Distribution of Phthalate Esters in Sediments of ...

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Distribution of Phthalate Esters in Sediments of Kaohsiung Harbor, Taiwan a

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Chiu-Wen Chen , Chih-Feng Chen & Cheng-Di Dong

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Department of Marine Environmental Engineering, National Kaohsiung Marine University, Kaohsiung, Taiwan, Republic of China Accepted author version posted online: 28 Aug 2012.

To cite this article: Chiu-Wen Chen , Chih-Feng Chen & Cheng-Di Dong (2013): Distribution of Phthalate Esters in Sediments of Kaohsiung Harbor, Taiwan, Soil and Sediment Contamination: An International Journal, 22:2, 119-131 To link to this article: http://dx.doi.org/10.1080/15320383.2013.722141

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Soil and Sediment Contamination, 22:119–131, 2013 Copyright © Taylor & Francis Group, LLC ISSN: 1532-0383 print / 1549-7887 online DOI: 10.1080/15320383.2013.722141

Downloaded by [National Kaohsiung Marine University], [Chiu-Wen Chen] at 10:34 12 January 2013

Distribution of Phthalate Esters in Sediments of Kaohsiung Harbor, Taiwan CHIU-WEN CHEN, CHIH-FENG CHEN, AND CHENG-DI DONG Department of Marine Environmental Engineering, National Kaohsiung Marine University, Kaohsiung, Taiwan, Republic of China The major objectives of this research are to study the species and concentration of phthalate esters (PAEs), an organic endocrine disruptor, in the sediments of Kaohsiung Harbor, Taiwan. Twenty monitoring stations were installed in the waterways of Kaohsiung Harbor to collect sediment samples for analyzing six species of PAEs. Results of laboratory analyses show that concentrations of PAE6 in the harbor sediment are between 0.40 and 34.8 mg/kg with an average of 5.02 mg/kg. Among all chemicals, di-(2-ethylhexyl) phthalate (DEHP) is the major species that constitutes 92% of all chemicals found in the sediment. Where the spatial distribution of the chemicals is concerned, all rivers (i.e., Love River, Canon River, and Salt River) show the highest concentrations near the mouth where they discharge into the harbor. This indicates that major sources of pollution originate from the upstream municipal and industrial wastewater discharges. Distributions of PAEs during both wet and dry seasons show that PAEs are more easily disbursed in the receiving sea water, leading to a wider range of chemical distribution, and hence most of the chemicals are accumulated in the harbor water channel. The assessment of ecological toxicity indicates that concentrations of the 88% DEHP found in the sediment are higher than environmental risk limits (ERLs), implying that the Kaohsiung Harbor sediments pose potential risks to the local ecological system. Hence, an effective PAE management and control strategy must be developed and implemented in order to improve the harbor sediment quality, and keep the harbor ecological environment free from the interference of chemicals that interrupt endocrine hormones. Keywords Phthalate esters (PAEs), endocrine disruptors, di-(2-ethylhexyl) phthalate (DEHP), sediment, harbor

Introduction Phthalate esters (PAEs) are commonly found in domestic and industrial products because PAEs with low molecular weights, e.g. dimethyl phthalate (DMP), diethyl phthalate (DEP), di-isobutyl phthalate (DIBP), and di-n-butyl phthalate (DBP), are often used as ingredients for cosmetic and personal hygienic products. Additionally, DIBP and DBP are also used in the preparation of epoxy resins, cellulose esters, and special bonding agents. PAEs with long and branching chains such as butylbenzyl phthalate (BBP), di-cyclohexyl phthalate

Address correspondence to C.W. Chen, Associate Professor, Department of Marine Environmental Engineering, National Kaohsiung Marine University, Kaohsiung 81157, Taiwan. E-mail: [email protected]

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(DCHP), di-n-octyl phthalate (DOP), di-n-nonyl phthalate (DNP), and di-(2-ethylhexyl) phthalate (DEHP) have been widely applied as non-reactive agents (i.e., plasticizers) in plastic polymers. DEHP constitutes about 50–60% of the total consumption of all the aforementioned chemicals (Liu et al., 2010). Additionally, plasticizers may constitute 10–60% of 15 billion tons of annual plastic products (Zeng et al., 2009). PAEs bind physically with plastic but do not react chemically with the molecular bonds of plastic polymers. Hence, PAEs may be discharged into the environment directly when raw materials and products are produced and applied so that PAEs commonly exist in the various environmental media such as food, air, water, soil, sediment, and living creatures (Fromme et al., 2002; Yuan et al., 2002; Lin et al., 2003; Klamer et al., 2005; Vethaak et al., 2005; Xie et al., 2005; Peijnenburg and Struijs, 2006; Teil et al., 2006; Fernandez et al., 2007). Results of recent research have led to defining several PAEs as “environmental hormones” because they interrupt biological hormones (Kambia et al., 2001) to cause great impact on living creatures. The long-term accumulation of PAEs in humans may interfere with the secretion of hormones and the normal function of the nerve and immune systems, causing significant damage. Several countries have taken steps to manage risks associated with phthalates. For example, eight PAEs, i.e. DBP, DIBP, BBP, di-n-pentyl phthalate (DPP), DEHP, DOP, di-isononyl phthalate (DINP), and di-isodecyl phthalate (DIDP)), have been included in the list of priority pollutants compiled by the U.S. Environmental Protection Agency (USEPA) (USEPA, 2009) with stringent MCLs (maximum contaminant levels); the MCL for DEHP is 6 μg/L (Liu et al., 2010). The European Commission banned the use of DEHP, DBP, and BBP totally in PVC and other plasticized materials for making any toys and childcare articles that might be placed in the mouth by children, even if this is unlikely (European Parliament, 2005). Thus, PAE pollution has become an environmental pollution issue of serious concern. According to reports, global water bodies and sediments contain about 0.3–300 μg/L and 0.1–100 μg/g PAEs (Sung et al., 2003) on average. In Taiwan, although major research efforts on PAE pollution have been directed toward stream water bodies and sediments (Yuan et al., 2002), very few have been carried out on PAE distribution in harbor sediments. Therefore, the objective of this research is to study the concentration and distribution of PAEs in Kaohsiung Harbor channel sediments using on-site monitoring and sampling so that the major sources and latent impacts of the PAEs contained in the sediment can be accessed, in addition to establishing a database on the sediment PAEs.

Methods and Procedures Study Area and Sampling Locations Kaohsiung Harbor is located on the southwest shore of Taiwan; it controls the major shipping route from the Indian Ocean to northwest Asia between the Taiwan Strait and Bashi Strait. It is the largest international harbor in Taiwan with a total quantity of annual import and export products ranking thirteenth in the world. The harbor is a narrow bay that is 12 km long and 1.0 to 1.5 km wide with a water depth ranging from 11 to 16 m. The total water area is 162.36 km2 (KHB, 2011), and the harbor receives effluents from four streams, i.e. Love River, Jen-Gen River, Canon River, and Salt River, which flow through metropolitan Kaohsiung. Additionally, the harbor also receives municipal wastewater from the 1.5 million residents living in metropolitan Kaohsiung, municipal surface runoff, and discharges from industries and harbor water crafts and vessels. These sources of pollution


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Figure 1. Study area and sampling locations (Color figure available online).

may lead to high concentrations of organic substances accumulated in the harbor sediment, especially organic substances of low solubility such as PAEs. In this research, 20 sampling points were established in the harbor channel, as shown in Figure 1, for collecting sediment samples. The sampling points were located at the river mouth (#4: Love River, #6: Canon River, #10: Jen-Gen River, and #18: Salt River), channels entering and leaving the harbor (#1: First Harbor, and #19, 20: Second Harbor), and major navigation channel (#2, #3, #5, #7, #8 and #9: north navigation channel, and #11–17: south navigation channel). These sampling points were selected based in order to collect representative samples to cover the whole harbor water body evenly, and represent the possible pollution sources so that an overall evaluation of the harbor sediment pollution can be carried out. Details about the sampling stations are listed in Table 1.

Sample Collection On-site sampling of all 80 surface sediments was done on board a fishing boat in March, May, August, and October 2006 at 20 locations in Kaohsiung Harbor (Figure 1). A global positioning system (GPS) was employed to identify the precise location of each site. After collection with a 6”×6”×6” Ekman Dredge grab sampler (Jae Sung International Co., Taiwan), the surface sediment (0–10 cm) samples were stored in glass jars (sealed with a Teflon-lined cap), which were submerged in crushed ice for transportation back to the laboratory. In the laboratory, the samples were freeze-dried for 72 h, ground to pass through a 0.5 mm sieve, fully homogenized, and then dried. The dried sediments were stored at

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C.-W. Chen et al. Table 1 Sample information of surface sediments from Kaohsiung Harbor


Station Latitude (North) Longitude (East) Water depth (m) 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20

22◦ 37.173 22◦ 37.023 22◦ 36.873 22◦ 37.130 22◦ 36.582 22◦ 35.947 22◦ 36.598 22◦ 35.984 22◦ 35.448 22◦ 34.976 22◦ 34.389 22◦ 33.967 22◦ 33.580 22◦ 33.445 22◦ 33.310 22◦ 33.116 22◦ 32.866 22◦ 32.683 22◦ 33.305 22◦ 33.166

120◦ 15.294 120◦ 16.005 120◦ 16.516 120◦ 16.958 120◦ 17.147 120◦ 17.429 120◦ 16.366 120◦ 16.664 120◦ 17.039 120◦ 17.476 120◦ 17.884 120◦ 18.296 120◦ 18.628 120◦ 18.970 120◦ 18.675 120◦ 19.056 120◦ 19.332 120◦ 19.675 120◦ 18.264 120◦ 17.983

10.9–11.4 9.8–10.7 9.7–10.8 4.6–6.6 10.3–11.5 4.6–6.4 11.4–11.8 10.9–11.7 11.2–11.9 11.3–14.7 14.3–15.4 14.4–16.8 14.4–16.2 14.3–14.6 15.9–16.3 14.6–16.6 13.8–14.4 13.4–16.7 17.1–185 16.4–17.6

Description First Harbor North Navigation Channel North Navigation Channel Love River Mouth North Navigation Channel Canon River Mouth North Navigation Channel North Navigation Channel North Navigation Channel Jen-Gen River Mouth South Navigation Channel South Navigation Channel South Navigation Channel South Navigation Channel South Navigation Channel South Navigation Channel South Navigation Channel Salt River Mouth Second Harbor Second Harbor

−20◦ C in amber glass bottles prewashed with n-hexane and covered with solvent-rinsed aluminum foil to be processed and analyzed later.

Sample Preparation and Analyses Analyses of particle size were done using a laser particle analyzer (Coulter LS100) that is effective for particle sizes ranging from 0.4 to 900 μm. Organic matter (OM) was analyzed according to Standard Method 209F. PAEs contained in the sediment samples were analyzed using the following procedures. Five grams (accuracy ± 0.0001 g) of dry homogenized sediment sample was placed in a clean centrifuge tube; 10 mL of a 1:1 (v/v) acetone/n-hexane and 0.2 mL of 10 mg/L surrogate standard mixture solutions (2-Fluorobiphenyl and 4-Terphenyl-d14 ) were added, and the tube was sealed with a Teflonlined screw cap. A blank without the sediment sample was prepared following the same procedure; a check standard mixture was prepared by adding 1:1 (v/v) acetone/n-hexane to another blank. The spiked sample was prepared by adding the standard mixture to the sediment sample. All samples were vortexed for 1 min; the mixture was ultrasonicated for 15 min and then centrifuged for 10 min at 2000 rpm for extracting PAEs. The organic layer containing the extracted compounds was siphoned out with a Pasteur pipette and the sediment was re-extracted twice with 10 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 0.8 mL using a gentle stream of nitrogen, added to 0.2 mL of 5 mg/L internal standard (Acenaphthene-d10 ,


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Phenanthrene-d10 , and Chrysene-d12 ) mixture solutions, and analyzed using gas chromatography (GC) with a 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 μm), and an Agilent 5975 mass selective detector (MSD) was used to separate and quantify the PAE compounds. The samples were injected in splitless mode at 280◦ C. The column temperature was initially held at 35◦ C for 2 min, raised to 140◦ C at a rate of 5◦ C/min, then to 300◦ C at a rate of 10◦ C/min, and held at this temperature for 15 min. Detector temperature was kept at 280◦ C. Helium was used as a carrier gas at a constant flow rate of 1.5 mL/min. Mass spectrometry was acquired using the electron ionization (EI) and scan model that has a scanning range of 35 to 500 amu at 1.6 times per second. Identity of PAEs in the samples was confirmed by the retention time and abundance of quantification/confirmation ions in the authentic PAH standards (AccuStandard M-8270IS-WL-4X). Six PAE components were quantified using the response factors related to the respective internal standards based on a five-point calibration curve for individual compounds. In this study, the concentrations of PAE compounds were expressed on a dry-weight basis. Quality Assurance and Quality Control (QA/QC) The reliability of the analysis results were maintained by performing QA/QC on the various procedures, including: (1) developing calibration curve; (2) using procedure blank; (3) establishing lower limit of detection; (4) accessing precision; and (5) calculating recovery percentage. All relative standard deviation (RSD) for PAEs analyzed are less than 15%. Hence, the relative response factors are considered as constant so that the average response factor can be used for conducting quantitative analyses. The procedural blank values were always smaller than the detection limit. For the various chemicals, lower detective limits (3SD) are between 0.004 and 0.008 mg/kg; quantification limits (10SD) are between 0.013 and 0.027 mg/kg; average relative errors for repeated analyses are between 5.1 and 11.3%; recovery efficiencies for the surrogate standards are between 89.2 ± 7.6% (2Fluorobiphenyl), and 99.4 ± 9.4% (4-Terphenyl-d14 ); and the average recovery efficiencies for the spiked samples are between 88.6 and 114.3%.

Results and Discussion PAEs Contained in the Harbor Sediments Table 2 lists concentrations of PAEs contained in Kaohsiung Harbor sediments. There are obvious differences in concentrations of six PAEs analyzed (PAE6 ). On a yearly basis, PAE6 concentrations range between 0.40 and 34.8 mg/kg with an average of 5.02 mg/kg. PAEs are found in all sediment samples collected from the harbor, indicating that they are common pollutants in the harbor environment. Among the six PAE species analyzed in this research, DEHP is detected in all sediment samples with concentrations between 0.40 and 34.8 mg/kg, and an average of 4.90 mg/kg. For DBP, the detectable percentage is 38.8%, and its concentrations are between 0.013 and 1.31 mg/kg with an average of 0.29 mg/kg. For DOP, the detectable percentage is 10%; its concentrations are between 0.013 and 0.60 mg/kg with an average of 0.14 mg/kg. The other three PAE species (i.e., DMP, DEP, and BBP) have the lowest concentrations of below detectable limits in all sediment samples. These results indicate that the major PAE species in the harbor sediments are mostly DEHP, followed by DBP and DOP (Figure 2). Results

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0.1 8.9 1.1 0.8 NDd ND ND ND 0.40 ND 0.40

Sand (%) Silt (%) Clay (%) Organic matter (%) DMP (mg/kg) DEP (mg/kg) DBP (mg/kg) BBP (mg/kg) DEHP (mg/kg) DOP (mg/kg) PAE6 (mg/kg)

90.1 86.1 15.9 15.8 ND ND 1.31 ND 34.80 0.60 34.82

Max. 30.3 60.8 9.0 3.1 — — 0.29 — 4.90 0.14 5.02

Aver.a

b

Aver.: average. SD: standard deviation. c DF: detection frequency (%). d ND: non-detectable (lower than detectable limit).

a

Min.

Item 24.8 21.4 3.7 2.0 — — 0.32 — 5.97 0.20 6.03

SDb

Yearly (n = 80)

— — — — 0 0 38.8 0 100 10.0 100

DFc 0.1 10.2 1.1 0.8 ND ND ND ND 1.13 ND 1.13

Min. 88.7 86.1 15.9 15.8 ND ND 1.31 ND 34.80 0.60 34.82

Max. 31.9 58.8 9.3 3.1 — — 0.31 — 7.20 0.18 7.44

Aver. 26.5 22.7 4.1 2.5 — — 0.33 — 7.20 0.24 7.22

SD

Dry season (n = 40)

— — — — 0 0 70.0 0 100 12.5 100

DF 4.8 8.9 1.1 1.5 ND ND ND ND 0.40 ND 0.40

Min.

Table 2 Distribution of particle size, organic matter, and concentrations of PAEs

90.1 83.5 13.7 8.1 ND ND 0.16 ND 16.80 0.15 16.80

Max.

28.6 62.8 8.6 3.0 — — 0.06 — 2.59 0.07 2.60

Aver.

23.1 20.2 3.3 1.3 — — 0.09 — 3.09 0.07 3.09

SD

Wet season (n = 40)


— — — — 0 0 7.5 0 100 7.5 100

DF


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Figure 2. Concentration percentages of major PAE species contained in Kaohsiung Harbor sediments.

of several environmental surveys published in literature also indicate that DEHP and DBP are the major PAE species with the highest concentrations (Yuan et al., 2002; Zeng et al., 2008; Zeng et al., 2009; Liu et al., 2010). The abundant distribution of DEHP and DBP in the harbor sediment conforms to the observations that they are the most manufactured PAE species. In this research, Pearson correlations of the particle size, OM, and PAEs concentration in the sediment of Kaohsiung Harbor were examined. The results show that there is no significant correlation between the concentrations and the two factors. This observation indicates that the PAEs in water and sediment phases are not at equilibrium (Sha et al., 2007). In addition, the differences of PAE content in Kaohsiung Harbor sediments are mainly caused by different pollution sources, such as various factories, residences, and discharge outlets. Wide variations among the species and quantities of PAEs have been reported by various researchers; hence, a direct comparison of the total PAE concentrations for different regions is not a simple task. Among the many PAE species, DEHP and DBP are often the target chemicals for study because they have higher concentrations than other PAE species. Additionally, DEHP and DBP are also the predominant PAEs found in Kaohsiung Harbor sediments. Therefore, concentrations of DEHP and DBP obtained in this research will be compared with those published in the literature to understand how serious the problem is of PAE pollution in Kaohsiung Harbor. As shown by the data listed in Table 3, Kaohsiung Harbor has a similar DBP level to that of the North Sea, the Netherlands (Vethaak et al., 2005), and Qiantang River, China (Zhang et al., 2003), higher DBP level than Jinshan, China (Zhang et al., 2003), and lower DBP level than Ygnzi River (Wuhan section) (Wang et al., 2008), and middle and lower Yellow River (Sha et al., 2007). Where DEPH is concerned, Kaohsiung Harbor has a similar concentration as or slightly higher concentration than most other regions, but a much lower concentration than the Yangzi Raiver (Wuhan section) (Wang et al., 2008), and River Aire, UK (Long et al., 1998). Spatial Distribution of PAEs in Kaohsiung Harbor Sediments Figure 3 shows the PAE6 spatial distribution in Kaohsiung Harbor sediments. The PAE6 concentrations in the samples collected at the mouth of the four contributing rivers are the highest of 15.0 ± 9.3 mg/kg for Canon River, followed by 14.0 ± 15.6 mg/kg for Salt River and 6.7 ± 2.8 mg/kg for Love River. Canon River, Salt River, and Love River discharge into the deeper portion of the harbor where the flow is sluggish so that the fresh river water is not easily mixed with sea water. Hence, the pollutants brought over by river water are mostly accumulated at the river mouth. In comparison, the Jen-Gen River mouth is located

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Table 3 Comparisons of PAEs concentrations in sediments between Kaohsiung Harbor and other regions


Region

DBP (mg/kg)

DEHP (mg/kg)

References

NAa NA NA 0.3–30.3

0.49–15.0 0.84–31.0 7.89–115 0.5–23.9

Tan (1995) Long et al. (1998) Long et al. (1998) Yuan et al. (2002)

0.019–0.05 NDb–0.605 NA

0.032–0.048 ND–0.131 1.0–2.0

3.625–72.15

5.35–258.5

Zhang et al. (2003) Zhang et al. (2003) Yuwatini et al. (2006) Sha et al. (2007)

11.7–246.0

48.0–232.5

Wang et al. (2008)

NA 0.034–1.0

0.10–20.22 < 0.123–7.6

A

0.003–0.18

German Bight, Germany Tuas Bay, Singapore Hudson’s Bay, Canada Spanish coast, Spain

NA NA NA NA

0.045–0.22 0.89–2.79 0.0038–0.231 0.19–2.6

Hamilton Harbour, Ontario, Canada Kaohsiung Harbor, Taiwan

NA

6.5–29.7

ND–1.13

0.4–34.8

Lin et al. (2009) Vethaak et al. (2005) Peterson and Freeman (1982) Ernst et al. (1988) Chee et al. (1996) Morin (2003) Antizar-Ladislao (2009) McDowell and Metcalfe (2001) This study

Klang River, Malaysia River Trent, UK River Aire, UK Zhonggang, Keya, Erren, Gaoping, Donggang, Danshui Rivers, Taiwan Jinshan, China Qiantang River, China Furu River, Japan Middle and lower Yellow River, China Yangtze River (Wuhan section), China Houjing River, Taiwan North Sea, the Netherlands Chesapeake Bay, USA

a NA: not available. b ND: non-detectable.

in the middle section of the harbor; the shallower water depth favors the exchange between river water and sea water so that the pollutants move with sea current to be dispersed toward the First Harbor or the Second Harbor. Therefore, except for the Jen-Gen River, all of the other three rivers have higher PAE6 concentrations in the mouth than the major navigation channels (south navigation channel: 4.8 ± 5.2 mg/kg, and north navigation channel: 3.6 ± 2.7 mg/kg), and the entering and exiting harbors (First Harbor: 1.8 ± 1.1 mg/kg, and Second Harbor: 2.4 ± 3.1 mg/kg). These observations clearly indicate that the upstream pollutants brought over by rivers are the major source of harbor PAE pollution. Those rivers receive a great amount of industrial and domestic PAEs from Kaohsiung city because about 58% of domestic wastewater is discharged directly without adequate treatment. Moreover, several industrial plants (e.g., metal processing, plastics, paint and dye, chemical manufacturing, electronic, motor vehicle plating and finishing, paper and board mills, and foundries)


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Figure 3. Distributions of PAE6 in Kaohsiung Harbor sediments.

discharge industrial wastewater effluents into the tributaries in or adjacent to Kaohsiung city (Chen et al., 2007). Therefore, high levels of heavy metals, organic matter (OM), total nitrogen (TN), total phosphorus (TP), and polycyclic aromatic hydrocarbons (PAHs) in sediments have been reported (Chen et al., 2007; Chen and Chen, 2011; Lin et al., 2011). Additionally, the order of magnitude for PAE6 spatial distribution in Kaohsiung Harbor sediments (Canon River and Love River>North navigation channel>First Harbor; and Salt River>South navigation channel>Second Harbor) reveals that, after discharg into the harbor, PAEs are gradually dispersed toward the direction of entering and exiting harbors. In other words, PAEs will be transported to regions outside the harbor, causing a larger area of PAE pollution. Distribution of PAEs in Harbor Sediments During Wet and Dry Seasons About 88% of the annual precipitation in the study region (Kaohsiung, Taiwan) is concentrated in the wet season of June to September (CWB, 2011). All 80 surface sediment samples were collected in March, May, July, and October 2006, and during the period of June to July 2006 the accumulated rainfall was 1,470 mm, which was 72% of the total annual precipitation (CWB, 2011). The concentrated precipitation may cause pollutants from non-point sources to be carried by surface runoff and stream directly into the harbor and seashore regions, or even the surface sediment at the bottom of river to be scoured up and carried to the downstream river mouth. The research results obtained by Lin et al. (2009) show that, under the continual discharge of pollutants from the source, streams will accumulate the pollutants during dry season. The abundant rainwater during the wet season will erode the river bottom to scour up the surface sediments so that the pollutants accumulated during the dry season will be re-suspended. Hence, the harbor may receive more pollutants from the stream discharges and has higher pollution concentrations during the wet season than the dry season. However, in this research, Kaohsiung Harbor shows higher sediment PAEs during the dry season than the wet season (Figure 4). There are several possibilities for this observation. (1) During the wet season, the storm caused the stream flow to increase abruptly; e.g., 51.1–95.5 m3/s for Love River, 3.4–11.9 m3/s for Canon River, 30.4–138.5 m3/s for Jen-Gen River, and 1.4–22.0 m3/s for Salt River (SSOPWB, 2006).


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Figure 4. Distributions of PAE6 in Kaohsiung Harbor sediments during dry and wet seasons.

Hence, the large quantity of storm water causes a new re-distribution of PAEs in the solid (sediment)/liquid phase, which leads to release of PAEs from the sediments to water bodies. Additionally, the large quantity of fresh stormwater discharged into the harbor lowers the seawater salinity, which is unfavorable to the distribution of PAEs in the sediments (Turner and Rawling, 2000; Xu and Li, 2008). (2) The large quantity of rainwater flowing into the harbor will scour up the surface sediments, re-suspend the settled particles, and transport them into the open sea. On the contrary, the water-borne particles carried by stream water will deposit in the harbor during dry season. Further, the small quantity of base stream flow during the dry season (e.g., 0.7–19.2 m3/s for Love River, 0.9–7.5 m3/s for Canon River, 1.0–14.6 m3/s Jen-Gen River, and 0.4–8.5 m3/s for Salt River (SSOPWB, 2006)) will cause the salinity to increase, which favors the deposit of more PAEs (Turner and Rawling, 2000; Xu and Li, 2008). However, these two considerations may cause PAEs to be dispersed in the sea environment so that this hormone-interfering organic matter becomes widely distributed in the seashore region. The above discussion indicates that the distribution of PAEs in the sediment of Kaohsiung Harbor is affected by three major factors: the inputs of the rivers, the sewage discharge caused by human activities, and the rainfall. Assessment of Ecological Toxicity Effects There has not been much research effort directed toward how aquatic organisms react to the toxicity of contaminants in sediment because of the complexity in the composition of contaminants in sediment (van Wezel et al., 2000). However, a great quantity of data on chemical analyses of the contaminants and their effects on aquatic lives has been converted by many researchers to SQGs (sediment quality guidelines, SQGs) so that the potent toxicity influence of contaminants in sediment on aquatic lives can be evaluated (Zeng et al., 2008). The most commonly cited SQGs include the effects level SQGs that were derived for Florida coastal waters (MacDonald et al., 1996), and the effects range SQGs that were formulated under the National Oceanic and Atmospheric Administration’s (NOAA) National Status and Trends Program (NSTP; Long et al., 1995). However, the effects found in these SOGs can provide the effects level of PAEs found in harbor sediment; the threshold effect level (TEL) and the probable effect level (PEL) are 0.182 mg/kg and 2.647 mg/kg, respectively.


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These SQGs can be used to identify three ranges of chemical concentrations, including a low range of unlikely adverse biological effects (e.g., below the TEL values), a middle range of possible adverse biological effects (e.g., between the TEL and PEL values), and an upper range of likely adverse biological effects (e.g., above the PEL values). Additionally, based on the characteristics of ecological toxicology and environmental chemistry, van Wezel et al. (2000) derived the environmental risk limits (ERLs) for DBP (0.7 mg/kg) and DEHP (1 mg/kg). The ERL for DBP is derived by multiplication by the partition coefficient between organic carbon in the sediment and water (Koc), whereas the ERL for DEHP is derived by a factor based on no observed effect concentrations (NOECs) for Rana arvalis. In this research, the DEHP is between TEL and PEL in 37 samples (45%), and exceeds PEL in 43 samples (54%) with 1–13 times of the PEL. This indicates that the concentration of DEPH found in the Kaohsiung Harbor deposit may cause adverse impact on aquatic lives. Comparisons of ERLs show that in this research, 70 out of the 80 sediment samples (88%) have 1 to 35 times higher ERLs, whereas 31 samples have DBP concentrations ranging from 0.013 to 1.31 mg/kg; three samples have DBP concentrations higher than ERLs (i.e., 0.78, 0.79, and 1.31 mg/kg), with the other 28 samples having DBP concentrations lower than ERLs. Among the 80 sediment samples collected, eight have relatively low DOP concentrations between 0.013 and 0.60 mg/kg. Further, there is no information in the literature showing that DOP interferes with hormone secretion. Hence, only DEHP is considered to cause a risk of environmental pollution for all PAEs contained in the harbor sediment because 88% of DEHP concentrations are higher than ERLs.

Conclusions The PAE6 concentrations for PAEs contained in Kaohsiung Harbor sediments are between 0.40 and 34.8 mg/kg with an average of 5.02 mg/kg. Among these PAE species, DEPH (92%) is the major species, followed by DBP (5%) and DOP (3%). Where the spatial distribution is concerned, the river mouth sediments (i.e., Love River, Canon River, and Salt River) have the highest PAEs concentrations, whereas the entering and exiting harbors have lower PAEs concentrations. This indicates that major pollution sources include the upstream municipal and industrial wastewater discharges. Comparisons of the wet and dry season distributions of PAE concentrations indicate that the wet season favors the dispersion of PAEs in the sea environment, causing the chemicals to be distributed in a larger area. On the contrary, the dry season will cause PAEs to accumulate in the harbor. Results of ecological toxicity evaluation show that 88% of the harbor DEPH concentrations are higher than the ERLs value, so that the sediment PAEs pose a potential risk to the ecological environment. This implies that the harbor must develop and implement an effective strategy for controlling PAEs contained in the harbor sediments in order to improve the quality of harbor sediments and avoid damage to the harbor ecological environment caused by ecological hormone-interfering chemicals.

Acknowledgements This research was supported by the Kaohsiung Harbor Bureau, Taiwan. The authors would like to thank the personnel of the Kaohsiung Harbor Bureau for their support throughout this project.

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