from 5.37 to 16.40 ng g−1. Individual PAH concentrations in sediments exceeded those in bivalves for which only LMW PAHs were detected. A combination of techniques including Self-Organizing Maps (SOM), Positive Matrix Factorization (PMF), and Cluster Analysis (CA) were applied and both petrogenic and pyrogenic sources were identified. The risk of PAHs in the sediments was relatively low according to the sediment quality guidelines. The health risk indices suggest that exposure to PAHs through bivalve consumption does not impose harmful health effects upon consumers.

1. Introduction In the past few decades, rapid urbanization and increased pollution have resulted in increased demand for fossil fuels including petroleum and coal (Habibullah-Al-Mamun et al., 2018; Najmeddin and Keshavarzi, 2018). Oil and its refined products comprise various chemicals including heavy metals, organic compounds, and some rare elements, which have the potential to cause environmental pollution (Li et al., 2015). Aquatic environments receive pollutants from point and non-point sources. Severe human activities exacerbate environmental pollutions, especially in coastal areas (He et al., 2014; Li et al., 2014). Polycyclic aromatic hydrocarbons (PAHs) are persistent organic pollutants (POPs) and considered as environmental contaminants with more than two fused benzene rings (EPA, 2002). PAHs can be categorized into two main groups: Low Molecular Weight (LMW; two to three benzene rings) PAHs and High Molecular Weight (HMW; four to six rings) PAHs (Rocha and Palma, 2018; Wang et al., 2015). The European Union and the US Environmental Protection Agency (EPA)

⁎

consider PAHs as toxic pollutants because of their carcinogenic and mutagenic specifications (EPA, 2002). Their low solubility in water and high solubility in lipids is a key factor that affects their behavior in the environment (Fisner et al., 2013). PAHs pollute the environment via two sources: pyrogenic (incomplete combustion) and petrogenic (spills of crude oil and its products) (Zakaria et al., 2002). Another important POP with over 8 billion pounds annual production is Bisphenol A [BPA; 2,2-bis (4-Hydroxyphenyl) Propane] (Fu and Kawamura, 2010). It is generally used in polycarbonate plastics and epoxy resins production (Battal et al., 2014). During production, and through leaching from consumer products, BPA may be released into the environment (Huang et al., 2012). Effluent discharges from sewage treatment plants, industrial discharges and municipal waste are the main sources of bisphenol A and alkylphenols in aquatic media (Langford et al., 2005; Rice et al., 2003). Ethoxylate groups of alkylphenols ethoxylates are deleted hydrolytically and biodegraded into short-chain ethoxylates, following by the sewage treatment and converted to alkylphenols as more persistent and lipophilic metabolites

Corresponding author. E-mail address: [email protected] (B. Keshavarzi).

https://doi.org/10.1016/j.marpolbul.2020.110941 Received 3 November 2019; Received in revised form 19 January 2020; Accepted 25 January 2020 0025-326X/ © 2020 Elsevier Ltd. All rights reserved.

Marine Pollution Bulletin 152 (2020) 110941

F. Abootalebi Jahromi, et al.

from the top 5 cm that including 10 samples from the coastline of Bandar Abbas (S1–S10), five samples from the protected mangrove forest (S11–S15), and three blank samples from the west, east, and south of Hormozgan (S16–S18) to be far from the probable contamination sources. The all samples were collected from sites with 1500 m distance from the shoreline. To collect the samples, a stainless steel Van Veen grab sampler was used with approximate overall dimensions of 20 × 30 × 60 cm, 5 kg weight, and an area of 250 cm2. To determine the PAHs concentration in sediments, the collected samples were homogenized and immediately transferred into dark glass jars that were pre-washed with n-hexane. Screw aluminum foil caps were used to provide a gas-tight seal. All samples were cooled using an icebox at 4 °C during transportation to the laboratory where they were stored at −20 °C prior to further analysis. The collection of bivalve samples was carried out in December 2017 along the coastline of Bandar Abbas and Bandar Lengeh city. Seven bivalve species (> 30 samples for each species) were collected along the coasts of both cities (Table 1). Once collected, the samples were immediately placed inside an icebox and transferred to laboratory for further analysis. The bivalves' soft body was dissected with a clean scalpel. Ten composite soft tissue samples from each species were homogenized and freeze dried and kept at −20 °C for PAH and BPA analysis. Table 1 shows the scientific binomial names of the selected bivalves in this study.

(Lye et al., 1999; Nimrod and Benson, 1996). These contaminants that are ubiquitous in the marine environment have also been identified in sewage emissions as well as surface sediments in varying concentrations (Talmage, 1994). BPA remains stable in groundwater and sediment for up to 70 days (Corrales et al., 2015). The adverse effects of BPA on development and reproduction, cardiovascular, neural networks, metabolic and immune systems in humans are well-documented (Mortazavi et al., 2012). The marine environments are the most important ecosystems that receive persistent organic pollutants (POPs) (Robinson et al., 2017). Due to hydrophobic properties and long halflife, POPs accumulate and remain in sediments for many years (Česen et al., 2018). Thus, sediments are a good marker for sources and history of pollution in aquatic media (Dissanayake and Bamber, 2010). Bivalve mollusks and other shellfish have mostly the capability to accumulate PAHs pollutants (Aarab et al., 2011). The immobility of bivalves prevents their migration from areas with high concentrated contaminants (Thompson et al., 2017). They ingest the suspended contaminants in the sea water or take up onto sediment in a filter feeding process. Hence, bivalves can be selected for monitoring contamination (Schøyen et al., 2017). Furthermore, contaminated sediments participate in the incorporation of pollution into the marine food web (Grung et al., 2016). Therefore, the accumulation of PAHs in aquatic species may adversely affect their productivity and health (Thompson et al., 2017; Tolosa et al., 2005). Furthermore, it may influence the health and nutritional status of the population who routinely consume seafood. Human exposure to PAH components may also cause an increased rate of birth defects, mutations, and cancers (Barhoumi et al., 2016). Although many approaches exist for identification of PAHs in the Persian Gulf, which have been carried out by many past studies (Abbasi and Keshavarzi, 2019; Akhbarizadeh et al., 2016; Nozar et al., 2013; Nozar et al., 2014; Sereshk and Bakhtiari, 2014), the contamination level of BPA in the study area is still a gap which will be investigated in this study. The aims of the current study are to (i) report the 16 EPA's concentration, priority PAHs, and BPA in surface sediments and bivalves at coastal sites vulnerable to varying pollutants from different sources in Hormozgan Province, (ii) recognize possible contamination sources of PAHs utilizing diagnostic ratios, Self-Organizing Maps (SOM) and Generalized Estimating Equations (GEE), and (iii) evaluate the potential health risks associated with PAHs in sediments and bivalves and BPA in sediments.

2.3. Physicochemical properties The sediment samples were dried at below 30 °C ambient temperature and sifted by a 2 mm sieve. The grain size (clay, silt, and sand fraction) distribution was identified using a hydrometer procedure (Gee and Bauder, 1986). Cation exchange capacity (CEC), pH, and electrical conductivity (EC), were measured in suspensions and they were dried at 105 °C. To quantify Organic Matter (OM) content with setting stable mass, four hour Loss on Ignition method (LOI) was applied at 550 °C (Yavar Ashayeri et al., 2018). Consequently, a correction factor of 1.724 was applied to estimate the content of Total Organic Carbon (TOC) (OM = TOC × 1.724) (Yavar Ashayeri et al., 2018). 2.4. Extraction method and PAHs analysis As a preliminary step before extraction, in order to achieve optimal recovery, the sediment and biota samples were dried in a freeze-drier. The PAHs analysis of sediments was performed in accordance with MOOPAM (Moopam, 2005). The dried sediment and biota contents were weighed and put in a mixture of 50:50 hexane and dichloromethane (DCM) and subjected to microwave radiation under special conditions as follows: Temperature increase to 115 °C in 10 min; microwave power of 1200 W, 20 min extraction time at 115 °C, and cooling to the room temperature within 1 h (Moopam, 2005). To eliminate sulfur interference activated copper was applied. Removal of lipids was performed through a saponification reaction of fats with 2 M KOH solution under microwave radiation for 10 min at 90 °C. Instrumental analysis of sediment and biota extracts for PAHs was performed using a gas chromatography system (Agilent 7890 N) employing an auto-injection apparatus which is comprised of a mass selective detector (Agilent 5975C). The capillary column was an HP-5 (30 m fused silica, 0.25 mm i.d., 0.25 mm film). The carrier gas applied at a constant pressure at 100 kg/cm2 was Helium. The temperature of the injection port was fixed at 300 °C and the splitless mode was applied for the injection of the sample followed by these steps: purge 1 min after the column temperature was set at 40 °C for 1 min, then programmed at 15 °C/min to 100 °C, held for 10 min, then 5 °C/min to 225 °C and held for 0 min, then 15 °C/min to 320 °C and held for 7 min (Moopam, 2005). Quantification and identification and of 16 PAHs compounds were achieved using the GC–MS solution software according to their suitable maintenance time with a combination of PAH

2. Materials and methods 2.1. Study area Hormozgan Province is situated in the south of Iran and to the north of the Persian Gulf, facing the United Arab Emirates and Oman. The province has fourteen islands in the Persian Gulf and 1000 km of coastline, covering an area of 71,193 km2 with a population of 1,500,000 people (Hatam et al., 2015). It is well-known nationally and internationally for its strategic position in oil production and export. Also, Hormozgan Province has rich marine resources, many potential tourism areas, natural ore reserves and related industries, and ports. Nevertheless, many industries have been established along the coastal lines of Hormozgan Province, which resulted in the release of untreated or imperfect treated urban and industrial wastewater to the marine ecosystem. Bandar Abbas, the most important city of this province, is the most urbanized and industrialized city. 2.2. Sediment and bivalve sample collection The sediment sampling stations were selected along the coastline where there is influence from urban and industrial discharges (Fig. 1). Sediment sampling was carried out in November 2017, coincident with a period of high tide. A total of 18 surface sediment samples were taken 2

Marine Pollution Bulletin 152 (2020) 110941

F. Abootalebi Jahromi, et al.

Fig. 1. Sediment sampling stations along the coastline of Hormozgan Province.

analysis. Analysis was conducted through an HPLC system (Knauer, Germany) which equipped with a 20 μL sample loop manual injector, a smart-line pump 1000, UV detector set at 220 nm. An isocratic elution was used to separate the compound on a Eurospher 100–5-C18 column (Particle size of 5 μm 250 mm × 4.5 mm) Acetonitrile-water (80:20, v/ v) solution with 0.001 L min−1 flow rate was used as the mobile phase (Mortazavi et al., 2013, 2012).

Table 1 Summary of collected bivalves and respective sampling locations. No

Scientific name

Family

Location

B1 B2 B3 B4 B5 B6 B7

Saccostrea sp. Circenita callipyga Barbatia helblingii Solen brevis Amiantis umbonella Telescopium telescopium Saccostrea sp.

Ostreidae Veneridae Arcidae Solenidae Veneridae Potamididae Ostreidae

Bandar Bandar Bandar Bandar Bandar Bandar Bandar

Lengeh Coast Lengeh Coast Lengeh Coast Abbas Coast Abbas Coast Abbas Coast Abbas Coast

2.6. Quality control and quality assurance (QC/QA) The quality assurance (QA) plan summarized here that was used to prevent any imperfections and errors while doing the experimental analysis in the laboratory and to produce high point quality and reasonable data. The essential necessities of a QA plan are to identify the probable errors, recognize the used measurement system, and improve methods and plans in order to reduce possible errors (Sakari et al., 2012; Zakaria et al., 2002). Quality assessment comprises replicates, reference materials (IAEA-417 and IAEA-406 for PAHs and BPA-d16 for BPA), spikes, splits, surrogates, collaborative tests, and statistical analysis, all of which were conducted for this work. All internal and native standards were prepared daily and utilized during the analysis. Blanks were regularly tested to investigate any cross-contamination from the glassware and also form the analytical procedure. By running the method blanks, it was confirmed that interferences from sources such as sample preparation glassware were avoided. If the levels of the target analyte exceeded the quality control or if any contamination was detected in target compounds, the samples were re-extracted and reanalyzed (Zakaria et al., 2002). The analytical procedure validation was performed by analyzing samples, spiked with a specific quantity of the compounds, and measured in duplicate. The spikes mean recovery in bivalve, and sediment samples varied in the range of 85–96%, and 92–97% respectively. Thus, the analytical accuracy on 10% order was

standards. All 16 target PAHs were analyzed. They were Naphthalene (Nap), Acenaphthylene (Ac), Acenaphthene (Ace), Fluorene (Fl), Phenanthrene (Phe), Anthracene (Ant), Fluoranthene (Flu), Pyrene (Pyr), Benzo[a]anthracene (BaA), Chrysene (Chr), Benzo[b]fluoranthene (BbF), Benzo[k]fluoranthene (BkF), Benzo[a]pyrene (BaP), Dibenzo[a,h]anthracene (DahA), Benzo[g,h,i]perylene (BgP), and Indeno[1,2,3-cd]pyrene (InP). The PAHs concentration was illustrated as ng g−1 based on the dry weight in the sediment and bivalve samples. 2.5. Extraction and analysis of BPA The extraction of BPA in sediment and biota samples was conducted with an adapted method (Mortazavi et al., 2013, 2012). Fractions of each samples (5.00 ± 0.10 g) were weighed and extracted using a 5 mL solution mixture of methanol (MeOH) and dichloromethane (DCM) (9:1, v/v) (Mortazavi et al., 2013, 2012). Extraction of BPA was performed by 60 min sonication at fixed temperature of 25 °C following by shaking for 3 h at 25 °C in a rotary. Samples were centrifuged for 45 min at a speed of 4000 rpm, (Hettich Rotina 380, Germany), later they were filtered and prepared by a 0.45 μm PTFE filter for HPLC 3

Marine Pollution Bulletin 152 (2020) 110941

F. Abootalebi Jahromi, et al.

where TEFi denotes the ith PAH toxic equivalent quantity; CPAHi refers to the concentration of the ith PAH; TEQPAH represents the toxicity level of ∑PAHs, which is equivalent to the toxic BaP concentration. TEF values of Chr, BaA, BkF, BbF, InP, BaP, and DahA are 0.01, 0.1, 0.1, 0.1, 0.1, 1, and 1, respectively.

achieved. No target PAHs, or BPA were observed in the method's blank samples. The detection limits for different PAH components varied from 0.1 to 2.1 ng g−1 (Table S1 in supplementary information), and for BPA was 0.05 ng g−1 in sediment and bivalve samples. 2.7. Statistical analysis and source apportionment of PAHs

2.9. Eco-toxicity assessment Data statistical analysis was performed using SPSS 21 for Windows. The level of significance in all analysis was 0.05. The Shapiro-Wilk normality test was applied to normalize all PAHs. If PAH levels were below detection limit (DL), then they were considered as 0.75 of the detection limit (Yavar Ashayeri and Keshavarzi, 2019). In order to understand the variation patterns, the PAHs' total, mean, and standard deviation were measured for each site. The data were analyzed further utilizing diagnostic PAH ratios, and source apportionment methods, Generalized Estimating Equations (GEE), Self-Organizing Maps (SOM), Positive Matrix Factorization (PMF), Cluster Analysis (CA), and the ttest. For information about the GEE and PMF models, the readers can refer to previous studies (Abbasi and Keshavarzi, 2019). A SOM is a type of unsupervised artificial neural network method which was introduced by Kohonen (1990). This technique is specifically designed for multidimensional datasets analysis, and two dimensional visualization when the rigid hypotheses of traditional statistical linearity methods is absent (Alvarez-Guerra et al., 2008; Tobiszewski, 2014). SOM categorizes information based on resemblance using a learning process. The learning algorithm used in standard SOM is separated into six steps (Peeters et al., 2007). In brief, a Self-organizing map network structure includes an interconnected input and neurons layers. There is a connection between every input vector with another neurons. Hence, the neuron dimension is equal to the number of input variables and possesses a weight vector. Devoting the weight vectors is based on the best matching unit (BMU) while in the learning algorithm of each data vector Euclidean distances is estimated, and compared. Ultimate SOM is obtained in a manner that the resembling information has the BMUs closer to each other (Alvarez-Guerra et al., 2008; Coz et al., 2008; Peeters et al., 2007). SOM Toolbox 2.0 for Matlab was also applied to carry out the SOM analysis. In general, aromatic compounds can be categorized based on features such as chemical composition, production origins, and the organic matter's combustion temperature. PAHs' source identification is challenging due to probable coexistence of the diversity of pollution sources, and also some possible conversion processes which PAHs may experience prior to their last deposition in the investigated sediments (Tobiszewski, 2014; Tobiszewski and Namieśnik, 2012). Nevertheless, to distinguish different sources of PAHs based on pyrogenic (coal, biomass and fuels combustion) and petrogenic (liquid fuels leakage) origins, diagnostic ratios of various PAHs can be applied (Tobiszewski, 2014). The diagnostic ratios utilized in the study, involve a combination of three ratios: LPAH/HPAH, Ant/(Ant + Phe), and Flu/ (Flu + Pyr) (Xue et al., 2016).

Eco-toxicity of target compounds in sediments was estimated based on the risk quotient (RQ) estimation, which is widely applied to assess the risk properties of BPA in the aquatic ecosystem (Yan et al., 2017). The RQ value is defined as the ratio of maximum measured environmental concentration (MEC) to the predicted no-effect concentration (PNEC), described by the following Eq. (3):

RQ =

MECpore water =

TEQPAH = Σ TEQi

(2)

Cs.i K oc × f oc

(4)

where Koc is the organic carbon partitioning coefficient (Log Koc = 3.64) (Lee et al., 2015), Cs,i is the concentration in the sediment, ng g−1, and foc (=0.1) is the fraction of organic carbon in sediment (Xiong et al., 2016). 2.10. Health risk assessment The cancer risk level is estimated based on the toxic level of total PAHs. It is focused on evaluating the health risk of PAH components in the sediments through skin contact and ingestion. To calculate the exposure via the above pathways by USEPA, (2004), the following equations are proposed:

Cancer riskingest = Csed ×IR × EF × ED × SFO × CF BW × AT

(5)

where, Cancer riskingest denotes carcinogenic risk via ingestion; Csed represents BaP quantity concentration; IR represents the ingestion rate (100 mg/day); EF and ED are the exposure frequency (350 days/year), and the exposure duration (30 years for adults, 6 years for children) respectively; CF refers to conversion factor unit (10−6 kg/mg); BW represents the body weight (70 kg for adults and 16 kg for children). AT represents the average lifespan (25,550 days). SFO represents the oral slope factor (7.3 (mg/kg/day)−1).

The U.S. National Oceanographic and Atmospheric Administration's sediment quality guidelines were compared with the results concluded through the adverse biological effects of each PAHs in Iran's Hormozgan Province costal sediment samples for evaluation purposes (Nozar et al., 2014). There are seven with high toxic and carcinogenic impacts among the 16 EPA priority PAHs: Chr, BaA, BkF, BbF, BaP, DahA and InP (Nisbet and LaGoy, 1992) Through Toxic Equivalent Quantity (TEQ) toxicity of ∑PAHs in sediments could be evaluated and calculated using the following equations (Tian et al., 2013): (1)

(3)

For RQ estimation in the present study, MEC was measured in sediment samples. The PNEC values are often derived from the lowest toxicity value (i.e., lowest short-term L(E)C50 or long-term NOEC value) available in the literature divided by an assessment factor (AF) of 100. The toxicity data used in this study were collected from literature (Liu et al., 2017; Xiong et al., 2016; Yan et al., 2017). Substances with a log Kow value ≥ 3 were likely to be absorbed to sediment organic matter, which caused secondary pollution and threatened the health of the aquatic organisms. Due to the relatively high hydrophobic characteristics, BPA tends to accumulate in sediments. Because of no toxicity information for BPA in sediments, the MEC for the sediment (MECpore water) was converted into corresponding pore water concentrations (Cpore water) using the following equation (Di Toro et al., 1991):

2.8. Ecological risk assessment

TEQ = TEFi × CPAHi

MEC PNEC

Cancer risk dermal = Csed × SA × AF × ABS × EF × ED × × CF × SFO BW × AT

(6)

where Cancer risk dermal denotes carcinogenic risk through dermal contact; AF refers to sediment adherence factor to skin (0.07 mg/cm2); SA represents the surface area of exposed skin (5700 cm2); ABS represents sediment dermal absorption (0.13). Based on the various carcinogenic risk levels, the characteristics of carcinogenic risk could be qualitatively defined (Man et al., 2013): Very low risk when value is ≦1E−6; low risk between 1E−6 < and < 1 4

Marine Pollution Bulletin 152 (2020) 110941

F. Abootalebi Jahromi, et al.

E−4; moderate risk between 1E−4 ≦ and < 1E−3; high risk between 1E−3 ≦ and < 1E−1; and very high risk when the value is ≧1E−1. Several methods have been developed for the health risk assessment of the PAHs in seafood. To estimate the magnitude of exposure to PAHs by consumption of bivalve, we computed the dietary daily intakes (DDI; ng day−1) of each selected PAH for adult population using Eq. (7).

Port (S1 station), indicative of a potential pollution source affecting this station. High molecular weight PAHs (HMW) were also abundant in Shahid Bahonar Port sediments. The highest PAH concentration in this commercial port is due to the high traffic density associated with transportation of general cargo, ores, oil and passengers (Nozar et al., 2014). The lowest concentration of total PAHs in sediments was detected at Hotel Amin station (S10). The results of an IndependentSamples t-Test showed that there is no significant relationship between all PAH compounds at the different stations with the background station (p > 0.05). A comparison of PAH values at stations near urban and industrial discharges with background samples emphasized the detrimental role of the contaminating sources in polluting the aquatic ecosystem in Hormozgan Province. The ∑PAHs contamination level in sediments can be categorized into four classes: 0–100 ng g−1 (low level); 100–1000 ng g−1 (moderate); 1000–5000 ng g−1 (high); and 5000 ng g−1 < very high (Baran et al., 2017; Baumard et al., 1999; He et al., 2016). According to this categorization, the present total contamination of Hormozgan coastline sediments can be assessed as “low level.” The ∑PAHs measured at background sampling sites varied from 16.60 to 29.97 ng g−1 with an average concentration of 24.82 ng g−1, representative of the background concentration in this study area. There was significant variation of PAHs compounds in Hormozgan Province sediments along the Bandar Abbas coastline (Fig. 2). Acenaphthene, Naphthalene, Chrysene, and Fluoranthene were dominant in sediments. Their average values were 6.64, 5.11, 3.43, and 3.17 ng g−1, respectively, as shown in Table 2. The LMW PAH (low molecular weight PAH) and HMW PAH (high molecular weight PAH) concentrations ranged from 9.07 to 37.60 ng g−1 and 3.20 to 56.60 ng g−1, respectively. The mean concentration of HMW and LMW PAHs in sediments were 15.23 and 19.68 ng g−1, respectively (Table 2). Generally, the LMW PAH concentrations were considerably higher than those of HMW PAHs in the sediments. Relatively higher amounts of LMW PAHs were detected at S14 (37.60 ng g−1) and S1 (28.40 ng g−1), indicating potential contamination at these sampling sites. PAHs emitted from different sources indicate various molecular compositions; hence, analysis of PAH compositions helps elucidate PAH sources. Dominance of LMW PAHs probably reflects the existence of a recently generated LMW PAHs of a local origin, including discharge of petrogenic/petroleum-related materials. On the other hand, when PAHs enter an aquatic ecosystem, they can adhere strongly to sediments particles owing to their high hydrophobicity and weak degradation. Although LMW PAHs can be degraded during the process of reaching deep waters and marine sediments with aging (Hu et al., 2010), this process is comparatively short in shallow water (Li et al., 2018), and the final concentration of LMW PAHs in sediments is slightly affected by their degradation and thus tend to persist for longer periods and accumulate in high concentrations (Liu et al., 2000). There are very few studies available on distribution of PAHs in Hormozgan Province. In 2005, Regional Organization for the Protection of Marine Environment (ROPME), gathered sediments from Arab countries coastlines, and four sites in Iran; which two stations were placed in Hormozgan Province (Larak Island and Bandar Abbas). The measured ∑PAHs in sediment samples collected from Bandar Abbas was 155 ng g−1 (de Mora et al., 2010), which is comparable with the ∑PAH of the current study. In another study carried out in the area, the total concentration of PAHs varied from 55.3 to 161.8 ng g−1 of sediment (Nozar et al., 2014). Also, in previous ROPME investigation, the total dry weight of concentrated PAHs in sediment samples collected from Arab countries in Persian Gulf varied between 0.02 and 6140 ng g−1. The high PAH content was related to the Askar stations and BAPCO refinery in Bahrain (Tolosa et al., 2005). Also, ∑PAHs in coastal sediments of Persian Gulf varied from 3.63 to 21.75 ng g−1 averaging 6.35 ng g−1 (Abbasi et al., 2019). The sediment samples of Bushehr Province on the north side of Persian Gulf were also analyzed (Mirza et al., 2012) and the reported total dry weight of PAH concentration varied between 41.72 and 227.57 ng g−1. The high level of PAHs in

(7)

DDI = C × BDC −1

where C represents the concentration (ng g ) of PAHs in bivalve samples, BDC represents bivalve daily consumption. The daily bivalve consumption value (0.0002 g day−1) was obtained by the Hormozgan University of Medical Science and Hormozgan Fishery Office (Nozar et al., 2013). The non-carcinogenic risk due to dietary exposure of PAHs was estimated using a hazard quotient (HQ) method.

DDI RfD

HQ =

(8)

where RfD is oral reference dose. To evaluate the overall potential impacts posed by PAH mixture the HQs computed for each PAH were summed and represented as a hazard index (HI). If the HI did not exceed the threshold (1 > HI), it can be assumed that there is no possibility of an adverse health effect (Barhoumi et al., 2016). The individual lifetime carcinogenic risk level (CRL) is applied to estimate the carcinogenic risk related to the dietary intake of PAHs in the investigated bivalves (Sun et al., 2018). CRL is computed according to the equation:

CRL =

BDC × CSF × PEC BW

(9)

where CSF represents the cancer slope factor, which is applied to evaluate an upper bound possibility that an individual will develop cancer over a lifetime of 70 years if exposed to a given dose of carcinogen (Thompson et al., 2017). Because BaP is the only PAH that has been well characterized toxicologically, we use a CSF of BaP (7.3 per mg/kg/d). PEC (ng g−1) was described as the potency equivalent concentration of ∑PAHs, which was computed based on the Eq. (10) (Xu et al., 2011). n

PEC =

∑ (TEFi × Ci) i=1

(10)

where TEFi represents the toxic equivalent factor of each PAH and Ci represents the concentration of each PAH. The TEF is 0.01 for Ant and 0.001 for and Ace, Acy, Nap, Fl, Phe, Pyr and Flu (Lv et al., 2014). PEC amounts were also compared with a screening value (SV) for carcinogenic PAHs. The SV (ng g−1) was measured using the following equation (Moslen et al., 2019):

SV =

[(RL/CSF) × BW] BDC

(11) −5

where RL (dimensionless) is maximum acceptable risk level of 10 . There is no significant data indicating the carcinogenic potential of bisphenol A (BPA); thus, according to Gu et al. (2016), the non-cancer hazard quotient was used to characterize the health risk posed by this compound based on Eqs. (7) and (8). The RfD for BPA was 50 μg/kg/ day, which was obtained from the regional screening level summary table (USEPA, 2017). 3. Results and discussion 3.1. Distribution and concentration of PAHs in sediment The statistical summary of 16 USEPA-PAHs in sediment samples of Hormozgan Province is depicted in Table 2. Total concentration of PAHs in sediment samples varied greatly, ranging from 14.54 to 85.00 ng g−1 with an average of 34.92 ng g−1. Relatively higher concentration of total PAHs (85.00 ng g−1) was found at Shahid Bahonar 5

Marine Pollution Bulletin 152 (2020) 110941

F. Abootalebi Jahromi, et al.

Table 2 Statistical summary of the concentration of PAH compounds (ng g−1) in Persian Gulf sediments along the Bandar Abbas coastline. PAH compound

Minimum

Maximum

Mean

Std. deviation

Skewness

Kurtosis

Naphthalene Acenaphthylene Acenaphthene Fluorene Phenanthrene Anthracene Fluoranthene Pyrene Benzo[a]anthracene Chrysene Benzo[b]fluoranthene Benzo[k]fluoranthene Benzo[a]pyrene Dibenzo[a,h]anthracene Benzo[g,h,i]perylene Indeno[1,2,3-cd]pyrene Total PAHs LMWa HMWb Total TEQc

1.70 0.60 0.50 0.60 0.30 ND 0.50 0.40 0.10 ND ND ND ND 0.10 0.27 1.40 14.54 9.07 3.20 0.49

8.70 5.70 27.30 7.90 4.60 6.80 7.70 9.50 13.70 12.60 4.90 4.70 3.00 0.13 3.60 1.50 85.00 37.60 56.40 17.10

5.11 2.61 6.64 2.64 2.03 0.65 3.17 2.88 1.07 3.43 0.81 0.86 0.64 0.11 0.80 1.47 34.92 19.68 15.23 4.69

1.82 1.58 7.29 1.91 1.28 1.54 2.62 2.41 3.18 3.69 1.20 1.33 0.92 0.02 1.06 0.05 16.11 7.33 14.05 4.57

−0.03 0.20 1.47 1.38 0.85 4.18 0.46 1.29 4.12 1.11 2.63 2.05 1.75 0.77 2.22 −0.77 1.79 0.56 2.46 1.38

−0.05 −0.61 2.36 1.93 −0.28 17.62 −1.42 1.84 17.27 0.65 7.80 3.78 2.06 −1.59 3.99 −1.59 4.78 0.74 7.66 1.83

ND, not detected. a Low molecular weight PAHs. b High molecular weight PAHs. c Toxic equivalent quantity.

Yinma River Basin, China (914.17–5678.46 ng g−1, mean 1943.71 ng g−1) (Sun et al., 2017), Pacific Coast of Japan (2.5–1447 ng g−1, mean 256.91 ng g−1) (Onozato et al., 2016), and the southern Caspian Sea, Iran (12.2–926.7 ng g−1, mean 225.31 ng g−1) (Baniemam et al., 2017). The physicochemical properties of sediments are given in Table 3. Values of pH ranged from 8.1 to 8.83 depending on the sampling points in the aquatic environment. The CEC values varied between 17.56 and 126.44 meq/100 g, with a mean of 31.12 meq/100 g. On average, the sediment samples were relatively coarse-grained (clay 12.82%, silt 30.81%, and sand 56.38%). The EC was between 2.23 and 10.2 ms/cm, averaging 5.04 ms/cm. The variation in EC, a fact often observed in the

Bushehr sediment samples compared to Hormozgan Province is because of higher petroleum activity in the former area. Also, a comparison of the results for the present study with other related studies worldwide showed that the overall contamination level of PAHs was significantly lower than that reported for the sediments from Tiber River and estuary, Italy (36.2–545.6 ng g−1, mean 155.3 ng g−1) (Montuori et al., 2016), Zhanjiang Harbor, Chine (152–453 ng g−1, mean 263 ng g−1) (Sun et al., 2018), West Coast of Peninsular Malaysia (151–4973 ng g−1, mean 1342.80 ng g−1) (Vaezzadeh et al., 2019), Coastal areas of Bangladesh (349.8–11,058.8 ng g−1, mean 4571.0 ng g−1) (Habibullah-Al-Mamun et al., 2019), the northern Gulf of Mexico (68–160 ng g−1, mean 114 ng g−1) (Adhikari et al., 2016),

Fig. 2. Range of changes in the concentration of PAH compounds in the coastline of Hormozgan Province sediments along the Bandar Abbas coastline (ng g−1). 6

Marine Pollution Bulletin 152 (2020) 110941

F. Abootalebi Jahromi, et al.

Table 3 Statistical summary of physicochemical properties in sediments of the Hormozgan Province.

pH EC (ms/cm) TOC (%) CEC (meq/100 g) Sand (%) Silt (%) Clay (%)

Minimum

Maximum

Mean

Std. deviation

Skewness

Kurtosis

8.1 2.23 0.004 17.56 17.1 0.4 4.4

8.83 10.2 0.04 126.44 93.4 57.2 35.9

8.41 5.04 0.01 31.12 56.38 30.81 12.82

0.17 2.39 0.008 24.92 25.54 18.87 9.43

0.51 0.94 3.09 3.93 −0.08 −0.31 1.28

1.64 −0.18 11.09 15.86 −1.27 −1.18 0.71

Our results agree with previous investigations in the ROPME areas (De Mora et al., 2010). TOC cannot be taken as a marker for PAH pollution in the study area (Al-Lihaibi and Al-Omran, 1996; Al-Lihaibi and Ghazi, 1997). Furthermore, Simpson et al. (1996) reported that the relationship between TOC and total PAHs concentration was considerable only in severely polluted areas where total PAH contents were higher than 2 μg g−1. No considerable relations of physiochemical properties including pH, EC, and grain size in sediments were found with concentrations of total PAHs, which explains PAHs concentration in sediment samples are related to the contamination origins greater than the sediments texture (Yavar Ashayeri et al., 2018).

semi-arid regions in north of the Persian Gulf, may happen by seawater buffering systems (Lababpour, 2015). Surface sediments collected along the coastline of Hormozgan Province are characterized by a low TOC content. TOC ranged from 0.004 to 0.04%, with a mean of 0.01%. The highest and lowest TOC percentages in sediments were detected at S8 and S13 stations, with total PAH concentrations being 33.77 and 27.87 ng g−1, respectively. TOC plays a major role in absorbing PAHs, particularly when its content in sediments is > 0.1% (Wang et al., 2014). According to Xu et al. (2007), sediments with high organic carbon content usually contained high concentration of PAHs. On the contrary, the sediments with low organic carbon content usually have low concentration of PAHs. This finding suggested a probable relationship between the sediment organic carbon content and PAH concentrations. However, some authors reported that PAH concentrations in sediments are independent of TOC content (Tam et al., 2001). In general, when sedimentary TOC content is lower than 1%, it has a low impact on the environment, TOC content between 1% and 3% has medium impact, and those above 3% has high impact (Baniemam et al., 2017). Therefore, considering the TOC content classification, sediments from all sampling sites in the Hormozgan Province coastline showed low impact. Moreover, the source of contamination could define the concentration and distribution of PAHs. Also, a linear regression analysis illustrated that total PAH concentrations in the sediments was insignificantly correlated with the sediment TOC content as the correlation coefficient was 2.13E−4 (Fig. 3), revealing that sediment TOC content does not play an important role in controlling PAH concentrations. Thus, both the distribution and concentration of PAHs are likely controlled by direct entry rather than sediments' TOC content.

3.2. PAHs concentrations in bivalve Only LMW PAHs were detected in bivalves. The total PAHs concentration in the seven species of bivalves ranged between 5.37 and 16.40 ng g−1 with mean value 10.27 ng g−1 (Table 4). The highest PAH concentration among bivalves belonged to B4 (Solen brevis) collected by the Bandar Abbas coast. Bivalve molluscs are capable of accumulating contamination, including organic and inorganic species, to various degrees and proportional to the levels found in the environment (Pourang et al., 2010). Molluscs are widely believed to be reliable indicators of bioavailability of pollutants. There is some limited published data regarding PAH contamination in edible seafood, especially bivalves in southern Iran. The ∑PAHs in clams collected from Bushehr Province coastline was 421.86 ng g−1, the high level of which is thought to be the result of Bushehr being the main area for Iranian oil export (Safahieh et al., 2011). In 18 species of seafood including fish, shrimp, crab and bivalve collected along the coastline of Hormozgan Province, the concentrations of 16 PAHs ranged between 16 ± 8.4 and 28.18 ± 3.74 ng g−1 dry weight (Nozar et al., 2013). PAHs content in bivalve samples varied from being undetectable to 5.1 ng g−1 dry weight. The highest concentrations were associated with Naphthalene (5.1 ng g−1), and Acenaphthylene (3.20 ng g−1). Furthermore, Phenanthrene occurs in soft tissue of bivalves. León showed that Phenanthrene proportion increased in mussels with distance from the main PAH sources (Hong et al., 2016). The investigated samples were already categorized as minimally contaminated (Nozar et al., 2013). The level of the individual PAHs in bivalves from RSA (ROPME Sea Area), varied between 2 and 419 ng g−1 dry weight (de Mora et al., 2010). The difference in PAHs content between sediment and bivalve in the study area clearly illustrated that the concentration of PAH compounds in sediment samples is higher than in bivalves (Fig. 4). Recent studies have indicated that some bivalve species have the capability to adjust filtration and select particles according to their shape, size, or chemical components on the surface of the particles (Arapov et al., 2010). On the other hand, only LMW PAH compounds were detected in bivalves. Also, owing to their direct contact with sediments, benthic organisms receive more pollutants. Another reason is probably the high concentration of LMW PAHs in water. This result is consistent with the results obtained from the concentration of PAHs in sediments in Section 3.1. In general, the results confirmed that LMW PAHs are dominant in the study area. Various studies revealed that lipids can accumulate PAHs contaminants.

Fig. 3. Correlation plots of TOC (%) and total PAHs measured in sediments. The dashed line represents a linear fit to the data (n = 18, R2 = 2.13E−4). 7

Marine Pollution Bulletin 152 (2020) 110941

F. Abootalebi Jahromi, et al.

Table 4 Statistical summary of PAH concentrations (ng g−1) in bivalves of the Hormozgan Province. Compound

Minimum

Maximum

Mean

Std. deviation

Skewness

Kurtosis

Naphthalene Acenaphthylene Acenaphthene Fluorene Phenanthrene Anthracene Fluoranthene Pyrene Total PAHs LMW PAHs HMW PAHs

2.60 0.30 0.40 1.00 0.60 ND 0.30 0.10 5.37 4.97 0.40

5.10 3.20 1.80 1.60 1.00 0.30 1.40 2.90 16.40 12.30 4.10

3.66 1.74 0.70 1.30 0.80 0.27 0.89 0.91 10.27 8.47 1.80

0.82 0.89 0.55 0.20 0.13 0.09 0.45 0.93 3.49 2.43 1.24

0.72 −0.05 1.76 0.18 0.00 −2.65 −0.50 2.07 0.69 0.32 0.98

0.76 1.24 2.36 −0.15 0.31 7.00 −1.75 4.80 1.05 −0.03 1.19

ND, not detected.

detection limit (MDL) > 50% were considered as weak variables (Cao et al., 2011). Fig. 6 shows the source profiles of PMF model in the sediment samples of Hormozgan Province coastline. HMW PAHs can be observed in the first profile. BkF, BaP, DahA, BghiP, and InP are categorized in the first profile with high factor loading values, probably from urban sources, along with HMW PAHs. HMW PAHs have the same physical and chemical attributes and are released by motor vehicles and internal combustion engines. In the second profile, LMW PAHs are dominant and originate from discharges released into the marine environment by industrial sources such as refineries and petrochemical units. Bandar Abbas Oil Refinery is an example of such a source which releases LMW PAHs in to the Persian Gulf. Discharges from this source contains a variety of chemicals including crude oil, solvents, petroleum hydrocarbons, organic acids, heavy metals, grease and phenols (Dehghani, 2007). The third profile portrays properties of four-ring PAHs, which are very much like LMW and HMW PAHs and are categorized as MMW PAHs (Abbasi and Keshavarzi, 2019). They probably originate from mixed petrogenic and pyrogenic origins. Another reason for the inclusion of some of these compounds in a profile is their concentration change at different stations. For example, as the concentration of the pollutants increased at station S1, they declined at stations S16, S17, and S18 and most of the sediment stations in the mangrove forest. Generally, the concentration difference of LMW compounds at different stations is higher than HMW. This is due to mostly to the LMW compounds that change more in concentration between sites.

The lipid content in the selected bivalves in this study varied from 1.3 to 2.8%. The Backward GEE model results in current study revealed that there is a significant relation between the concentrations of most PAH compounds and lipid content (Table 5). Moreover, there is a negative relation between some of these compounds and lipid content, which can be the result of limited number of relevant samples or a difference in bivalve species. 3.3. Identification of PAH sources The result of cluster analysis illustrated that station S1 and S3 (sewage discharge points into the sea) form a separate cluster (Fig. 5). This is due to the higher concentrations of contaminants at these stations. Both stations are related to two important commercial Ports in Bandar Abbas City. S1 is the Shahid Bahonar and S3 is the Shahid Rajaei port. Higher concentrations of PAHs were found at Shahid Bahonar Port (S1 station), as already noted. Another cluster included areas with much lower concentrations including stations S16, S17 and S18 (background samples). Furthermore, stations located close to Bandar Abbas city also form a separate cluster. Because, runoff can transport Bandar Abbas street dust particles to the coastal sediments of the sea (Sajjad et al., 2018). 3.3.1. Source identification by PMF model To conduct the PAHs' source apportionment, a PMF model was applied in the study. The coastal sediments of the Hormozgan Province are probably affected by three PAHs sources comprising, (i) petrogenic, (ii) pyrogenic, and (iii) medium molecular weight (MMW) PAHs (Lawal, 2017). The PMF model was repeated over 20 times for the above factors; PAHs with a signal-to-noise (S/N) ratio between 0.2 and 2 (Abbasi and Keshavarzi, 2019), and missing or below medium

3.3.2. Source identification by SOM network In the current study, a 5 × 5 map was used to train the SOM network. Fig. 7 represents the results of SOM analysis for contaminated sediments in the coastline Hormozgan Province of Persian Gulf. Fig. 8 indicates the component planes of 16 PAHs providing an overview of

Fig. 4. Average PAH concentrations in the analyzed sediments and bivalves (ng g−1). 8

Marine Pollution Bulletin 152 (2020) 110941

F. Abootalebi Jahromi, et al.

Table 5 Backward GEE matrix indicating lipid content effect on PAH concentrations. Parameter estimates

95% Wald confidence interval

Hypothesis test

Parameter

B

Std. error

Lower

Upper

Wald chi-square

df

Sig.

(Intercept) Naphthalene Acenaphthylene Acenaphthene Fluorene Phenanthrene Anthracene Fluoranthene Pyrene (Scale)

2.884 −0.763 0.685 0.343 2 −2.875 1.033 0.087 −0.017 0.052

0.6472 0.2906 0.2319 0.0853 0.6562 1.3096 0.6318 0.2245 0.0653

1.615 −1.332 0.231 0.176 0.714 −5.442 −0.206 −0.353 −0.145

4.152 −0.193 1.14 0.51 3.286 −0.308 2.271 0.527 0.111

19.855 6.891 8.735 16.181 9.29 4.819 2.671 0.151 0.068

1 1 1 1 1 1 1 1 1

0 0.009 0.003 0 0.002 0.028 0.102 0.697 0.794

Dependent variable: lipid. Model: (intercept), naphthalene, acenaphthylene, acenaphthene, fluorene, phenanthrene, anthracene, fluoranthene, pyrene.

Bouldin, 1979). Also, SOM results were similar to CA. Each map corresponds to one attribute (component). They should be compared with the map representing the distribution of the sediments illustrated in Fig. 6. Hexagons in the same place on various component planes correspond to the same map unit. Colours show the component value in the weight vector of each unit according to the colour bars on the right. Isomeric ratios were applied to obtain a more accurate analysis of PAH compositions (Fig. 9). As can be seen in the background stations and most samples of mangrove forest, in addition to the low concentrations of these compounds, the concentration of HMW compounds is also low. On the other hand, the results clearly show that in areas with high contamination, the concentration of HMW PAHs is also high. According to (Menzie et al., 2002; Zakaria et al., 2002), in urban areas, due to emissions of pyrogenic PAH compounds and even the entry of street dust into the coastal sediments, HMW compounds increase (Abbasi and Keshavarzi, 2019). The commercial ship and boat traffic by the Bandar Abbas coast can be a reason for increased concentrations of PAH compounds, especially HMW.

the spreading values of each PAH. Relations between PAHs were distinguished by contrasting the component planes with the same patterns (Wang et al., 2015). Four well-defined patterns of correlated PAHs and some PAHs with high concentrations occur at the same station. The first pattern was dominated by LPAH pollutants, such as Ace, Acy, Nap, and Fl, which are presumably released from similar petrogenic origins, including the volatilization and oil-based products spill (Liu et al., 2009). The next pattern connects Ant and Phe, which are LPAHs, suggesting that both have similar petrogenic origins. The third pattern is organized by Pyr, Flu, Chr and BaA. They are HPAHs generally released by coal combustion (Hu et al., 2011; Lin et al., 2013). The last pattern contains BkF, BbF, BghiP and InP; they are also HPAHs of pyrogenic origins. Among the mentioned PAHs, BghiP and InP represent motor vehicles' exhaust sources (Hu et al., 2011; Lin et al., 2013; Wang et al., 2015). Kmeans algorithm was used in order to train the SOM map and group the datasets. The optimal clustering with the lowest value on the Davies–Bouldin index (DBI = A function ratio of the sum of within-cluster scatter, and between-cluster separation) was chosen (Davies and

Fig. 5. Cluster analysis based on different stations. 9

Marine Pollution Bulletin 152 (2020) 110941

F. Abootalebi Jahromi, et al.

Fig. 6. Source profiles of the sediment samples from PMF model analysis.

to 0.6, with an average value of 0.19. Flu/(Flu + Pyr) > 0.5 ratio commonly indicates the abundance of pyrogenic sources, while PAHs from petroleum sources are characterized by Flu/(Flu + Pyr) < 0.4 (Yunker et al., 2002). In the Hormozgan Province sediments, the Flu/ (Flu + Pyr) ratio varied between 0.39 and 0.9, with an average of 0.49. The LPAH/HPAH ratio was in the range of 0.5 to 24.7 with a mean value of 4.7, revealing that there was a petrogenic source of PAHs. The distribution of data diagnostic ratios corroborated that PAHs originated from different types of pyrogenic and petrogenic sources. Refining products such as gasoline and crude oil represent petrogenic sources of PAHs in the study area (Liu et al., 2009). The petrogenic sources of PAHs in Hormozgan Province can be classified and related to river and urban inputs that contain the street runoff, road surface washout, crude oil exporting activities (Zakaria et al., 2002), and illegally smuggled petroleum products such as gasoline that cause coastal pollution through pipe leakage or petroleum released into the marine environment (Nozar et al., 2014). Heavy marine traffic as well as the establishment of some industrial plants along the coastline contributes to the pyrogenic sources of PAHs.

Fig. 7. Distribution of sediment samples on the SOM. The four shown clusters (I-IV) have been derived from the k-means algorithm applied to the trained SOM.

3.4. Ecological risk assessment 3.3.3. Source identification by PAHs isomer ratios The PAHs' Pyrogenic, and petrogenic sources can be determined by calculating LPAH/HPAH ratio (Lin et al., 2013). The pyrogenic sources were the dominant source in this area, because fossil fuel combustion contains higher levels of heavy PAHs than light ones (Dong et al., 2012; Li et al., 2015; Nozar et al., 2014). Diagnostic ratios in current study and diagnostic ratios of PAHs' source identification are shown in Table 6. Ant/(Ant + Phe) < 0.1 ratio indicates petroleum as the source of PAHs, whereas Ant/(Ant + Phe) > 0.1 suggests pyrogenic origins (Liu et al., 2009). The Ant/(Ant + Phe) ratio ranged from 0.01

The negative biological effects of PAHs in sediments was evaluated using the effects-based sediment quality guideline (SQG) values. The SQG values contain effects range-low (ERL) and effects range-median (ERM), which are based on field studies and several toxicity tests for different aquatic organisms. The two benchmarks determine three value ranges for PAHs: (1) < ERL (rarely), (2) ≥ERL and < ERM (harmful occasionally), and (3) ≥ERM (frequently) associated with negative effects (Long et al., 1995). In this study, the mean concentration of PAHs was compared with the ERL and ERM values. Fortunately, the mean PAHs value in sediments was found to be less than 10

Marine Pollution Bulletin 152 (2020) 110941

F. Abootalebi Jahromi, et al.

Fig. 8. The component planes of the SOM for the 16 PAHs.

suggested ERL and ERM values as shown in Table 7. The data revealed that the biological risks caused by PAHs were rare in Hormozgan province. Furthermore, the environmental risk of PAHs in the aquatic ecosystem has mostly been computed based on BaP value as BaP is welldescribed toxicologically (Sun et al., 2017). In this study, toxic equivalent quantity (TEQ) was used to evaluate environmental health risk of PAHs in the sediments from Hormozgan province. As shown in Table 2, the total TEQs of all PAHs in sediments ranged from 0.49 to 17.10 ng g−1 with an average of 4.69 ng g−1. The highest value of total TEQ was found at S1 (Shahid Bahonar Port) and followed by the S3 station (Shahid Rajaei port). Based on the results of sources identification, S1 and S3 were exposed to PAHs released from sewage

Table 6 Values of selected ratios suggestive of PAH sources. Origin/source

LPAH/HPAH

Ant/(Ant + Phe)

Flu/(Flu + Pyr)

Petrogenic Pyrogenic Gasoline emissions Current study Reference

>1 <1 –

< 0.1 > 0.1 –

< 0.4 > 0.5 0.4–0.5

4.7 (Zakaria et al., 2002)

0.19 (Liu et al., 2009)

0.49 (Yunker et al., 2002)

Fig. 9. Percentage of total PAHs according to ring numbers in sediment samples. 11

Marine Pollution Bulletin 152 (2020) 110941

F. Abootalebi Jahromi, et al.

less than the priority risk level, but slightly more than the maximum acceptable risk level (Table 8).

Table 7 Comparison of the mean with U.S. NOAA's SQGs and reference values.

a

Threshold effect concentration ERL Probable effect concentration ERMb Detected value at reference site The achieved mean for areas which are facing to pollution source a b

∑PAHs (ng g−1)

Reference

350 2358 34.55 50.82

(Sun et al., 2016) (Sun et al., 2016) Current study Current study

3.5.2. Potential human health risk from bivalve consumption The likely risk to human health from PAH components could be determined by comparing the dietary daily intake (DDI) with toxicological threshold limits (RfD). In the current study, we estimated the human health risks related to dietary exposure to PAH components though consumption of bivalves. Consumption of bivalves is considered to be an important route of human exposure to PAH components. The calculated DDI, HQ, HI, PEC and CRL values based on PAHs concentration in bivalves are presented in Table 9. The average DDI of investigated PAHs varied between 5.3E−05 ng day−1 and 7.3E−04 ng day−1. The DDI of all PAHs were lower than available RfD. All calculated HQ values for the analyzed PAHs were < 1. Furthermore, HI values for all species were below the acceptable lifetime risk (HI < 1). The CRL values of PAHs via bivalve consumption ranged from 1E−07 to 4E−07 with a mean 3E−07. From these results, it could be concluded no harmful health impacts (either non-carcinogenic or carcinogenic) are associated with the bivalve's consumption from the Hormozgan Province with respect to PAH components. PEC measured in the bivalve samples were compared to screening value (SV) to estimate consumer cancer risk. If the PEC value of total PAHs in bivalves exceeds the SV (screening value), the health risk of total PAHs via consumption of bivalves would be more than the maximum acceptable risk level of 1E−5; otherwise, it would be less than 1E−5 (Xu et al., 2011). It can be seen from Table 9 that the PEC amounts (6E−03 to 2E−02, mean 1E−02 ng g−1) for all bivalve samples were below the SV of 0.48 ng g−1. Therefore, the results suggested that consumption of bivalves at a rate of 0.0002 g day−1 had no harmful health impacts.

Effect range-median. Effect range-low.

discharge. Also, both stations are related to two important commercial Ports in Bandar Abbas City. As reported by the Canadian soil quality guidelines for human health and protection of environment based on cancer effects of PAHs, TEQ value should be lower than a safe value of 600 ng g−1 (Yu et al., 2015). In the current study, the TEQ value of PAHs in all sediments was also lower than the threshold. 3.5. Human health risks 3.5.1. Human health risk of PAHs via exposure of sediments In Table 8, the results of carcinogenic risk assessment for PAH compounds via dermal adsorption and ingestion proposed by the US EPA protocol, are given. The ILCR values of PAHs via ingestion for children and adults were in the range of 9.2E−07–3.2E−05 (8.9E−06, mean) and 7.0E−07–2.5E−05 (6.7E−06, mean), respectively. According to different cancer risk ranges, the carcinogenic risk values of PAHs though ingestion pathway were < 10−4 in all stations, suggesting very low to moderate risks. Furthermore, the mean ILCR of PAHs via dermal contact pathway were 2.1E−05 and 1.7E−05 for children and adults, respectively, which are within the acceptable level (1E−6 to 1E−4). The total cancer risks were used as the sum of the risks exposed through these paths. The additional lifetime carcinogenic risk of one in 100,000 exposed was introduced as the maximum acceptable risk level (1E−5) by US EPA. The carcinogenic risk level of 1E−4 is considered significant and requires a high priority attention to such health impacts (Sun et al., 2018). In this study, the mean amounts of total cancer risk

3.6. Bioaccumulation factor Bioaccumulation factors (BAF) for each compound (i.e., 8 BAFs) and for each station were calculated: BAF = CPAH/Csed, where CPAH is the concentration of PAHs in the bivalves, and Csed is the concentration of PAHs in the adjacent sediments (Zuloaga et al., 2009). In cases where the concentration of a pollutant in sediments is potentially bioavailable, the value of BAF is close to unity (Oliva et al., 2017). As shown in Table S2 in supplementary information, the BAF values ranged from 0.01 to 7.3. BAFs for Naphthalene, Acenaphthylene, Acenaphthene, Fluorene, Phenanthrene, Anthracene, Fluoranthene, and Pyrene were higher than 1 in 27.3, 39.4, 12.1, 27.3, 21.2, 36.4, 27.3, and 30.3% bivalves respectively. These results reflect the contribution of sediments in the bioaccumulation of those PAHs. As is shown in Table S2, Naphthalene, Anthracene, and Fluoranthene at S2, S7, and S15 Stations had the highest BAF values, respectively. In S5 and S10 stations, Acenaphthylene had the highest BAF value, followed by Anthracene. Also, the highest value of BAF was found for Pyrene and recorded in Solen brevis at the S6 and S16 stations. These results indicate that Pyrene was the most bioavailable PAH compound, while Acenaphthene (0.01) was the least bioavailable PAH compound. Also, values of BAFs may be less than one if the bivalves metabolize the chemical or the system has not reached steady state (chemicals may not be fully available to the bivalves because of very slow desorption, or very strongly binding) (Keshavarzifard et al., 2017).

Table 8 Cancer risks via ingestion and dermal for PAHs in sediments of the Hormozgan province. Compound

S1 S2 S3 S4 S5 S6 S7 S8 S9 S10 S11 S12 S13 S14 S15 S16 S17 S18 Average Maximum Minimum

Child

Adult

ILCRing

ILCRder

Total cancer risk

ILCRing

ILCRder

Total cancer risk

3.2E−05 1.9E−05 2.1E−05 6.4E−06 1.7E−05 9.7E−06 8.4E−06 1.0E−05 8.7E−06 2.6E−06 2.3E−06 8.7E−06 7.3E−06 1.3E−06 9.2E−07 9.2E−07 1.0E−06 1.4E−06 8.9E−06 3.2E−05 9.2E−07

7.8E−05 4.6E−05 5.1E−05 1.5E−05 4.1E−05 2.3E−05 2.0E−05 2.5E−05 2.1E−05 6.2E−06 5.6E−06 2.1E−05 1.7E−05 3.1E−06 2.2E−06 2.2E−06 2.4E−06 3.3E−06 2.1E−05 7.8E−05 2.2E−06

1.1E−04 6.5E−05 7.2E−05 2.2E−05 5.9E−05 3.3E−05 2.8E−05 3.5E−05 3.0E−05 8.7E−06 7.9E−06 3.0E−05 2.5E−05 4.4E−06 3.1E−06 3.1E−06 3.4E−06 4.7E−06 3.0E−05 1.1E−04 3.1E−06

2.5E−05 1.4E−05 1.6E−05 4.8E−06 1.3E−05 7.4E−06 6.3E−06 7.9E−06 6.6E−06 1.9E−06 1.8E−06 6.6E−06 5.5E−06 9.7E−07 7.0E−07 7.0E−07 7.6E−07 1.0E−06 6.7E−06 2.5E−05 7.0E−07

6.0E−05 3.6E−05 4.0E−05 1.2E−05 3.2E−05 1.8E−05 1.6E−05 1.9E−05 1.6E−05 4.8E−06 4.3E−06 1.6E−05 1.4E−05 2.4E−06 1.7E−06 1.7E−06 1.9E−06 2.6E−06 1.7E−05 6.0E−05 1.7E−06

8.5E−05 5.0E−05 5.6E−05 1.7E−05 4.5E−05 2.5E−05 2.2E−05 2.7E−05 2.3E−05 6.7E−06 6.1E−06 2.3E−05 1.9E−05 3.4E−06 2.4E−06 2.4E−06 2.6E−06 3.6E−06 2.3E−05 8.5E−05 2.4E−06

3.7. BPA concentration in sediment and bivalve BPA was not detected in bivalves except in Saccostrea sp. (340.16 ng g−1) from Bandar Abbas. On the other hand, all of the 18 analyzed sediment samples in this study contained BPA with concentrations range of 94.64 to 1595.04 ng g−1 and an average concentration of 787.04 ng g−1. The highest BPA concentrations were observed at S2 (1595.04 ng g−1), S6 (1311.20 ng g−1) and S9 12

Marine Pollution Bulletin 152 (2020) 110941

F. Abootalebi Jahromi, et al.

Table 9 Calculated dietary daily intakes (DDI), hazard quotient (HQ), hazard index (HI), potency equivalent concentration (PEC) and cancer risk (CRL) by consumption of bivalves. Compound

Naphthalene Acenaphthylene Acenaphthene Fluorene Phenanthrene Anthracene Fluoranthene Pyrene Bivalve species Saccostrea sp. (B1) Circenitacallipyga (B2) Barbatia helblingii (B3) Solen brevis (B4) Amiantis umbonella (B5) Telescopium (B6) Saccostrea sp. (B7) Min Max Mean SVb

RfDa

0.02 0.06 0.06 0.04 0.04 0.3 0.04 0.03 HI 4E−02 6E−02 6E−02 1E−01 8E−02 6E−02 6E−02 4E−02 1E−01 7E−02 0.48

DDI (ng day−1)

HQ

Min

Max

Mean

Min

Max

Mean

5.2E−04 6.0E−05 8.0E−05 2.0E−04 1.2E−04 1.4E−05 6.0E−05 2.0E−05 PEC (ng g−1) 6E−03 1E−02 1E−02 2E−02 2E−02 1E−02 1E−02 6E−03 2E−02 1E−02

1.0E−03 6.4E−04 3.6E−04 3.2E−04 2.0E−04 6.0E−05 2.8E−04 5.8E−04 CRL 1E−07 2E−07 2E−07 4E−07 3E−07 2E−07 3E−07 1E−07 4E−07 3E−07

7.3E−04 3.5E−04 1.4E−04 2.6E−04 1.6E−04 5.3E−05 1.8E−04 1.8E−04

2.6E−02 1.0E−03 1.3E−03 5.0E−03 3.0E−03 4.7E−05 1.5E−03 6.7E−04

5.1E−02 1.1E−02 6.0E−03 8.0E−03 5.0E−03 2.0E−04 7.0E−03 1.9E−02

3.7E−02 5.8E−03 2.3E−03 6.5E−03 4.0E−03 1.8E−04 4.4E−03 6.1E−03

kurtosis: is a measure of the "tailedness" of the probability distribution of a real-valued random variable. Skewness: is a measure of the asymmetry of the probability distribution of a real-valued random variable about its mean. a RfD reference dose mg/kg-day. b SV screening value for carcinogenic effect of PAHs. Table 10 Comparison of BPA concentration in analyzed sediments from this study in contrast with those from other regions. Location

Year

Mean (ng g−1)

Rang (ng g−1)

Ref

Elbe River, Germany Okinawa and Ishigaki islands, Japan Venice lagoon, Italy Pearl River Estuary, China Saginaw River watershed and Michigan inland lakes, U.S. Pearl River Delta, China Liao River, China Anzali Wetland, Iran Masan Bay, Korea Several rivers and bays, U.S. Tokyo Bay, Japan Lake Shihwa, Korea Coastal lines of Hormozgan Province, Persian Gulf

1998 2001–2002 2001–2002 2003 1999–2004 2006–2007 2008 2010 1998 1998–2012 2012 2008 2018

163 2.71 45 3.7 3.10 94.5 5.3 671 11.5 6.65 8.17 567 787.01

66–343 0.5–13 2–118 4.3–12 0.25–13.4 1.7–430 2.6–33.8 10–6970 2.70–50.3 0.25–106 1.88–2.30 0.25–13,370 94.64–1595.04

(Heemken et al., 2001) (Kawahata et al., 2004) (Kawahata et al., 2004) (Peng et al., 2007) (Liao et al., 2012) (Gong et al., 2011) (Wang et al., 2011) (Mortazavi et al., 2012) (Khim et al., 1999) (Liao et al., 2012) (Liao et al., 2012) (Liao et al., 2012) This study

(1027.30 ng g−1). S2 and S6 are stations that receive municipal (domestic) wastewater. The average wastewater discharge rate from Bandar Abbas is estimated to be 140,000 m3/day, which is transferred to coastal water via different outflow distributions (Dehghani, 2007). SP9 is related to the oil refinery station in Bandar Abbas. The Bandar Abbas Oil Refinery is one of the eight oil refineries in Iran and is located west of this city. The product of this refinery is medium-distillation petroleum products, such as benzene, liquid gas, jet fuel, paraffin, diesel fuel, furnace mazut and fuel oil and sulfur. Effluents of the Bandar Abbas Oil Refinery cause environmental contamination via diverse pathways. This refinery pollutes water as well as air in Bandar Abbas. Furthermore, wastewaters from various sources eventually get released into the seawater and bear a variety of chemicals including crude oils, solvents, petroleum hydrocarbons, organic acids, grease, heavy metals and phenols (Dehghani, 2007). The lowest concentration of BPA belonged to sediments of the protected mangrove forest. There is very scarce information on the presence of BPA in study area. However, a few studies reported BPA in sediments (Table 10). The average concentrations of BPA in the collected surface sediments along the coastline of the Hormozgan Province was 787.01 ng g−1, comparable with those measured in the sediments of Anzali Wetland, Iran (671 ng g−1)

(Mortazavi et al., 2012), Lake Shihwa, and Korea (567 ng g−1) (Liao et al., 2012). To estimate BPA accumulation from adjacent sediments, bioaccumulation factors (BAFs) were calculated for the detected BPA in Saccostrea sp. (B7). The value of BAFs in the selected stations varied from 0.21 to 1.07. The results in Fig. S1 demonstrate that samples of Saccostrea sp. (B7) from S5 (> 1) had high BAF values for BPA, indicating that Saccostrea sp. samples taken from this location have strong affinity for the accumulate BPA compound. The order of BAF in soft tissues of Saccostrea sp. (B7) from study areas is: S5 > S16 > S10 > S9 > S7 > S6 > S2. 3.7.1. Risk quotient The eco-toxicity of BPA in the surface sediments was assessed by the risk quotient (RQ) approach as recommended by the European Commission (2003). RQ values ranged from 0.3 to 5.7 (Table S3). The highest RQ values were observed at S2 station. In the case of S2, its pollution is mostly produced by high concentrations of BPA. The obtained RQs were characterized using maximum probable risks for ecological effect guidelines proposed by Marcus et al. (2010): RQ < 1.0 indicates no significant risk; 1.0 ≤ RQ < 10 indicates a small potential 13

Marine Pollution Bulletin 152 (2020) 110941

F. Abootalebi Jahromi, et al.

for adverse effects; 10 ≤ RQ < 100 indicates significant potential for adverse effects; and RQ ≥ 100 indicates that adverse effects should be expected. Regarding the RQ values in individual sampling sites, there are small potential adverse effects at all sites (except for S11). The S11 site bears no risk for aquatic organisms. In general, the results indicated no high risk in sampling sites of the Hormozgan province coastline for aquatic organisms (RQ < 10).

Acknowledgements The authors wish to express their gratitude to the Research Committee and Medical Geology Center of Shiraz University for logistical and technical assistance. Appendix A. Supplementary data Supplementary data to this article can be found online at https:// doi.org/10.1016/j.marpolbul.2020.110941.

3.7.2. Human health risk of BPA Food is a major source of daily intake of BPA. Hence, for coastal residents of the Hormozgan Province, seafood is an important pathway for BPA intake. Thus, the human health risk of BPA through consumption of Saccostrea sp. was estimated in this study. The HQ value was 0.001. Overall, the HQ of BPA for different age groups of the population through the consumption of this bivalve was much less than the acceptable lifetime risk (HQ < 1), suggesting that the exposure to this compound presents no remarkable human health risk.

References Aarab, N., Godal, B.F., Bechmann, R.K., 2011. Seasonal variation of histopathological and histochemical markers of PAH exposure in blue mussel (Mytilus edulis L.). Mar. Environ. Res. 71, 213–217. Abbasi, S., Keshavarzi, B., 2019. Source identification of total petroleum hydrocarbons and polycyclic aromatic hydrocarbons in PM10 and street dust of a hot spot for petrochemical production: Asaluyeh County, Iran. Sustain. Cities Soc. 45, 214–230. Adhikari, P.L., Maiti, K., Overton, E.B., Rosenheim, B.E., Marx, B.D., 2016. Distributions and accumulation rates of polycyclic aromatic hydrocarbons in the northern Gulf of Mexico sediments. Environ. Pollut. 212, 413–423. Akhbarizadeh, R., Moore, F., Keshavarzi, B., Moeinpour, A., 2016. Aliphatic and polycyclic aromatic hydrocarbons risk assessment in coastal water and sediments of Khark Island, SW Iran. Mar. Pollut. Bull. 108, 33–45. https://doi.org/10.1016/j. marpolbul.2016.05.004. Al-Lihaibi, S.S., Al-Omran, L., 1996. Petroleum hydrocarbons in offshore sediments from the Gulf. Mar. Pollut. Bull. 32, 65–69. Al-Lihaibi, S.S., Ghazi, S.J., 1997. Hydrocarbon distributions in sediments of the open area of the Arabian Gulf following the 1991 Gulf War oil spill. Mar. Pollut. Bull. 34, 941–948. Alvarez-Guerra, M., González-Piñuela, C., Andrés, A., Galán, B., Viguri, J.R., 2008. Assessment of self-organizing map artificial neural networks for the classification of sediment quality. Environ. Int. 34, 782–790. Arapov, Jasna, Ezgeta-Balić, Daria, Peharda, Melita, Ninčević Gladan, Živana, 2010. Bivalve feeding—how and what they eat. Croat. J. Fish. 68, 105–116. Baniemam, M., Moradi, A.M., Bakhtiari, A.R., Fatemi, M.R., Khanghah, K.E., 2017. Seasonal variation of polycyclic aromatic hydrocarbons in the surface sediments of the southern Caspian Sea. Mar. Pollut. Bull. 117, 478–485. Baran, A., Tarnawski, M., Urbański, K., Klimkowicz-Pawlas, A., Spałek, I., 2017. Concentration, sources and risk assessment of PAHs in bottom sediments. Environ. Sci. Pollut. Res. 24, 23180–23195. Barhoumi, B., El Megdiche, Y., Clérandeau, C., Ameur, W.B., Mekni, S., Bouabdallah, S., Derouiche, A., Touil, S., Cachot, J., Driss, M.R., 2016. Occurrence of polycyclic aromatic hydrocarbons (PAHs) in mussel (Mytilus galloprovincialis) and eel (Anguilla anguilla) from Bizerte lagoon, Tunisia, and associated human health risk assessment. Cont. Shelf Res. 124, 104–116. Battal, D., Cok, I., Unlusayin, I., Aktas, A., Tunctan, B., 2014. Determination of urinary levels of bisphenol A in a Turkish population. Environ. Monit. Assess. 186, 8443–8452. Baumard, P., Budzinski, H., Garrigues, P., Dizer, H., Hansen, P., 1999. Polycyclic aromatic hydrocarbons in recent sediments and mussels (Mytilus edulis) from the Western Baltic Sea: occurrence, bioavailability and seasonal variations. Mar. Environ. Res. 47, 17–47. Cao, Q., Wang, H., Chen, G., 2011. Source apportionment of PAHs using two mathematical models for mangrove sediments in Shantou coastal zone, China. Estuar. Coasts 34, 950–960. Česen, M., Lenarčič, K., Mislej, V., Levstek, M., Kovačič, A., Cimrmančič, B., Uranjek, N., Kosjek, T., Heath, D., Dolenc, M.S., Heath, E., 2018. The occurrence and source identification of bisphenol compounds in wastewaters. Sci. Total Environ. 616–617, 744–752. Corrales, J., Kristofco, L.A., Steele, W.B., Yates, B.S., Breed, C.S., Williams, E.S., Brooks, B.W., 2015. Global assessment of bisphenol A in the environment: review and analysis of its occurrence and bioaccumulation. Dose-Response 13, 1559325815598308. Coz, A., Rodríguez-Obeso, O., Alonso-Santurde, R., Álvarez-Guerra, M., Andrés, A., Viguri, J.R., Mantzavinos, D., Kalogerakis, N., 2008. Toxicity bioassays in core sediments from the Bay of Santander, northern Spain. Environ. Res. 106, 304–312. Davies, D.L., Bouldin, D.W., 1979. A cluster separation measure. IEEE Trans. Pattern Anal. Mach. Intell. 224–227. Dehghani, M., 2007. Industeries of Hormozgan Province. Hormozgan Department of Environment (in Persian). Di Toro, D.M., Zarba, C.S., Hansen, D.J., Berry, W.J., Swartz, R.C., Cowan, C.E., Pavlou, S.P., Allen, H.E., Thomas, N.A., Paquin, P.R., 1991. Technical basis for establishing sediment quality criteria for nonionic organic chemicals using equilibrium partitioning. Environ. Toxicol. Chem. 10, 1541–1583. Dissanayake, A., Bamber, S.D., 2010. Monitoring PAH contamination in the field (South west Iberian Peninsula): biomonitoring using fluorescence spectrophotometry and physiological assessments in the shore crab Carcinus maenas (L.) (Crustacea: Decapoda). Mar. Environ. Res. 70, 65–72. Dong, C.-D., Chen, C.-F., Chen, C.-W., 2012. Determination of polycyclic aromatic hydrocarbons in industrial harbor sediments by GC-MS. Int. J. Environ. Res. Public Health 9, 2175–2188.

4. Conclusion The study results illustrated that the PAHs' concentration decreased with increasing distance from coastal areas and nearby cities. Enhanced levels by the coastline stem from a combination of marine traffic near beaches, urban wastewater and sewage discharge and even street run off. The contaminants are then transported from the coastline outwards and far from coastal areas and were observed even in protected areas of a mangrove forest. Moreover, the industrial zones and urban areas' rapid growth and expansion along the coast are major factors leading to PAH contamination. The results also showed that in areas where the concentration of PAHs increased, the HMW/LMW ratio decreased. PAHs were also identified in bivalves, where LMWs are thought to have originated from seawater. Comparing the PAHs concentration with sediment quality guidelines (ERL and ERM) revealed that there was no adverse biological effect in these sediments. The total cancer values for both adults and children were also within the acceptable level. Also, the comparison of obtained PEC amounts with computed SV for consumers of Hormozgan Province revealed that the risk level of ∑PAHs are significantly less than the maximum acceptable risk level for the human consumption of all bivalves. However, the accumulation of different pollutants in sediment and marine organisms might induce negative health effects on local residents over time and thus preventative measures are necessary and recommended. Although the RQ values indicated small potential adverse effects in most sampling sites for aquatic organisms (RQ < 10), the calculated RQ values in this study can be used for management purposes and as benchmark levels for identifying the areas of the coastline Hormozgan province in the Northern Persian Gulf that can be of special concern in relation to sediment contamination by BPA. CRediT authorship contribution statement Fatemeh Abootalebi Jahromi: Conceptualization, Methodology, Software, Investigation, Writing - original draft, Writing - review & editing. Farid Moore: Supervision, Project administration. Behnam Keshavarzi: Supervision, Project administration. Seyedeh Laili Mohebbi-Nozar: Methodology. Zargham Mohammadi: Writing - review & editing. Armin Sorooshian: Writing - review & editing. Sajjad Abbasi: Software, Validation. 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. 14

Marine Pollution Bulletin 152 (2020) 110941

F. Abootalebi Jahromi, et al.

Li, Q., Wu, J., Zhao, Z., 2018. Spatial and temporal distribution of Polycyclic Aromatic Hydrocarbons (PAHs) in sediments from Poyang Lake, China. PLoS One 13, e0205484. https://doi.org/10.1371/journal.pone.0205484. Liao, C., Liu, F., Moon, H.-B., Yamashita, N., Yun, S., Kannan, K., 2012. Bisphenol analogues in sediments from industrialized areas in the United States, Japan, and Korea: spatial and temporal distributions. Environmental Science & Technology 46, 11558–11565. Lin, T., Qin, Y., Zheng, B., Li, Y., Chen, Y., Guo, Z., 2013. Source apportionment of polycyclic aromatic hydrocarbons in the Dahuofang Reservoir, Northeast China. Environ. Monit. Assess. 185, 945–953. Liu, M., Baugh, P.J., Hutchinson, S.M., Yu, L., Xu, S., 2000. Historical record and sources of polycyclic aromatic hydrocarbons in core sediments from the Yangtze Estuary, China. Environ. Pollut. 110, 357–365. Liu, Y., Chen, L., Huang, Q., Li, W., Tang, Y., Zhao, J., 2009. Source apportionment of polycyclic aromatic hydrocarbons (PAHs) in surface sediments of the Huangpu River, Shanghai, China. Sci. Total Environ. 407, 2931–2938. Liu, Y., Zhang, S., Song, N., Guo, R., Chen, M., Mai, D., Yan, Z., Han, Z., Chen, J., 2017. Occurrence, distribution and sources of bisphenol analogues in a shallow Chinese freshwater lake (Taihu Lake): implications for ecological and human health risk. Sci. Total Environ. 599–600, 1090–1098. Long, E.R., Macdonald, D.D., Smith, S.L., Calder, F.D., 1995. Incidence of adverse biological effects within ranges of chemical concentrations in marine and estuarine sediments. Environ. Manag. 19, 81–97. https://doi.org/10.1007/BF02472006. Lv, J., Xu, J., Guo, C., Zhang, Y., Bai, Y., Meng, W., 2014. Spatial and temporal distribution of polycyclic aromatic hydrocarbons (PAHs) in surface water from Liaohe River Basin, northeast China. Environ. Sci. Pollut. Res. 21, 7088–7096. Lye, C.M., Frid, C.L.J., Gill, M.E., Cooper, D.W., Jones, D.M., 1999. Estrogenic alkylphenols in fish tissues, sediments, and waters from the UK Tyne and Tees estuaries. Environmental Science & Technology 33, 1009–1014. Man, Y.B., Kang, Y., Wang, H.S., Lau, W., Li, H., Sun, X.L., Giesy, J.P., Chow, K.L., Wong, M.H., 2013. Cancer risk assessments of Hong Kong soils contaminated by polycyclic aromatic hydrocarbons. J. Hazard. Mater. 261, 770–776. Marcus, M.D., Covington, S., Liu, B., Smith, N.R., 2010. Use of existing water, sediment, and tissue data to screen ecological risks to the endangered Rio Grande silvery minnow. Sci. Total Environ. 409, 83–94. Menzie, C.A., Hoeppner, S.S., Cura, J.J., Freshman, J.S., LaFrey, E.N., 2002. Urban and suburban storm water runoff as a source of polycyclic aromatic hydrocarbons (PAHs) to Massachusetts estuarine and coastal environments. Estuaries 25, 165–176. Mirza, R., Mohammadi, M., Sohrab, A.D., Safahieh, A., Savari, A., Hajeb, P., 2012. Polycyclic aromatic hydrocarbons in seawater, sediment, and rock oyster Saccostrea cucullata from the northern part of the Persian Gulf (Bushehr Province). Water Air Soil Pollut. 223, 189–198. Montuori, P., Aurino, S., Garzonio, F., Sarnacchiaro, P., Nardone, A., Triassi, M., 2016. Distribution, sources and ecological risk assessment of polycyclic aromatic hydrocarbons in water and sediments from Tiber River and estuary, Italy. Sci. Total Environ. 566–567, 1254–1267. Moopam, 2005. Manual of Oceanographic Observations and Pollutant Analyses Methods (MOOPAM). Regional Organization for the Protection of the Marine Environment. de Mora, S., Tolosa, I., Fowler, S.W., Villeneuve, J.-P., Cassi, R., Cattini, C., 2010. Distribution of petroleum hydrocarbons and organochlorinated contaminants in marine biota and coastal sediments from the ROPME Sea Area during 2005. Mar. Pollut. Bull. 60, 2323–2349. Mortazavi, S., Riyahi Bakhtiari, A., Sari, A.E., Bahramifar, N., Rahbarizade, F., 2012. Phenolic endocrine disrupting chemicals (EDCs) in Anzali Wetland, Iran: elevated concentrations of 4-nonylphenol, octhylphenol and bisphenol A. Mar. Pollut. Bull. 64, 1067–1073. Mortazavi, S., Bakhtiari, A.R., Sari, A.E., Bahramifar, N., Rahbarizadeh, F., 2013. Occurrence of endocrine disruption chemicals (bisphenol a, 4-nonylphenol, and octylphenol) in muscle and liver of, Cyprinus carpino common, from Anzali Wetland, Iran. Bull. Environ. Contam. Toxicol. 90, 578–584. Moslen, M., Miebaka, C.A., Boisa, N., 2019. Bioaccumulation of Polycyclic Aromatic Hydrocarbon (PAH) in a bivalve (Arca senilis-blood cockles) and health risk assessment. Toxicol. Rep. 6, 990–997. Najmeddin, A., Keshavarzi, B., 2018. Health risk assessment and source apportionment of polycyclic aromatic hydrocarbons associated with PM 10 and road deposited dust in Ahvaz metropolis of Iran. Environ. Geochem. Health 1–24. Nimrod, A.C., Benson, W.H., 1996. Estrogenic responses to xenobiotics in channel catfish (Ictalwus punctatus). Mar. Environ. Res. 42, 155–160. Nisbet, I.C.T., LaGoy, P.K., 1992. Toxic equivalency factors (TEFs) for polycyclic aromatic hydrocarbons (PAHs). Regul. Toxicol. Pharmacol. 16, 290–300. Nozar, S.L.M., Ismail, W.R., Zakaria, M.P., 2013. Residual concentration of PAHs in seafood from Hormozgan Province, Iran: human health risk assessment for urban population. Int J Environ Sci Dev 4, 393–397. Nozar, S.L.M., Ismail, W.R., Zakaria, M.P., 2014. Distribution, sources identification, and ecological risk of PAHs and PCBs in coastal surface sediments from the Northern Persian Gulf. Human and Ecological Risk Assessment: An International Journal 20, 1507–1520. Oliva, A.L., Arias, A.H., Quintas, P.Y., Buzzi, N.S., Marcovecchio, J.E., 2017. Polycyclic aromatic hydrocarbons in mussels from a South American estuary. Arch. Environ. Contam. Toxicol. 72, 540–551. https://doi.org/10.1007/s00244-017-0392-y. Onozato, M., Nishigaki, A., Okoshi, K., 2016. Polycyclic aromatic hydrocarbons in sediments and bivalves on the Pacific Coast of Japan: influence of tsunami and fire. PLoS One 11, e0156447. https://doi.org/10.1371/journal.pone.0156447. Peeters, L., Bação, F., Lobo, V., Dassargues, A., 2007. Exploratory data analysis and clustering of multivariate spatial hydrogeological data by means of GEO3DSOM, a variant of Kohonen’s Self-Organizing Map. Hydrol. Earth Syst. Sci. 11, 1309–1321.

EPA, 2002. Emergency Planning and Community Right-to-know Act - Section 313: Guidance for Reporting Toxic Chemicals: Polycyclic Aromatic Compounds Category. EPA Publications. European Commission, 2003. Technical Guidance Document on Risk Assessment in Support of Commission Directive 93/67/EEC on Risk Assessment for New Notified Substances and Commission Regulation (EC) No. 1488/94 on Risk Assessment for Existing Substances. Part II. EUR 20418 EN/2. European Commission Joint Research Centre, pp. 7–179 EUR Part II. Fisner, M., Taniguchi, S., Majer, A.P., Bícego, M.C., Turra, A., 2013. Concentration and composition of polycyclic aromatic hydrocarbons (PAHs) in plastic pellets: implications for small-scale diagnostic and environmental monitoring. Mar. Pollut. Bull. 76, 349–354. Fu, P., Kawamura, K., 2010. Ubiquity of bisphenol A in the atmosphere. Environ. Pollut. 158, 3138–3143. Gee, G., Bauder, J., 1986. Particle-size analysis. Madison, particlesize analysis. In: Klute, A. (Ed.), Methods of Soil Analysis, Part 1. Physical and Mineralogical Methods, 2nd edn. Agronomy 9. Soil Science Society of America, Madison, pp. 383–411. Gong, Jian, Ran, Yong, Chen, Di-Yun, Yang, Yu, 2011. Occurrence of endocrine-disrupting chemicals in riverine sediments from the Pearl River Delta, China. Mar. Pollut. Bull. 63, 556–563. Grung, M., Petersen, K., Fjeld, E., Allan, I., Christensen, J.H., Malmqvist, L.M.V., Meland, S., Ranneklev, S., 2016. PAH related effects on fish in sedimentation ponds for road runoff and potential transfer of PAHs from sediment to biota. Sci. Total Environ. 566–567, 1309–1317. Gu, Y., Yu, J., Hu, X., Yin, D., 2016. Characteristics of the alkylphenol and bisphenol A distributions in marine organisms and implications for human health: a case study of the East China Sea. Sci. Total Environ. 539, 460–469. Habibullah-Al-Mamun, M., Ahmed, M.K., Islam, M.S., Tokumura, M., Masunaga, S., 2018. Distribution of polycyclic aromatic hydrocarbons (PAHs) in commonly consumed seafood from coastal areas of Bangladesh and associated human health implications. Environ. Geochem. Health 1–17. Habibullah-Al-Mamun, M., Kawser Ahmed, M., Hossain, A., Masunaga, S., 2019. Distribution, source apportionment, and risk assessment of polycyclic aromatic hydrocarbons (PAHs) in the surficial sediments from the coastal areas of Bangladesh. Arch. Environ. Contam. Toxicol. 76, 178–190. Hatam, G., Nejati, F., Mohammadzadeh, T., 2015. Population-based Seroprevalence of Malaria in Hormozgan Province, Southeastern Iran: A Low Transmission Area. (Malaria research and). Heemken, O.P., Reincke, H., Stachel, B., Theobald, N., 2001. The occurrence of xenoestrogens in the Elbe river and the North Sea. Chemosphere 45, 245–259. He, X., Pang, Y., Song, X., Chen, B., Feng, Z., Ma, Y., 2014. Distribution, sources and ecological risk assessment of PAHs in surface sediments from Guan River Estuary, China. Mar. Pollut. Bull. 80, 52–58. He, Y., Meng, W., Xu, J., Zhang, Y., Guo, C., 2016. Spatial distribution and potential toxicity of polycyclic aromatic hydrocarbons in sediments from Liaohe River Basin, China. Environ. Monit. Assess. 188, 1–10. Hong, Wen-Jun, Jia, Hongliang, Li, Yi-Fan, Sun, Yeqing, Liu, Xianjie, Wang, Luo, 2016. Polycyclic aromatic hydrocarbons (PAHs) and alkylated PAHs in the coastal seawater, surface sediment and oyster from Dalian, Northeast China. Ecotoxicol. Environ. Saf. 128, 11–20. Hu, N., Shi, X., Liu, J., Huang, P., Liu, Y., Liu, Y., 2010. Concentrations and possible sources of PAHs in sediments from Bohai Bay and adjacent shelf. Environ. Earth Sci. 60, 1771–1782. Hu, N.J., Shi, X.F., Huang, P., Liu, J.H., 2011. Polycyclic aromatic hydrocarbons in surface sediments of Laizhou Bay, Bohai Sea, China. Environ. Earth Sci. 63, 121–133. Huang, Y.Q., Wong, C.K.C., Zheng, J.S., Bouwman, H., Barra, R., Wahlström, B., Neretin, L., Wong, M.H., 2012. Bisphenol A (BPA) in China: a review of sources, environmental levels, and potential human health impacts. Environ. Int. 42, 91–99. Kawahata, Hodaka, Ohta, Hidekazu, Inoue, Mayuri, Suzuki, Atsushi, 2004. Endocrine disrupter nonylphenol and bisphenol A contamination in Okinawa and Ishigaki Islands, Japan––within coral reefs and adjacent river mouths. Chemosphere 55, 1519–1527. Keshavarzifard, M., Zakaria, M.P., Hwai, T.S., 2017. Bioavailability of polycyclic aromatic hydrocarbons (PAHs) to short-neck clam (Paphia undulata) from sediment matrices in mudflat ecosystem of the west coast of Peninsular Malaysia. Environ. Geochem. Health 39, 591–610. Khim, Jong Seong, Villeneuve, Daniel L., Kannan, Kurunthachalam, Koh, Chul Hwan, Giesy, John P., 1999. Characterization and distribution of trace organic contaminants in sediment from Masan Bay, Korea. Environ. Sci. Technol. 23, 4206–4211. Kohonen, T., 1990. The self-organizing map. Proc. IEEE 78, 1464–1480. Lababpour, A., 2015. Phytoplankton community and physico-chemical characteristics of seawater in the Bandar Abbas coastal water, Persian Gulf: an environmental and process perspective. Journal of the Persian Gulf 6, 39–50. Langford, K.H., Scrimshaw, M.D., Birkett, J.W., Lester, J.N., 2005. Degradation of nonylphenolic surfactants in activated sludge batch tests. Water Res. 39, 870–876. Lawal, A.T., 2017. Polycyclic aromatic hydrocarbons. A review. Cogent Environmental Science 3. Lee, S., Liao, C., Song, G.-J., Ra, K., Kannan, K., Moon, H.-B., 2015. Emission of bisphenol analogues including bisphenol A and bisphenol F from wastewater treatment plants in Korea. Chemosphere 119, 1000–1006. Li, F., Zeng, X., Yang, J., Zhou, K., Zan, Q., Lei, A., Tam, N.F.Y., 2014. Contamination of polycyclic aromatic hydrocarbons (PAHs) in surface sediments and plants of mangrove swamps in Shenzhen, China. Mar. Pollut. Bull. 85, 590–596. Li, J., Dong, H., Zhang, D., Han, B., Zhu, C., Liu, S., Liu, X., Ma, Q., Li, X., 2015. Sources and ecological risk assessment of PAHs in surface sediments from Bohai Sea and northern part of the Yellow Sea, China. Mar. Pollut. Bull. 96, 485–490.

15

Marine Pollution Bulletin 152 (2020) 110941

F. Abootalebi Jahromi, et al.

Science and Technology 69. Tobiszewski, M., Namieśnik, J., 2012. PAH diagnostic ratios for the identification of pollution emission sources. Environ. Pollut. 162, 110–119. Tolosa, I., De Mora, S.J., Fowler, S.W., Villeneuve, J.-P., Bartocci, J., Cattini, C., 2005. Aliphatic and aromatic hydrocarbons in marine biota and coastal sediments from the Gulf and the Gulf of Oman. Mar. Pollut. Bull. 50, 1619–1633. USEPA, 2017. Regional screening levels (RSLs) - generic tables. Date accessed: 2018-0515. Available online. https://www.epa.gov/risk/regional-screening-levels-rslsgeneric-tables. USEPA, 2004. Risk Assessment Guidance for Superfund Volume I: Human Health Evaluation Manual (Part E, Supplemental Guidance for Dermal Risk Assessment). Office of Superfund Remediation and Technology Innovation. Vaezzadeh, V., Zakaria, M.P., Bong, C.W., Masood, N., Mohsen Magam, S., Alkhadher, S., 2019. Mangrove oyster (Crassostrea belcheri) as a biomonitor species for bioavailability of polycyclic aromatic hydrocarbons (PAHs) from sediment of the west coast of peninsular Malaysia. Polycycl. Aromat. Compd. 39, 470–485. Wang, Z., Liu, Z., Xu, K., Mayer, L.M., Zhang, Z., Kolker, A.S., Wu, W., 2014. Concentrations and sources of polycyclic aromatic hydrocarbons in surface coastal sediments of the northern Gulf of Mexico. Geochem. Trans. 15. Wang, Y.-B., Liu, C.-W., Kao, Y.-H., Jang, C.-S., 2015. Characterization and risk assessment of PAH-contaminated river sediment by using advanced multivariate methods. Sci. Total Environ. 524, 63–73. Wang, Li, Ying, Guang-Guo, Zhao, Jian-Liang, Liu, Shan, Yang, Bin, Zhou, Li-Jun, Tao, Ran, Su, Hao-Chang, 2011. Assessing estrogenic activity in surface water and sediment of the Liao River system in northeast China using combined chemical and biological tools. Environ. Pollut. 159, 148–156. Xiong, J., Li, G., An, T., Zhang, C., Wei, C., 2016. Emission patterns and risk assessment of polybrominated diphenyl ethers and bromophenols in water and sediments from the Beijiang River, South China. Environ. Pollut. 219, 596–603. Xu, J., Yu, Y., Wang, P., Guo, W., Dai, S., Sun, H., 2007. Polycyclic aromatic hydrocarbons in the surface sediments from Yellow River, China. Chemosphere 67, 1408–1414. Xu, F.-L., Wu, W.-J., Wang, J.-J., Qin, N., Wang, Y., He, Q.-S., He, W., Tao, S., 2011. Residual levels and health risk of polycyclic aromatic hydrocarbons in freshwater fishes from Lake Small Bai-Yang-Dian, Northern China. Ecol. Model. 222, 275–286. Xue, R., Chen, L., Lu, Z., Wang, J., Yang, H., Zhang, J., Cai, M., 2016. Spatial distribution and source apportionment of PAHs in marine surface sediments of Prydz Bay, East Antarctica. Environ. Pollut. 219, 528–536. Yan, Z., Liu, Y., Yan, K., Wu, S., Han, Z., Guo, R., Chen, M., Yang, Q., Zhang, S., Chen, J., 2017. Bisphenol analogues in surface water and sediment from the shallow Chinese freshwater lakes: occurrence, distribution, source apportionment, and ecological and human health risk. Chemosphere 184, 318–328. Yavar Ashayeri, N., Keshavarzi, B., 2019. Geochemical characteristics, partitioning, quantitative source apportionment, and ecological and health risk of heavy metals in sediments and water: a case study in Shadegan Wetland, Iran. Mar. Pollut. Bull. 149, 110495. Yavar Ashayeri, N., Keshavarzi, B., Moore, F., Kersten, M., Yazdi, M., Lahijanzadeh, A.R., 2018. Presence of polycyclic aromatic hydrocarbons in sediments and surface water from Shadegan wetland – Iran: a focus on source apportionment, human and ecological risk assessment and sediment-water exchange. Ecotoxicol. Environ. Saf. 148, 1054–1066. Yu, W., Liu, R., Xu, F., Shen, Z., 2015. Environmental risk assessments and spatial variations of polycyclic aromatic hydrocarbons in surface sediments in Yangtze River Estuary, China. Mar. Pollut. Bull. https://doi.org/10.1016/j.marpolbul.2015.09.004. Yunker, M.B., Macdonald, R.W., Vingarzan, R., Mitchell, R.H., Goyette, D., Sylvestre, S., 2002. PAHs in the Fraser River basin: a critical appraisal of PAH ratios as indicators of PAH source and composition. Org. Geochem. 33, 489–515. Zakaria, M.P., Takada, H., Tsutsumi, S., Ohno, K., Yamada, J., Kouno, E., Kumata, H., 2002. Distribution of polycyclic aromatic hydrocarbons (PAHs) in rivers and estuaries in Malaysia: a widespread input of petrogenic PAHs. Environmental Science & Technology 36, 1907–1918. Zuloaga, O., Prieto, A., Usobiaga, A., Sarkar, S.K., Chatterjee, M., Bhattacharya, B.D., Bhattacharya, A., Alam, M.A., Satpathy, K.K., 2009. Polycyclic aromatic hydrocarbons in intertidal marine bivalves of sunderban mangrove wetland, India: an approach to bioindicator species. Water Air Soil Pollut. 201, 305–318.

Peng, Xianzhi, Wang, Zhendi, Mai, Bixian, Chen, Fanrong, Chen, Shejun, Tan, Jianhua, Yu, Yiyi, Tang, Caiming, Li, Kechang, Zhang, Gan, Yang, Chun, 2007. Temporal trends of nonylphenol and bisphenol A contamination in the Pearl River Estuary and the adjacent South China Sea recorded by dated sedimentary cores. Sci. Total Environ. 384, 393–400. Pourang, N., Richardson, C.A., Mortazavi, M.S., 2010. Heavy metal concentrations in the soft tissues of swan mussel (Anodonta cygnea) and surficial sediments from Anzali wetland, Iran. Environ. Monit. Assess. 163, 195–213. Rice, C.P., Schmitz-Afonso, I., Loyo-Rosales, J.E., Link, E., Thoma, R., Fay, L., Altfater, D., Camp, M.J., 2003. Alkylphenol and alkylphenol-ethoxylates in carp, water, and sediment from the Cuyahoga River, Ohio. Environmental Science & Technology 37, 3747–3754. Robinson, C.D., Webster, L., Martínez-Gómez, C., Burgeot, T., Gubbins, M.J., Thain, J.E., Vethaak, A.D., McIntosh, A.D., Hylland, K., 2017. Assessment of contaminant concentrations in sediments, fish and mussels sampled from the North Atlantic and European regional seas within the ICON project. Mar. Environ. Res. 124, 21–31. Rocha, A.C., Palma, C., 2018. Source identification of polycyclic aromatic hydrocarbons in soil sediments: application of different methods. Sci. Total Environ. 652, 1077–1089. Safahieh, A., Mahmoodi, M., Nikpoor, Y., Ghanemi, K., 2011. PAHs concentration in ark clam (Barbatia helblingii) from South Persian Gulf, Bushehr, Iran. International Journal of Environmental Science and Development 2, 394. Sajjad, Abbasi, Behnam, Keshavarzi, Moore, Farid, Turner, Andrew, Kelly, Frank J., Dominguez, Ana Oliete, Jaafarzadeh, Neemat, 2018. Distribution and potential health impacts of microplastics and microrubbers in air and street dusts from Asaluyeh County, Iran. Environ. Pollut. 244, 153–164. Sakari, M., Zakaria, M.P., Lajis, N.H., Mohamed, C.A.R., Abdullah, M.H., 2012. Three centuries of polycyclic aromatic hydrocarbons and teriterpane records in Tebrau Strait, Malaysia; recent pollution concern in a pristine marine environment. Polycycl. Aromat. Compd. 32, 364–389. Schøyen, M., Allan, I.J., Ruus, A., Håvardstun, J., Hjermann, D., Beyer, J., 2017. Comparison of caged and native blue mussels (Mytilus edulis spp.) for environmental monitoring of PAH, PCB and trace metals. Mar. Environ. Res. 130, 221–232. Sereshk, Z.H., Bakhtiari, A.R., 2014. Distribution patterns of PAHs in different tissues of annulated sea snake (Hydrophis cyanocinctus) and short sea snake (Lapemis curtus) from the Hara protected area on the north coast of the Persian Gulf, Iran. Ecotoxicol. Environ. Saf. 109, 116–123. Simpson, C.D., Mosi, A.A., Cullen, W.R., Reimer, K.J., 1996. Composition and distribution of polycyclic aromatic hydrocarbon contamination in surficial marine sediments from Kitimat Harbor, Canada. Sci. Total Environ. 181, 265–278. Sun, C., Zhang, J., Ma, Q., Chen, Y., Ju, H., 2017. Polycyclic aromatic hydrocarbons (PAHs) in water and sediment from a river basin: sediment–water partitioning, source identification and environmental health risk assessment. Environ. Geochem. Health 39, 63–74. Sun, R., Sun, Y., Li, Q.X., Zheng, X., Luo, X., Mai, B., 2018. Polycyclic aromatic hydrocarbons in sediments and marine organisms: implications of anthropogenic effects on the coastal environment. Sci. Total Environ. 640–641, 264–272. Sun, Lin, Run-Xia, Ke, Qin, Du, Chang-Liang, Gu, Fei-Yan, Cao, Yang-Guang, Luo, Kun, Xiao-JunMai, Bi-Xian, 2016. Polycyclic aromatic hydrocarbons in surface sediments and marine organisms from the Daya Bay, South China. Mar. pollut. Bull. 103, 325–332. Talmage, S.S., 1994. Environmental and Human Safety of Major Surfactants: Alcohol Ethoxylates and Alkylphenol Ethoxylates. CRC Press. Tam, N.F.Y., Ke, L., Wang, X.H., Wong, Y.S., 2001. Contamination of polycyclic aromatic hydrocarbons in surface sediments of mangrove swamps. Environ. Pollut. 114, 255–263. Thompson, K.-L., Picard, C.R., Chan, H.M., 2017. Polycyclic aromatic hydrocarbons (PAHs) in traditionally harvested bivalves in northern British Columbia, Canada. Mar. Pollut. Bull. 121, 390–399. https://doi.org/10.1016/j.marpolbul.2017.06.018. Tian, Y.-Z., Li, W.-H., Shi, G.-L., Feng, Y.-C., Wang, Y.-Q., 2013. Relationships between PAHs and PCBs, and quantitative source apportionment of PAHs toxicity in sediments from Fenhe reservoir and watershed. J. Hazard. Mater. 248, 89–96. Tobiszewski, M., 2014. Application of diagnostic ratios of PAHs to characterize the pollution emission sources. In: 2014 5th International Conference on Environmental

16