Polycyclic aromatic hydrocarbons in surface sediments from the Coast of Weihai, China: Spatial distribution, sources and ecotoxicological risks

MPB-07698; No of Pages 7 Marine Pollution Bulletin xxx (2016) xxx–xxx

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Polycyclic aromatic hydrocarbons in surface sediments from the Coast of Weihai, China: Spatial distribution, sources and ecotoxicological risks Daolai Zhang a,b,c, Jinqing Liu a,b,c, Ping Yin b,c, Xuehui Lin b,c, Na Liu b,c, Xianwei Meng d,⁎ a

Qingdao Institute of Marine Geology, Qingdao, China Key Laboratory of Marine Hydrocarbon Resources and Environmental Geology, Ministry of Land and Resources, Qingdao, China College of Marine Geosciences, Ocean University of China, Qingdao, China d First Institute Oceanography of SOA, Qingdao 266100, China b c

a r t i c l e

i n f o

Article history: Received 29 November 2015 Received in revised form 4 May 2016 Accepted 9 May 2016 Available online xxxx Keywords: PAHs Distribution Source Ecotoxicological risk Sediment Weihai

a b s t r a c t This study was conducted to measure the polycyclic aromatic hydrocarbon (PAH) concentrations and evaluate the distribution, sources in surface sediments from various coastal sites in Weihai, which create good conditions for rapid development because of their excellent geographical location and abundant marine resources. The results indicated that the total PAHs contents in the sediments of Weihai ranged from 2.69 to 166.50 ng g−1, with an average of 67.44 ng g−1. Phenanthrene, Fluoranthene, Benzo(b)fluoranthene, Chrysene, and Pyrene were dominant in sediments, primarily as a result of high temperature combustion and biomass. Molecular ratios suggested that these PAHs in the sediments of Weihai were predominantly from pyrogenic sources such as grass, wood and charcoal combustion, as well as engine exhaust which is similar to the result of the study of the Yellow River Delta, China. The result of probability risk assessment additionally elucidated low PAH ecological risk in the surface sediments of Weihai, China. © 2016 Elsevier Ltd. All rights reserved.

Polycyclic aromatic hydrocarbons (PAHs) are a group of persistent organic pollutants formed by two or more fused aromatic rings of carbon and hydrogen atoms that are ubiquitous in the environment and known to be toxic, carcinogenic and mutagenic (Callén et al., 2013; Cébron et al., 2013). Because of their high toxicological risk, 16 selected PAHs are listed as priority pollutants by the United States Environmental Protection Agency (USEPA), seven of which are potentially carcinogenic to humans according to the International Agency for Research on Cancer. Because of their low aqueous solubility and high octanol/ water partition coefficient, PAHs entering the ocean tend to associate with particulate material and accumulate in the sediments (Lindgren et al., 2014; Naes et al., 1995). PAHs in the sediments will remobilize in the water column, then pose a threat to native aquatic organisms and finally accumulate in higher trophic levels because their half-life can range from years to decades (Cachot et al., 2006; Lindgren et al., 2014; Siddall et al., 1994; Tobiszewski and Namieśnik, 2012; Vane et al., 2013). Most PAHs persist in sediments until they are degraded (Tobiszewski and Namieśnik, 2012; Valentín et al., 2006), therefore, sediment studies can be effective approaches to PAHs contamination research, and PAHs are good indicators of historical anthropogenic impacts on the sedimentary environment.

⁎ Corresponding author. E-mail address: mxw@fio.org.cn (X. Meng).

PAHs in marine sediments have been receiving increased attention because of their negative effects on marine aquatic systems and humans around the world (Aoki et al., 2014; Commendatore et al., 2012; Culotta et al., 2006; Guzzella et al., 2005; Li et al., 2014; Soliman et al., 2014; Yuan et al., 2014). Large amounts of PAHs have been discharged into the ocean, predominantly through human activities associated with combustion and petroleum production (Bouloubassi et al., 2012; Bragato et al., 2012; Callén et al., 2014; Carver et al., 1986; Kaivosoja et al., 2012; Lea-Langton et al., 2013; Readman et al., 2002). Previous studies have shown that PAHs are widely distributed in marine aquatic environments, such as estuaries, coastal areas, wetlands, off-shore areas and the deep sea due to anthropogenic processes and their comparatively long half-life (Counihan et al., 2014; Jörundsdóttir et al., 2014; Oros et al., 2007; Porte and Escartín, 2000; Yancheshmeh et al., 2014). Many studies have shown that there were also PAH contaminants in sediments from marine systems around China, including the Bohai, Yellow, East China and South seas (Deng et al., 2013; Hung et al., 2014; Ma et al., 2001; Men et al., 2009; Yang, 2000; Zong et al., 2014). While many studies have investigated the specific spatial distribution and sources of PAHs in the above seas and many important bays, little is known about PAHs contaminants in marine sediments around the city on the beach of the Yellow Sea (Weihai Beach), which has been designated a major region of the Shandong Peninsula Blue Economic Zone by the government of China (Bouloubassi et al., 2001; He et al., 2014; Li et al., 2012; Maskaoui et al., 2002; Yuan et al., 2001; Zhang et al., 2009). Similar to

http://dx.doi.org/10.1016/j.marpolbul.2016.05.018 0025-326X/© 2016 Elsevier Ltd. All rights reserved.

Please cite this article as: Zhang, D., et al., Polycyclic aromatic hydrocarbons in surface sediments from the Coast of Weihai, China: Spatial distribution, sources and ecotoxico..., Marine Pollution Bulletin (2016), http://dx.doi.org/10.1016/j.marpolbul.2016.05.018

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D. Zhang et al. / Marine Pollution Bulletin xxx (2016) xxx–xxx

other coastal regions worldwide, Weihai is facing increasing anthropic pressure through population growth, economic development and industrialization. The City of Weihai has developed rapidly in past decades because of exploitation of the ocean (Ning and Hoon, 2011). In addition, rapid economic growth in the coast around Weihai has raised concern of significant pollution of aquatic environments, especially of sediments that act as a natural repository of organic pollutants. The state and quality of the marine environment around Weihai has been the source of some concern during the past few years. However, only a few studies of the characteristics of inorganic geochemistry and the distribution and amount of heavy metal contaminants present in sediments in the coast around Weihai have been conducted (Jiang et al., 2014; Huang et al., 2013). Accordingly, there is a lack of data describing sediment PAHs concentrations for the Weihai coast. Therefore, this study was conducted to investigate the present level of PAHs pollution and their spatial distribution in surface sediments collected from the Weihai coast. Isomeric PAHs ratios were analyzed to estimate their potential sources in the target area, and the toxicological effects of PAHs to marine organisms were evaluated by comparing PAHs concentrations in sediments with the Sediment Quality Guidelines (SQGs) and threshold levels proposed by Long et al. (1995) and Maliszewska-Kordybach (1996), respectively. The results of this study will serve as a baseline to assess future anthropogenic effects and will be valuable to local governments. This study focused on sediments (121°21′00″–122°43′00″E, 36°37′ 00″–37°35′00″N) collected from the coast of Weihai, Shandong, China (Fig. 1). Weihai has a length of 29 km along the west coast of the North Yellow Sea. The mean annual temperature of this area is 24.6 ° C, the annual precipitation is 1579.70 mm, and the average salinity of the open water ranges from 23‰ to 26‰. Nearshore development includes aquaculture, container and bulk cargo ship terminals, as well as food production. Nearly 2.8 million people live in urban centers on the shores of this coast. Nineteen sampling sites were selected along the Weihai coast and grouped into three transects divided into three groups based on their coordinates from south to north in a 3949.98 km2 area. Surface sediments (depth 0–5 cm) were collected from 19 locations in April 2013 using Smith-Mcintyre grab samplers (Fig. 1). Each sediment sample analyzed in this study was packed into cleaned solventrinsed glass flasks and stored at −20 °C until chemical analysis. Extraction from sediments was carried out according to the method described by Nicola et al. (2005). A total of 10–15 g of freeze dried sediments were dissolved in a mixture of perdeuterated internal standards ([d-10]phenanthrene, [d-10]pyrene, [d-12]chrysene, [d-12]perylene

and [d-12]benzo(g,h,i)perylene) and then mixed with equal quantities of anhydrous sodium sulfate three times in 60 mL of a dichloromethane:acetone (1:1, v:v) mix for 20 min while sonicating. The extract was then concentrated and solvent exchanged with hexane, after which it was further reduced to approximately 1 mL under weak nitrogen flow. The extract was subsequently applied to a 1:2 alumina/ silica gel glass column for clean-up and fractionation. The first fraction, which contained aliphatic hydrocarbons, was eluted with 15 mL of hexane. The second fraction, which contained PAHs, was collected by eluting 5 mL hexane and 70 mL of methylene chloride: hexane (30:70). The PAHs fractions were concentrated to 0.4 mL under a gentle N2 stream. Known quantities of internal standard were added to the sample prior to instrumental analysis. Consecutively, the dried residues were dissolved in 1 mL of hexane. Concentrations of PAHs were measured by gas chromatography (HP 5890 GC with a HP-5MS capillary column 30 m, 0.25 mm i.d., 0.25 μm film thickness) coupled to a mass spectrometer (HP 5975 mass selective detector). Helium was applied as the carrier gas at a constant flow rate of 1.0 mL min−1. The oven temperature program started at 70 °C, then increased at 20 °C min−1 to 280 °C, where it was held for 24 min. Quantitations were conducted using the primary ions for each compound, after which two to three secondary ions were used for qualitative confirmation. Glassware and sodium sulfate were solvent-rinsed and heated for 4 h at 450 °C prior to use. For each batch of 10 samples, a spiked blank, a procedural blank, matrix spikes and a duplicate sample were processed in the same way as the sample for quality assurance and control. No quantifiable targets were detected in these blanks. Analysis of a reagent blank demonstrated that the analytical system and glassware were free of contamination. The recovery was 75.0%–120.0% for spiked blanks. The results reported in this study were not corrected for recoveries. The relative standard deviation for parallel samples (n = 3) was b15%. A total of 16 PAHs compounds listed as priority pollutants by the USEPA were identified and quantified. The concentrations of individual PAHs compounds and total PAHs from 19 sampling sites on the Weihai coast are shown in Table 1. Total PAHs occurred in variable amounts at the 19 sites. The ∑PAHs in the 19 sediments from the research area ranged from 2.69 ng g−1 to 166.50 ng g−1 of dry matrix with a mean of 67.44 ng g−1 of dry matrix. The highest and lowest sediment total PAHs concentrations were found for sites WHB20 and WHB16, respectively. The highest concentrations of ∑ PAHs were found at site WHB20, which also contained all 16 compounds, followed by station

Fig. 1. Location on the coast of Weihai, Shandong, China.

Please cite this article as: Zhang, D., et al., Polycyclic aromatic hydrocarbons in surface sediments from the Coast of Weihai, China: Spatial distribution, sources and ecotoxico..., Marine Pollution Bulletin (2016), http://dx.doi.org/10.1016/j.marpolbul.2016.05.018

0.93 4.3 0 0.07 0.41 0 12 0.25 0.18 0.29 0.08 0.02 0.21 0 0.31 0.19 19.24 0.67 0 0 0.11 0.92 0.12 8.74 0.7 0.12 1.22 0.02 0.02 0.13 0 0.42 0.4 13.59 0 0 0 0.69 0.06 5.35 61.53 0 1.78 16.6 0.25 0 0.2 0.35 0 0.22 87.03 6.74 43.28 0.36 0.39 1.71 0.63 74.46 2.33 8.06 16.57 0.58 0.1 4.73 0.37 5.83 0.36 166.5 0.53 4.52 0.04 0.12 1.14 0.24 22.84 0.9 0.19 0.81 0.06 0.04 0.24 0 0.61 0.23 32.51 0.2 0 0 0 0.33 0 1.48 0.14 0.05 0 0.06 0 0 0 0 0.43 2.69 9.98 42.78 0.38 0.58 2.17 1.7 63.29 0.87 0.51 0.64 0.09 0.03 0.56 0 0.97 0.31 124.86 10.87 18.88 0.3 0.68 2.21 1.27 82.52 1.08 0.41 0.78 0.14 0.03 0.34 0 0.65 0.71 120.87 0.8 4.46 0.06 0.05 0.47 0.15 9.02 0.31 0.11 0.53 0.12 0.02 0 0 0 0.62 16.72 9.46 17.13 0.28 0.92 3.12 1.27 108.13 1.77 0.47 1.13 0.33 0 0.34 0 0.71 1.36 146.42 1.41 11.47 0.08 0.21 1.31 0.19 19.39 0.84 0.18 0.51 0.05 0 0.14 0 0.55 0 36.33 4.01 0 0.14 0.35 3.26 0.8 93.69 2.29 1.87 3.51 0.69 0.02 0.63 0.32 1.69 0.38 113.65 1.66 6.68 0.1 0.26 3.9 0.37 60.41 3.12 0.81 0.77 0.36 0.01 0.87 0.96 2.95 2.24 85.47 1.52 5.06 0.51 0.11 0.49 0.27 24.92 0.88 0.52 0.78 0.17 0.03 0.57 0 1.04 0.52 37.39 0.72 3.64 0 0.08 0.8 0 19.2 0.85 0.35 0.63 0.12 0.02 0.56 0 0.64 0.49 28.1 4.21 3.5 0.2 0.2 0.69 0.58 24.85 0.22 0.16 0.18 0.08 0 0.11 0 0 0.54 35.52 9.12 5.61 0.27 0.7 1.79 1.15 64.61 0.67 0.37 0.38 0.1 0.01 0.26 0 0.49 0.44 85.97 4.58 10.32 0.62 0.47 14.55 1.52 0 1.46 4.06 19.62 1.01 0.03 0.52 0 0.89 1.24 60.89 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 ∑PAHs

5.71 11.14 0.17 0.5 1.32 0.83 39.49 0.69 1.39 3.79 0.14 0 0.85 0 0.78 0.57 67.37

WHB6 WHB5 WHB4 WHB3 WHB2 WHB1 PAHs

Table 1 Concentrations (ng g−1, dw.) of 16 EPA priority PAHs in surface sediments from Weihai coast.

WHB7

WHB8

WHB11

WHB12

WHB13

WHB14

WHB15

WHB16

WHB17

WHB20

WHB21

WHB22

WHB23

D. Zhang et al. / Marine Pollution Bulletin xxx (2016) xxx–xxx

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WHB12. WHB20 and WHB12 were located close to the beach in areas heavily impacted by human activities. The total PAHs at site WHB16 (2.69 ng g−1) were found to be much lower than the concentrations at the other sites. While all 16 PAHs were found at WHB1, WHB7 and WHB20, only Naphthalene, Phenanthrene, Fluoranthene, Pyrene, Benzo(a)anthracene, Benzo(b)fluoranthene and Indeno(1,2,3-cd)pyrene were detected at WHB16. There was a high degree of variability observed for individual PAH compounds at the 19 sites. Phenanthrene, Benzo(a)anthracene, and Benzo(b)fluoranthene were the major PAH compounds in the sediments, and were found in all of sediment samples, while Dibenzo(a,h)anthracene was only detected in WHB7, WHB8, WHB20 and WHB21. The concentration of the individual PAHs in the 19 samples occurred in the following order: FluorantheneNAcenaphthyleneNNaphthaleneNChryseneNPhenanthreneNAcenaphthyleneNNaphthaleneNChryseneNPhenanthreneNBenzo(a)antAcenaphthyleneNNaphthaleneNChryseneNPhenanthreneNBenzo(a)antha)anthraceneNPyreneNBenzo(g,h,i)peryleneNAnthraceneNBenzo(a)pyrea)pyrene N Indeno(1,2,3-cd)pyrene N Fluorene N Benzo(b)fluoranthene N Acenaphthene N Dibenzo(a,h)anthracene N Benzo(k)fluoranthene. The distribution patterns of individual PAHs at the 19 locations are illustrated in Fig. 2. The results revealed that 4- and 3-ring PAHs were dominant in the sediments, followed by 2-ring PAHs, while the relative abundance of 5- and 6-ring PAHs was lowest. The 4-ring PAHs were most abundant, ranging from 41.27% to 91.82% of the total 16 PAHs in the 19 sediments. In general, the relative abundance of PAH analytes was similar among the 19 sites. This behavior might be due to the source of the PAHs. A similar uniform distribution of individual PAHs was also observed in the Pearl River Estuary coastal wetland soils (Khadhar et al., 2010), but the patterns differed from those in Qatar, which were dominated by 4–6 ringed PAHs (Soliman et al., 2014). The fine-grained sediment (clay and silt) ranged from 75.4% to 99.2% with an average of 89.5% in the study area. The organic carbon content showed little variation and the content ranged from 0.1 to 0.6%, with a mean value of 0.3%. The 2-tailed Pearson correlation analyses revealed no significant correlations among ∑PAHs, grain size and organic carbon content. All sites were divided into three groups based on their coordinates, the east transect, middle transect, and west transect. The distribution of PAHs differed in the three transects. The average total sediment PAHs concentration in the eight sites in the east transect was 64.30 ng g−1, with the highest concentration being found in WHB8 (113.66 ng g−1) and the lowest in WHB5 (28.09 ng g−1). The average total sediment PAHs concentration in the middle transect, which included six sites, was 68.63 ng g− 1, with the highest concentration being found in WHB12 (146.43 ng g− 1) and the lowest in WHB16 (2.69 ng g−1). The average total sediments PAHs concentrations in the west transect, which contained six sites, was 71.59 ng g− 1, with the highest concentration being found in WHB22 (166.50 ng g−1) and the lowest in WHB20 (13.59 ng g−1). The average concentration of the 16 PAHs in the three transects of the research coast occurred in the following order: west transect N middle transect N east transect. Additionally, the PAHs concentrations in the sediment of the Weihai coast decreased with increasing distance from the beach in all three transects, suggesting that PAHs are transported by the longshore currents from the coastal point sources to offshore. The concentrations of total PAHs in sediments of Weihai were compared with those of other coastal areas, and the PAHs isomeric ratios were used to identify the sources of PAHs in the study area. Overall, hazard assessment of PAHs showed that the sediments of Weihai coast will not pose a threat to the ecological environment. The 16 EPA priority PAHs have been used to evaluate anthropogenic pollution levels in sediments in many studies. The concentrations of total PAHs in sediments of Weihai were relatively lower than in the sediments of the Arabian Gulf in Qatar (Soliman et al., 2014), the Yellow River Delta in China (Yuan et al., 2014), the Liaohe estuary in China (Li et al., 2014), Stagnone coastal lagoon in Italy (Culotta et al., 2006) and

Please cite this article as: Zhang, D., et al., Polycyclic aromatic hydrocarbons in surface sediments from the Coast of Weihai, China: Spatial distribution, sources and ecotoxico..., Marine Pollution Bulletin (2016), http://dx.doi.org/10.1016/j.marpolbul.2016.05.018

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D. Zhang et al. / Marine Pollution Bulletin xxx (2016) xxx–xxx

sediments in the Yatsushiro Sea in Japan (Aoki et al., 2014). Values recorded in sediments in this study from the Weihai coast are comparable to those observed in the Hugli estuary of northeast India (Guzzella et al., 2005). However, the PAHs levels found in the present study were higher than those in Ushuaia Bay of Argentina (Commendatore et al., 2012). PAHs are generated via many pathways, so the sources were mixed. There are four main processes that lead to generation of PAHs, combustion, petroleum leaking, diagenetic processes and leaching from aquatic timberworks (Callén et al., 2013). Because of its large surface area, the origins of PAHs in the sediments of the Weihai coast may be difficult to accurately identify. Based on each source giving rise to characteristic patterns, there are some useful indicators to discriminate the processes that generate PAHs, including identification of source specific compound distributions, isomer ratios, and stable carbon isotope values of individual PAHs. The majority of PAHs in marine sediments originate from pyrogenic and petrogenic sources. Pyrolytic PAHs, which are produced during incomplete combustion of carbon, wood and fossil fuels, are characterized by compounds with four or more aromatic rings, while pyrogenic PAHs generally have low molecular weight. Therefore, the ratio of low molecular weight (LMW) to high molecular weight (HMW) has been used to distinguish pyrogenic (b1) and petrogenic (N 1) sources. Only WHB1 and WHB15 had ratios N 1, indicating that the PAHs in sediments of the two sites primarily originated from petrogenic sources, while the rest originated from pyrolytic sources (Table 2). A complementary approach to characterizing sources of PAHs (petrogenic vs. pyrolytic) in sediments is the use of PAHs isomeric ratios. Ratios of Ph/An, Fl/Py, An/(An + Ph) and Fl/(Fl + Py) have been shown to be useful in the identification of PAHs (Budzinski et al., 1997; Magi et al., 2002; Nilsen et al., 2015; Sicre et al., 1987; Soclo et al., 2000) (Fig. 3). Phenanthrene is the more thermodynamically stable of the two structural isomers. Therefore, a higher Ph/An ratio (N10) is observed in petrogenic pollution, while a lower ratio (b 10) is associated with pyrolytic pollution. It is also assumed that petroleum contains more thermodynamically stable compounds such as Naphthalene, Fluorene, Phenanthrene and Chrysene, while Fluorene and Pyrene are usually the most abundant compounds in pyrolytic PAHs such as petroleum, grass, wood and coal combustion (Sicre et al., 1987). Therefore, Fl/ Py ratios N 1 indicate pyrolytic origin, while values b 1 are attributed to petrogenic sources (Magi et al., 2002). The ratios of Ph/An in the sediments of WHB3 were b 10 and the ratios of Fl/Py were N 1, which

suggested that the source of the site was pyrolytic, while those at WHB7 originated from petrogenic sources. PAHs in most sites of the study area originated from mixed sources and consisted of pyrogenic and pyrolytic compounds. In addition, the ratios of An/(An + Ph) and Fl/(Fl + Py) were N1, while that of Fl/(Fl + Py) was N0.5, indicating that they originated from the combustion of grass, wood and charcoal. Sources of the PAHs in Weihai coastal sediments predicted by the three different methods were similar, indicating a heavy impact of combustion. The large amount of fossil fuels and grass combustion for domestic heating within the study area likely contributes to a local atmospheric source of PAHs, however, urban runoff may be the major source of PAHs to this environment. Based on the sources of PAHs, we can infer that the Weihai coast has been slightly polluted by the modern industry, which is similar to the results of a study of the Yellow River Delta, China (Wang et al., 2009). The toxicity of sediments to marine organisms was evaluated based on the biological thresholds proposed by Long et al. (1995), which have been used in many previous studies to estimate the potential risks and effects of PAHs in sediments. The sediment quality guidelines (SQGs) for PAHs developed by Long et al. include two effects-based guideline values, the effects range-low (ERL) and the effects range-median (ERM). The measured concentrations of 12 PAHs in this study were compared with the ERL and ERM values (Table 3). None of the PAHs in the Weihai coastal area were present at levels exceeding the SQG threshold. The concentration of the 12 PAHs in the 19 sediments was obviously lower than the ERL. Relatively high PAHs concentrations were detected at WHB8, WHB12, WHB14, WHB15 and WHB20, which were also much lower than the ERL, but Acenaphthylene concentrations at WHB 12, 14, 15 were between the ERL and ERM. In addition, there are still no reported values of SQG for high molecular weight PAHs (benzo(b)fluoranthene, benzo(k)fluoranthene, Benzo(a)pyrene and indeno(1,2,3-cd)pyrene), which may also contribute to toxicity in the sediments. Therefore, we evaluated the toxicological implications of the above four PAHs in sediment at the ISQG range recommended by the Canadian sediment Guidelines for the Protection of Aquatic Life in our research (Long et al., 1995; Behnisch et al., 2003). The Low Effect Limits (LELs) of Benzo(b)fluoranthene (BbF), Benzo(k)fluoranthene (BkF), Indeno(1,2,3-cd)pyrene (InP) and Benzo(g,h,i)perylene (BghiP) are 200, 240, 200, and 170 ng g− 1, respectively, with Serious Effect Limits (SELs) of 320,000, 1,340,000, 320,000, and 32,000 ng g−1. The concentrations for individual PAHs of each site in the Weihai coastal

Fig. 2. The composition patterns of PAHs by ring size of the coast sediments in Weihai, China.

Please cite this article as: Zhang, D., et al., Polycyclic aromatic hydrocarbons in surface sediments from the Coast of Weihai, China: Spatial distribution, sources and ecotoxico..., Marine Pollution Bulletin (2016), http://dx.doi.org/10.1016/j.marpolbul.2016.05.018

WHB22

2.1 19.82 0.11 0.28 – 0.93 0.94 2.36 39.43 0.06 0.16 7.67 0.85 0.94 14.36 50.31 0.29 – 0.01 0.88 0.98

WHB21 WHB20

14.21 24.4 0.58 0.17 2.71 1 0.96 15.93 58.34 0.27 0.13 4.75 0.89 0.97

WHB17 WHB16 WHB15

13.89 10.62 1.31 0.67 1.28 0.85 0.9

WHB14

3.73 8.39 0.44 0.63 1.74 0.76 0.97

5

area did not exceed the LEL value. These findings indicate that PAHs in the sediment from Weihai coast will not cause adverse biological effects. Additionally, according to the classification of Maliszewska-Kordybach (1996), Soil pollution is divided into several levels: non-contaminated soil (200 ng g−1), weakly contaminated soil (200–600 ng g−1), contaminated soil (600–1000 ng g−1) and heavily contaminated soil (1000 ng g− 1), all sediment locations in the Weihai coast were noncontaminated by PAHs in this research. According to the SQG values reported by Long et al. (1995) and MacDonald et al. (1996), the sediments of Weihai coast will not pose a threat to the ecological environment. This study reports the concentrations and distributions of 16 PAHs in sediments collected from a 29 km coast around Weihai, located at the Yellow Sea in China. The observed PAH concentrations were lower than in most other reported coastal sediments, indicating that pollution in the Weihai coast is lower than in other areas. The molecular ratios suggested that these PAHs primarily originated from pyrogenic sources such as charcoal, coal and fuelwood combustion, and engine exhaust. Toxicity assessment showed that the PAHs in Weihai coast had a low potential for ecotoxicological contamination since the local managers are very aware of the deterioration of this environment and because of the economic development style over the past several decades (Bing, 2011). The result of this coastal persistent organic pollutants research could provide a basic data for the choice of mariculture sites and the PAHs remediation et al.

20.55 39.68 0.52 0.00 – 0.87 0.98

WHB23

D. Zhang et al. / Marine Pollution Bulletin xxx (2016) xxx–xxx

2.5 14.65 0.17 0.16 3.13 0.74 0.96

e

d

c

b

Not calculated due to the concentration of individual PAH compound being below the detection limits. Fluorene/Pyrene. Phenanthrene/Anthracene. Anthracene/(Anthracene + Phenanthrene). Fluorene/(Fluorene + Pyrene).

The study was jointly funded by National Natural Science Foundation of China (grant no. 41306064, 41376075), Ministry of Land and Resources program: “Special foundation for scientific research on public causes” (grant no. 201411072), the China Geological Survey (grant no. 12120113015400), and the MOST Founding (no. 2013FY112200). We also thank the reviewers for comments, suggestions, and corrections that improved the manuscript.

a

WHB12

20.76 33.73 0.62 0.52 2.46 0.83 0.97

WHB11

8.56 105.1 0.08 0.15 4.08 0.8 0.98 12.97 72.5 0.18 0.08 10.54 0.91 0.95

WHB7 WHB6

7.96 29.44 0.27 0.13 1.81 0.64 0.97 5.24 22.84 0.23 0.09 –a 1 0.96

WHB5 WHB4

9.38 26.14 0.36 0.91 1.19 0.55 0.99 18.65 67.32 0.28 1.04 1.56 0.61 0.99

WHB3 WHB2

19.67 47.7 0.41 0.72 1.59 0.61 0.98 32.06 28.83 1.11 0.32 9.57 0.91 1

WHB1

Table 2 Comparison of source indices of the sediments from Weihai coast.

LMW HMW LMW/HMW Fl/Pyb Ph/Anc An/(An + Ph)d Fl/(Fl + Py)e

WHB8

14.66 21.66 0.68 0.25 6.89 0.87 0.96

WHB13

Acknowledgements

References Aoki, K., Onitsuka, G., Kuroda, M.S.H., Matsuo, H., Kitadai, Y., Sakurada, K., Ando, H., Nishi, H., Tahara, Y., 2014. Variability of factors driving spatial and temporal dispersion in river plume and Chattonella antiqua bloom in the Yatsushiro Sea, Japan. Mar. Pollut. Bull. 81 (1), 131–139. Behnisch, P.A., Hosoe, K., Sakai, S., 2003. Brominate dioxin-like compounds: invitro assessment in comparison to classical dioxin-like compounds and other polyaromatic compounds. Environ. Int. 29 (6), 861–877. Bing, F., 2011. Study on development path of Shandong sports industry from the perspective of low-carbon economy. Energy Procedia 5 (0), 879–883. Bouloubassi, I., Fillaux, J., Saliot, A., 2001. Hydrocarbons in surface sediments from the Changjiang (Yangtze River) Estuary, East China Sea. Mar. Pollut. Bull. 42 (12), 1335–1346. Bouloubassi, I., Roussiez, V., Azzoug, M., Lorre, A., 2012. Sources, dispersal pathways and mass budget of sedimentary polycyclic aromatic hydrocarbons (PAH) in the NW Mediterranean margin, Gulf of Lions. Mar. Chem. 142–144 (0), 18–28. Bragato, M., Joshi, K., Carlson, J.B., Tenório, J.A.S., Levendis, Y.A., 2012. Combustion of coal, bagasse and blends thereof: part II: speciation of PAH emissions. Fuel 96 (0), 51–58. Budzinski, H., Jones, I., Bellocq, J., Pierrad, C., Garrigues, P., 1997. Evaluation of sediment contamination by polycyclic aromatic hydrocarbons in the Gironde estuary. Mar. Chem. 58, 85–97. Cachot, J., Geffard, O., Augagneur, S., Lacroix, S., Le, M.K., Peluhet, L., Couteau, J., Denier, X., Devier, M.H., Pottier, D., Budzinski, H., 2006. Evidence of genotoxicity related to high PAH content of sediments in the upper part of the Seine estuary (Normandy, France). Aquat. Toxicol. 79 (3), 257–267. Callén, M.S., López, J.M., Iturmendi, A., Mastral, A.M., 2013. Nature and sources of particle associated polycyclic aromatic hydrocarbons (PAH) in the atmospheric environment of an urban area. Environ. Pollut. 183 (0), 166–174. Callén, M.S., Iturmendi, A., López, J.M., 2014. Source apportionment of atmospheric PM2.5bound polycyclic aromatic hydrocarbons by a PMF receptor model. Assessment of potential risk for human health. Environ. Pollut. 195 (0), 167–177. Carver, J.H., Machado, M.L., MacGregor, J.A., 1986. Application of modified Salmonella/microsome prescreen to petroleum-derived complex mixtures and polynuclear aromatic hydrocarbons (PAH). Mutat. Res. Lett. 174 (4), 247–253. Cébron, A., Faure, P., Lorgeoux, C., Ouvrard, S., Leyval, C., 2013. Experimental increase in availability of a PAH complex organic contamination from an aged contaminated soil: consequences on biodegradation. Environ. Pollut. 177 (0), 98–105.

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D. Zhang et al. / Marine Pollution Bulletin xxx (2016) xxx–xxx

Fig. 3. PAHs ratios and their sources in sediments from the coast of Weihai, China.

Commendatore, M.G., Nievas, M.L., Amin, O., Esteves, J.L., 2012. Sources and distribution of aliphatic and polyaromatic hydrocarbons in coastal sediments from the Ushuaia Bay (Tierra del Fuego, Patagonia, Argentina). Mar. Environ. Res. 74, 20–31. Counihan, T.D., Waite, I.R., Nilsen, E.B., Hardiman, J.M., Elias, E., Gelfenbaum, G., Zaugg, S.D., 2014. A survey of benthic sediment contaminants in reaches of the Columbia River Estuary based on channel sedimentation characteristics. Sci. Total Environ. 484 (0), 331–343. Culotta, L., Stefano, C.D., Gianguzza, A., Mannino, M.R., Orecchio, S., 2006. The PAH composition of surface sediments from Stagnone coastal lagoon, Marsala (Italy). Mar. Chem. 99, 117–127. Deng, W., Li, X.G., Li, S.Y., Ma, Y.Y., Zhang, D.H., 2013. Source apportionment of polycyclic aromatic hydrocarbons in surface sediment of mud areas in the East China Sea using diagnostic ratios and factor analysis. Mar. Pollut. Bull. 70 (1–2), 266–273. Guzzella, L., Roscioli, C., Viganò, L., Saha, M., Sarkar, S.K., Bhattacharya, A., 2005. Evaluation of the concentration of HCH, DDT, HCB, PCB and PAH in the sediments along the lower stretch of Hugli estuary, West Bengal, northeast India. Environ. Int. 31, 523–534. 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 (1–2), 52–58. Huang, L.L., Pu, X.M., Pan, J.F., Wang, B., 2013. Heavy metal pollution status in surface sediments of Swan Lake lagoon and Rongcheng Bay in the northern Yellow Sea. Chemosphere 93 (9), 1957–1964. Hung, C.C., Ko, F.C., Gong, G.C., Chen, K.S., Wu, J.M., Chiang, H.L., Peng, S.C., Santschi, P.H., 2014. Increased zooplankton PAH concentrations across hydrographic fronts in the East China Sea. Mar. Pollut. Bull. 83 (1), 248–257. Jiang, X., Teng, A.K., Xu, W.Z., Liu, X.S., 2014. Distribution and pollution assessment of heavy metals in surface sediments in the Yellow Sea. Mar. Pollut. Bull. 83 (1), 366–375. Jörundsdóttir, H.Ó., Jensen, S., Hylland, K., Holth, T.F., Gunnlaugsdóttir, H., Svavarsson, J., Ólafsdóttir, Á., El-Taliawy, H., Rigét, F., Strand, J., Nyberg, E., Bignert, A., Hoydal, K.S., Halldórsson, H.P., 2014. Pristine Arctic: background mapping of PAHs, PAH metabolites and inorganic trace elements in the North-Atlantic Arctic and sub-Arctic coastal environment. Sci. Total Environ. 493 (0), 719–728.

Kaivosoja, T., Virén, A., Tissari, J., Ruuskanen, J., Tarhanen, J., Sippula, O., Jokiniemi, J., 2012. Effects of a catalytic converter on PCDD/F, chlorophenol and PAH emissions in residential wood combustion. Chemosphere 88 (3), 278–285. Khadhar, S., Higashi, T., Hamdi, H., Matsuyama, S., Charef, A., 2010. Distribution of 16 EPApriority polycyclic aromatic hydrocarbons (PAHs) in sludges collected from nine Tunisian wastewater treatment plants. J. Hazard. Mater. 183, 98–102. Lea-Langton, A.R., Ross, A.B., Bartle, K.D., Andrews, G.E., Jones, J.M., Li, H., Pourkashanian, M., Williams, A., 2013. Low temperature PAH formation in diesel combustion. J. Anal. Appl. Pyrolysis 103 (0), 119–125. Li, B., Feng, C., Li, X., Chen, Y., Niu, J., Shen, Z., 2012. Spatial distribution and source apportionment of PAHs in surficial sediments of the Yangtze Estuary, China. Mar. Pollut. Bull. 64 (3), 636–643. Li, G.L., Lang, Y.H., Yang, W., Peng, P., Wang, X.M., 2014. Source contributions of PAHs and toxicity in reed wetland soils of Liaohe estuary using a CMB-TEQ method. Sci. Total Environ. 490, 199–204. Lindgren, J.F., Hassellöv, I.-M., Dahllöf, I., 2014. PAH effects on meio- and microbial benthic communities strongly depend on bioavailability. Aquat. Toxicol. 146 (0), 230–238. 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 (1), 81–97. Ma, M., Feng, Z., Guan, C., Ma, Y., Xu, H., Li, H., 2001. DDT, PAH and PCB in sediments from the intertidal zone of the Bohai Sea and the Yellow Sea. Mar. Pollut. Bull. 42 (2), 132–136. MacDonald, D.D., Carr, R.S., Calder, F.D., Long, E.R., Ingersoll, C.G., 1996. Development and evaluation of sediment quality guidelines for Florida coastal waters. Ecotoxicology 5, 253–278. Magi, E., Bianco, R., Ianni, C., Carro, M., 2002. Distribution of polycyclic aromatic hydrocarbons in the sediments of the Adriatic Sea. Environ. Pollut. 119, 91–98. Maliszewska-Kordybach, B., 1996. Polycyclic aromatic hydrocarbons in agricultural soils in Poland: preliminary proposals for criteria to evaluate the level of soil contamination. Appl. Geochem. 11 (1–2), 121–127. Maskaoui, K., Zhou, J.L., Hong, H.S., Zhang, Z.L., 2002. Contamination by polycyclic aromatic hydrocarbons in the Jiulong River Estuary and Western Xiamen Sea, China. Environ. Pollut. 118 (1), 109–122.

Table 3 Concentration ranges of PAHs in Surface Sediments from the Coast of Weihai, China and toxicity guidelines. Compound

Concentration range

Mean values

Guideline values (ng

Sites

g−1 dw)

Naphthalene Acenaphthene Acenaphthylene Fluorene Phenanthrene Anthracene Fluoranthene Pyrene Benzo(a)anthracene Chrysene Benzo(a)pyrene Dibenzo(a,h)anthracene ∑PAHs

(ng g−1 dw)

(ng g−1 dw)

ERL

ERM

bERL

ERL–ERM

NERM

ND–10.87 ND–0.62 ND–43.28 ND–0.92 0.06–14.55 ND–5.35 ND–108.13 ND–3.12 0.05–8.06 ND–19.62 0.02–1.01 ND–0.96 2.69–166.5

3.85 0.18 10.15 0.34 2.14 0.87 41.61 1.02 1.14 3.62 0.23 0.11 67.43

160 44 16 19 240 85.3 600 665 261 384 430 63.4 4022

2100 640 500 540 1500 1100 5100 2600 1600 2800 1600 260 44792

All sites All sites All sites except WHB 12, 14, 15 All sites All sites All sites All sites All sites All sites All sites All sites All sites All sites

– – WHB12, 14, 15 – – – – – – – – – –

– – – – – – – – – – – – –

Please cite this article as: Zhang, D., et al., Polycyclic aromatic hydrocarbons in surface sediments from the Coast of Weihai, China: Spatial distribution, sources and ecotoxico..., Marine Pollution Bulletin (2016), http://dx.doi.org/10.1016/j.marpolbul.2016.05.018

D. Zhang et al. / Marine Pollution Bulletin xxx (2016) xxx–xxx Men, B., He, M., Tan, L., Lin, C., Quan, X., 2009. Distributions of polycyclic aromatic hydrocarbons in the Daliao River Estuary of Liaodong Bay, Bohai Sea (China). Mar. Pollut. Bull. 58 (6), 818–826. Naes, K., Knutzen, J., Berglind, L., 1995. Occurrence of PAH in marine organisms and sediments from smelter discharge in Norway. Sci. Total Environ. 163 (1–3), 93–106. Nicola, F.D., Maisto, G., Prati, M.V., Alfani, A., 2005. Temporal variations in PAH concentrations in Quercus ilex L. (holm oak) leaves in an urban area. Chemosphere 61, 432–440. Nilsen, E.B., Rosenbauer, R.J., Fuller, C.C., Jaffe, B.J., 2015. Sedimentary organic biomarkers suggest detrimental effects of PAHs on estuarine microbial biomass during the 20th century in San Francisco Bay, CA, USA. Chemosphere 119, 961–970. Ning, C., Hoon, O.D., 2011. Sustainable development strategy of tourism resources offered by regional advantage: exploring the feasibility of developing an ‘exotic culture’ resource for Weihai City of China. Proc. Eng. 21 (0), 543–552. Oros, D.R., Ross, J.R.M., Spies, R.B., Mumley, T., 2007. Polycyclic aromatic hydrocarbon (PAH) contamination in San Francisco Bay: a 10-year retrospective of monitoring in an urbanized estuary. Environ. Res. 105 (1), 101–118. Porte, V.C., Escartín, E., 2000. Polycyclic aromatic hydrocarbon (PAH) metabolites in fish bile: a tool to assess PAH transport to the deep-sea environment. Comp. Biochem. Physiol. A Mol. Integr. Physiol. 126 (Supplement 1(0)), 122. Readman, J.W., Fillmann, G., Tolosa, I., Bartocci, J., Villeneuve, J.P., Catinni, C., Mee, L.D., 2002. Petroleum and PAH contamination of the Black Sea. Mar. Pollut. Bull. 44 (1), 48–62. Sicre, M.A., Marty, J.C., Saliot, A., Aparicio, X., Grimalt, J., Albaiges, J., 1987. Aliphatic and aromatic hydrocarbons in different sized aerosols over the Mediterranean Sea: occurrence and origin. Atmos. Environ. 21, 2247–2259. Siddall, R., Robotham, P.W.J., Gill, R.A., Pavlov, D.F., Chuiko, G.M., 1994. Relationship between polycyclic aromatic hydrocarbon (PAH) concentrations in bottom sediments and liver tissue of bream (Abramis brama) in Rybinsk Reservoir, Russia. Chemosphere 29 (7), 1467–1476. Soclo, H.H., Garrigues, P.H., Ewald, M., 2000. Origin of polycyclic aromatic hydrocarbons (PAHs) in coastal marine sediments: case studies in Cotonou (Benin) and Aquitaine (France) areas. Mar. Pollut. Bull. 40, 387–396.

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Soliman, Y.S., Ansari, E.M.S.A., Wade, T.L., 2014. Concentration, composition and sources of PAHs in the coastal sediments of the exclusive economic zone (EEZ) of Qatar, Arabian Gulf. Mar. Pollut. Bull. 85, 542–548. Tobiszewski, M., Namieśnik, J., 2012. PAH diagnostic ratios for the identification of pollution emission sources. Environ. Pollut. 162 (0), 110–119. Valentín, L., Feijoo, G., Moreira, M.T., Lema, J.M., 2006. Biodegradation of polycyclic aromatic hydrocarbons in forest and salt marsh soils by white-rot fungi. Int. Biodeterior. Biodegrad. 58 (1), 15–21. Vane, C.H., Rawlins, B.G., Kim, A.W., Moss-Hayes, V., Kendrick, C.P., Leng, M.J., 2013. Sedimentary transport and fate of polycyclic aromatic hydrocarbons (PAH) from managed burning of moorland vegetation on a blanket peat, South Yorkshire, UK. Sci. Total Environ. 449 (0), 81–94. Wang, L.L., Yang, Z.F., Niu, J.F., Wang, J.Y., 2009. Characterization, ecological risk assessment and source diagnostics of polycyclic aromatic hydrocarbons in water column of the Yellow River Delta, one of the most plenty biodiversity zones in the world. J Hazard. Mater. 169, 460–465. Yancheshmeh, R.A., Bakhtiari, A.R., Mortazavi, S., Savabieasfahani, M., 2014. Sediment PAH: contrasting levels in the Caspian Sea and Anzali Wetland. Mar. Pollut. Bull. 84 (1–2), 391–400. Yang, G.P., 2000. Polycyclic aromatic hydrocarbons in the sediments of the South China Sea. Environ. Pollut. 108 (2), 163–171. Yuan, D., Yang, D., Wade, T.L., Qian, Y., 2001. Status of persistent organic pollutants in the sediment from several estuaries in China. Environ. Pollut. 114 (1), 101–111. Yuan, H.M., Li, T.G., Ding, X.G., Zhao, G.M., Ye, S.Y., 2014. Distribution, sources and potential toxicological significance of polycyclic aromatic hydrocarbons (PAHs) in surface soils of the Yellow River Delta, China. Mar. Pollut. Bull. 83, 258–264. Zhang, P., Song, J.M., Yuan, H., 2009. Persistent organic pollutant residues in the sediments and mollusks from the Bohai Sea coastal areas, North China: an overview. Environ. Int. 35 (3), 632–646. Zong, H., Ma, X., Na, G., Huo, C., Yuan, X., Zhang, Z., 2014. Polycyclic aromatic hydrocarbons (PAHs) in the mariculture zones of China's northern Yellow Sea. Mar. Pollut. Bull. 85 (1), 172–178.

Please cite this article as: Zhang, D., et al., Polycyclic aromatic hydrocarbons in surface sediments from the Coast of Weihai, China: Spatial distribution, sources and ecotoxico..., Marine Pollution Bulletin (2016), http://dx.doi.org/10.1016/j.marpolbul.2016.05.018