Marine Pollution Bulletin xxx (2014) xxx–xxx

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Distributions of polycyclic aromatic hydrocarbons and alkylated polycyclic aromatic hydrocarbons in Osaka Bay, Japan Shizuho Miki a,b, Seiichi Uno a,⇑,1, Kazuki Ito a, Jiro Koyama a, Hiroyuki Tanaka c a

Education and Research Center for Marine Resources and Environment, Fisheries, Kagoshima University, 50-20 Shimoarata 4-Chome, Kagoshima 890-0056, Japan Laboratory of Marine Environmental Science, Division of Marine Biological Chemistry, Department of Bioscience and Biotechnology, Faculty of Agriculture, Kyushu University, Hakozaki 6-10-1, Higashi-ku, Fukuoka 812-8581, Japan c Environment Conservation Division, National Research Institute of Fisheries and Environment of Inland Sea, Hiroshima 739-0452, Japan b

a r t i c l e

i n f o

Keywords: Alkylated polycyclic aromatic hydrocarbons Osaka Bay Polycyclic aromatic hydrocarbons Source recognition

a b s t r a c t Contaminations in sediments by polycyclic aromatic hydrocarbons (PAHs) and alkylated PAHs were investigated at 44 sites in Osaka Bay, Japan. Concentrations of total PAHs and alkylated PAHs were in the range 6.40–7800 ng/g dry weights and 13.7–1700 ng/g dry weights, respectively. The PAH concentrations tended to be higher along the shoreline in the vicinities of big ports, industrialized areas, and densely populated regions such as the cities of Osaka and Kobe. The major sources appeared to be pyrogenic or both pyrogenic and petrogenic at most of the sites. PAH concentrations were remarkably high at a site near Kobe, where the concentrations of dibenzo(a,h)anthracene and benzo(g,h,i)perylene exceeded the effects-range-medium concentration and eight PAHs were above the corresponding effects-range-low concentrations. Those PAHs may have been derived from the great fire associated with the large earthquake in 1995. Ó 2014 Elsevier Ltd. All rights reserved.

1. Introduction Osaka Bay, with an area of 1450 km2, is located adjacent to one of the most closes to populated areas in Japan. The surrounding watershed includes the cities of Osaka, Kobe, and Sakai, which have populations of about 2,670,000, 1,540,000, and 840,000, respectively. The ports of Osaka and Kobe are among the largest in Japan, and a major industrial area is located along the coast from Kobe to Sakai. The bay is surrounded by the islands of Honshu and Awaji and is classified as an enclosed coastal sea, because it has only two narrow mouths. Water exchange in the bay is therefore limited, and there is a potential for the accumulations of toxic pollutants associated with human activity. Polycyclic aromatic hydrocarbons (PAHs) are derived from petrogenic sources such as oil spill or from pyrogenic sources, which associated with the smoke from industrial operations and the exhaust gas from vehicles that use gasoline or diesel fuel. The composition of pyrogenic PAHs is characterized by parent PAHs with molecular weights P 202 and 4–6 aromatic rings ⇑ Corresponding author. Tel.: +81 99 286 4262; fax: +81 99 286 4296. E-mail addresses: [email protected] (S. Miki), uno@fish.kagoshima-u. ac.jp (S. Uno), [email protected] (K. Ito), koyama@fish.kagoshima-u.ac.jp (J. Koyama), [email protected] (H. Tanaka). 1 Co-first author.

(Wang et al., 1999). In contrast, petrogenic PAHs consist mainly of low-molecular-weight and alkylated PAHs with one to a few methyl groups (Jiang et al., 2009). Alkylated PAHs are thermodynamically unstable compared to parent PAHs, and their presence generally indicates a petrogenic origin (Saha et al., 2009; Harris et al., 2011). Parent PAHs are known to cause acute toxicities to organisms (Roberts et al., 1989), and PAHs with high-molecularweight as benzo(a)pyrene are mutagenic and carcinogenic to organisms, including fish (Gravato and Santos, 2002; Cheikyula et al., 2009). The United Sates Environmental Protection Agency (EPA) has therefore included 16 PAHs that are the risks from standpoint of their toxicities on a list of priority pollutants (Manoli et al., 2000). The toxicities of alkylated PAHs to fish are suspected to reflect their effects on early life stages, mainly embryo development (Heintz et al., 2000; Rhodes et al., 2005). After parent and alkylated PAHs are released into the environment, some of them reach aquatic systems, although their movements with transport and diffusion depend strongly on weather conditions such as temperature, wind velocity, and rainfall. Most previous monitoring for PAHs in sediments has been performed in heavily contaminated coastal areas after oil spills (Franco et al., 2006; Uno et al., 2010; Neff et al., 2011). However, little comprehensive monitoring of parent and alkylated PAHs even in coastal areas near big cities has been done in Japan, while the distributions of these compounds have been well documented in

http://dx.doi.org/10.1016/j.marpolbul.2014.04.004 0025-326X/Ó 2014 Elsevier Ltd. All rights reserved.

Please cite this article in press as: Miki, S., et al. Distributions of polycyclic aromatic hydrocarbons and alkylated polycyclic aromatic hydrocarbons in Osaka Bay, Japan. Mar. Pollut. Bull. (2014), http://dx.doi.org/10.1016/j.marpolbul.2014.04.004

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S. Miki et al. / Marine Pollution Bulletin xxx (2014) xxx–xxx

Fig. 1. Sampling sites in Osaka Bay. Circles show the sites where samples were collected from a research vessel. Triangles indicate sites where samples collected from the shoreline.

some other countries, such as the United States (Pereira et al., 1999; Vane et al., 2007). In general, urban and industrial areas have been polluted by parent and alkylated PAHs, as a result of inputs from specific anthropogenic sources such as discharges of industrial wastewater, particles deposited from automobile exhaust gas, and spills from oil tankers (Hites et al., 1977; Gschwend and Hites, 1981; Witt and Trost, 1999). Because PAHs are persistent and hydrophobic, they can accumulate and remain in coastal sediments for a long time and result potentially continuously exposures of PAHs to benthic and other organisms. It is therefore important to gather information about PAH contaminations in sediments around coastal areas. In this study, we investigated

the distributions of parent and alkylated PAHs in sediments throughout Osaka Bay. We also estimated their sources in the bay and examined differences in the patterns of their distributions.

2. Materials and methods 2.1. Collection of sediments Sediments were collected from 44 sites in Osaka Bay in April 2000 (sites 1–22 in Fig. 1), May 2001 (sites 23–28) and May 2002 (site 6), and October 2006 (sites C1–C20). Samples were

Table 1 Target compounds and quantified ions. Compounds

Quantification ions

PAHs 2-Ring Naphthalene

128, 127

3-Ring Acenaphthylene Acenaphthene Fluorene Dibenzothiophene Phenanthrene Anthracene

152, 154, 166, 184, 178, 178,

153 153 165 152 176 176

4-Ring Fluoranthene Pyrene Benz(a)anthracene Chrysene

202, 202, 228, 228,

201 201 226 226

5 or 6-Ring Benzo(b)fluoranthene Benzo(k)fluoranthene Benzo(a)pyrene Perylene Benzo(g,h,i)perylene Dibenzo(a,h)anthracene Indeno(1,2,3-cd)pyrene

252, 252, 252, 252, 276, 278, 276,

253 253 253 253 277 279 277

Compounds

Quantification ions

Alkylated PAHs 2-Ring C1-Naphthalenes C2-Naphthalenes C3-Naphthalenes C4-Naphthalenes

142, 156, 170, 184,

141 141 155 169

3-Ring C1-Fluorenes C2-Fluorenes C3-Fluorenes C1-Dibenzothiophenes C2-Dibenzothiophenes C3-Dibenzothiophenes C4-Dibenzothiophenes C1-Phenanthrenes/anthracenes C2-Phenanthrenes/anthracenes C3-Phenanthrenes/anthracenes C4-Phenanthrenes/anthracenes

180, 194, 208, 198, 212, 226, 240 192, 206, 220, 234,

165 179 193 184 197 211 191 191 205 219

4-Ring C1-Fluoranthrenes/pyrenes C2-Fluoranthrenes/pyrenes C3-Fluoranthrenes/pyrenes C1-Chrysenes/benz(a)anthracene C2-Chrysenes/benz(a)anthracene C3-Chrysenes/benz(a)anthracene

216, 230, 244, 242, 256, 270,

215 215 229 241 241 255

Please cite this article in press as: Miki, S., et al. Distributions of polycyclic aromatic hydrocarbons and alkylated polycyclic aromatic hydrocarbons in Osaka Bay, Japan. Mar. Pollut. Bull. (2014), http://dx.doi.org/10.1016/j.marpolbul.2014.04.004

S. Miki et al. / Marine Pollution Bulletin xxx (2014) xxx–xxx

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Fig. 2. Distribution of total PAHs in sediments at Osaka Bay. Concentrations are proportional to areas of circles.

collected from a Smith-McIntyre grab sampler with R.V. Shirafuji Maru (National Research Institute of Fisheries and Environment of Inland Sea, Japan) at sites (St.) 1–28 and with an Ekman-Berge

grab sampler from shoreline at C1 through C20 (C8, C11, C15, and C16 were the vacant sites in this study). All sediments were dried at 60 °C for 12 h, and then were sorted by passage through

Fig. 3. Distribution of total alkylated PAHs in sediments of Osaka Bay. Concentrations are proportional to areas of circles.

Please cite this article in press as: Miki, S., et al. Distributions of polycyclic aromatic hydrocarbons and alkylated polycyclic aromatic hydrocarbons in Osaka Bay, Japan. Mar. Pollut. Bull. (2014), http://dx.doi.org/10.1016/j.marpolbul.2014.04.004

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S. Miki et al. / Marine Pollution Bulletin xxx (2014) xxx–xxx

14

ST.2

120

12

100

10

80

8

ST.13

60

6 20

0

0 Nap C1-Nap C2-Nap C3-Nap C4-Nap Acy Acp Flu C1-Flu C2-Flu C3-Flu DB C1-DB C2-DB C3-DB C4-DB Phe Ant C1-Phe/Ant C2-Phe/Ant C3-Phe/Ant C4-Phe/Ant Fla Pyr C1-Pyr/Fla C2-Pyr/Fla C3-Pyr/Fla BaA Chr C1-Chr/BaA C2-Chr/BaA C3-Chr/BaA BbF BkF BaP Per BP DA IP

2

1200

ST.21

1000

400 350

Nap C1-Nap C2-Nap C3-Nap C4-Nap Acy Acp Flu C1-Flu C2-Flu C3-Flu DB C1-DB C2-DB C3-DB C4-DB Phe Ant C1-Phe/Ant C2-Phe/Ant C3-Phe/Ant C4-Phe/Ant Fla Pyr C1-Pyr/Fla C2-Pyr/Fla C3-Pyr/Fla BaA Chr C1-Chr/BaA C2-Chr/BaA C3-Chr/BaA BbF BkF BaP Per BP DA IP

40

4

C4

300

800

250

600

200 150

400

100 50

0

0 Nap C1-Nap C2-Nap C3-Nap C4-Nap Acy Acp Flu C1-Flu C2-Flu C3-Flu DB C1-DB C2-DB C3-DB C4-DB Phe Ant C1-Phe/Ant C2-Phe/Ant C3-Phe/Ant C4-Phe/Ant Fla Pyr C1-Pyr/Fla C2-Pyr/Fla C3-Pyr/Fla BaA Chr C1-Chr/BaA C2-Chr/BaA C3-Chr/BaA BbF BkF BaP Per BP DA IP

Nap C1-Nap C2-Nap C3-Nap C4-Nap Acy Acp Flu C1-Flu C2-Flu C3-Flu DB C1-DB C2-DB C3-DB C4-DB Phe Ant C1-Phe/Ant C2-Phe/Ant C3-Phe/Ant C4-Phe/Ant Fla Pyr C1-Pyr/Fla C2-Pyr/Fla C3-Pyr/Fla BaA Chr C1-Chr/BaA C2-Chr/BaA C3-Chr/BaA BbF BkF BaP Per BP DA IP

200

250

C10

1200

C18

1000

200

800

150

600 100 400 50

200

0

Nap C1-Nap C2-Nap C3-Nap C4-Nap Acy Acp Flu C1-Flu C2-Flu C3-Flu DB C1-DB C2-DB C3-DB C4-DB Phe Ant C1-Phe/Ant C2-Phe/Ant C3-Phe/Ant C4-Phe/Ant Fla Pyr C1-Pyr/Fla C2-Pyr/Fla C3-Pyr/Fla BaA Chr C1-Chr/BaA C2-Chr/BaA C3-Chr/BaA BbF BkF BaP Per BP DA IP

Nap C1-Nap C2-Nap C3-Nap C4-Nap Acy Acp Flu C1-Flu C2-Flu C3-Flu DB C1-DB C2-DB C3-DB C4-DB Phe Ant C1-Phe/Ant C2-Phe/Ant C3-Phe/Ant C4-Phe/Ant Fla Pyr C1-Pyr/Fla C2-Pyr/Fla C3-Pyr/Fla BaA Chr C1-Chr/BaA C2-Chr/BaA C3-Chr/BaA BbF BkF BaP Per BP DA IP

0

Fig. 4. Compositions of individual parent and alkylated PAHs in sediments at representative sites in Osaka Bay. The scales of the vertical axes are ng/g dry weight. Abbreviations of PAHs follow Section 2.2. C1 indicates methyl; C2, dimethyl; C3, trimethyl; and C4, tetramethyl. The concentrations of alkylated PAHs are the sum of all the isomers at each level of alkylation.

a sieve with a mesh size of 1 mm. The sediments that passed through the sieve were stored at 20 °C until analysis. 2.2. Chemicals We purchased a solution containing a mixture of the following 16 PAHs from Supelco (USA): naphthalene (Nap), acenaphthylene (Acy), acenaphthene (Acp), fluorene (Flu), phenanthrene (Phe), anthracene (Ant), fluoranthene (Fla), pyrene (Pyr), chrysene (Chr), benz(a)anthracene (BaA), benzo(b)fluoranthene (BbF), benzo(k)fluoranthene (BkF), benzo(a)pyrene (BaP), benzo(g,h,i)perylene (BP), dibenz(a,h)anthracene (DA), and indeno(1,2,3-cd)pyrene (IP). We purchased 1-methylnaphthalene, 2-methylnaphthalene, 4-methyldibenzothiophene, 1-methylanthracene, 4,6-dimethyldibenzothiophene, 7-methylbenzo(a)pyrene, and 7,12-dimethylbenz (a)anthracene from Supelco (USA); dibenzothiophene (DB), 1,2dimethylnaphthalene, 2,3,5-trimethylnaphthalene, and 1methylpyrene from Tokyo Chemical Industry Co., Ltd. (Japan); 1-methylfluorene from Alfa Aesar (USA); 2,3-dimethylanthracene, 2-methylfluoranthene, 1-methylbenz(a)anthracene, and 4-methylchrysene from AccuStandard Inc. (USA); Perylene (Per) from Cambridge Isotope Laboratories Inc. (USA); and naphthalene-d8,

anthracene-d10, chrysene-d10, and pyrene-d10 from Wako Pure Chemical Industries, Ltd. (Japan). Hexane, acetone and dichloromethane were all pesticide-grades (Wako). Wako-gel (C-100, silica gel) was also purchased from Wako, heated at 160 °C for 8 h, and then added 5% water (w/w) before use. High-purity water was obtained from a Milli-Q water system (Millipore, France).

2.3. Analysis for parent and alkylated PAHs Analyses for parent and alkylated PAHs in sediments were performed according to the protocol in Miki et al. (2010). The PAHs were extracted with dichloromethane-hexane (1:1, v/v) at 100 °C and 1450 psi by using a pressurized liquid extraction system (Applied Separations, USA). The extraction solvent was completely exchanged for hexane, and the resulting hexane solution was loaded on a silica gel column (20 cm  8 mm i.d.) that had been washed hexane. Parent and alkylated PAHs were eluted with hexane followed by dichloromethane-hexane (1:3, v/v). The eluents were combined, spiked with internal standards (naphthalene-d8, anthracene-d10, pyrene-d10 and chrysene-d12), and then concentrated to 0.1 mL with a gentle stream of nitrogen gas.

Please cite this article in press as: Miki, S., et al. Distributions of polycyclic aromatic hydrocarbons and alkylated polycyclic aromatic hydrocarbons in Osaka Bay, Japan. Mar. Pollut. Bull. (2014), http://dx.doi.org/10.1016/j.marpolbul.2014.04.004

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S. Miki et al. / Marine Pollution Bulletin xxx (2014) xxx–xxx

The parent and alkylated PAHs were measured by using a gas chromatograph (Agilent 6890, Agilent technologies, USA) equipped with a mass spectrometer (Agilent 5973 MSD). An aliquot of 2 lL of the sample was injected by the automatic injector (Agilent 7683B) into a DB-5MS (0.25 mm i.d.  30 m, film thickness 0.25 lm: Agilent). The temperatures of the injector, detector, and oven of the GC/MS were regulated according to the protocol of Miki et al. (2010). Target parent and alkylated PAHs (Table 1) were quantified according to Uno et al. (2010). 2.4. Statistical analysis Cluster analysis using Ward’s method with squared Euclidean distances was performed to identify the sources of PAHs in sediments at each site by the R project language (http://www.r-project. org/). The standardized data of parent and alkylated PAHs through Z-scores were used in this analysis. 3. Results and discussion 3.1. Distribution of total parent and alkylated PAHs P Concentrations of the total parent PAHs ( PAHs) of the 18 target compounds ranged from 6.40 to 7765 ng/g dry weights and were higher at sites near the shoreline and in the inner part of Osaka Bay (Fig. 2). An especially highest concentration (7765 ng/ g dry weight) was detected at St. 21 near the port of Kobe. In addiP tion, high concentrations of PAHs were detected at sites C14 northeast of Kansai Airport (4717 ng/g dry weight), C7 near Sakai city (2063 ng/g dry weight), and C1, C4, and C18 near Osaka (1955, 1830, and 4136 ng/g dry weights, respectively). In general, PAH concentrations depend on the location to sources such as a harbor, a densely populated region, or an industrialized region. However, the distributions of PAH concentrations can be complex, even in a bay. Baumard et al. (1998) categorized P total concentrations of the 16 USA EPA priority PAHs ( 16PAHs) of 0–100, 100–1000, 1000–5000, and >5000 ng/g as low, moderate, high, and very high, respectively. In present investigation, P 16PAHs at sites 2, 3, 4, 6, 7, and 24 near bay mouths were in the low category and ranged from 6.04 to 43.3 ng/g dry weight. P In contrast, the 16PAHs were in the very high category at St. 21 (6938 ng/g dry weight), and in the high category at sites C3, P C7, C13, C14, and C18 (1022–4307 ng/g dry weight). The 16PAHs at the other 32 sites fell into the moderated category (123–993 ng/ g dry weight). As a result, Osaka Bay can be considered moderate pollution with PAHs, although some sites are highly polluted. P Although concentrations of total alkylated PAHs ( alkPAHs) P were relatively low compared to PAHs, their high concentrations were found near the shoreline, especially near large ports such as the ports of Kobe (1716 ng/g dry weight at St. 21), Osaka (1126 and 919 ng/g dry weight at sites C7 and C18, respectively), and Sakai-Semboku (1498 ng/g dry weight at site C4) (Fig. 3). This tendency was stronger than was the case for the parent PAHs. This result suggests that vessels accounted for much of the discharge of alkylated PAHs into Osaka Bay, because, methylated naphthalene, phenanthrene/anthracene, pyrene/fluoranthene, chrysene/ benz(a)anthracene, and dibenzothiophene in particular are known to originate primarily from oil (Jiang et al., 2009). The minimum P concentration of alkPAHs was 13.7 ng/g dry weight at St. 6. 3.2. Composition of individual parent and alkylated PAHs and their origins Some patterns in the composition and relative abundance of the individual parent and alkylated PAHs in the sediments of Osaka

Bay are apparent in Fig. 4. For example, the individual concentrations of the parent and alkylated PAHs were low, and the differences among the concentrations of PAHs were small such as St. 2, while the concentrations of some alkylated PAHs tended to be high in the measured target PAHs such as sites 13, C4 and C10. In another pattern, the concentrations of PAHs with high-molecular-weight were much higher than those with low-molecularweight and additionally the concentrations of parent PAHs were relatively high compared with alkylated PAHs such as sites 21 and C18. We considered those patterns to reflect differences in the principal sources of PAHs among sites. The sources of the PAHs in marine sediments can be divided into three main categories; petrogenic, pyrogenic, and biogenic sources (Readman et al., 2002; Barakat et al., 2011). In this study, individual concentrations of parent and alkylated PAHs were used to group the sites with cluster analysis. Sites were categorized on the basis of the composition of the PAHs, in order to find the primary source of the PAHs within groups of sites. The compositional patterns divided into 4 large groups in the cluster analysis, but St. 21 and C4 did not belong to any group (Fig. 5). Several ratios of concentrations of selected parent and alkylated PAH compounds have frequently been used to identify the sources of PAHs (Prahl and Carpenter, 1983; Budzinski et al., 1997; Wang et al., 1999; Yunker et al., 2002; Zakaria et al., 2002; Barakat et al., 2011; Tobiszewski and Namies´nik, 2012). In this study, we estimated the sources of the PAHs according to the following scheme of Barakat et al. (2011): (1) Ratio of sum of 3-methylphenanthrene, 2-methylphenanthrene, 9-methylphenanthrene, and 1-methylphenanthrene to phenanthrene (MP/P): 2, petrogenic origin 1–2, mixed sources (2) Ratio of sum of benzo(a)anthracene and chrysene to benzo(a)anthracene (BaA/(BaA + Chr)): 0.35, pyrogenic 0.2–0.35, mixed sources (3) Ratio of sum of alkylated PAHs to the sum of parent PAHs (APAHs/P-PAHs):

Group 3

Fig. 5. Tree diagram resulting from cluster analysis of the composition of parent and alkylated PAHs in the sediments of Osaka Bay.

Please cite this article in press as: Miki, S., et al. Distributions of polycyclic aromatic hydrocarbons and alkylated polycyclic aromatic hydrocarbons in Osaka Bay, Japan. Mar. Pollut. Bull. (2014), http://dx.doi.org/10.1016/j.marpolbul.2014.04.004

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Fig. 6. Plots of calculated (a) HMW/LMW versus A-PAHs/P-PAHs; (b) BaA/BaA + Chr versus MP/P; and (c) MP/P versus pyrogenic index.

Please cite this article in press as: Miki, S., et al. Distributions of polycyclic aromatic hydrocarbons and alkylated polycyclic aromatic hydrocarbons in Osaka Bay, Japan. Mar. Pollut. Bull. (2014), http://dx.doi.org/10.1016/j.marpolbul.2014.04.004

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S. Miki et al. / Marine Pollution Bulletin xxx (2014) xxx–xxx Table 2 Concentration ranges of PAHs in sediment of Osaka Bay (ng/g dry weight) and at sites where individual PAH concentrations with exceeded the ERL or ERM.

a b

Compound

ERLa

ERMa

Naphthalene Acenaphthylene Acenaphthene Fluorene Dibenzothiophene Phenanthrene Anthracene Fluoranthene Pyrene Benz(a)anthracene Chrysene Benzo(a)pyrene Indeno(1,2,3-cd)pyrene Dibenzo(a,h)anthracene Benzo(g,h,i)perylene

160 44 16 19 190 240 85 600 665 260 380 430 240 63 85

2100 640 500 540 1200 1500 1100 5100 2600 1600 2800 1600 950 260 330

PAH concentrations

Sites with PAH concentration above the ERL or ERM

Min

Max

Between ERL and ERM

Above ERM

NDb NDb NDb NDb NDb NDb NDb NDb 2.20 NDb NDb NDb NDb NDb NDb

51.0 33.0 25.8 37.4 66.7 492 97.0 1029 1088 631 894 678 653 265 448

– – C14 C14, C18 – 21, C14, C18 St. 21 21, C14, C18 21, C18 21 21, C18 21 21, C4, C7, C14 C14 C6, C7, C14, C18

– – – – – – – – – – – – – 21 21

According to Long et al. (1995). ND, not detected.

low, pyrogenic high, petrogenic (4) Ratio of four- to six-ring parent PAHs to the sum of two- and three-ring parent PAHs (HMW/LMW): 1, pyrogenic (5) Ratio of the sum of concentrations of priority unsubstituted three- to six-ring PAHs to the sum of the concentrations of five alkylated PAH homologues of naphthalenes, phenanthrenes, dibenzothiophenes, fluorenes, and chrysenes (pyrogenic index): 0.8, pyrogenic 0.233–0.8, mixed sources The relationships between HMW/LMW and A-PAHs/P-PAHs, between BaA/(BaA + Chr) and MP/P, and between MP/P and the pyrogenic index are shown in Fig. 6a–c, respectively. The relationship between A-PAHs/P-PAHs and HMW/LMW indicates that the PAHs at sites 2, 3, 4, 6, and 7 were mainly petrogenic. All of these sites are near two mouths of Osaka Bay (Akashi Strait and Tomgashima Channel), and PAHs from petroleum could accumulate at such locations, depending on current conditions of sea water. These sites were assigned to Group 1 in cluster analysis (Fig. 5). Although we considered that Group 1 included sites polluted by oil, St. 24 is very different from the other Group 1 sites in Fig. 6a. From the relationships between BaA/(BaA + Chr) and MP/P (Fig. 6b), and/or MP/P and the pyrogenic index (Fig. 6c), the PAHs at Group 2 sites (Fig. 5) were strongly pyrogenic. The PAHs at Group 4 sites were both pyrogenic and petrogenic, but the pyrogenic contribution appeared to be larger, because the MP/P indicated that the PAHs at most of the sites were not derived from oil and mixed sources, whereas the BaA/(BaA + Chr) indicated that most of the PAHs were derived from mixed sources (Fig. 6b and c). Most of sites at Group 4 gather around the inner part of Osaka bay, and the PAHs at those sites could be derived from exhaust gas from automobiles, because those sites close to Osaka city with a densely populated region. PAHs in sites C14 and C18 at Group 3 (Fig. 5) could largely derived from pyrogenic, because the MP/P and pyrogenic index strongly indicated that the PAHs were derived from pyrogenic (Fig. 6c). Sites C14 and C18 are surrounded by a large industrial area and the PAHs in that area could be derived from smoke of industries. The composition of the parent and alkylated PAHs at sites C4 and 21 were different from one another and from the sites in Groups 1–4 resulted from cluster analysis. Site 21 is close to Kobe, where there was a large earthquake that caused a

great fire in 1995. Total and individual PAH concentrations at St. 21 were remarkably high among sites (vide supra). Those PAHs could have been generated by the great fire and fallen directly from the air into the water around this site. 3.3. Risk to aquatic organisms To evaluate the biological effects of some of the individual PAHs, we compared their concentrations at all sites with the effects-range-low (ERL) and the effects-range-medium (ERM) concentrations proposed by Long et al. (1995) (Table 2). In the present study, the concentrations of only dibenzo(a,h)anthracene and benzo(g,h,i)perylene at St. 21 exceeded the ERM. The concentrations of eight PAHs at St. 21 were greater than the ERL, and the PAHs at this site could frequently affect aquatic organisms. The concentrations of some PAHs were above the ERL, and organisms could occasionally be affected by the PAH concentrations at sites C14 and C18. However, concentrations of PAHs at most of the sites were below the ERL and ERM.

4. Conclusion Concentrations of parent and alkylated PAHs in the sediments of Osaka Bay were higher along the shoreline than elsewhere. The high concentrations were concentrated near large ports, industrialized regions, and densely populated regions such as the cities of Osaka and Kobe. The levels of PAH pollution in Osaka Bay were moderate at most locations, but sometimes sites were highly polluted, such as St. 21 and sites in some shoreline areas. The major PAH sources were estimated, and the PAHs were of pyrogenic or both pyrogenic and petrogenic origin at many sites, whether the PAHs were derived mainly from petroleum at some sites. Acknowledgments This study was supported by a Grant-in-Aid-for Young Scientists (B) from the Japan Society for the Promotion of Science (JSPS), and the Development Fund, ‘‘Research on Dynamics of Nitroarenes in Inner Bay Region and Influence on Marine Organisms’’ from the Ministry of the Environment, Japan. The authors would like to acknowledge the considerable supports and cooperation from the officers and crews of the R/V Shirafuji Maru.

Please cite this article in press as: Miki, S., et al. Distributions of polycyclic aromatic hydrocarbons and alkylated polycyclic aromatic hydrocarbons in Osaka Bay, Japan. Mar. Pollut. Bull. (2014), http://dx.doi.org/10.1016/j.marpolbul.2014.04.004

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Please cite this article in press as: Miki, S., et al. Distributions of polycyclic aromatic hydrocarbons and alkylated polycyclic aromatic hydrocarbons in Osaka Bay, Japan. Mar. Pollut. Bull. (2014), http://dx.doi.org/10.1016/j.marpolbul.2014.04.004

Distributions of polycyclic aromatic hydrocarbons and alkylated polycyclic aromatic hydrocarbons in Osaka Bay, Japan.

Contaminations in sediments by polycyclic aromatic hydrocarbons (PAHs) and alkylated PAHs were investigated at 44 sites in Osaka Bay, Japan. Concentra...
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