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Distribution, origin, and potential toxicological significance of polycyclic aromatic hydrocarbons (PAHs) in sediments of Kaohsiung Harbor, Taiwan
Marine Pollution Bulletin 63 (2011) 417–423
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Marine Pollution Bulletin journal homepage: www.elsevier.com/locate/marpolbul
Distribution, origin, and potential toxicological significance of polycyclic aromatic hydrocarbons (PAHs) in sediments of Kaohsiung Harbor, Taiwan Chiu-Wen Chen ⇑, Chih-Feng Chen Department of Marine Environmental Engineering, National Kaohsiung Marine University, Kaohsiung 811, Taiwan
a r t i c l e
i n f o
Keywords: Polycyclic aromatic hydrocarbons (PAHs) Sediment Sediment Quality Guidelines (SQGs) Toxic equivalent (TEQcarc)
a b s t r a c t Sediment samples were collected from 12 locations of Kaohsiung Harbor, Taiwan and analyzed for polycyclic aromatic hydrocarbons (PAHs). Total PAH concentrations varied from 472 to 16,201 ng g1 dry weight. The highest PAH concentrations were from the industrial zone docks situated in south Kaohsiung Harbor. Diagnostic ratios showed that the possible source of PAHs in the industrial zone dock could be coal combustion while in the other zones it could be petroleum combustion. The toxic equivalent concentrations (TEQcarc) of PAHs varied from 55 to 1964 ng TEQ g1 dry weight. Higher total TEQcarc values were found at industrial zone docks (from 1404 to 1964 ng TEQ g1 dry weight). As compared with the US Sediment Quality Guidelines (SQGs), the observed levels of PAHs at industrial zone docks exceeded the effects range low (ERL), and could thus cause acute biological damage. However, the lower levels of PAHs at the other zones would probably not exert adverse biological effects. Ó 2011 Elsevier Ltd. All rights reserved.
1. Introduction Polycyclic aromatic hydrocarbons (PAHs) are included in the European Union and US EPA priority pollutant lists because PAHs represent the largest group of compounds that are mutagenic, carcinogenic, and teratogenic (Sverdrup et al., 2002; Qiao et al., 2006). They could also pose potential threat to the marine environment. The major sources of PAHs could be both natural and anthropogenic. For examples, the terrestrial deposit of coals, atmospheric input from incomplete combustion (wood burning, forest fire, fossil fuel, and coke oven), oil leaks or spills, and exhaust emission from vehicles are the major sources PAHs in environments (van Metre et al., 2000). The effect of PAHs is usually widespread and permanent in environmental media, and thus, PAHs can be eventually deposited and persist in bed sediment (as a sink) in the aquatic system. This occurs because most PAHs, with their high hydrophobicity, sorb strongly to the organic in sediment, and are resistant to bacterial degradation in an anoxic environment. Under favorable environmental conditions, PAHs may be released to the water as a continuing source and threaten the aquatic marine ecosystem through bioaccumulation in food chains. Kaohsiung Harbor, the largest international port in Taiwan, is located on the southwestern coast of Taiwan, and is connected with the key trade waterway running through the Taiwan Strait and Bashi Channel. More than 35,000 inbound and outbound vessels used the harbor every year between 2000 and 2007, and its ⇑ Corresponding author. Tel.: +886 7 3617141 3762; fax: +886 7 365 0548. E-mail address: [email protected] (C.-W. Chen). 0025-326X/$ - see front matter Ó 2011 Elsevier Ltd. All rights reserved. doi:10.1016/j.marpolbul.2011.04.047
container traffic volume ranks the sixth in the world (http:// www.khb.gov.tw/). The harbor has 118 docks including several industrial zone docks, fishing ports, and shipyards. Moreover, the port receives water flows from four contaminated rivers including the Love River, Canon River, Jen-Gen River, and Salt River, which run through the heart of metropolitan Kaohsiung City, the largest industrial city in Taiwan with a population of over 1.5 million. The harbor is connected to these rivers, whose upstream reaches receive domestic, agricultural and industrial wastewaters, and, thus, those wastes contribute to the pollution and potential environmental effects of the Kaohsiung Harbor (Chen et al., 2007). The objectives of this study were to: (a) examine the spatial distribution, composition, and relative pollution levels of PAHs in the sediments of Kaohsiung Harbor, (b) identify possible sources of PAHs, and (c) evaluate the potential toxicological and biological impacts on humans and the environment. 2. Materials and methods 2.1. Sampling strategy Sediment samples were collected from river mouth, fishing ports, shipyards and industrial docks in Kaohsiung Harbor. Fig. 1 shows the study area and sampling sites in Kaohsiung Harbor. Twelve sampling stations selected in this study included four river mouth stations (Love River Mouth, Canon River Mouth, Jen-Gen River Mouth, and Salt River Mouth), two fishing port stations (Chyi-Jihn Fishing Port and Jen-Gen Fishing Port), two shipyard stations (Private Shipyard and Navy Shipyard) and four industrial
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zo[g,h,i]perylene (BP). Deuterated PAHs internal standard solutions (acenaphthene-d10, phenanthrene-d10, and chrysene-d12) at 4000 mg L1 and surrogate standard solutions (2-fluorobiphenyl and 4-terphenyl-d14) at 2000 mg L1 were obtained from AccuStandard Chem. Co., (USA). Internal and surrogate standards were used for sample quantification and quantifying procedural recovery. PAH working standards, internal standard mixture solutions and surrogate standard mixture solutions were properly diluted with HPLC grade n-hexane and prepared daily before the analysis. Glassware was washed before use with n-hexane and dried in an oven at 105 °C. Other materials were previously washed with ultrapure water and acetone. 2.4. Sample preparation and analysis
Fig. 1. Study area and sampling sites.
dock stations (2 China Ship Building Docks and 2 China Steel Docks) (Fig. 1). Location, depth, grain size (sand, silt, and clay) distribution, and organic matter (OM) content in sediment samples are shown in Table 1. 2.2. Sample collection Sediment samples were collected from selected locations in the Kaohsiung Harbor in May 2006. About 3 kg of sediment samples were collected using an Ekman Dredge grab sampler (600 600 600 ) manufactured by Jae Sung International Co., Taiwan. Immediately after collection, the samples were scooped into glass bottles, which have been pre-washed with n-hexane and kept in an icebox, and then transported to the laboratory for analysis. In the laboratory, the samples were freeze-dried for 72 h, ground to pass through an 0.5 mm sieve and fully homogenized (De Luca et al., 2005). The dried sediments were placed at 20 °C in pre-washed with n-hexane amber glass bottles covered with solvent-rinsed aluminum foil until further processing and analysis. 2.3. Chemicals All solvents and reagents used were of trace analysis (TA), chromatographic (HPLC) or ACS grade. Standards of 17 PAHs in a mixture solution of 80 mg L1 were obtained from AccuStandard Chem. Co., (USA), including naphthalene (NA), 2-methylnaphthalene (2-MP), acenaphthylene (ACY), acenaphthene (ACE), fluorene (FL), phenanthrene (PH), anthracene (AN), fluoranthene (FLU), pyrene (PY), benzo[a]anthracene (BaA), chrysene (CH), benzo[b]fluoranthene (BbF), benzo[k]fluoranthene (BkF), benzo[a]pyrene (BaP), indeno[1,2,3-cd]pyrene (IP), dibenzo[a,h]anthracene (DA), and ben-
Particle size was determined with Coulter LS Particle Size Analyzer (Hung and Hsu, 2004; Chen et al., 2007). Wet sediment samples were placed in an oven at 105 °C and heated to a constant weight. The water content of sediments was then calculated by the weight difference before and after heating. The dry sediments were further heated to 550 °C overnight, and the weight difference with respect to dry weight was determined as the organic matter content (OM) (APHA, 2001). For PAHs analyses, the sediment samples were extracted using the following procedure. One gram (accuracy ± 0.0001 g) of dry and homogenized sediment sample was introduced into a clean centrifuge tube, then 5 mL of a 1:1 (v/v) acetone/n-hexane and 0.1 mL of 10 mg L1 surrogate standard mixture solutions were added. A blank was prepared following the same procedure without sediment sample. A check standard mixture was prepared by adding to 1:1 (v/v) acetone/n-hexane. All samples were vortexed for 1 min. Then, the mixture was ultrasonicated for 15 min to extract PAHs. The tube was then centrifuged for 10 min at 2000 rpm. The organic layer containing the derivatized compounds was siphoned out with a Pasteur pipette and the sediment was reextracted twice with 5 mL of a 1:1 (v/v) acetone/n-hexane. The extracts were pooled together. Activated copper was added to the extract for desulphurization. The extract was dried over anhydrous sodium sulfate, concentrated to 1.0 mL using a gentle stream of nitrogen, added to 0.1 mL of 5 mg L1 internal standard mixture solutions, and analyzed by gas chromatography (GC) with mass selective detector (MSD). An Agilent 6890N GC equipped with an Agilent 7683B Injector, a HP-5MS capillary column (30 m 0.25 mm 1 lm) and an Agilent 5975 mass selective detector (MSD) was used to separate and quantify the PAH compounds. The samples were injected in the splitless mode at an injection temperature of 280 °C. The column temperature was initially held at 35 °C for 2 min, raised to 140 °C at the rate of 5 °C min1, then to 300 °C at the rate of 10 °C min1, and held at this temperature for 15 min. Detector temperature was
Table 1 Location, depth, grain size (sand, silt, and clay) and organic matter (OM) content of sediments in Kaohsiung Harbor. Site
Localization
Water depth (m)
Clay (%)
Silt (%)
Sand (%)
OM (%)
1 2 3 4 5 6 7 8 9 10 11 12
Love River Mouth Canon River Mouth Navy Shipyard Chyi-Jihn Fishing Port Jen-Gen River Mouth Private Shipyard Jen-Gen Fishing Port China Ship Building Dock (1) China Ship Building Dock (2) China Steel Dock (1) China Steel Dock (2) Salt River Mouth
4.6 7.2 9.7 5.5 11.2 7.6 13.6 11.6 10.1 10.1 12.1 11.3
4.7 8.9 12.3 13.4 10.1 12.3 8.7 7.2 14.5 10.6 15.5 15.6
50.8 54.5 74.6 77.7 76.2 78.6 55.0 70.5 71.0 73.3 67.1 67.4
44.5 36.6 13.1 9.0 13.7 9.2 36.2 22.3 14.5 16.1 17.4 17.0
11.0 8.1 4.0 6.1 6.7 7.1 4.0 6.4 5.3 12.5 10.8 7.8
C.-W. Chen, C.-F. Chen / Marine Pollution Bulletin 63 (2011) 417–423
kept at 280 °C. Helium was used as a carrier gas at a constant flow rate of 1 mL min1. Mass spectrometry was acquired using the electron ionization (EI) and selective ion monitoring (SIM) modes. Identity of PAHs in the samples was confirmed by the retention time and abundance of quantification/confirmation ions in the authentic PAH standards. Seventeen PAH components were quantified using the response factors related to the respective internal standards based on five-point calibration curve for individual compounds. In this study, the concentrations of PAH compounds were expressed on a dry-weight basis. 2.5. Quality control Five-point calibration curve (0.08–4 ng), procedural blank, check standard and sample duplicates were carried out for every set of samples. The response factors based on the five-point calibration curve for individual compounds showed acceptable relative standard deviation (RSD) values (1.1–14.1%), the procedural blank values were always smaller than the detection limit, the recoveries of individual PAHs in check standards ranged from 80% to 119% (n = 3) and the relative percent differences of sample duplicates ranged from 0.89% to 18.2% (n = 3) for all of the target analyses. The surrogate standard recoveries were 89.2 ± 7.6% for 2-fluorobiphenyl and 99.4 ± 9.4% for 4-terphenyl-d14 with sediment samples (n = 15). The detection limits of the analytical procedure were estimated from three times standard deviation from repeated (n = 7) analysis 17 PAHs of 8 pg, and the amount of sample extracted. The detection limits were 0.6 (FL)–5.4 (DA) ng g1 dry weight for individual PAHs. Reference materials SES-1 (polycyclic aromatic hydrocarbons in spiked estuarine sediment) from National Research Council of Canada (NRCC) were used. Recoveries of individual PAHs in SES-1 were between 82% and 128% (n = 3) of the certified values. 2.6. Data analysis Data analysis (e.g., mean, standard deviation, maximum, and minimum concentrations) using statistical methods were performed in this study. To test the relationship between sediment characteristics and PAH concentrations, linear correlation of Pearson technique analysis was used. Pearson correlation analysis was performed using SAS 9.1.3 (SAS Institute Inc., Cary, NC, 2004). The following analytical data were taken into account: (a) the amount of each PAH; (b) the sum of 17 PAHs, RPAHs; (c) the sum of seven PAHs with low molecular weight (i.e., NA, 2-MP, ACY, ACE, FL, PH, and AN), RLPAHs; (d) the sum of 10 PAHs with high molecular weight (i.e., FLU, PY, BaA, CH, BbF, BkF, BaP, B, DA, and IP), RHPAHs; and (e) the sum of potentially carcinogenic PAHs (i.e., BaA, CH, BbF, BkF, BaP, IP, and DA), RCPAHs. 3. Results and discussion 3.1. Distribution of PAHs Table 2 lists the PAHs concentration in sediments of the 12 selected stations. The total amount of PAHs (RPAHs) varied from 472 to 16,201 ng g1 dry weight, with a mean concentration of 5764 ng g1 dry weight. Higher RPAHs concentrations were detected in sediments collected from Stations 8 to 12, ranging from 8788 to 16,201 ng g1 dry weight. This indicates that the major sources of sediment PAHs came from the industrial zone situated in south Kaohsiung Harbor area. Fig. 2 presents the PAHs composition of sediments collected from the Kaohsiung Harbor. According to the number of aromatic
419
rings, the 17 PAH compounds were divided into three groups: (a) 2- and 3-ring, (b) 4-ring, and (c) 5- and 6-ring PAHs. The 5- and 6-ring PAHs were predominant in sediments from Kaohsiung Harbor, ranging from 42% to 71%, except the sediments from China Steel Dock (Stations 10 and 11) (Fig. 2), where the 2- and 3-ring PAHs were predominant at 42% and 37%, respectively. The result suggests that the PAHs contamination in China Steel Dock came from a different source. It has been reported that the organic matter content can influence the distribution of PAHs in sediments (Kim et al., 1999; Wang et al., 2001). High organic matter content was characterized with high PAHs concentration in sediments (Yang, 2000; Wang et al., 2001; De Luca et al., 2005). In addition, Chiou et al. (1998) used soil-state 13C to determine relative amounts of different structural carbon in sediment organic matter, and found that the high partitioning of PAHs to organic matter was mainly due to significant aromatic fraction of organic matter. In this study, no significant correlation was found between RPAHs and organic matter content (r = 0.54, p > 0.05) in Stations 1–12. However, based on the concentrations of RPAHs, all stations were divided into two groups, one for high concentration (Stations 8–12), one for low concentration (Stations 1–9), and the significant correlation between RPAHs and organic matter content was found in Stations 1–7 (r = 0.82, p < 0.05), so was Stations 8–12 (r = 0.85, p < 0.05). The results suggest that the sediment organic matter played an important role in controlling the PAH distribution in sediments, whereas composition of organic matter can influence the partition of PAH in organic matter. Table 3 presents the PAHs concentrations in sediments at different locations around the world. Due to the differences in number and type of PAH compounds analyzed, the sediments fraction screened, and geological characteristics of each sampling area, it is difficult to directly compare the RPAHs concentrations reported in different regions of the world. However, the pollutant levels suggested by Baumard et al. (1998) can be used to classify the relative contamination level. Baumard et al. (1998) classified RPAHs pollution into four categories or groups: (a) low, 0–100 ng g1; (b) moderate, 100–1000 ng g1; (c) high, 1000–5000 ng g1; and (d) very high, >5000 ng g1. Sediments from Kaohsiung Harbor can be characterized as moderately to very highly PAHs pollution in comparison to other regions of the world (Table 3): (a) Stations 1–2 (high); (b) Stations 3–7 (moderate); and (c) Stations 8–12 (very high). 3.2. Sources of PAHs in Kaohsiung Harbor PAH isomeric ratios have been used to identify different sources that contribute PAHs to environmental samples (Yunker et al., 2002; Budzinski et al., 1997; Baumard et al., 1998). Environmental sources of PAHs include petroleum, sewage, biomass combustion (grass, wood, or coal combustion), or petroleum combustion and are generally derived from anthropogenic sources. The predominant sources of PAHs in estuarine/marine sediments originate from pyrolytic (combustion) or petrogenic (fossil fuel) related activities (Zakaria et al., 2002; Stout et al., 2004). Characterized by predominance of parent compounds with four or more aromatic rings, pyrolytic PAHs are derived during combustion. In contrast, petrogenic PAHs (from petroleum and its products) contain only two or three aromatic ring compounds. Therefore, a ratio of low (2- and 3-ring) to high (4- to 6-ring) PAHs has been used to identify pyrogenic (<1) and petrogenic (>1) sources of PAHs in sediments (Budzinski et al., 1997; De Luca et al., 2005). The RLPAHs include NA, 2-MP, ACY, ACE, FL, PH, and AN; the RHPAHs include FLU, PY, BaA, CH, BbF, BkB, BaP, IP, DA, and BP (Table 2). In all Kaohsiung Harbor stations, RLPAHs/RHPAHs ratios were <1, indicating they originated from pyrogenic sources.
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Table 2 PAHs concentration (ng g1 dry weight) and selected molecular ratios in sediments of Kaohsiung Harbor. Site
NA
2-MP
ACY
ACE
FL
PH
AN
FLU
PY
BaA
CH
BbF
BkF
BaP
IP
DA
BP
1 2 3 4 5 6 7 8 9 10 11 12 ERL(a) ERM(a)
142 56 23 24 32 38 4.6 290 153 1076 1567 450 160 2100
53 43 14 17 21 23 12 14 53 763 458 136 70 670
3.4 6.1 2.8 6.4 5.3 6.8 4.8 43 89 154 259 210 44 640
8.1 13 4.4 5.0 9.9 13 9.0 182 69 1132 1067 41 16 500
3.0 34 10 1.9 7.7 4.6 2.5 191 115 960 652 207 19 540
15 28 15 17 18 22 22 659 184 1936 1335 310 240 1500
11 10 0.9 4.2 13 12 5.0 197 6.2 557 681 11 85.3 1100
141 153 48 49 88 111 60 1194 754 1236 1917 927 600 5100
162 197 60 74 115 143 77 1221 685 1068 1703 954 665 2600
58 77 23 24 32 37 18 453 356 456 477 626 261 1600
12 39 58 53 13 21 11 828 85 867 764 123 384 2800
161 234 136 125 150 193 96 2743 2127 1883 1874 2193 – –
90 133 75 62 85 96 55 1548 1196 1062 1057 1237 – –
69 79 38 43 52 67 33 1188 1105 896 912 1178 430 1600
43 34 12 26 44 42 20 786 751 559 646 698 – –
5.1 10 10 4.9 11 18 6.1 344 293 193 237 287 63.4 260
69 66 53 56 68 83 36 961 764 697 593 657 – –
1 2 3 4 5 6 7 8 9 10 11 12 ERL ERM a
RPAHs
RLPAHs
RHPAHs
RLPAHs RHPAHs
PH AN
AN ðPHþANÞ
FLU PY
FLU ðFLUþPYÞ
RCPAHs
TEQcarc
1045 1211 583 591 765 928 472 12,843 8788 15,495 16,201 10,245 4022 44,792
235 190 69 75 106 119 60 1576 670 6578 6020 1365 552 3160
810 1021 514 516 659 809 412 11,267 8118 8917 10,181 8881 1700 9600
0.29 0.19 0.13 0.15 0.16 0.15 0.14 0.14 0.08 0.74 0.59 0.15 – –
1.4 2.7 16.8 4.0 1.4 1.8 4.3 3.3 29.7 3.5 2.0 29.0 – –
0.41 0.27 0.06 0.20 0.42 0.36 0.19 0.23 0.03 0.22 0.34 0.03 – –
0.87 0.77 0.81 0.66 0.76 0.78 0.78 0.98 1.10 1.16 1.13 0.97 – –
0.47 0.44 0.45 0.40 0.43 0.44 0.44 0.49 0.52 0.54 0.53 0.49
464 638 394 366 412 513 256 8067 5928 6054 5915 6302 – –
104 128 60 69 89 117 55 1964 1736 1404 1455 1825 – –
ERL and ERM refers to the effects range low and median (Long et al., 1995).
Fig. 2. PAHs composition of sediments of Kaohsiung Harbor, 2,3-ring: NA, 2-MP, ACY, ACE, FL, PH, AN. 4-ring: FLU, PY, BaA, CH. 5,6-ring: BbF, BkF, BaP, IP, DA, BP.
Other isomeric ratios have been used to assess the pyrogenic or petrogenic sources of PAHs in sediments: (a) PH/AN (Soclo et al., 2000; Magi et al., 2002) or alternatively, AN/(PH + AN) ratio (Baumard et al., 1998; Yunker et al., 2002; Zhang et al., 2004; Li et al., 2006; Qiao et al., 2006); (b) FLU/PY (Magi et al., 2002); and (c) FLU/(FLU + PY) (Magi et al., 2002; Guinan et al., 2001). The PH is thermodynamically more stable and its prevalence over AN indicates that the sediment PAHs were mainly from petrogenesis activities. Indeed, petroleum product usually exhibits a quite high PH/AN ratio. Therefore, if the PH/AN ratio is higher than 10 (or AN/(PH + AN) > 0.1), it reveals that the sediment is mainly contaminated by petrogenic inputs. Moreover, if the PH/AN ratio is less than 15 (or AN/(PH + AN) < 0.1), it typically reveals that the PAH source is from pyrolytic activities (Baumard et al., 1998;
Qiao et al., 2006). As showed in Table 2, the ratios of PH/AN and AN/(PH + AN) at Stations 3, 9, and 12 were higher than 15 and lower than 0.1, respectively, this indicates that the main PAH source was petroleum products. Other stations were lower than 10 and higher than 0.1, respectively, this implies that the PAH source could be combustion activities. The FLU/PY and FLU/(FLU + PY) ratios are also useful indicators in evaluating the attribution of PAH pollution in sediment (Guinan et al., 2001; Magi et al., 2002; Zhang et al., 2004; Li et al., 2006). Baumard et al. (1998) concluded that the source of contamination is mainly from pyrolytic sources if the ratio of FLU/PY is higher than 1. Their results also revealed that petrogenic discharges would cause the increase in PAH in sediments if the ratio of FLU/ PY is less than 1 (Baumard et al., 1998). In this study, the ratios of FLU/PY at Stations 9–11 were higher than 1 (Table 2), this indicates that the main PAH source was petroleum products. The other stations were lower than 1 (Table 2), indicating they originated from combustion activities. Moreover, when FLU/(FLU + PY) is higher than 0.5, biomass combustion (grass, wood, or coal combustion) would cause the increase in PAHs in sediments (Budzinski et al., 1997; Yunker et al., 2002; Zhang et al., 2004; Qiao et al., 2006). However, if the ratio of FLU/(FLU + PY) is between 0.4 and 0.5, PAHs are mainly from combustion of petroleum; if the ratio is less than 0.4, typical petroleum contamination is usually the cause of PAHs in sediments (Budzinski et al., 1997; Yunker et al., 2002; Zhang et al., 2004; Qiao et al., 2006). As showed in Table 2, the ratios of FLU/(FLU + PY) at Stations 9–11 were higher than 0.5, this indicates that the main PAH source was biomass combustion. The other stations were between 0.4 and 0.5, indicating they originated from petroleum combustion. Results of PAH isomeric ratios were gives an inconsistent picture of the origins in Kaohsiung harbor. With the evaluation of both PH/AN and FLU/PY ratios, misleading estimate of PAH sources can be prevented (Tam et al., 2001; Yunker et al., 2002; Zhang et al.,
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C.-W. Chen, C.-F. Chen / Marine Pollution Bulletin 63 (2011) 417–423 Table 3 PAHs concentrations in sediments at different locations. Location
na
RPAHs (ng g1 dry weight)
Pollution levelb
References
Kaohsiung Harbor, Taiwan Xiamen Harbor, China Victoria Harbor, Hong Kong Incheon Harbor, Korea Hsin-ta Harbor, Taiwan Baltimore Harbor, USA Boston Harbor, USA Olbia Harbor, Italy Genoa-Voltri Harbor, Italy Taranto Gulf, Italy Norwegian Harbor, Norway Izmit Bay, Turkey Gemlik Bay, Turkey Commercial ports from Spain Santander Bay, Northern Spain Western Harbor, Alexandria, Egypt
17 9 9 23 30 21 16 16 16 8 16 17 14 12 16 20
472–16,207 2900–61,000 1200–14,000 12–1400 1156–3382 2944–29,590 7300–358,000 160–770 4500–20,800 335–5193 2000–76,000 2500–25,000 50.8–13,482 260–66,710 20–25,800 8–131,150
Moderate to very high High to very high High to very high Low to moderate High High to very high Very high Moderate High to very high Moderate to very high High to very high High to very high Low to very high Moderate to very high Low to very high Low to very high
This study Hong et al. (1995) Hong et al. (1995) Kim et al. (1999) Fang et al. (2003) Pereira et al. (1999) Wang et al. (2001) De Luca et al. (2005) Salvo et al. (2005) Storelli and Marcotrigiano (2000) Oen et al. (2006) Tolun et al. (2001) Ünlü and Alpar (2006) Casado-Martínez et al. (2006) Viguri et al. (2002) Mostafa et al. (2003)
a
n: number of PAH compounds analyzed in each study. Pollution levels are assigned as low: 0–100 ng g1 dry weight, moderate: 100–1000 ng g1 dry weight, high: 1000–5000 ng g1 dry weight, very high: >5000 ng g1 dry weight (Baumard et al., 1998). b
PAHs (i.e., BaA, CH, BbF, BkF, BaP, IP, and DA), RCPAHs (Qiao et al., 2006; Savinov et al., 2003; Nadal et al., 2004). The RCPAHs concentration varied from 256 to 8067 ng g1 dry weight, with a mean concentration of 2942 ng g1 dry weight (Table 2). The RCPAHs accounted for 37% to 68% of RPAHs in sediments of Kaohsiung Harbor. The potential toxicity of sediment was evaluated using the total toxic benzo[a]pyrene equivalent (TEQcarc) (Qiao et al., 2006; Savinov et al., 2003; Nadal et al., 2004). The TEQcarc for all CPAHs was calculated using the following equation:
TEQ carc ¼
X
Ci TEFcarc i
ð1Þ
i
Fig. 3. PAHs cross plots for the ratios of FLU/(PY + FLU) vs. AN/(AN + PH).
2004; Li et al., 2006). Fig. 3 shows the distribution AN/(PH + AN) and FLU/(FLU + PY) ratios in sediments of Stations 1–12. Ratios of FLU/(FLU + PY) in sediment of nine stations (Stations 1–8 and 12) ranged between 0.4 and 0.5 indicate that petroleum combustion could be a possible source of PAHs; ratios of FLU/(FLU + PY) at Stations 9–11 were higher than 0.5 suggesting that grass, wood, and coal combustion would make the possible contributions to PAHs. Results from the ratio calculations suggest that Stations 9–11, located in the industrial area, had different PAH ratios from other stations because coal burning was used for the energy source in this area. In addition, results show that ratios of AN/(PH + AN) were lower than 0.1 at Stations 3, 9 and 12; ratios of FLU/(FLU + PY) were between 0.4 and 0.5 at Stations 3 and 12, and higher than 0.5 at Station 9. This indicates that different PAH sources occurred in this area. 3.3. Sediment potential human toxicity and biological effects based on PAHs The assessment of sediment toxicity in this study was performed based on the total concentration of potentially carcinogenic
where, Ci is the carcinogenic PAHs concentration (ng g1 dry weight); TEFcarc (toxic equivalency factors) is the toxic factor of cari cinogenic PAHs relative to benzo[a]pyrene (BaP). Among all known potentially carcinogenic PAHs, benzo[a]pyrene is the only PAH for which toxicological data are sufficient for derivation of a carcinogenic potency factor (Peters et al., 1999). According to US EPA (1993), TEFs for BaA, CH, BbF, BkF, BaP, IP, and DA are 0.1, 0.001, 0.1, 0.01, 1, 0.1, and 1, respectively. In this study, the total TEQcarc values of sediment samples varied from 55 to 1964 ng TEQ g1 dry weight, with the mean value of 750 ng TEQ g1 dry weight. The higher total TEQcarc values were found at Stations 8–12 (varied from 1404 to 1964 ng TEQ g1 dry weight) located in the south Kaohsiung Harbor. The TEQcarc found in sediments from Kaohsiung Harbor were lower than in sediments from Naples harbor (Italy), but were higher than in Barents Sea (Russia) and Meiliang Bay (China) (Table 4). Fig. 4 shows the CPAHs and relative contents of BaPeq dose in total TEQcarc. Among different CPAHs, contribution to the total TEQcarc decreased in the following order: BaP (61.2 ± 3.6%), BbF (15.5 ± 2.6%), DA (12.9 ± 4.2%), IP (5.9 ± 1.5%), BaA (3.6 ± 1.1%), BkF (0.9 ± 0.1%), and CH (0.04 ± 0.03%). A widely used sediment toxicity screening guideline of the US National Oceanic and Atmospheric Administration provides two target values to estimate potential biological effects: effects range low (ERL) and effect range median (ERM) (Long et al., 1995). The guideline was developed by comparing various sediment toxicity responses of marine organisms or communities with observed PAHs concentrations in sediments. These two values delineate three concentration ranges for each particular chemical. When the concentration is below the ERL, it indicates that the biological effect is rare. If concentration equals to or greater than the ERL but below the ERM, it indicates that a biological effect would occur
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Table 4 CPAHs concentrations and TEQcarc in sediments at different locations.
a
Location
na
RCPAHs (ng g1 dry weight)
TEQcarc (ng TEQ g1 dry weight)
References
Kaohsiung Harbor, Taiwan Meiliang Bay, China
7 7
256–8067 621–2737
55–1964 94–845
This study Qiao et al. (2006)
Barents Sea, Russia Vardø Harbor Vadsø Harbor Jarfjord Korsfjord Kola Bay Guba Pechenga
5 5 5 5 5 5
870–1412 68–124 30–70 30–134 240–1211 63–864
472–733 40–66 19–35 18–60 71–583 18–300
Savinov Savinov Savinov Savinov Savinov Savinov
Naples harbor, Italy Commercial area Eastern area External area Industrial area Shipping area Touristic area
6 6 6 6 6 6
3–9102 3–5047 3–4109 3–6316 21–7832 3–9879
6–4528 2–1973 2–1629 4–4723 45–3578 10–2250
Sprovieri Sprovieri Sprovieri Sprovieri Sprovieri Sprovieri
et et et et et et
al. al. al. al. al. al.
et et et et et et
(2003) (2003) (2003) (2003) (2003) (2003)
al. al. al. al. al. al.
(2007) (2007) (2007) (2007) (2007) (2007)
n: number of CPAH compounds analyzed in each study.
centrations exceeded ERL, and that could cause acute biological damage. The possible source of PAHs in the industrial zone dock could be coal combustion, while petroleum combustion could be the possible source in the other zones. Results from this study suggest that these industrial activities played important roles in the leaching of PAHs into the environments.
Acknowledgements This work was supported by the Kaohsiung City Marine Bureau, Taiwan. The authors would like to thank the personnel of the Kaohsiung City Marine Bureau for their support throughout this project.
References Fig. 4. Relative contents of toxic benzo[a]pyrene doses of potentially carcinogenic PAHs in sediments from the Kaohsiung Harbor.
occasionally. Concentrations at or above the ERM indicate that a negative biological effect would frequently occur. Table 2 shows the measured concentrations of PAHs in comparison with the ERM and ERL values. The RLPAHs, RHPAHs and RPAHs at Stations 1–7 were below the ERL but Stations 8–12 were above the ERL and below ERM. For an individual PAH, Stations 1–7 were below the ERL. This indicates that biological effects would rarely occur. However, most PAHs were above the ERL but below ERM in Stations 8–12, which indicates that biological effects would occur occasionally. Moreover, some PAHs exceeded ERM in Stations 8–12 (e.g., Stations 8, 9 and 12: DA, Station 10: 2-MP, ACE, FL and PH, and Station 11: ACE and FL), which indicates that biological effect would occur frequently.
4. Conclusions PAHs were detected in sediment samples collected from various locations in Kaohsiung Harbor. The highest levels of PAHs were recorded for sediment samples collected in the vicinity of industrial zone docks situated in the south Kaohsiung Harbor where the con-
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Contents lists available at ScienceDirect
Marine Pollution Bulletin journal homepage: www.elsevier.com/locate/marpolbul
Distribution, origin, and potential toxicological significance of polycyclic aromatic hydrocarbons (PAHs) in sediments of Kaohsiung Harbor, Taiwan Chiu-Wen Chen ⇑, Chih-Feng Chen Department of Marine Environmental Engineering, National Kaohsiung Marine University, Kaohsiung 811, Taiwan
a r t i c l e
i n f o
Keywords: Polycyclic aromatic hydrocarbons (PAHs) Sediment Sediment Quality Guidelines (SQGs) Toxic equivalent (TEQcarc)
a b s t r a c t Sediment samples were collected from 12 locations of Kaohsiung Harbor, Taiwan and analyzed for polycyclic aromatic hydrocarbons (PAHs). Total PAH concentrations varied from 472 to 16,201 ng g1 dry weight. The highest PAH concentrations were from the industrial zone docks situated in south Kaohsiung Harbor. Diagnostic ratios showed that the possible source of PAHs in the industrial zone dock could be coal combustion while in the other zones it could be petroleum combustion. The toxic equivalent concentrations (TEQcarc) of PAHs varied from 55 to 1964 ng TEQ g1 dry weight. Higher total TEQcarc values were found at industrial zone docks (from 1404 to 1964 ng TEQ g1 dry weight). As compared with the US Sediment Quality Guidelines (SQGs), the observed levels of PAHs at industrial zone docks exceeded the effects range low (ERL), and could thus cause acute biological damage. However, the lower levels of PAHs at the other zones would probably not exert adverse biological effects. Ó 2011 Elsevier Ltd. All rights reserved.
1. Introduction Polycyclic aromatic hydrocarbons (PAHs) are included in the European Union and US EPA priority pollutant lists because PAHs represent the largest group of compounds that are mutagenic, carcinogenic, and teratogenic (Sverdrup et al., 2002; Qiao et al., 2006). They could also pose potential threat to the marine environment. The major sources of PAHs could be both natural and anthropogenic. For examples, the terrestrial deposit of coals, atmospheric input from incomplete combustion (wood burning, forest fire, fossil fuel, and coke oven), oil leaks or spills, and exhaust emission from vehicles are the major sources PAHs in environments (van Metre et al., 2000). The effect of PAHs is usually widespread and permanent in environmental media, and thus, PAHs can be eventually deposited and persist in bed sediment (as a sink) in the aquatic system. This occurs because most PAHs, with their high hydrophobicity, sorb strongly to the organic in sediment, and are resistant to bacterial degradation in an anoxic environment. Under favorable environmental conditions, PAHs may be released to the water as a continuing source and threaten the aquatic marine ecosystem through bioaccumulation in food chains. Kaohsiung Harbor, the largest international port in Taiwan, is located on the southwestern coast of Taiwan, and is connected with the key trade waterway running through the Taiwan Strait and Bashi Channel. More than 35,000 inbound and outbound vessels used the harbor every year between 2000 and 2007, and its ⇑ Corresponding author. Tel.: +886 7 3617141 3762; fax: +886 7 365 0548. E-mail address: [email protected] (C.-W. Chen). 0025-326X/$ - see front matter Ó 2011 Elsevier Ltd. All rights reserved. doi:10.1016/j.marpolbul.2011.04.047
container traffic volume ranks the sixth in the world (http:// www.khb.gov.tw/). The harbor has 118 docks including several industrial zone docks, fishing ports, and shipyards. Moreover, the port receives water flows from four contaminated rivers including the Love River, Canon River, Jen-Gen River, and Salt River, which run through the heart of metropolitan Kaohsiung City, the largest industrial city in Taiwan with a population of over 1.5 million. The harbor is connected to these rivers, whose upstream reaches receive domestic, agricultural and industrial wastewaters, and, thus, those wastes contribute to the pollution and potential environmental effects of the Kaohsiung Harbor (Chen et al., 2007). The objectives of this study were to: (a) examine the spatial distribution, composition, and relative pollution levels of PAHs in the sediments of Kaohsiung Harbor, (b) identify possible sources of PAHs, and (c) evaluate the potential toxicological and biological impacts on humans and the environment. 2. Materials and methods 2.1. Sampling strategy Sediment samples were collected from river mouth, fishing ports, shipyards and industrial docks in Kaohsiung Harbor. Fig. 1 shows the study area and sampling sites in Kaohsiung Harbor. Twelve sampling stations selected in this study included four river mouth stations (Love River Mouth, Canon River Mouth, Jen-Gen River Mouth, and Salt River Mouth), two fishing port stations (Chyi-Jihn Fishing Port and Jen-Gen Fishing Port), two shipyard stations (Private Shipyard and Navy Shipyard) and four industrial
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zo[g,h,i]perylene (BP). Deuterated PAHs internal standard solutions (acenaphthene-d10, phenanthrene-d10, and chrysene-d12) at 4000 mg L1 and surrogate standard solutions (2-fluorobiphenyl and 4-terphenyl-d14) at 2000 mg L1 were obtained from AccuStandard Chem. Co., (USA). Internal and surrogate standards were used for sample quantification and quantifying procedural recovery. PAH working standards, internal standard mixture solutions and surrogate standard mixture solutions were properly diluted with HPLC grade n-hexane and prepared daily before the analysis. Glassware was washed before use with n-hexane and dried in an oven at 105 °C. Other materials were previously washed with ultrapure water and acetone. 2.4. Sample preparation and analysis
Fig. 1. Study area and sampling sites.
dock stations (2 China Ship Building Docks and 2 China Steel Docks) (Fig. 1). Location, depth, grain size (sand, silt, and clay) distribution, and organic matter (OM) content in sediment samples are shown in Table 1. 2.2. Sample collection Sediment samples were collected from selected locations in the Kaohsiung Harbor in May 2006. About 3 kg of sediment samples were collected using an Ekman Dredge grab sampler (600 600 600 ) manufactured by Jae Sung International Co., Taiwan. Immediately after collection, the samples were scooped into glass bottles, which have been pre-washed with n-hexane and kept in an icebox, and then transported to the laboratory for analysis. In the laboratory, the samples were freeze-dried for 72 h, ground to pass through an 0.5 mm sieve and fully homogenized (De Luca et al., 2005). The dried sediments were placed at 20 °C in pre-washed with n-hexane amber glass bottles covered with solvent-rinsed aluminum foil until further processing and analysis. 2.3. Chemicals All solvents and reagents used were of trace analysis (TA), chromatographic (HPLC) or ACS grade. Standards of 17 PAHs in a mixture solution of 80 mg L1 were obtained from AccuStandard Chem. Co., (USA), including naphthalene (NA), 2-methylnaphthalene (2-MP), acenaphthylene (ACY), acenaphthene (ACE), fluorene (FL), phenanthrene (PH), anthracene (AN), fluoranthene (FLU), pyrene (PY), benzo[a]anthracene (BaA), chrysene (CH), benzo[b]fluoranthene (BbF), benzo[k]fluoranthene (BkF), benzo[a]pyrene (BaP), indeno[1,2,3-cd]pyrene (IP), dibenzo[a,h]anthracene (DA), and ben-
Particle size was determined with Coulter LS Particle Size Analyzer (Hung and Hsu, 2004; Chen et al., 2007). Wet sediment samples were placed in an oven at 105 °C and heated to a constant weight. The water content of sediments was then calculated by the weight difference before and after heating. The dry sediments were further heated to 550 °C overnight, and the weight difference with respect to dry weight was determined as the organic matter content (OM) (APHA, 2001). For PAHs analyses, the sediment samples were extracted using the following procedure. One gram (accuracy ± 0.0001 g) of dry and homogenized sediment sample was introduced into a clean centrifuge tube, then 5 mL of a 1:1 (v/v) acetone/n-hexane and 0.1 mL of 10 mg L1 surrogate standard mixture solutions were added. A blank was prepared following the same procedure without sediment sample. A check standard mixture was prepared by adding to 1:1 (v/v) acetone/n-hexane. All samples were vortexed for 1 min. Then, the mixture was ultrasonicated for 15 min to extract PAHs. The tube was then centrifuged for 10 min at 2000 rpm. The organic layer containing the derivatized compounds was siphoned out with a Pasteur pipette and the sediment was reextracted twice with 5 mL of a 1:1 (v/v) acetone/n-hexane. The extracts were pooled together. Activated copper was added to the extract for desulphurization. The extract was dried over anhydrous sodium sulfate, concentrated to 1.0 mL using a gentle stream of nitrogen, added to 0.1 mL of 5 mg L1 internal standard mixture solutions, and analyzed by gas chromatography (GC) with mass selective detector (MSD). An Agilent 6890N GC equipped with an Agilent 7683B Injector, a HP-5MS capillary column (30 m 0.25 mm 1 lm) and an Agilent 5975 mass selective detector (MSD) was used to separate and quantify the PAH compounds. The samples were injected in the splitless mode at an injection temperature of 280 °C. The column temperature was initially held at 35 °C for 2 min, raised to 140 °C at the rate of 5 °C min1, then to 300 °C at the rate of 10 °C min1, and held at this temperature for 15 min. Detector temperature was
Table 1 Location, depth, grain size (sand, silt, and clay) and organic matter (OM) content of sediments in Kaohsiung Harbor. Site
Localization
Water depth (m)
Clay (%)
Silt (%)
Sand (%)
OM (%)
1 2 3 4 5 6 7 8 9 10 11 12
Love River Mouth Canon River Mouth Navy Shipyard Chyi-Jihn Fishing Port Jen-Gen River Mouth Private Shipyard Jen-Gen Fishing Port China Ship Building Dock (1) China Ship Building Dock (2) China Steel Dock (1) China Steel Dock (2) Salt River Mouth
4.6 7.2 9.7 5.5 11.2 7.6 13.6 11.6 10.1 10.1 12.1 11.3
4.7 8.9 12.3 13.4 10.1 12.3 8.7 7.2 14.5 10.6 15.5 15.6
50.8 54.5 74.6 77.7 76.2 78.6 55.0 70.5 71.0 73.3 67.1 67.4
44.5 36.6 13.1 9.0 13.7 9.2 36.2 22.3 14.5 16.1 17.4 17.0
11.0 8.1 4.0 6.1 6.7 7.1 4.0 6.4 5.3 12.5 10.8 7.8
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kept at 280 °C. Helium was used as a carrier gas at a constant flow rate of 1 mL min1. Mass spectrometry was acquired using the electron ionization (EI) and selective ion monitoring (SIM) modes. Identity of PAHs in the samples was confirmed by the retention time and abundance of quantification/confirmation ions in the authentic PAH standards. Seventeen PAH components were quantified using the response factors related to the respective internal standards based on five-point calibration curve for individual compounds. In this study, the concentrations of PAH compounds were expressed on a dry-weight basis. 2.5. Quality control Five-point calibration curve (0.08–4 ng), procedural blank, check standard and sample duplicates were carried out for every set of samples. The response factors based on the five-point calibration curve for individual compounds showed acceptable relative standard deviation (RSD) values (1.1–14.1%), the procedural blank values were always smaller than the detection limit, the recoveries of individual PAHs in check standards ranged from 80% to 119% (n = 3) and the relative percent differences of sample duplicates ranged from 0.89% to 18.2% (n = 3) for all of the target analyses. The surrogate standard recoveries were 89.2 ± 7.6% for 2-fluorobiphenyl and 99.4 ± 9.4% for 4-terphenyl-d14 with sediment samples (n = 15). The detection limits of the analytical procedure were estimated from three times standard deviation from repeated (n = 7) analysis 17 PAHs of 8 pg, and the amount of sample extracted. The detection limits were 0.6 (FL)–5.4 (DA) ng g1 dry weight for individual PAHs. Reference materials SES-1 (polycyclic aromatic hydrocarbons in spiked estuarine sediment) from National Research Council of Canada (NRCC) were used. Recoveries of individual PAHs in SES-1 were between 82% and 128% (n = 3) of the certified values. 2.6. Data analysis Data analysis (e.g., mean, standard deviation, maximum, and minimum concentrations) using statistical methods were performed in this study. To test the relationship between sediment characteristics and PAH concentrations, linear correlation of Pearson technique analysis was used. Pearson correlation analysis was performed using SAS 9.1.3 (SAS Institute Inc., Cary, NC, 2004). The following analytical data were taken into account: (a) the amount of each PAH; (b) the sum of 17 PAHs, RPAHs; (c) the sum of seven PAHs with low molecular weight (i.e., NA, 2-MP, ACY, ACE, FL, PH, and AN), RLPAHs; (d) the sum of 10 PAHs with high molecular weight (i.e., FLU, PY, BaA, CH, BbF, BkF, BaP, B, DA, and IP), RHPAHs; and (e) the sum of potentially carcinogenic PAHs (i.e., BaA, CH, BbF, BkF, BaP, IP, and DA), RCPAHs. 3. Results and discussion 3.1. Distribution of PAHs Table 2 lists the PAHs concentration in sediments of the 12 selected stations. The total amount of PAHs (RPAHs) varied from 472 to 16,201 ng g1 dry weight, with a mean concentration of 5764 ng g1 dry weight. Higher RPAHs concentrations were detected in sediments collected from Stations 8 to 12, ranging from 8788 to 16,201 ng g1 dry weight. This indicates that the major sources of sediment PAHs came from the industrial zone situated in south Kaohsiung Harbor area. Fig. 2 presents the PAHs composition of sediments collected from the Kaohsiung Harbor. According to the number of aromatic
419
rings, the 17 PAH compounds were divided into three groups: (a) 2- and 3-ring, (b) 4-ring, and (c) 5- and 6-ring PAHs. The 5- and 6-ring PAHs were predominant in sediments from Kaohsiung Harbor, ranging from 42% to 71%, except the sediments from China Steel Dock (Stations 10 and 11) (Fig. 2), where the 2- and 3-ring PAHs were predominant at 42% and 37%, respectively. The result suggests that the PAHs contamination in China Steel Dock came from a different source. It has been reported that the organic matter content can influence the distribution of PAHs in sediments (Kim et al., 1999; Wang et al., 2001). High organic matter content was characterized with high PAHs concentration in sediments (Yang, 2000; Wang et al., 2001; De Luca et al., 2005). In addition, Chiou et al. (1998) used soil-state 13C to determine relative amounts of different structural carbon in sediment organic matter, and found that the high partitioning of PAHs to organic matter was mainly due to significant aromatic fraction of organic matter. In this study, no significant correlation was found between RPAHs and organic matter content (r = 0.54, p > 0.05) in Stations 1–12. However, based on the concentrations of RPAHs, all stations were divided into two groups, one for high concentration (Stations 8–12), one for low concentration (Stations 1–9), and the significant correlation between RPAHs and organic matter content was found in Stations 1–7 (r = 0.82, p < 0.05), so was Stations 8–12 (r = 0.85, p < 0.05). The results suggest that the sediment organic matter played an important role in controlling the PAH distribution in sediments, whereas composition of organic matter can influence the partition of PAH in organic matter. Table 3 presents the PAHs concentrations in sediments at different locations around the world. Due to the differences in number and type of PAH compounds analyzed, the sediments fraction screened, and geological characteristics of each sampling area, it is difficult to directly compare the RPAHs concentrations reported in different regions of the world. However, the pollutant levels suggested by Baumard et al. (1998) can be used to classify the relative contamination level. Baumard et al. (1998) classified RPAHs pollution into four categories or groups: (a) low, 0–100 ng g1; (b) moderate, 100–1000 ng g1; (c) high, 1000–5000 ng g1; and (d) very high, >5000 ng g1. Sediments from Kaohsiung Harbor can be characterized as moderately to very highly PAHs pollution in comparison to other regions of the world (Table 3): (a) Stations 1–2 (high); (b) Stations 3–7 (moderate); and (c) Stations 8–12 (very high). 3.2. Sources of PAHs in Kaohsiung Harbor PAH isomeric ratios have been used to identify different sources that contribute PAHs to environmental samples (Yunker et al., 2002; Budzinski et al., 1997; Baumard et al., 1998). Environmental sources of PAHs include petroleum, sewage, biomass combustion (grass, wood, or coal combustion), or petroleum combustion and are generally derived from anthropogenic sources. The predominant sources of PAHs in estuarine/marine sediments originate from pyrolytic (combustion) or petrogenic (fossil fuel) related activities (Zakaria et al., 2002; Stout et al., 2004). Characterized by predominance of parent compounds with four or more aromatic rings, pyrolytic PAHs are derived during combustion. In contrast, petrogenic PAHs (from petroleum and its products) contain only two or three aromatic ring compounds. Therefore, a ratio of low (2- and 3-ring) to high (4- to 6-ring) PAHs has been used to identify pyrogenic (<1) and petrogenic (>1) sources of PAHs in sediments (Budzinski et al., 1997; De Luca et al., 2005). The RLPAHs include NA, 2-MP, ACY, ACE, FL, PH, and AN; the RHPAHs include FLU, PY, BaA, CH, BbF, BkB, BaP, IP, DA, and BP (Table 2). In all Kaohsiung Harbor stations, RLPAHs/RHPAHs ratios were <1, indicating they originated from pyrogenic sources.
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Table 2 PAHs concentration (ng g1 dry weight) and selected molecular ratios in sediments of Kaohsiung Harbor. Site
NA
2-MP
ACY
ACE
FL
PH
AN
FLU
PY
BaA
CH
BbF
BkF
BaP
IP
DA
BP
1 2 3 4 5 6 7 8 9 10 11 12 ERL(a) ERM(a)
142 56 23 24 32 38 4.6 290 153 1076 1567 450 160 2100
53 43 14 17 21 23 12 14 53 763 458 136 70 670
3.4 6.1 2.8 6.4 5.3 6.8 4.8 43 89 154 259 210 44 640
8.1 13 4.4 5.0 9.9 13 9.0 182 69 1132 1067 41 16 500
3.0 34 10 1.9 7.7 4.6 2.5 191 115 960 652 207 19 540
15 28 15 17 18 22 22 659 184 1936 1335 310 240 1500
11 10 0.9 4.2 13 12 5.0 197 6.2 557 681 11 85.3 1100
141 153 48 49 88 111 60 1194 754 1236 1917 927 600 5100
162 197 60 74 115 143 77 1221 685 1068 1703 954 665 2600
58 77 23 24 32 37 18 453 356 456 477 626 261 1600
12 39 58 53 13 21 11 828 85 867 764 123 384 2800
161 234 136 125 150 193 96 2743 2127 1883 1874 2193 – –
90 133 75 62 85 96 55 1548 1196 1062 1057 1237 – –
69 79 38 43 52 67 33 1188 1105 896 912 1178 430 1600
43 34 12 26 44 42 20 786 751 559 646 698 – –
5.1 10 10 4.9 11 18 6.1 344 293 193 237 287 63.4 260
69 66 53 56 68 83 36 961 764 697 593 657 – –
1 2 3 4 5 6 7 8 9 10 11 12 ERL ERM a
RPAHs
RLPAHs
RHPAHs
RLPAHs RHPAHs
PH AN
AN ðPHþANÞ
FLU PY
FLU ðFLUþPYÞ
RCPAHs
TEQcarc
1045 1211 583 591 765 928 472 12,843 8788 15,495 16,201 10,245 4022 44,792
235 190 69 75 106 119 60 1576 670 6578 6020 1365 552 3160
810 1021 514 516 659 809 412 11,267 8118 8917 10,181 8881 1700 9600
0.29 0.19 0.13 0.15 0.16 0.15 0.14 0.14 0.08 0.74 0.59 0.15 – –
1.4 2.7 16.8 4.0 1.4 1.8 4.3 3.3 29.7 3.5 2.0 29.0 – –
0.41 0.27 0.06 0.20 0.42 0.36 0.19 0.23 0.03 0.22 0.34 0.03 – –
0.87 0.77 0.81 0.66 0.76 0.78 0.78 0.98 1.10 1.16 1.13 0.97 – –
0.47 0.44 0.45 0.40 0.43 0.44 0.44 0.49 0.52 0.54 0.53 0.49
464 638 394 366 412 513 256 8067 5928 6054 5915 6302 – –
104 128 60 69 89 117 55 1964 1736 1404 1455 1825 – –
ERL and ERM refers to the effects range low and median (Long et al., 1995).
Fig. 2. PAHs composition of sediments of Kaohsiung Harbor, 2,3-ring: NA, 2-MP, ACY, ACE, FL, PH, AN. 4-ring: FLU, PY, BaA, CH. 5,6-ring: BbF, BkF, BaP, IP, DA, BP.
Other isomeric ratios have been used to assess the pyrogenic or petrogenic sources of PAHs in sediments: (a) PH/AN (Soclo et al., 2000; Magi et al., 2002) or alternatively, AN/(PH + AN) ratio (Baumard et al., 1998; Yunker et al., 2002; Zhang et al., 2004; Li et al., 2006; Qiao et al., 2006); (b) FLU/PY (Magi et al., 2002); and (c) FLU/(FLU + PY) (Magi et al., 2002; Guinan et al., 2001). The PH is thermodynamically more stable and its prevalence over AN indicates that the sediment PAHs were mainly from petrogenesis activities. Indeed, petroleum product usually exhibits a quite high PH/AN ratio. Therefore, if the PH/AN ratio is higher than 10 (or AN/(PH + AN) > 0.1), it reveals that the sediment is mainly contaminated by petrogenic inputs. Moreover, if the PH/AN ratio is less than 15 (or AN/(PH + AN) < 0.1), it typically reveals that the PAH source is from pyrolytic activities (Baumard et al., 1998;
Qiao et al., 2006). As showed in Table 2, the ratios of PH/AN and AN/(PH + AN) at Stations 3, 9, and 12 were higher than 15 and lower than 0.1, respectively, this indicates that the main PAH source was petroleum products. Other stations were lower than 10 and higher than 0.1, respectively, this implies that the PAH source could be combustion activities. The FLU/PY and FLU/(FLU + PY) ratios are also useful indicators in evaluating the attribution of PAH pollution in sediment (Guinan et al., 2001; Magi et al., 2002; Zhang et al., 2004; Li et al., 2006). Baumard et al. (1998) concluded that the source of contamination is mainly from pyrolytic sources if the ratio of FLU/PY is higher than 1. Their results also revealed that petrogenic discharges would cause the increase in PAH in sediments if the ratio of FLU/ PY is less than 1 (Baumard et al., 1998). In this study, the ratios of FLU/PY at Stations 9–11 were higher than 1 (Table 2), this indicates that the main PAH source was petroleum products. The other stations were lower than 1 (Table 2), indicating they originated from combustion activities. Moreover, when FLU/(FLU + PY) is higher than 0.5, biomass combustion (grass, wood, or coal combustion) would cause the increase in PAHs in sediments (Budzinski et al., 1997; Yunker et al., 2002; Zhang et al., 2004; Qiao et al., 2006). However, if the ratio of FLU/(FLU + PY) is between 0.4 and 0.5, PAHs are mainly from combustion of petroleum; if the ratio is less than 0.4, typical petroleum contamination is usually the cause of PAHs in sediments (Budzinski et al., 1997; Yunker et al., 2002; Zhang et al., 2004; Qiao et al., 2006). As showed in Table 2, the ratios of FLU/(FLU + PY) at Stations 9–11 were higher than 0.5, this indicates that the main PAH source was biomass combustion. The other stations were between 0.4 and 0.5, indicating they originated from petroleum combustion. Results of PAH isomeric ratios were gives an inconsistent picture of the origins in Kaohsiung harbor. With the evaluation of both PH/AN and FLU/PY ratios, misleading estimate of PAH sources can be prevented (Tam et al., 2001; Yunker et al., 2002; Zhang et al.,
421
C.-W. Chen, C.-F. Chen / Marine Pollution Bulletin 63 (2011) 417–423 Table 3 PAHs concentrations in sediments at different locations. Location
na
RPAHs (ng g1 dry weight)
Pollution levelb
References
Kaohsiung Harbor, Taiwan Xiamen Harbor, China Victoria Harbor, Hong Kong Incheon Harbor, Korea Hsin-ta Harbor, Taiwan Baltimore Harbor, USA Boston Harbor, USA Olbia Harbor, Italy Genoa-Voltri Harbor, Italy Taranto Gulf, Italy Norwegian Harbor, Norway Izmit Bay, Turkey Gemlik Bay, Turkey Commercial ports from Spain Santander Bay, Northern Spain Western Harbor, Alexandria, Egypt
17 9 9 23 30 21 16 16 16 8 16 17 14 12 16 20
472–16,207 2900–61,000 1200–14,000 12–1400 1156–3382 2944–29,590 7300–358,000 160–770 4500–20,800 335–5193 2000–76,000 2500–25,000 50.8–13,482 260–66,710 20–25,800 8–131,150
Moderate to very high High to very high High to very high Low to moderate High High to very high Very high Moderate High to very high Moderate to very high High to very high High to very high Low to very high Moderate to very high Low to very high Low to very high
This study Hong et al. (1995) Hong et al. (1995) Kim et al. (1999) Fang et al. (2003) Pereira et al. (1999) Wang et al. (2001) De Luca et al. (2005) Salvo et al. (2005) Storelli and Marcotrigiano (2000) Oen et al. (2006) Tolun et al. (2001) Ünlü and Alpar (2006) Casado-Martínez et al. (2006) Viguri et al. (2002) Mostafa et al. (2003)
a
n: number of PAH compounds analyzed in each study. Pollution levels are assigned as low: 0–100 ng g1 dry weight, moderate: 100–1000 ng g1 dry weight, high: 1000–5000 ng g1 dry weight, very high: >5000 ng g1 dry weight (Baumard et al., 1998). b
PAHs (i.e., BaA, CH, BbF, BkF, BaP, IP, and DA), RCPAHs (Qiao et al., 2006; Savinov et al., 2003; Nadal et al., 2004). The RCPAHs concentration varied from 256 to 8067 ng g1 dry weight, with a mean concentration of 2942 ng g1 dry weight (Table 2). The RCPAHs accounted for 37% to 68% of RPAHs in sediments of Kaohsiung Harbor. The potential toxicity of sediment was evaluated using the total toxic benzo[a]pyrene equivalent (TEQcarc) (Qiao et al., 2006; Savinov et al., 2003; Nadal et al., 2004). The TEQcarc for all CPAHs was calculated using the following equation:
TEQ carc ¼
X
Ci TEFcarc i
ð1Þ
i
Fig. 3. PAHs cross plots for the ratios of FLU/(PY + FLU) vs. AN/(AN + PH).
2004; Li et al., 2006). Fig. 3 shows the distribution AN/(PH + AN) and FLU/(FLU + PY) ratios in sediments of Stations 1–12. Ratios of FLU/(FLU + PY) in sediment of nine stations (Stations 1–8 and 12) ranged between 0.4 and 0.5 indicate that petroleum combustion could be a possible source of PAHs; ratios of FLU/(FLU + PY) at Stations 9–11 were higher than 0.5 suggesting that grass, wood, and coal combustion would make the possible contributions to PAHs. Results from the ratio calculations suggest that Stations 9–11, located in the industrial area, had different PAH ratios from other stations because coal burning was used for the energy source in this area. In addition, results show that ratios of AN/(PH + AN) were lower than 0.1 at Stations 3, 9 and 12; ratios of FLU/(FLU + PY) were between 0.4 and 0.5 at Stations 3 and 12, and higher than 0.5 at Station 9. This indicates that different PAH sources occurred in this area. 3.3. Sediment potential human toxicity and biological effects based on PAHs The assessment of sediment toxicity in this study was performed based on the total concentration of potentially carcinogenic
where, Ci is the carcinogenic PAHs concentration (ng g1 dry weight); TEFcarc (toxic equivalency factors) is the toxic factor of cari cinogenic PAHs relative to benzo[a]pyrene (BaP). Among all known potentially carcinogenic PAHs, benzo[a]pyrene is the only PAH for which toxicological data are sufficient for derivation of a carcinogenic potency factor (Peters et al., 1999). According to US EPA (1993), TEFs for BaA, CH, BbF, BkF, BaP, IP, and DA are 0.1, 0.001, 0.1, 0.01, 1, 0.1, and 1, respectively. In this study, the total TEQcarc values of sediment samples varied from 55 to 1964 ng TEQ g1 dry weight, with the mean value of 750 ng TEQ g1 dry weight. The higher total TEQcarc values were found at Stations 8–12 (varied from 1404 to 1964 ng TEQ g1 dry weight) located in the south Kaohsiung Harbor. The TEQcarc found in sediments from Kaohsiung Harbor were lower than in sediments from Naples harbor (Italy), but were higher than in Barents Sea (Russia) and Meiliang Bay (China) (Table 4). Fig. 4 shows the CPAHs and relative contents of BaPeq dose in total TEQcarc. Among different CPAHs, contribution to the total TEQcarc decreased in the following order: BaP (61.2 ± 3.6%), BbF (15.5 ± 2.6%), DA (12.9 ± 4.2%), IP (5.9 ± 1.5%), BaA (3.6 ± 1.1%), BkF (0.9 ± 0.1%), and CH (0.04 ± 0.03%). A widely used sediment toxicity screening guideline of the US National Oceanic and Atmospheric Administration provides two target values to estimate potential biological effects: effects range low (ERL) and effect range median (ERM) (Long et al., 1995). The guideline was developed by comparing various sediment toxicity responses of marine organisms or communities with observed PAHs concentrations in sediments. These two values delineate three concentration ranges for each particular chemical. When the concentration is below the ERL, it indicates that the biological effect is rare. If concentration equals to or greater than the ERL but below the ERM, it indicates that a biological effect would occur
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C.-W. Chen, C.-F. Chen / Marine Pollution Bulletin 63 (2011) 417–423
Table 4 CPAHs concentrations and TEQcarc in sediments at different locations.
a
Location
na
RCPAHs (ng g1 dry weight)
TEQcarc (ng TEQ g1 dry weight)
References
Kaohsiung Harbor, Taiwan Meiliang Bay, China
7 7
256–8067 621–2737
55–1964 94–845
This study Qiao et al. (2006)
Barents Sea, Russia Vardø Harbor Vadsø Harbor Jarfjord Korsfjord Kola Bay Guba Pechenga
5 5 5 5 5 5
870–1412 68–124 30–70 30–134 240–1211 63–864
472–733 40–66 19–35 18–60 71–583 18–300
Savinov Savinov Savinov Savinov Savinov Savinov
Naples harbor, Italy Commercial area Eastern area External area Industrial area Shipping area Touristic area
6 6 6 6 6 6
3–9102 3–5047 3–4109 3–6316 21–7832 3–9879
6–4528 2–1973 2–1629 4–4723 45–3578 10–2250
Sprovieri Sprovieri Sprovieri Sprovieri Sprovieri Sprovieri
et et et et et et
al. al. al. al. al. al.
et et et et et et
(2003) (2003) (2003) (2003) (2003) (2003)
al. al. al. al. al. al.
(2007) (2007) (2007) (2007) (2007) (2007)
n: number of CPAH compounds analyzed in each study.
centrations exceeded ERL, and that could cause acute biological damage. The possible source of PAHs in the industrial zone dock could be coal combustion, while petroleum combustion could be the possible source in the other zones. Results from this study suggest that these industrial activities played important roles in the leaching of PAHs into the environments.
Acknowledgements This work was supported by the Kaohsiung City Marine Bureau, Taiwan. The authors would like to thank the personnel of the Kaohsiung City Marine Bureau for their support throughout this project.
References Fig. 4. Relative contents of toxic benzo[a]pyrene doses of potentially carcinogenic PAHs in sediments from the Kaohsiung Harbor.
occasionally. Concentrations at or above the ERM indicate that a negative biological effect would frequently occur. Table 2 shows the measured concentrations of PAHs in comparison with the ERM and ERL values. The RLPAHs, RHPAHs and RPAHs at Stations 1–7 were below the ERL but Stations 8–12 were above the ERL and below ERM. For an individual PAH, Stations 1–7 were below the ERL. This indicates that biological effects would rarely occur. However, most PAHs were above the ERL but below ERM in Stations 8–12, which indicates that biological effects would occur occasionally. Moreover, some PAHs exceeded ERM in Stations 8–12 (e.g., Stations 8, 9 and 12: DA, Station 10: 2-MP, ACE, FL and PH, and Station 11: ACE and FL), which indicates that biological effect would occur frequently.
4. Conclusions PAHs were detected in sediment samples collected from various locations in Kaohsiung Harbor. The highest levels of PAHs were recorded for sediment samples collected in the vicinity of industrial zone docks situated in the south Kaohsiung Harbor where the con-
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