Article

SPECIAL TOPIC September 2013 Vol.58 No.27: 33483356 Simulation and Regulation of Water Cycle in Haihe River Basin doi: 10.1007/s11434-013-5677-6

Pollution characteristics and ecological risk of polycyclic aromatic hydrocarbons (PAHs) in surface sediments of the southern part of the Haihe River system in

LIU Feng, LIU JingLing*, CHEN QiuYing, WANG BinBin & CAO ZhiGuo

State Key Joint Laboratory of Environmental Simulation and Pollution Control, School of Environment, Beijing Normal University, Beijing 100875, China

Received August 15, 2012; accepted January 7, 2013; published online March 7, 2013

The southern part of the Haihe River system, the largest river system in the Haihe River Basin, is important to maintain a healthy ecosystem and safe drinking water as well as for the economic development of China. To assess the effect of rapid industrializa- tion and urbanization on the pattern of polycyclic aromatic hydrocarbon (PAH) contamination, the PAH pollution characteristics of the southern part of the Haihe River system was investigated. Sixteen PAHs in surface sediments samples collected from 24 sites covering the southern part of the Haihe River system from the upstream to the estuaries were detected and analyzed. The total PAH concentration ranged from 258.77 to 11296.66 ng/g dry weight. On average, 2-, 3-, 4-, 5- and 6-ring PAHs comprised 25.32%, 27.22%, 22.62%, 14.89% and 9.96% of the total PAHs, respectively. Sites with high concentrations were concentrated in the Fuhe River, Fuyang River and , which are located near cities. A risk quotient (RQ) was used to assess the ecological risk of PAHs. The mean values of the RQ(MPCs) of individual PAHs were lower than 1.00, except for those of naphthalene (2.00) and pyrene (1.67). The RQPAHs calculated for the samples indicated that the Xidayang reservoir and the estuary of the were determined to be at a low risk level, while Baoding City, Handan City and Aixinzhuang were determined to be at a high risk level. polycyclic aromatic hydrocarbons, surface sediments, the southern part of the Haihe River system, distribution, composi- tion profile, ecological risk assessment

Citation: Liu F, Liu J L, Chen Q Y, et al. Pollution characteristics and ecological risk of polycyclic aromatic hydrocarbons (PAHs) in surface sediments of the southern part of the Haihe River system in China. Chin Sci Bull, 2013, 58: 33483356, doi: 10.1007/s11434-013-5677-6

Polycyclic aromatic hydrocarbons (PAHs) are persistent effects [6]. Therefore, the accumulation of PAHs in sedi- organic pollutants and have been listed as priority pollutants ments has received much attention [7,8]. Existing research by both the US Environmental Protection Agency and the on PAHs in Haihe River Basin has mainly focused on a few European Union due to their toxicity, carcinogenicity and important reaches, such as rivers in and Beijing mutagenicity [1]. PAHs are known to enter the aquatic en- [9,10]. Research focusing on other river systems in Haihe vironment through industrial and urban discharge, petrole- River Basin has rarely been reported. Only a few studies um spills, fossil fuel combustion and atmospheric deposi- about PAHs in the Tuhai-Majia River [11], [12] tion [2]. Due to their lipophilicity, PAHs in water tend to and Zhangweinan River [13] have been reported. Previously, accumulate in bottom sediments [3], which acts as a long- there were no integrated and detailed studies on PAHs in term reservoir [4]. PAHs also can bio-accumulate through surface sediments of the southern part of the Haihe River the food chain [5], and the exposure of humans to PAHs system. may enhance the risk of cancer and other adverse health The southern part of the Haihe River system is the largest of the four river systems in Haihe River Basin, with an area 5 2 *Corresponding author (email: [email protected]) of 1.24×10 km . The Haihe River system includes some

© The Author(s) 2013. This article is published with open access at Springerlink.com csb.scichina.com www.springer.com/scp Liu F, et al. Chin Sci Bull September (2013) Vol.58 No.27 3349 big cities, such as Shijiazhuang City, Handan City, Xingtai City and Baoding City. It is mainly composed of three riv- ers named Qaqing River, Ziya River and Zhangweinan Riv- er. With the growth of the population and economy, intense land utilization and water resources development has oc- curred. The contamination of this river system has been aggravated by the increased discharge of industrial, agri- cultural and urban wastewater. However, there are ten water resource fields used for drinking and transportation in the southern part of the Haihe River system, so the level of PAHs in this water system are closely related to the safety of the drinking water. However, no research specifically focusing on the PAHs pollution levels in this river system have been reported. Because sediments are the ultimate sink and reservoir of PAHs, identifying the pollution characteris- tics of PAHs in the surface sediments of the southern part of the Haihe River system represents important work. The aims of this study are (i) to investigate the concen- trations and distribution of PAHs in superficial sediments from the southern part of the Haihe River system and (ii) to evaluate the ecological risk of PAHs using a risk quotient Figure 1 Location and sampling sites of the southern part of the Haihe (RQ). To achieve these goals, sediment samples were col- River system. S1: Wangkuai; S2: Xidayang; S3: Baoding; S4: Fuhe; S5: Bazhou; S6: Jinghai; S7: Estuary of Duliujian river; S8: Gangnan; S9: lected from locations ranging from upstream to estuaries in Huangbizhuang; S10: Shijiazhaung; S11: Handan; S12: Aixinzhuang; S13: the southern part of the Haihe River system. Sixteen PAHs, Hengshui Lake; S14: Xianxian; S15: Cangzhou; S16: Estuary of Ziyaxin listed as United States Environmental Protection Agency River; S17: Yucheng; S18: Xiaonanhai; S19: Xinxiang; S20: Weihui; S21: (USEPA) priority pollutants, were investigated. Longwangmiao; S22: Guantao; S23: Dezhou; S24: Estuary of Zhangwei- nan River.

1 Materials and methods within a distance of 5 m [16]. Triplicate samples were mixed 1.1 Sampling thoroughly to make a composite sample to minimize within- site variability and ensure that the sediment samples col- The sampling sites are shown in Figure 1. Among the 24 lected were representative of each site [17]. sampling stations, 7 were located in suburban areas, 6 in S1 to S7 were located in the Daqing River. S1 and S2 cities, 6 in reservoirs and 3 in estuaries. Samples from sub- were located in reservoirs, while S3 was located in Baoding urban areas that were not under the direct impact of indus- City and was directly affected by the wastewater of the city. trial and traffic activities could reflect the “background” S4 was located in the Fuhe River at the entrance to Bai- level of the PAHs in the study area, while sites close to cities yangdian Lake, which is a natural reservoir. S5 and S6 were could reflect the “maximum” value and the effect on PAHs located in suburban areas, and S7 was located in a port. contamination caused by rapid industrialization and urbani- Nine sampling sites (S8–S16) were located in the Ziya River, zation. Water resource areas, natural reservation regions and of which S13 was located in a natural reservoir named estuaries were the most important and sensitive areas in the Hengshui Lake. S14 was at the confluence of the Fuyanghe basin. Thus, sampling sites in these areas were essential for River and the Hutuohe River, and S16 was in the estuary. the management and maintenance of safe drinking water in The Zhangweinan River had 8 sampling sites (S17–S24). Of the southern part of the Haihe River system. these 8 sites, S17 and S18 were located in two reservoirs, Samples of surface sediments were collected in May S19 and S23 were close to Xinxiang City and Dezhou City, 2010. Global positioning system (GPS) was used to locate S20 and S22 were located in suburban areas and S24 was in the sampling sites. Surface sediment samples (1–5 cm deep) the estuary of the Zhangweinan River. were collected with a grab sampler, and the top 1 cm of the surface layer was carefully removed with a stainless steel 1.2 Sample extraction spoon [14] and stored in aluminum jars that had been pre- washed with methylene chloride. The samples were cooled Frozen sediment samples were dried using a freeze-drying on ice during transportation to the laboratory, where they apparatus. Prior to extraction, these samples were ground were stored at 20°C before being freeze-dried. The dried into granular powder that was passed through a 100-mesh sediment samples were sieved to obtain particles of less sieve and homogenized. Mashed samples were first mixed than 180 m [15]. At each site, 3 samples were collected with anhydrous sodium sulfate in a weight ratio of 5:1 and 3350 Liu F, et al. Chin Sci Bull September (2013) Vol.58 No.27 with activated copper sheets in a ratio of 1:1, to desulfurize showed that precision was generally satisfactory. the extract. The mixtures were extracted by accelerated sol- vent extraction (ASE300, Dionex, Sunnyvale, CA) with n- 2 Results and discussion hexane/dichloromethane (1:1, v/v) for 10 min (two static cycles). The extraction temperature was set at 125°C and 2.1 Concentrations and composition profiles pressure at 1500 Pa. The extracts were reduced to about 2 The concentrations of PAHs in sediments from the 24 sam- mL using a rotary evaporator and purified using a silica gel pling sites are listed in Table 1. The concentration ranges of column packed with anhydrous sodium sulfate. The column total PAHs in sediments of the Daqing River, Ziya River was first rinsed with 10 mL n-hexane solvent to remove and Zhangweinan River were 258.77–1346.01, 326.89– non-PAH impurities, such as aliphatic hydrocarbons. Then, 11296.66 and 470.88–2315.19 ng/g dry weight, respectively. the column was rinsed with 15 mL of mixed dichloromethane For the Daqing River, Ziya River and Zhangweinan River, : and n-hexane (1 1, v/v). The second eluate contained the the mean concentrations of total PAHs of the three rivers PAHs and was collected and concentrated using a rotary were 1249.72, 2926.40 and 1049.30 ng/g, respectively, and evaporator. The effluent was then reduced to about 0.5 mL the median concentrations were 1184.91, 1138.40 and under a stream of purified N2 in KD vessels and adjusted to 719.75 ng/g, respectively. The median concentrations were 1.0 mL with hexane for GC-MS analysis. generally lower than the mean concentrations, suggesting that the majority of these sites contained lower concentra- 1.3 PAHs analyses tions than the mean. Comparing the mean and median con- centrations of the total PAHs from the three rivers, it was All of the extracted samples were analyzed using a Hewlett- clear that the PAHs of the Zhangweinan River were at a Packard 6890 Gas Chromatograph (GC) connected to a relatively low level. According to the water resources bulletin Hewlett-Packard 5973 N Mass Selective Detector (MSD) of Haihe River Basin (conventional pollutants) in 2010, the (Agilent, Wilmington, DE). The chromatographic column water quality of the Wei River and the Zhangweixin River was a 30 m, 0.25 mm inner diameter, 0.25 lm film thickness was worse than grade V [18], and the Zhangweinan River HP-5MS capillary column (#19091s-433, Agilent, J and W had worse water quality than the other two rivers of the Scientific, Folsom, CA). Helium was used as the carrier gas southern part of the Haihe River system. However, the lev- at a constant flow rate of 1 mL/min. The oven temperature els of PAHs in the water [13] and sediments of the Zhang- was ramped from 60 to 260°C at 6°C/min and then held for weinan River were not serious, so the other pollutants 15 min. The MSD was operated in the electron impact mode should be controlled first. at 70 eV. The ion source temperature was 280°C. The mass The concentrations of PAHs in the sediments from Haihe spectra were recorded at a scan mode covering the range of River Basin were much higher than those from rivers both 45–400 mass units for sediment samples. Quantification overseas and domestic, such as Malaysian rivers, the was performed using the external standard method with a 16 Hyeongsan River, the River, and the PAH standard mixture (PPH-10JM, Chem Service Inc., (Table 2). The PAHs pollution in Haihe River Basin was West Chester, PA). The retention time and identity of the relatively high compared to other rivers of the world. Com- PAHs were also confirmed using this standard. The GC/MS pared with rivers within Haihe River Basin, the concentra- data were acquired and processed using Enhanced Chem- tions of PAHs in the southern part of the Haihe River sys- Station (HPG1701CA, Agilent). The 16 PAHs detected in tem was higher than that of the Luan River and the Tuhai- sequence were the following: naphthalene (Nap), Majia River system but lower than that of rivers in Tianjin. ace-naphthylene (Ace), acenaphthene (Acp), fluorene (Fl), As PAHs lack functional groups, they are among the most phenanthrene (Phe), anthracene (An), fluoranthene (Flu), stable organic indicators, and their concentrations in sedi- pyrene (Pyr), benz[a]anthracene (BaA), chrysene (Chr), ments have accurately recorded their history input [24]. There- benzo[b]fluoranthene (BbF), benzo[k]fluoranthene (BkF), fore, these results could be attributed to the fact that Tianjin benzo[a]pyrene (BaP), indeno[1,2,3-cd] pyrene (InP), diben- was an old, large and established industrial city with the zo[a,h]anthracene (DbA), and benzo [ghi]perylene (BghiP). largest port in north China, while the Luan River and the Tuhai-Majia River system were primarily utilized for agri- 1.4 Analytical quality control culture. Thus, in Haihe River Basin, the PAH concentra- tions appeared to be consistent with the respective regions’ All data were subjected to strict quality control procedures. degree of industrialization. Naphthalene-d8, acenaphthylene-d10, phenanthrene-d10, In the southern part of the Haihe River system, most sites chrysene-d12 and perylene-d12 were used as surrogates, were dominated by Nap, Phe and Flu, and the mean concen- and their recoveries were 51.8±10.7%, 78.6±10.9%, 83.8± trations of the three PAHs were 267.77, 261.56 and 191.37 10.5%, 93.2±9.1% and 88.9±10.1%, respectively. The lim- ng/g, respectively. However, the concentrations of Pyr, BaA, its of detection ranged from 1.5 to 9.3 ng/g. The results Chr, BbF, BkF, BaP, InP, BghiP were also high at Handan Liu F, et al. Chin Sci Bull September (2013) Vol.58 No.27 3351

66 PAHs ∑ River; ZYR2, the mean concentra- ND ND ND 326.89 326.89 ND the median concentration in the Ziya in the median concentration 35.90 12.31 ND 12.17 12.83 ND 446.13 15.35 BaA Chr BbF BkF Bap InP DbA BghiP BghiP Bap BkF BaA Chr BbF InP DbA

a) 73 ND ND ND ND ND ND ND 73 20.52 ND ND ND ND ND ND ND ND 470.88 470.88 ND ND ND 20.52 concentration in the Daqing River; ZYR1, , the mean concentration in the Zhangweina n River. tration in tration the Daqing River; the mean DR2, oncentration in the Zhangweinan River; ZWR2 River; in the Zhangweinan oncentration 216.75 5.87 13.61 41.66 133.20 15.95 60.16 43.95 22.12 34.96 49.15 18.35 37.05 30.75 10.10 35.01 719.75 719.75 35.01 10.10 30.75 37.05 18.35 49.15 34.96 22.12 43.95 60.16 15.95 133.20 216.75 41.66 13.61 5.87 1049.30 56.58 15.54 48.34 49.08 29.13 66.52 54.23 37.61 77.78 97.49 34.91 185.73 213.38 59.21 16.48 7.30

system the Haihe River (ng/g) of part th e southern from PAHs of in sediments Concentrations Nap Ace Acp Fl Ace Phe An Flu Pyr Nap a) concen the a) ND, not detected; DR1, median S13 S13 150.20 ND 63.02 18.21 13.63 ND 12. 19.10 S14 250.20 ND 18.71 21.61 12.92 37.67 18.07 12.91 ND 26.08 35.88 10.40 136.10 ND 661.82 40.12 26.15 S15 254.20 ND 724.54 37.33 10.31 30.70 27.31 20.77 51.01 28.52 19.51 ND 31.55 43.82 10.54 109.90 39.07 1138.40 S16 125.10 ND 250.20 83.93 18.80 66.44 48.54 30.47 86.34 49.81 39.67 ND 70.27 ND 93.38 27.40 222.20 34.06 38.77 15.91 35.43 22.84 20.16 38.10 52.92 12.00 86.17 24.72 75.31 20.14 ND 559.75 ZYR1 38.57 323.99 ZYR2 32.49 374.57 134.88 28.99 255.16 188.74 163.89 253.78 334.06 81.88 668.46 113.70 2926.40 179.95 209.33 93.89 34.80 10.07 32.86 37.07 19.23 36.36 30.63 20.45 46.83 68.86 9.21 29.04 S17 11.13 10.72 157.50 212.16 58.64 948.80 S18 201.10 65.52 17.30 51.42 47.39 24.01 61.93 40.93 30.38 52.78 ND 79.94 19.08 171.50 62.02 18.50 S19 246.90 6.74 624.36 28.49 27.33 13.80 34.24 21.88 16.89 30.21 39.55 12.74 123.80 S20 161.70 32.15 7.93 43.19 23.43 7.03 6.38 209.70 236.60 119.80 300.20 75.88 144.50 149.20 96.44 S21 2035.71 109.60 103.60 91.03 284.10 114.80 24.34 13.90 432.80 155.30 34.80 S22 222.20 197.20 245.80 73.35 ND 160.30 134.10 96.40 24.66 20.64 94.87 31.20 11.79 2315.19 119.70 118.50 51.97 771.04 152.40 44.57 S23 213.00 35.22 10.13 28.63 37.03 17.47 63.03 39.28 23.79 41.07 ND 51.46 12.82 142.60 40.13 10.38 S24 220.50 11.02 16.72 10.51 26.81 12.80 11.51 23.92 ND 33.05 11.63 106.40 ND 559.93 36.91 15.42 12.73 ZWR1 S7 185.90 17.90 14.88 44.40 172.00 20.27 158.30 120.60 70.02 85.05 90.33 45.35 105.00 88.54 30.01 97.46 1346.01 1346.01 S6 97.46 30.01 88.54 105.00 1184.91 610.30 45.35 25.39 90.33 27.66 85.05 70.02 18.12 120.60 53.81 32.44 63.97 38.93 ND 63.68 13.36 128.80 ND 158.30 48.81 14.08 35.56 20.27 172.00 S7 44.40 14.88 17.90 1184.91 185.90 202.10 1249.72 44.31 10.49 35.34 42.22 20.79 53.81 44.07 43.77 61.19 ND 87.61 20.27 172.00 DR1 48.81 14.81 2040.80 82.89 21.69 71.37 70.44 31.76 82.19 65.60 54.66 85.93 115.22 23.20 202.92 257.66 137.30 DR2 60.72 14.55 8.92 44.86 109.40 118.70 1138.40 54.53 166.20 S8 127.80 83.93 18.80 66.44 48.54 30.47 86.34 49.81 39.67 70.27 93.38 28.01 222.20 183.20 86.45 111.60 89.22 20.14 7.98 160.80 27.40 288.10 S9 89.56 25.20 10.60 482.30 S10 11296. 238.40 ND 1074.00 S11 301.40 887.60 1065.00 7359.85 304.50 375.90 227.40 529.90 440.90 462.10 801.40 1195.00 172.30 639.50 23.28 394.70 1199.00 321.20 84.26 264.20 977.60 521.00 42.69 283.00 75.31 830.80 704.20 1005.00 185.90 174.90 125.00 187.30 222.60 39.48 1183.00 S12 2228.85 163.10 183.10 83.35 339.90 1205.00 592.80 186.00 53.13 316.70 121.00 76.56 S2 114.70 1.85 4.51 16.22 45.04 4.92 13.29 11.40 6.20 7.50 3.05 1.86 9.11 7.45 2.22 9.46 258.77 258.77 9.46 2.22 7.45 1131.81 9.11 1.86 3.05 7.50 6.20 11.40 S1 13.29 211.00 44.31 10.49 35.34 42.22 20.79 41.47 44.07 29.76 4.92 61.19 45.04 ND 87.61 34.16 364.60 16.22 84.99 14.81 S2 4.51 1.85 114.70 S3 1256.04 306.70 18.91 92.61 20.75 73.31 53.56 33.62 95.26 54.96 43.77 77.53 103.00 S4 377.20 102.40 26.33 30.90 245.20 202.10 255.50 222.90 163.90 275.80 359.40 53.80 98.44 22.22 3124.39 8.81 257.40 242.70 97.57 285.50 78.38 S5 ND 172.90 ND ND 87.59 ND 16.07 29.77 21.24 ZWR2 tion in the Ziya River; ZWR1, the ZWR1, median c River; tion in the Ziya Table 1

3352 Liu F, et al. Chin Sci Bull September (2013) Vol.58 No.27

Table 2 Concentration ranges of PAHs in sediments of rivers in the world

a) Region Location N Concentration (ng/g) Ref Overseas Athabasca River, Canada 16 10–34700 [19] Malaysian rivers 16 4–924 [20]

Hyeongsan River, Korea 16 5.30–7680 [17] Domestic Qiangtang River, China 15 91–614 [21] Yangtze River, China 16 72.4–995.2 [22] Yellow River, China 16 31–133 [23] Daliao River 28 102.9–3419.2 [16] Haihe River Basin Rivers in Tianjin 16 787–1943000 [9] Haihe River, Tianjin 16 774.8–255371.91 [10] Tuhai-Majia River system 9 311.69–3736.32 [11]

Luan River 20 20.9–287 [12] South part of Haihe River system 24 258.77–11296.66 This study a) N, number of kinds of PHAs.

(S11) and Aixinzhuang (S12). The composition pattern of 16 PAHs in sediments of the southern part of the Haihe River system is shown in Figure 2. On average, 2-, 3-, 4-, 5- and 6-ring PAHs comprised 25.32%, 27.22%, 22.62%, 14.89% and 9.96% of the total PAHs, respectively. The measured PAHs at most stations consisted mainly of 2-, 3- and 4-ring PAHs, and the composition profile was the same with the Jialu River [25], except for Baoding City (S3), the estuary of the Daqing River (S7), Shijiazhuang City (S10), Aixinzhuang (S12) and Xinxiang (S19), which were mainly composed of high molecular weight (5- and 6-ring) PAHs and were all directly or indirectly affected by cities. PAHs formed in high temperature combustion processes have a condensed structure (4-, 5- and 6-ring) and were usually Figure 2 The percentages of PAHs of different ring numbers in surface identified as the majority of PAHs input from urban sediments from the southern part of the Haihe River system. wastewater and industrial runoff [26]. PAHs originating from unburned products have a smaller number of rings (2- and 3-ring) [16]. The predominate source of PAHs for most stations was discharging of crude oil and related products. The PAHs found at sites S3, S7, S10, S12 and S19 were mainly from industrial and urban emissions.

2.2 Distribution

The distribution of PAHs in sediments is shown in Figure 3. For the Daqing River, the lowest concentration was found at S2, the Xidayang reservoir, which was the main water source for Baoding City and one of the emergency water reserves for Beijing. The highest concentration was found at S3, which was located downstream in the Fuhe River. The Figure 3 Distribution pattern of total PAHs in sediments from the south- Fuhe River was mainly influenced by the sewage and in- ern part of the Haihe River system. dustrial wastewater from Baoding City [27]. The most pol- luted sites were found in the middle and lower reaches of the region; the main reason might be that the large city of similar to the result derived from the Yellow River [23]. Baoding was located in the middle reach and the municipality For the Ziya River, the highest concentration of PAHs Tianjin was located in the lower reach. This finding was was found at S12 (11296.66 ng/g), which was located in Liu F, et al. Chin Sci Bull September (2013) Vol.58 No.27 3353

Aixinzhuang, which is a rural area. This finding might be because of the proximity of Xingtai City. Xingtai City is a big industrial city with an area of 12486 km2 and a popula- tion of 6.7 million. It is famous for equipment manufactur- ing, coal salt chemical production and auto manufacturing. Industrial waste and urban runoff might be the reason for the high concentration of PAHs in Aixinzhuang. In contrast, the concentration of total PAHs in some cities, such as Cangzhou City (724.54 ng/g) and Shijiazhuang City (2228.85 ng/g), were much lower. The lowest concentration was de- tected at Hengshui Lake (326.89 ng/g), and the second low- est was in the estuary (559.75 ng/g). Because Handan City is located upstream and is a mining city, the Fuyang River was one of the most polluted rivers in province [28]. Figure 4 Contrast of the PAHs in different regions of the Daqing River, For the Ziya River, the highly polluted sites were concen- the Ziya River and the Zhangweinan River. trated in the middle and upper reaches, while the lower reaches and the estuary had relatively low PAH concentra- different sampling sites. This finding was true of the CVs of tions. the Daqing River (n=7, CV=74%), the Ziya River (n=9, For the Zhangweinan River, relatively high concentra- 130%) and the Zhangweinan River (n=8, CV=68%). The tions of PAHs were detected at S20 (Xinxiang City, highly polluted sites were concentrated in the middle and 2035.71 ng/g) and S22 (Longwangmiao, 2315.19 ng/g), and lower reaches of the Daqing River and in the upper and relatively low concentrations were detected at S23 (Guantao, middle reaches of the Ziya River and the Zhangweinan 470.88 ng/g) and S25 (estuary, 559.93 ng/g). Longwang- River. However, the spatial distribution patterns of PAHs in miao is located in the lower reach of the Wei River, and the three rivers were in accordance with the distribution wastewater from upstream (Xinxiang City and Hebi City) pattern of cities. Generally, sites located in cities exhibited resulted in the relatively high concentration of PAHs in this higher PAHs concentrations than those in rural areas. The sampling site. Xinxiang was directly affected by its indus- relatively high concentrations were closely related to the trial emissions and traffic pollution, which caused the high discharge of industrial wastewater, urban runoff and emis- concentration of PAHs. Guantao is in a rural area less af- sion of atmospheric particles from the cities. In the southern fected by cities, which led to the lowest concentration of part of the Haihe River system, the highly polluted sections PAHs. were the Fuhe River, the lower reach of the Daqing River, The concentrations of PAHs in cities were higher than the Fuyang River and the Wei River. These highly polluted that in rural areas (Figure 4) in the Daqing River and the sections were mainly impacted by Baoding City, the Tianjin Zhangweinan River, and the distribution pattern was similar municipality, Handan City, Xinxiang City and Hebi City. to that in peninsular Malaysia [20] and different from the We suggest that the discharge of industrial waste water, Ziya River. This finding was mainly because of the extremely urban runoffs and emission of atmospheric particles in the high concentration observed at Aixinzhuang (11296.66 five cities should be controlled. ng/g), and the sites in the rural areas had much lower con- centrations (661.82 ng/g). Comparing the PAHs concentra- 2.3 Ecological risk assessment tions in reserves upstream with the estuaries downstream, the concentrations in the estuaries were relatively low in the PAHs accumulated in sediments could be used by emergent Ziya River and the Zhangweinan River. For the two rivers, macrophytes [29], such as cattail and reed, and enter aquatic which have large industrial and agricultural water consump- food webs [30]. Therefore, the PAHs in sediments pose a tion, the volume of water flowing into the sea was small, potential risk for aquatic ecosystems. Ecological risk as- and zero flow happened frequently in recent years [13]. The sessment has been shown to be a useful tool to characterize two estuaries were located in rural areas, so they had very the risk of PAHs to organisms and ecosystems [31]. Kalf et little input of PAHs from upriver or from the cities, so the al. [32] proposed assessing ecological risk of some organic concentration of PAHs in the estuaries was relatively low. substances using a risk quotient (RQ) in 1997, and Cao et In contrast, the concentration of total PAHs in the Daqing al. improved the method by considering toxic equivalency River estuary was relatively high, which may be because factors in 2010. The improved method was demonstrated to this estuary was located in Tianjin and affected by petrole- be more accurate and scientific [12]. This improved method um spills, industrial and urban discharges. was used here to assess the ecological risk of PAHs in sed- The coefficient of variation (CV) of total PAHs of the iments from the southern part of the Haihe River system. southern part of the Haihe River system was 138% (n=24), The levels of risk posed by certain PAHs were charac- suggesting great variation in the concentrations of PAHs in terized using a risk quotient (RQ), which was calculated as 3354 Liu F, et al. Chin Sci Bull September (2013) Vol.58 No.27 follows: dividual PAHs in the sediments are listed in Table 3, and the ecological risk classification is listed in Table 4. An CPAHs RQ  , RQ(NCs)<1.0 indicated that the single PAHs might be of neg- C QV ligible concern, an RQ(MPCs)>1.0 would indicate that the contamination of the single PAHs posed severe risk, and an where C was the concentration of certain PAHs in the PAHs RQ >1.0 and RQ <1.0 indicated that the contamina- medium and C was the corresponding quality values of (NCs) (MPCs) QV tion of the single PAHs was of moderate risk. certain PAHs in the medium [32]. In the present study, the The mean values of the RQ of individual PAHs were negligible concentrations (NCs) and the maximum permis- (NCs) all greater than 1.0, and the mean values of RQ of in- sible concentrations (MPCs) of PAHs in water, sediments (MPCs) dividual PAHs were less than 1.0, except for Nap and Pyr. and bank soil reported by Kalf et al. were used as the values Nap and Pyr showed a high level of ecological risk, and the in the medium. MPCs are the concentrations in the envi- other 14 PAHs were at a moderate level of risk. The ronment above which the risk of adverse effects is consid- RQ and the RQ of the southern part of ered unacceptable to ecosystems, and NCs are the concen- ∑PAHs(MPCs) ∑PAHs(MPCs) the Haihe River system are illustrated in Figure 5. The Xi- trations in the environment below which the occurrence of dayang reservoir (S2) and the estuary of the Ziya River (S17) adverse effects is considered to be negligible [33]. There- showed low ecological risk, Baoding City (S3), Handan fore, RQ and RQ were defined as follows: NCs MPCs City (S11) and Aixinzhuang (S12) showed high ecological C risk, and all of the other 19 sites showed moderate risk. The RQ  PAHs , NCs Fuhe River and the Fuyang River were the sections with the CQV(NCs) highest ecological risk, and they were also the most polluted C sections. These data indicated that adverse ecological risk RQ  PAHs , MPCs has already been detected in the southern part of the Haihe CQV(MPCs) River system. As industry and transportation develop fur- where CQV(NCs) was the values of the NCs of PAHs in the ther, PAH pollution will increase and do harm to the eco- medium and CQV(MPCs) was the values of the MPCs of PAHs system and human beings. Therefore, monitoring and con- in the medium. The RQ∑PAHs, RQ∑PAHs(NCs) and RQ∑PAHs(MPCs) trolling of PAHs should be taken into consideration in the were defined as follows: southern part of the Haihe River system. Cao et al. [12] as-

n16 sessed the ecological risk of PAHs in water, surface sedi- RQ RQ RQ 1 , ments and bank soil of the Luan River and water of the  PAHs  i  i  i1 Zhangweinan River with the same method. For the Luan n16 River, the RQ∑PAHs(MPCs) in water, sediments and bank soil RQ  RQ RQ 1 ,  PAHs(NCs)  i(NCs)  i(NCs)  were all zero except for water in Wuliehe (1.53). The mean i1 ecological risk in water was higher than that in sediments n16 and bank soil. Compared with the Luan River, the PAHs RQ  RQ RQ 1 .  PAHs(MPCs)  i(MPCs)  i(MPCs)  pollutants of the southern part of the Haihe River system i1 showed higher ecological risk. For water in the Zhangwei- The RQ(NCs) and RQ(MPCs) of individual PAHs which were nan River, all sites showed low ecological risk. The mean not less than 1 were added to calculate the RQ∑PAHs(NCs) and ecological risk in water was lower than that in sediments of the RQ∑PAHs(MPCs) of total PAHs to fully consider the eco- the Zhangweinan River, which was different from the ob- logical risk of individual PAHs. The NCs and MPCs of in- servations of the Luan River.

Table 3 NCs and MPCs of individual PAHs in sediments (ng/g)

PAHs NCs MPCs PAHs NCs MPCs

Nap 1.4 140 BaA 3.6 360 Ace 1.2 120 Chr 107.0 10700 Acp 1.2 120 BbF 3.6 360 Fl 1.2 120 BkF 24.0 2400 Phe 5.1 510 BaP 27.0 2700 An 1.2 120 DbA 27.0 2700 Flu 26.0 2600 InP 59.0 5900 Pyr 1.2 120 BghiP 75.0 7500

Liu F, et al. Chin Sci Bull September (2013) Vol.58 No.27 3355

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