http://www.paper.edu.cn Environ Monit Assess DOI 10.1007/s10661-006-9599-5

Distribution and sources of polycyclic aromatic hydrocarbons in Wuhan section of the River, China

Chenglian Feng & Xinghui Xia & Zhenyao Shen & Zhui Zhou

Received: 7 October 2006 /Accepted: 12 December 2006 # Springer Science + Business Media B.V. 2007

Abstract Polycyclic aromatic hydrocarbons (PAHs) coal and wood burning. PAHs may cause potential are important organic contaminants with great signif- toxic effect but will not cause acute biological effects icance for China, where coal burning is the main in sedimentary environment of the Wuhan section of source of energy. In this study, concentrations, the Yangtze River. distribution between different phases, possible sour- ces and eco-toxicological effect of PAHs of the Keywords Benzo[a]pyrene (BaP) . Polycyclic Yangtze River were assessed. PAHs in water, sus- aromatic hydrocarbons (PAHs) . Sediment . Sources . pended particulate matters (SPM) and sediment Suspended particulate matters (SPM) . Yangtze River samples at seven main river sites, 23 tributary and lake sites of the Yangtze River at the Wuhan section were analyzed. The total concentrations of PAHs in Introduction the studied area ranged from 0.242 to 6.235 μg/l in waters and from 31 to 4,812 μg/kg in sediment. The Polycyclic aromatic hydrocarbons (PAHs) are ubiqui- average concentration of PAHs in SPM was 4,677 μg/kg, tous contaminants in different compartments of higher than that in sediment. Benzo(a)pyrene was environment. Due to their toxic, mutagenic and detected only at two stations, but the concentrations carcinogenic characteristics, PAHs are considered to were above drinking water standard. The PAHs level of be hazardous to the biota and environment. These the Yangtze River was similar to that of some other compounds are generally produced by natural and rivers in China but higher than some rivers in foreign anthropogenic processes and can be introduced into countries. There existed a positive relationship be- the environment through various routes. Anthropo- tween PAHs concentrations and the TOC contents in genic input from incomplete combustion, oil spills, sediment. The ratio of specific PAHs indicated that domestic and industrial wastewater discharges, as PAHs mainly came from combustion process, such as well as atmospheric fallout of vehicle exhaust and industrial stack emission have caused significant : : : accumulation of PAHs in aquatic environment. C. Feng X. Xia (*) Z. Shen Z. Zhou It is believed that the environmental fate and State Key Laboratory of Water Environment Simulation, behavior of PAHs are ultimately determined by their School of Environment, Beijing Normal University, Beijing 100875, People’s Republic of China physicochemical properties and sediment character- e-mail: [email protected] istics, such as organic content, size distribution and C. Feng partition coefficient. For example, a positive linear e-mail: [email protected] relationship has been demonstrated between PAH

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concentrations and the total organic carbon (TOC) in distribution in the three phases of surface water, sediment (Simpson, Mosi, Cullen, & Reimer, 1996). sediments and SPM has not been particularly reported Because of their low water solubility and high in Wuhan section of the Yangtze River. partition coefficients, these compounds are strongly The purpose of the present research was to sorbed to the particles associated with the organic determine the concentration, distribution and sources compounds of solid phase matrix and can be of PAHs in water, sediment and SPM phases of the deposited to the underlying sediments. Wuhan section of the Yangtze River. Samples at In order to minimize or prevent the adverse effects seven main river sites and 23 tributary and lake sites of persistent organic pollutants (POPs), many studies of the section were collected in both high-water and illustrated the fate of PAHs in natural environments. low-water seasons in 2005. PAH concentrations in the PAHs occurrence in some European river waters were three phases were analyzed. Also, molecular-ratio extensively investigated (Manoli & Samara, 1999; method was applied to identify possible sources of Notar, Leskovsek, & Faganeli, 2001; Soclo, Garrigues, PAHs. Finally, the potential toxic effects of PAHs in & Ewald, 2000). In China, the major investigation the Yangtze River were assessed. focused on PAHs concentrations of offshore water and sediments (Mai et al., 2001; Zhou & Maskaoui, 2003). In addition, PAH distribution of inland rivers Materials and methods in some big cities such as Hangzhou and Tianjin were also investigated (Shi et al., 2005; Zhu, Chen, & Wang, Study area 2004). The Yangtze River is the longest river in China and Wuhan section is in the middle reach of the Yangtze the third longest river in the world. It is one of the River. There are many tributaries and lakes converg- most important rivers for water supply and irrigation ing to the main river in the Wuhan section. Among in southern China. Wuhan is the capital city of Hubei them the longest tributary is the , which province and a very important city along the stores almost 10,000,000 kw water energy and mainstream of the Yangtze River. The population of extends as long as 1,577 km with the average water Wuhan is about 7.86 million with a density of 919 flow of 1,640 m3/s. A total of 30 sampling stations in persons/km2. The gross domestic product (GDP) of the mainstream and its tributaries of the Wuhan Wuhan city accounted for about 31% of the whole section were selected (Fig. 1). Seven stations were GDP of Hubei province in 2004. Wuhan section of located in the main river, and 23 stations were located the Yangtze River provides about 764,660,000 m3 in the tributaries. The Jinkou sampling station (Station water per year for domestic, industrial and agricultural 2) represents the inflow to the Wuhan section of the uses of Wuhan city (Hubei Statistical Bureau, 2005). Yangtze River. The Wuhanguan (Station 18) and Wuhan city has five basic industries including Yujiatou (Station 19) stations reflect the PAHs electronic information, automobiles, steel, bioengi- contamination level after the main tributaries (such neering and pharmaceutics. Its industry is becoming as Han River) merge into the main river. The Yangluo stronger and stronger (Xiong, Gan, & Luo, 2004). In sampling station (Station 29) represents contamina- the past few decades, with the industrial and econom- tion level after the Yangtze River flow out of the ic development, water pollution has become more and Wuhan section. more serious, especially for the organic pollution. A few researchers have studied the pollution of organ- Sample collection and pre-treatment ochlorine pesticides (OCPs) and polychlorinated biphenyls (PCBs) of some sections of the Yangtze Samples were collected in July 27–30, 2005 (high River (Jiang, Xu, Martens, & Wang, 2000; H. L. Liu, water season) and December 6–10, 2005 (low water M. Liu, Cheng, & Ou, 2005). As for PAHs pollution, season). Surface sediment samples were collected although a few investigations have been carried out in using a pre-cleaned grab sampler and water samples some sections of the Yangtze River, most of them were collected using 3 l pre-cleaned aluminum jars focused on only one or two phases (Liu et al., 2001; with on-site extraction. Suspended particle samples Xu, Jiang, Wang, Quan, & Martens, 2000). PAH were taken with a press filter (0.8 μm, glass fiber 中国科技论文在线 http://www.paper.edu.cn Environ Monit Assess

Fig. 1 Map of sampling sites in Wuhan section of the Yangtze River (1. Jin- shui, 2. Jinkou, 3. Dongjing River, 4. Zhuankou, 5. Dongfengzha, 6. Baish- azhou, 7. Tangxun River, 8. Houguan Lake, 9. Long- yang Lake, 10. Moshui Lake, 11. Xunsi River, 12. Dong Lake, 13. Yanxi Lake, 14. Changfengqiao, 15. Qinduan River, 16. Guocikou, 17. Jijiazui, 18. Wuhanguan, 19. Yujia- tou, 20. Luojiadun, 21. Lijiadun, 22. , 23. Zhujia River, 24. Xiao Bay, 25. Hou Lake, 26. Tianxingzhou, 27. Qingshangang, 28. Wuhu, 29. Yangluo, 30. Daoshui River)

filter membrane). All sediment, suspended particle Chemicals and water extracts were quickly carried back to the laboratory where they were stored at 4°C before Standard PAHs in a mixture were obtained from state further analysis. standard center (Dr. Ehrenstorfer GmbH PAH-Mix9), Water samples were extracted using a solid-phase these compounds are as follows: naphthalene (Nap), extraction (SPE) system (Supelco). The SPE car- acenaphthylene (Acy), acenaphthene (Ace), fluorine tridges were first conditioned with 10 ml methanol (Fle), phenanthrene (Phe), anthracene (An), fluoran- followed by 10 ml de-ionized water. Two liters of thene (Flu), pyrene (Pyr), benzo(a)anthracene (BaA), water samples were filtered by 0.45 μm membrane chrysene (Chr), benzo(b)fluoranthene (BbF), benzo and then water samples passed through the cartridges (k)fluofanthene (BkF), benzo(a)pyrene (BaP), at a flow rate of 6 ml/min under vacuum. Following dibenzo(a,h)anthracene (DahA), benzo(ghi)perylene extraction, the cartridges were eluted with 10 ml (BghiP), indeno(1,2,3-cd)pyrene (InD). All solvents dichloromethane. The volume of the extracts was used for sample processing and analysis (dichloro-

reduced by N2 blow-down in a water bath and was methane, acetone, hexane petroleum ether, cyclohex- adjusted to 0.5 ml volume with methanol for analysis. ane, methanol) were HPLC grade. Anhydrous sodium After the sediment and SPM were freezing dried, sulfate was of analytical grade and was activated at they were grounded and sieved (100 mesh). Ten 450°C to remove impurities before using. grams of sediment was extracted three times based on the modified procedure of International Organization Analytical method for Standardization (1998); the detailed procedure for the pretreatment of sediment and SPM samples has The physicochemical properties of sediment were been described in the previous research (Li, Xia, & detected at the Analytical and Testing center. Particle Yang, 2006). size was measured using Laser Particle Size Ana- 中国科技论文在线 http://www.paper.edu.cn Environ Monit Assess

lyzer (Mastersizer 2000, UK). TOC was measured Quality control using Total Organic Carbon Analyzer (Elementar, Germany). A strict regime of quality control was operated in the The PAHs extracts of the water, sediment and SPM experiment. Quantification was performed by the samples were analyzed by high-performance liquid external standard method using a 16 PAHs reference chromatography (HPLC) using a Varian PAH special material mixture (16 PAHs, Dr.Ehrenstorfer GmbH column (Varian ChromSper 5 PAHs 250×4.6 mm) PAH-Mix9), with correlation coefficients for calibra- installed in a liquid chromatogram (Waters1525, tion curves all higher than 0.993. Recoveries of 16 USA) with fluorescence detector (Waters 474). PAHs ranged from 87.2 to 92.8% with Nap relatively Excitation wavelengths were automatically set by a low (64.4%) in water phase, and from 70.4 to 94.8% time program. The mobile phases were HPLC-grade in sediment. PAH concentrations were recovery- methanol and de-ionized water in a linear gradient corrected. Field and analytical duplicates were ana- program. The temperature of the column oven was lyzed on 20% of the samples taken. kept under the room temperature (around 25°C). Detailed instrumental conditions were as follows: eluent A, methanol (HPLC grade.); eluent B, de- Results and discussion ionized water plus methanol (1:1,v/v); methanol gradients were 75 to 100%; flow rate, 1 ml/min. PAHs contents in water phase Gradients were 50 to 100% A using curve 6 in 35 min, hold 10 min using curve 3, then back to We only analyzed PAHs concentrations in the water initial conditions. Before sample analysis, relevant phase in high water season. As shown in Table 1, standards were analyzed to check column perfor- concentrations of PAHs in water samples ranged from mance. Peak height and resolution and the limit of 0.322 to 6.235 μg/l with a mean value of 2.095 μg/ detection, with each set of samples to be analyzed, a l in the main river, and ranged from 0.242 to solvent blank, a standard mixture and procedural 1.379 μg/l with a mean value of 0.681 μg/l in the blank were run in sequence to check for contamina- tributaries. PAH concentrations in the mainstream tion peak identification and quantification. Identity were higher than those in the tributaries probably and retention time of PAHs were confirmed by the because of the re-suspension of sediment. In the mixture and reference materials of Phe, Flu, Chr, BaP, mainstream, the water flow rate is higher than the BghiP, acquired from the National Research Center tributaries and lakes, so sorbed PAHs could be for Certified Reference Materials of China. The 16 released from the suspended particles, which in- PAHs were identified mainly by their retention time. creased the water phase concentration. Meanwhile,

Table 1 PAHs concentrations in water samples of the Yangtze River (μg/l)

Location Nap Acy Ace Fle Phe An Flu Pyr BaA Chr B(a)P Σ11 PAHs

Main stream Zhuankou nd 0.297 nd 0.603 0.122 0.159 0.354 0.023 0.125 nd nd 1.684 Baishazhou 0.065 nd nd nd 0.399 0.194 nd nd nd nd 0.214 0.874 Left Wuhanguan 0.109 0.263 1.696 0.492 0.193 nd nd nd 0.214 0.120 nd 3.087 Right Wuhanguan 0.109 0.262 0.696 nd 0.193 nd 2.611 1.029 0.215 0.120 nd 6.235 Left Yujiatou nd nd nd nd 0.122 nd 0.248 nd nd nd nd 0.370 Right Yujiatou 0.322 nd nd nd nd nd nd nd nd nd nd 0.322 Tributaries Dongfengzha 0.470 nd nd nd nd nd nd nd nd nd nd 0.470 Jijiazui 0.046 0.104 nd 0.201 0.104 nd 0.162 nd 0.012 nd nd 0.629 Moshui Lake nd nd nd nd 0.397 nd nd 0.703 nd nd 0.279 1.379 Dong Lake 0.080 nd nd nd 0.116 nd nd 0.046 nd nd nd 0.242 Yanxi Lake 0.053 0.195 nd nd 0.115 0.108 0.215 nd nd nd nd 0.686

nd-not detected 中国科技论文在线 http://www.paper.edu.cn Environ Monit Assess

PAHs species detected in the tributary stations were Compared with other rivers in China, the total fewer than those in the mainstream mainly because of PAHs concentrations in water samples of the Yangtze the different origins of PAHs. River are higher than the levels found in the Yellow Of all the water sampling sites, the PAHs detected River (Li et al., 2006), the Tonghui River in Beijing in water phase were mainly two to four rings. The (Zhang, Huang, Yu, & Hong, 2004), the Gaoping detection frequencies of the predominant PAHs were River in Taiwan (Doong & Lin, 2004), but lower than as follows: Phe 81.8%, Nap 72.7%, Flu 45.5%. Phe the Jiulong River in Hong Kong (Maskaoui, Zhoub, was the most frequently detected PAHs in water Hong, & Zhang, 2002) (Table 2). Compared with the samples. Although the detection frequency of Nap rivers in some foreign countries, the PAH concen- was very high, its concentration was relatively low trations of the Yangtze River are higher than those of probably because of its high vaporization properties. the Seine River in France (Fernandes, Sicre, Fewer high-weight PAHs were detected mainly Boireau, & Tronszynski, 1997) and the Mississippi because of their low solubility and high partition River in the US (Mitra & Bianchi, 2003). coefficient. For example, five-ring PAHs was rarely detected, and Benzo(a)pyrene was detected only at PAHs contents in sediment Baishazhou of the mainstream and Moshui Lake of the tributaries, with the concentration exceeding the As shown in Table 3, the PAH concentrations in Environmental Quality Standard for Surface Water sediment at different sampling stations showed wide (2.8 ng/l, GB3838-2002) (SEPA, 2002a, 2002b). For variations. In high water season, the PAH concen- the six specified PAHs (Flu, BbF, BkF, BaP, BghiP, trations ranged from 303 to 3,995 μg/kg with a mean InD), their concentration in the water phase of the value of 2,032 μg/kg in the mainstream, and ranged main stream at Zhuankou, Wuhanguan, Baishazhou from 4,121 to 4,262 μg/kg with a mean value of and Yujiatou were above the standard (0.2 μg/l) 2,229 μg/kg in the tributaries. In low water season, (State standard of China (GB13198-91)); while in the the PAH concentrations ranged from 72 to 1,206 μg/ tributaries, only the concentrations in the Moshui kg with a mean value of 497 μg/kg in the mainstream, Lake and Yanxi Lake were above the standard. and ranged from 31 to 4,813 μg/kg with a mean value

Table 2 Total PAHs concentration in water and sediment from various sites in the world

Phase Locations ΣPAHs range (ng/L, μg/kg) Mean(ng/L, μg/kg) ±SD References

Water Seine River, France 4∼36 20±13 Fernandes et al. (1997) Mississippi River, US 5.6∼68.9 40.8±32.9 Mitra and Bianchi (2003) , China 179∼369 248±78 Li et al. (2006) Tonghui River, China 192.9∼2651 762.3±777.4 Zhang et al. (2004) Gaoping River, China 10∼940 430 Doong and Lin (2004) Jiulong River Estuary, China 6960∼26920 17050±5280 Maskaoui et al. (2002) Wuhan section of Yangtze 321.8∼6234.9 2095.2±2276.2 This study Sediment Chesapeake Bay, US 0.56∼180 52 Forster and Wright (1988) Kitimat Harbour, Canada 310∼528000 66700±140000 Simpson et al. (1996) Todos Santos Bay, Mexico 7.6∼813 96 Macias-Zamora et al. (2002) Malaysia 4∼924 187 Zakaria et al. (2002) Victoria Harbour, HongKong 700∼26100 5277±7904 Hong et al. (1995) Yellow River, China 31∼133 76.7±42.3 Li et al. (2006) Delta, China 156∼10811 2057±3063 Mai et al. (2002) Yangtze Estuary, China 263∼6372 1661±1915 Liu et al. (2001) Jiulong River Estuary, China 59∼1177 334±337 Maskaoui et al. (2002) Tonghui River, Beijing, China 127.1∼927.7 540.4±291.8 Zhang et al. (2004) Nanjing section of Yangtze 213.8∼550.3 – Xu et al. (2000) Wuhan section of Yangtze 72.4∼3995.2 1334.5±1215.1 This study 中国科技论文在线 http://www.paper.edu.cn Environ Monit Assess

Table 3 The concentration ranges and mean values of PAH in sediment of the mainstream and tributaries from the Yangtze River

PAH Range in the main Mean ± standard Range in the Mean ± standard river(μg/kg) deviation (μg/kg) tributaries (μg/kg) deviation (μg/kg)

Nap nd nd 16.9∼113.7 43.6±61.3 Acy 9.4∼595.3 146.5±222.7 31.2∼336.6 133.0±117.5 Ace 3.0∼567.6 173.6±228.3 0.5∼728.7 108.4±222.0 Fle 18.1∼671.8 360.8±317.8 16.8∼217.7 59.8±53.8 Phe 42.2∼146.3 103.0±42.8 0.4∼130.0 62.4±59.0 An 15.6∼506.6 302.4±185.4 41.6∼434.7 205.1±178.8 Flu 17.0∼1852.8 828.0±695.3 3.5∼1242.9 289.4±451.6 Pyr 18.9∼185.1 136.4±79.0 4.1∼189.7 69.5±71.6 BaA 5.4∼132.3 39.2±42.6 5.7∼409.5 108.3±126.2 Chr 8.2∼66.7 45.6±24.4 19.5∼247.5 125.7±112.0 BbF 7.0∼1115.1 259.1±479.9 8.8∼748.7 207.0±226.7 BkF 46.7∼62.0 52.5±8.3 5.9∼231.2 60.6±78.4 BaP 0.7∼95.4 49.5±44.1 1.8∼559.6 93.8±160.6 DahA 31.2∼316.8 146.2±115.4 24.4∼2796.9 655.8±965.7 BghiP 7.2∼369.3 102.2±150.8 0.9∼1934.6 319.0±661.2 InD 4.9∼328.1 104.1±124.4 7.4∼991.4 164.2±266.7 Total PAHs 72.4∼3995.2 1334.5±1215.1 31.1∼4812.6 1294.6±1543.1

of 1,119 μg/kg in the tributaries. Therefore, the PAH River are higher than the levels found in some other concentrations in the tributaries were higher than Chinese sites such as the Yellow River (Li et al., those in the mainstream. 2006), the Tonghui River (Zhang et al., 2004), the The PAHs contamination in sediment was mainly Jiulong River (Maskaoui et al., 2002) and the Nanjing dominated by three-, four- and five- ring PAHs. In section of the Yangtze River (Xu et al., 2000), but high water season, there was a high detection lower than the Victoria Harbour (Hong et al., 1995)of frequency for InD and BghiP (66.7%), and Phe and Hong Kong, the Pearl River Delta (Mai et al., 2002) Flu (55.6%). In low water season, the predominant and the Yangtze estuary (Liu et al., 2001). Compared PAH were BaA, Fle, InD with the detection frequen- with the rivers of some foreign countries, the PAHs cies of 90.9, 81.8 and 77.3%, respectively. This was concentrations of the study area are higher than the due to the fact that high-molecular-weight PAHs tend Chesapeake Bay, US (Forster & Wrighrt, 1988), the to be associated with sediment. Todos Santos Bay, Mexico (Macias-Zamora, Mendoza- According to the above mentioned data, the mean Vega, & Villaescusa-Celaya, 2002), but lower than the concentration of PAHs in high water season was Kitimat Harbour, Canada (Simpson et al., 1996). higher than that in low water season. This was probably due to the differences of total organic carbon PAHs contents in SPM (TOC) content in these two seasons. As shown in Table 4, TOC content was higher in the high-water PAH concentration in SPM samples from three season than in the low-water season. Since TOC sampling stations in high water season and six content in sediment is a major factor controlling the sampling stations in low water season were analyzed fate of PAHs, and a higher TOC content will lead to a (Table 5). In high water season, the concentration of higher partition coefficient of PAHs between sediment PAHs in SPM ranged from 4,287 to 5,001 μg/kg and water, the relatively higher concentration occurred with a mean value of 4,532 μg/kg. The predominant in the sediment samples of the high-water season. PAHs were Ace and Flu and they accounted for As shown in Table 2, the total PAHs concentration 37.95 and 35.11% of the total PAHs content, in sediment of the Wuhan section of the Yangtze respectively. In low water season, the total PAH 中国科技论文在线 http://www.paper.edu.cn Environ Monit Assess

Table 4 Physicochemical properties of sediments in the mainstream and tributaries of the Yangtze River

Time Sampling sites pH TOC/% Grain size analysis /%

<10∼ 10∼ 50∼ >250 μm 50 μm 250 μm

High water season Mainstream Zhuankou 7.99 2.09 33.4 32.3 34.3 0.01 Left Wuhanguan 7.84 1.82 34.9 34.7 30.4 0.01 Right Wuhanguan 7.88 2.02 38.8 35.6 25.6 0 Baishazhou 7.91 1.27 46.7 35.3 18.0 0 Left Yujiatou 8.02 0.66 14.1 19.2 66.4 0.35 Right Yujiatou 7.65 1.16 46.1 35.9 18.0 0 Tributaries Longyang Lake 7.03 8.47 48.5 41.1 10.4 0 Dongjing River 7.62 1.03 43.3 29.3 27.4 0.03 Low water season Mainstream Jinkou 7.89 1.06 44.8 37.8 17.4 0 Zhuankou 7.73 1.90 30.7 33.2 36.1 0.02 Wuhanguan 8.10 0.16 7.3 14.1 72.6 5.97 Wuhu 7.93 0.47 9.4 19.1 71.2 0.34 Yangluo 7.86 0.49 25.0 25.2 49.5 0.29 Tributaries Jinshui 7.51 8.98 44.3 40.6 15.1 0.00 Qinduan River 7.32 1.04 49.5 40.6 9.9 0 Qingshangang 7.70 1.41 53.0 44.1 2.9 0 Daoshui River 6.49 1.77 59.7 32.0 8.2 0 Tangxun Lake 6.25 1.09 50.3 43.6 6.2 0 Hou Lake 6.40 1.83 63.0 34.7 2.4 0 Xunsi River 7.12 7.83 61.8 33.8 4.3 0 Xiao Bay 7.08 0.97 73.4 25.3 1.3 0 Fu River 7.08 6.03 63.5 35.1 1.4 0 Lijiadun 7.10 1.63 57.7 40.4 2.0 0 Luojiadun 6.94 8.38 57.4 38.7 3.9 0 Zhujia River 7.46 1.49 49.1 40.2 10.6 0 Dong Lake 7.23 2.56 39.3 46.2 14.6 0 Jijiazui 7.91 0.32 11.7 25.5 59.3 3.48 Dongjing River 7.42 1.84 59.2 31.1 9.7 0 Changfengqiao 8.21 0.21 4.7 18.8 70.9 5.58 Guocikou 8.05 0.22 5.1 18.1 68.9 7.88

concentration ranged from 952 to 15,347 μg/kg with Relationship between PAHs concentration the average concentration of 4,822 μg/kg. The and physicochemical properties of sediment predominant compounds were Ace, Fle and BaA. Compared with sediment phase, more kinds of PAHs TOC and particle size (Table 4)analysisofthe were detected and relatively higher concentrations sediments demonstrated some differences among the of PAHs were found in SPM from the sampling characteristics of samples. TOC content of the tributary sites (Fig. 2). This indicated that SPM is the most sediments ranged from 0.22 to 8.98% with a mean active factor in water bodies, which plays an im- value of 2.92%. TOC of the mainstream sediment portant role in the whole transportation process of ranged from 0.16 to 2.09% with a mean value of PAHs. On the one hand, SPM can absorb organic 1.18%. It is obvious that the TOC content of the pollutants from water phase, and carry them into tributaries was higher than that of the mainstream. sediment; on the other hand, sediment can re-suspend Besides, the content of particles with size less than and become SPM and release organic pollutants into 50 μm was higher in the tributaries than in the main- water phase. stream. The relationship between total PAHs concen- 中国科技论文在线

Table 5 Distribution of PAHs concentrations in suspended particulate matters (μg/kg)

PAHs High water season Low water season Concentration range Mean ± SD

Zhuankou Wuhanguan Yujiatou Zhuankou Wuhanguan Zhujia River Jijiazui Xunsi River Changfengqiao

Nap 12.3 149.5 nd 13.8 nd nd 124.9 nd nd 12.3∼149.5 75.1±72.4 Acy nd nd nd 613.1 nd 3161.5 nd 2284.9 192.5 192.5∼3161.5 1563.0±1397.2 Ace 1648.7 2048.7 1482.6 196.8 14.7 109.9 536.1 2723.7 42.6 14.7∼2723.7 978.2±1016.2 Fle 476.2 515.3 nd 179.8 80.6 837.1 nd 727.9 86.7 80.6∼837.1 363.0±319.7 Phe 178.0 168.4 127.2 nd nd nd nd nd nd 127.3∼178.0 157.9±27.0 An 192.7 300.2 169.3 nd nd nd nd nd 278.9 169.4∼300.2 235.3±64.0 Flu 1178.5 1365.7 2175.6 nd nd 198.4 nd nd nd 198.4∼2175.6 1229.6±812.3 Pyr 288.2 305.2 259.4 nd nd 114.7 nd nd nd 114.7∼305.2 241.9±86.9 B(a)A nd nd nd 55.8 nd 367.4 24.3 699.5 12.7 12.7∼699.5 231.9±299.7 Chr nd nd nd 25.3 nd nd nd nd 31.9 25.3∼31.9 28.6±4.6 BbF nd nd nd nd nd 1735.6 69.5 2362.1 52.1 52.1∼2362.1 1054.8±1176.0 BaP 311.9 140.3 89.9 nd nd nd nd nd nd 89.9∼311.9 180.8±116.4 BghiP 1.0 7.7 2.1 nd nd 454.1 nd nd nd 1.0∼454.1 116.2±225.3

Total 4287.7 5001.5 4306.5 1084.6 95.3 6978.7 754.7 8798.1 697.3 95.3∼8798.1 3556.1±3092.0 http://www.paper.edu.cn nd-not detected nio oi Assess Monit Environ 中国科技论文在线 http://www.paper.edu.cn Environ Monit Assess

Fig. 2 Distribution of PAHs concentration in different phases of the Yangtze River

trations and TOC content was not obvious while some for PAHs. The ratios of individual PAHs could be used individual PAHs concentration correlated well with to assess the possible origins of PAHs. In an attempt to TOC content. The correlation coefficients were DahA identify sources for the PAHs detected in this study, a (R=0.9828), BghiP (R=0.8783) and BaA (R=0.9318) source analysis was undertaken. Concentration ratios in high water season, and Fle(R=0.8792), InD (R= of PAHs with the same molecular weight including An/ 0.9001), BbF(R=0.9154), BaP(R=0.8960) and Acy (An+Phe) and Flu/(Flu+Pyr) were used to distinguish (R=0.9256) in low water season. It demonstrated that between combustion and petroleum sources of PAHs the sorbed PAHs had a positive relationship with TOC (Yunker et al., 2002). PAHs ratios in sediment with content in the sediments. This was expected as it is An/(An+Phe)<0.1 are usually taken as an indication of well documented that hydrophobic organic substances petroleum sources, while a ratio of An/(An+Phe)>0.1 will be mainly sorbed into particles through partition, indicates a typical of fuel combustion source. Another which is in correlation with content of organic carbon molecular ratio used to differentiate the sources of (Chiou, Porter, & Schmeddling, 1983). PAHs is Flu/(Flu+Pyr), with 0.4 being defined as the When we conducted correlation analyses between petroleum/combustion transition point. A ratio of Flu/ the PAHs concentration and sediment particle size, we (Flu+Pyr)>0.5 is characteristic of grass, wood and coal didn’t find significant relationship between them. Only combustion, while PAHs ratio of 0.4

Parent PAHs has both natural (plant debris, forest and Eco-toxicity assessment of PAHs in sediment prairie fires) and anthropogenic sources (fossil fuels combustion, etc.). Incomplete combustion of fossil In order to assess whether PAH in the Wuhan section of fuels is always treated as a major production process the Yangtze River will cause toxic effect, we compared 中国科技论文在线 http://www.paper.edu.cn Environ Monit Assess

Fig. 3 Comparison of mean concentration of PAHs in sediment of Wuhan section of the Yangtze River and toxicity guidelines

the PAH levels in sediment against effects-based Conclusions guideline values such as the effect range-low (ER-L), effect range-median(ER-M) and apparent effects This study first documented the comprehensive anal- threshold values developed by the US Natural Oceanic ysis of PAHs in three phases of the Wuhan section of and Atmospheric Administration (Long, MacDonald, the Yangtze River, which provided very useful Smith, & Calder, 1995; Witt, 1995). ER-L and ER-M information for the evaluation of trace PAHs and values are useful in assessing sediment quality and probable sources of PAH in the Yangtze River. The provide qualitative guidelines on what needs to be results obtained in this study showed that PAH done to effectively protect the aquatic environment concentrations in surface water, SPM and sediment (Kim et al., 1999; Mai et al., 2002). In Wuhan section phases varied significantly among sampling locations. of the Yangtze River, the comparatively high PAHs Two- and three-ring PAHs were abundant in water total concentrations were found in the tributaries at samples with Phe as its dominant PAHs, whereas, Longyang Lake (4,262 μg/kg) and Qinduan River high-ring PAHs were major species in sediment (4,812 μg/kg) stations, which were higher than the ER-L samples with BaA as its dominant PAHs. In SPM value (4,000 μg/kg) but significantly lower than the samples, more kinds of PAHs were detected including ER-M (44,792 μg/kg). As to the individual com- low- and high-ring PAHs. The concentration of PAHs pounds, only the mean concentrations of Acy, Ace, Fle, in SPM was also higher than that in water and An and DahA (139.8, 134.4, 133.5, 253.8 and sediment, suggesting that SPM played an important 464.7 μg/kg) were higher than their respective ER-L role in the transportation process of PAHs. PAH values (44, 16, 19, 85.3 and 63.4 μg/kg) but far lower concentration of the sediment in high water season than their ER-M values (640, 500, 540, 1,100 and was higher than that in low water season probably 2,600 μg/kg), respectively. The concentrations of other because of the differences of TOC contents in sediment PAHs in these sediment samples were lower than their between the two seasons. PAH concentrations in water respective ER-L values (Fig. 3). Apart from this, and sediment of the Yangtze River were close to or a several individual PAHs such as BbF and BkF have bit higher than those of some other rivers in China, and no lowest safety value. That is to say, once these com- higher than some rivers in foreign countries. pounds exist, they will cause toxic effect to the sur- There existed a positive relationship between the rounding environment. In the Wuhan section, some of PAH concentrations and the TOC contents in sedi- these PAHs were also detected at many sampling sites. ments. Source analysis revealed that PAHs mainly Based on the mentioned above, it can be concluded that came from combustion process, such as coal and PAHs may cause mild toxic effect but will not cause wood burning. As to the eco-toxicological assess- acute biological effects in sedimentary environment in ment, the concentrations of most PAHs in sediments the Wuhan section of the Yangtze River. from the Yangtze River were much lower than 中国科技论文在线 http://www.paper.edu.cn Environ Monit Assess

guideline values such as the effect range-low (ER-L) Liu, H. L., Liu, M., Cheng, S. B., & Ou, D. N. (2005). and effect range-median (ER-M). It may be conclud- Occurrence of organochlorine pesticides (OCPs) in sus- pended particle matters (SPMs) and surface sediments of ed that PAHs would not cause immediate biological the south bank of the Yangtze estuary. China Environ- effects in sedimentary environment in the Yangtze mental Science, 25(5), 622–626. River. Long, E. R., MacDonald, D. D., Smith, S. L., & Calder, F. D. (1995). Incidence of adverse biological effects within Acknowledgements This study was supported by the Project range of chemical concentrations in marine and estuary – of National Basic Research Program of China (2003CB sediment. Environmental Management, 19,81 97. 415204) and the National Natural Science Foundation of China Macias-Zamora, J. V., Mendoza-Vega, E., & Villaescusa-Celaya, (No.40571138). J. A. (2002). 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