Marine Pollution Bulletin 62 (2011) 22202229

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Marine Pollution Bulletin

journal homepage: www.elsevier.com/locate/marpolbul

Water quality assessment by pollution-index method in the coastal waters of Hebei Province in western Bohai Sea, China
Shuguang Liu a, Sha Lou a,b, Cuiping Kuang a, Wenrui Huang a,c,, Wujun Chen d, Jianle Zhang d, Guihui Zhong a
a

Department of Hydraulic Engineering, Tongji University, Shanghai, China Department of Civil Engineering, Nagasaki University, Nagasaki, Japan Department of Civil and Environmental Engineering, Florida State University, FL, USA d Marine Environmental Monitoring Center of Hebei Province, Qinhuangdao, China
b c

a r t i c l e

i n f o

a b s t r a c t
Sources of pollution discharges and water quality samples at 27 stations in 2006 in the coastal waters of Hebei Province, western Bohai Sea, have been analyzed in this study. Pollutant loads from industrial sewages have shown stronger impact on the water environment than those from the general sewages. Analysis indicates that pollution of COD is mainly resulted from land-based point pollutant sources. For phosphate concentration, non-point source pollution from coastal ocean (shing and harbor areas) plays an important role. To assess the water quality conditions, Organic Pollution Index and Eutrophication Index have been used to quantify the level of water pollution and eutrophication conditions. Results show that pollution was much heavier in the dry season than ood season in 2006. Based on COD and phosphate concentrations, results show that waters near Shahe River, Douhe River, Yanghe River, and Luanhe River were heavily polluted. Water quality in the Qinhuangdao area was better than those in the Tangshan and Cangzhou areas. 2011 Elsevier Ltd. All rights reserved.

Keywords: Organic Pollution Index Eutrophication Index COD Phosphate Pollution source Coastal water quality Bohai Sea

The Bohai Sea, surrounded by land on three sides, is a semiclosed sea with poor water exchange condition. The Provinces of Liaoning, Hebei, Shandong and the City of Tianjin embrace it in the north, west and south. It is a populous and developed area surrounding the Bohai Sea. However, the area has also resulted in a large amount of pollutants from industrial and municipal waste water discharged into the Sea. At the same time, many oil elds and large ports are widely distributed along the coastal areas of the Bohai Sea. The accidents of oil spills and emissions of drainages have further exacerbated the pollution of the aquatic environment. Problems caused by ocean pollution in the coastal waters of the Hebei Province have ranged from the estuarine zone to the coastal region such as deterioration of water quality, frequent occurrence of red tides, imbalance of marine ecosystem, and decline of sheries resources. Therefore, it is very important to understand and analyze the pollution sources from both land and coastal water environments in the Hebei Province for the management of marine environment and improvement of water quality. Contaminants such as COD and phosphate have posed a grave threat to the marine ecology system in coastal waters. Based on a three-dimensional hydrodynamic and water quality models,
Corresponding author at: Department of Civil and Environmental Engineering, Florida State University, FL, USA. E-mail address: whuang@eng.fsu.edu (W. Huang).
0025-326X/$ - see front matter 2011 Elsevier Ltd. All rights reserved. doi:10.1016/j.marpolbul.2011.06.021

Gao et al. (2009) investigated the processes of transport, degradation and deposition of COD in the Bohai Sea and North Yellow Sea in different seasons. Through two cruises for water quality investigation in Bohai Sea from August 10 to 18 in 2002 and August 12 to 28 in 2003, Guo et al. (2005) analyzed the effect of COD concentrations to eutrophication. Using three years of monitoring data, Shen et al. (2004) evaluated the inuence of phosphate to the ocean primary production in Bohai Bay. Based on eld surveys conducted in 2003 and 2004, Yang et al. (2007) analyzed the eutrophication condition in coastal waters in Bohai Bay. Wu et al. (2007) included temperature, dissolved oxygen, salinity, PH, COD and other factors in an articial neural network (ANN) model to predict the concentrations of chlorophyll and eutrophication in Bohai Bay. Wang et al. (2009) collected water samples in 120 stations in Bohai Sea to analyze the distribution of dissolved nutrients and assess the degree of eutrophication. However, for coastal areas where pollution concentrations are usually higher than those in open sea, more intensive studies on water quality are needed. In this study, pollutant loads from point sources and water quality conditions at 27 stations have been investigated in coastal areas of Hebei Province in the western Bohai Sea. The impact of pollutant sources and the concentration distribution of COD and phosphate have been analyzed and discussed. Organic Pollution Index and Eutrophication Index have been calculated to quantify the assessment of the water pollution level and water quality

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condition in the dry and ood seasons in 2006. Results would provide useful technical supports for coastal pollution controls and environmental management in the study region, and a good example for similar studies in other coastal environmental studies. Field data samplings are important to water quality monitoring and assessments. Liu and Huang (2009) applied sediment data to investigate wind-induced sediment transport in Apalachicola Bay. Mortazavi et al. (2001) investigated nutrient budget based on nitrogen and nitrite data. Shi (2009, 2010) conducted analyses of environment in Asia Pacic harbors and sedimentation in estuaries. Chen et al. (2008) studied cadmium transportation under accident release in Pearl River Delta. Wang et al. (in press) investigated

water exchanges in Jiaozhou Bay. Braga et al. (2000) collected samples of water in natural channels of Baixada Santista Estuarine System at 15 stations positioned by GPS to investigate the eutrophication caused by industrial and domestic pollution. The distribution of inorganic nutrient and chlorophyll-a concentrations were determined during 19962001 cruises in the Izmir Bay by Kontas et al. (2004) to assess the level of nitrication and the limiting nutrients in the bay. Samples were collected in June 2006 at 32 stations in Flensburg Fjord of German by Nikulina and Dullo (2009) to evaluate the eutrophication and heavy metal pollution levels over the last three decades. Organic Pollution Index is a comprehensive index that includes more water quality constituents. It accounts for the multivariate

Fig. 1. Distribution of the sewages in the coastal areas of Hebei Province, China.

Table 1 Classication of pollution categories for sewage outfalls (Marine Environment Monitoring Center of Hebei Province, 2006). Categories of pollutant Indicators Standard Value I-class The second category of pollutants COD (chemical oxygen demand, mg/L) BOD5 (mg/L) Phosphate (mg/L) Ammonia nitrogen (mg/L) Suspended matter (mg/L) Cyanide (mg/L) Petroleum (mg/L) Volatile phenol (mg/L) Fecal coliform (L1) PH Hexavalent chromium (mg/L) Mercury (mg/L) Plumbum (mg/L) Cadmium (mg/L) Arsenic (mg/L) 100 20 0.5 15 70 0.5 5 0.5 500 69 0.5 0.05 1.0 0.1 0.5 II-class 150 30 1.0 25 150 0.5 10 0.5 1000 69 III-class 500 300 400 1.0 20 2.0 5000 69

The rst category of pollutants

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effects of COD, dissolved inorganic nitrogen, dissolved inorganic phosphorus, and dissolved oxygen. Through the comparison with standard values and combination of several pollutants in the same property, non-dimensional index is gained to assess organic matter in aquatic environment. Based on its advantage in the assessment of the level of organic pollution and water quality status, it has been applied to several coastal and estuarine waters, for examples, Bohai Bay (Zou et al., 1983), Huanghua Port (Liu, 1993), Dalian Bay (Yang et al., 2001), Yangtze Delta (Quan et al., 2005), and Guangzhou Bay (Peng and Jia, 2007). Eutrophication is the over-enrichment of a water body with too much nutrients, resulting in excessive accumulation of organic

material. This accumulation of organic material alters the trophic structure (food web) of the water body. Through the treatment of observed data, Eutrophication Index could demonstrate the associated impact of pollutant loads of chemical oxygen demand, dissolved inorganic nitrogen, and dissolved inorganic phosphorus on water quality. It is much more comprehensive and clear to show the entrophication level than single measured indicator. Costa et al. (1992) developed a Water Quality Eutrophication Index as a tool to summarize water quality monitoring data collected in the Citizens monitoring program in Buzzards Bay, USA (http:// www.buzzardsbay.org/eutroindex.htm), which was later adopted by Hillsborough County in Florida to evaluate changes of water

COD

C o n ce n tra tio n (m g /L)

1000 800 600 400 200 0

Erluanhe M ay

Shuanglonghe M ay.

Shuanglonghe Apr.

Shuanglonghe Sep.

Shanhaiguan Development Zone Apr. Shanhaiguan Development Zone Oct.

Laoshibeihe Xinshibeihe Oct. Jul.

Luanhe Oct.

Tanghe Oct.

Douhe Sep.

Shihe M ay

Phosphate

C o n ce n tra tio n (m g /L)

Erluanhe May
600

Beipaihe Jul. Beipaihe Oct.

Canglang drain May

Canglang drain Jul.

Canglang drain Sep.

Jiedijianhe May

Jiedijianhe Jun.

Jiedijianhe Jul.

Huangnan drain Sep.

Suspended Matter

500

C o n ce n tra tio n (m g /L)

400

300

200

100

r.

l.

Fig. 2. Pollution loads from the general sewages with concentrations exceeding the pollution standard in the corresponding water class.

lan Oc gd t. Ca ra i ng nM lan ay gd ra Ji e in S ep di ji a nh eA Ji e pr di ji a nh eJ Li u ao ji a n wa Ap Li ao r ji a wa Ju Li n ao ji a wa Li Ju ao l ji a wa Se Li p ao ji a wa Xi Oc ns hi b t eih eJ Na un . np Hu aih an eJ gn u l. an Hu d ra an in gn Ap an r dra Hu in an M gn ay an . d ra in Da l a n Oc t . gd i an Xu Ap an r. hu i he M ay

ay

pr

ay

ay

ay

ay

eM

Ap

eM

eM

eA

eM

ai h e

Ju

ai h e

gh

ai h e

nh

gh

gh

Be ip

Sh

Be ip

Er

Da

Da

Qi

ng

Be ip

Ca ng

Be ip

q in

l ua

q in

l on

ai h e

ah

Shanhaiguan Shipyard Jul

Douhe M ay

Huangnan drain Apr.

S. Liu et al. / Marine Pollution Bulletin 62 (2011) 22202229

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quality in Tampa Bay. Costa index classies water quality into 035 (for eutrophication condition), 3565 (fair condition), and 65100 (good to excellent condition). Zhou et al. (1983) developed an Eutrophication Index method for preliminary assessment of water quality in Bohai Bay, which accounts for the effects of chemical oxygen demand (COD), dissolved inorganic nitrogen (DIN), and dissolved inorganic phosphorus (DIP). The Eutrophication Index above or equal to 1 in a water body indicates the eutrophication condition because of excessive nutrients. Wang et al. (2009) applied the Eutrophication Index as given by Zhou et al. (1983) to evaluate the water quality in the open waters of Bohai Sea. Based on the their advantages for comprehensive assessment of water

quality, Organic Pollution Index and Eutrophication Index are adopted to this study for the assessment of water quality in the coastal water of Hebei Province in western Bohai Sea. Terrestrial sewages in Hebei Province (Marine Environment Monitoring Center of Hebei Province, 2006) can be divided into two categories: river outfall and industrial sewage directly discharged into the sea. There are 28 river outfalls where data are available (from north to south: Shihe River, Xinkaihe River, Tanghe River, Yanghe River, Renzaohe River, Dapuhe River, Luanhe River, ErLuanhe River, Daqinghe River, Erxiedazhuanghe River, Suhe River, Qinglonghe River, Shuanglonghe River, Shahe River, Douhe River, Beipaihe River, Canglang drainage, Jiedijianhe River,

Concentration (mg/L)

COD

Concentration (mg/L)

Ju l.

Oc t.

un .

ul .

Ap r.

M ay

Se p.

Ap r.

Ju l.

Ju n.

ao he J

M ay

Se p.

Oc t.

ao he J

gh e

gh e

uh e

gh e

gh e

uh e

Ya n

uh e

Ya n

D ap

uh e

Ya n

D ap

Da p

en z

Ya n

Ya n

Da p

Re nz

Fig. 3. Pollution loads from the major pollution-emission outlets with concentrations exceeding the pollution standard in the corresponding water class.

Fig. 4. Distribution of 27 stations for water water quality data sampling in coastal area of Hebei Province, Bohai Sea.

Da p

Da p

Sa n

yo u

gh e

uh e

uh e

ct.

ng h Ya e A n g p r. h Ya e Ju ng n. Ya h e n g Jul . h Ya e S n e R e gh e p. nz a Oc R e o he t. nz A p a R e o he r . nz M a a R e o he y nz J u ao n . R e he nz S e ao p . h Da e O p u ct. Da h e J p u ul . h Da e S p u ep. he S u Oc t he . M Su a y he J Su u n. he Su Ju l he . Zh Su S ep an he . g O Zh w ei an xi h ct. gw e M eix a y Sa i h e n y Oc o t. Sa u M n y ay o Sa u Ju n y n. Sa o u J ny ul . o Sa u S n y ep . ou O ct.

Phosphate

Ya

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S. Liu et al. / Marine Pollution Bulletin 62 (2011) 22202229

Laoshibeihe River, Liaojiawa drainage, Xinshibeihe River, Huanglang drainage, Nanpaihe River, Huangnan drainage, Liushiliu drainage, Dalangdian drainage, Xuanhui drainage and Zhangweixinhe River). No industry sewage in Cangzhou City is directly discharged into the sea. Therefore, only four sewages in Qinhuangdao and Tangshan industries are taken into account: sewage of Shanhaiguan Development Zone, Shanhaiguan Shipyard, Beidaihe West treatment plant and Chemical Industry of Sanyou. Among them, Yanghe River, Renzaohe River, Dapuhe River, Suhe River, Zhangweixinhe River and sewage of Chemical Industry of Sanyou are the major pollutant-emission outlets. Others are the general sewages. The distribution of the sewages is shown in Fig. 1. Six pollution source surveys were carried out in April, May, June, July, September and October, 2006. Indicators for major pollutantemission outlets are: fecal coliform, COD, BOD5, suspended matter, phosphate, ammonia nitrogen, petroleum, mercury, arsenic, volatile phenol, cadmium, plumbum. COD, ammonia nitrogen, phosphate, hexavalent chromium, cyanide and suspended matter are for other general sewages.

Index of each individual pollutant parameter is used to assess the status of the sewage outfall:

Pi

Mi Si

Pi: index of pollutant i. if Pi > 1, discharge of pollutant i has exceed the stipulated standard; Mi: measured concentration of pollutant i (mg/L); Si: the concentration of stipulated standard of pollutant i (mg/L). Concentrations of stipulated standard for evaluation sewage outfall are shown in Table 1. Dened by local government, the industry standard has specied the maximal allowable concentration of the pollution to meet the water quality criteria in different functional zone. Pollution loads from the general sewages with concentrations exceeding the pollution standard in the corresponding water class in 2006 are given in Fig. 2. The maximum of COD concentrations in most general sewages was in April. Parts of them occur in May, June and July. Very few appear in September and October. The

Table 2 Water quality measurement methods for analyzing water samples. Measurement element DO PH Total nitrogen Total phosphorus Nitrate Nitrite Ammonium salt Active phosphate Active silicate Dissolved nitrogen Dissolved phosphorus Suspended matter COD Measurement method Iodimetry PH meter method Potassium persulfate oxidation method Potassium persulfate oxidation method Spectrophotometer method Spectrophotometer method Spectrophotometer method Spectrophotometer method Spectrophotometer method Potassium persulfate oxidation method Potassium persulfate oxidation method Gravimetric method Alkaline potassium permanganate method Measurement instrument Buret Portable PH meter 7230G Spectrophotometer 7230G Spectrophotometer 7230 Spectrophotometer 7230 Spectrophotometer 7230 Spectrophotometer 7230 Spectrophotometer 7230 Spectrophotometer 7230G Spectrophotometer 7230G Spectrophotometer Electronic balance BS-1105 Buret electrothermal board Detection limitation 0.042 mg/L 3.78 lmol/L 0.09 lmol/L 0.05 lmol/L 0.02 lmol/L 0.03 lmol/L 0.02 lmol/L 0.45 lmol/L

2 mg/L 0.15 mg/L

4450000

4450000
0.11 5.60

4400000

5.20 4.80 4.40

4400000

0.10 0.09 0.08

4350000

4.00 3.60 3.20 2.80

4350000

0.07 0.06 0.05

4300000

2.40 2.00 1.60 1.20

4300000

0.04 0.03 0.02

4250000

0.80 0.40 0.00

4250000

0.01 0.00

4200000

4200000

550000

600000

650000

700000

750000

550000

600000

650000

700000

750000

(a) COD

(b) Phosphate

Fig. 5. Concentration contours in ood season (July 21st27th, 2006): (a) COD and (b) phosphate.

S. Liu et al. / Marine Pollution Bulletin 62 (2011) 22202229

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extreme values of ammonia nitrogen concentration in most general sewages appear in April, May and October. Some occur in June, July and September. In April, May, June, July and October, hexavalent chromium concentrations of some sewages are the

maximum. The minority appears in September. Cyanide concentrations of most general sewages outfall are maximum in May. Some of them are in June, September and October. Only a few appear in July. The maximum of phosphate concentrations are in April, May,

4450000

4450000

0.11

4400000

14.40 12.60 10.80

4400000

0.10 0.09 0.08

4350000
9.00 7.20

4350000

0.07 0.06 0.05

4300000

5.40 3.60

4300000

0.04 0.03

4250000

1.80 0.00

4250000

0.02 0.01 0.00

4200000

4200000

550000

600000

650000

700000

750000

550000

600000

650000

700000

750000

(a) COD

(b) Phosphate

Fig. 6. Concentration contours in dry season (November 20thDecember 1st, 2006): (a) COD and (b) phosphate.

Flood Season

Dry Season

0.08 0.06 0.04 0.02 0.00

ZD

Fig. 7. Comparison of measured concentration in ood and dry seasons, 2006: (a) measured COD concentration and (b) measured phosphate concentration.

H0 HB 52 BZ HB 02 ZD B Z - B 01 D H0 64 BD 05 BD 0 HB 6 BZ ZD - B 03 D H0 HB 65 BZ HB 04 BZ HB 05 BZ HB 06 ZD B Z - B 07 D H ZD 0 76 -T J0 HB 7 7 BZ HB 08 BZ ZD 09 -T J0 86 TJ 16 TJ 1 HB 4 BZ HB 10 BZ HB 11 NZ HB 0 1 NZ HB 0 2 NZ HB 0 3 NZ HB 0 4 NZ HB 0 6 NZ 05

-B D

H0 HB 52 BZ 0 HB 2 ZD B Z 0 1 -B D H0 64 BD 05 BD 0 HB 6 ZD B Z 0 3 -B D H0 HB 65 BZ 0 HB 4 BZ 0 HB 5 BZ 0 HB 6 ZD B Z - B 07 D H ZD 0 76 -T J0 7 HB 7 BZ HB 08 BZ ZD 09 -T J0 86 TJ 16 TJ 1 HB 4 BZ 1 HB 0 BZ HB 11 NZ 0 HB 1 NZ HB 0 2 NZ 0 HB 3 NZ 0 HB 4 NZ 0 HB 6 NZ 05

ZD -B D

(a) Measured COD concentration

Flood Season Dry Season

(b) Measured phosphate concentration

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S. Liu et al. / Marine Pollution Bulletin 62 (2011) 22202229

Table 3 Water quality classication by Organic Pollution Index and Eutrophication Index. Organic Pollution Index: A <0 Water Quality Classication Excellent 01 Good 12 Begin to be contaminated 23 Lightly polluted 34 Moderately polluted >4 Heavily polluted Eutrophication Index: E E>1 Eutrophication

July and October. A very small number appear in the June and September. The high concentrations of suspended matter in most general sewages occur in April, May and June. Among the general sewages, the main pollutants are COD, phosphate and suspended matter.
Table 4 Results of Pollution Index A and E in ood and dry seasons, 2006. Stations Organic Pollution Index: A Flood season ZD-BDH052 HBBZ02 HBBZ01 ZD-BDH064 BD05 BD06 HBBZ03 ZD-BDH065 HBBZ04 HBBZ05 HBBZ06 HBBZ07 ZD-BDH076 ZD-TJ077 HBBZ08 HBBZ09 ZD-TJ086 TJ16 TJ14 HBBZ10 HBBZ11 HBNZ01 HBNZ02 HBNZ03 HBNZ04 HBNZ06 HBNZ05 0.10 0.07 0.44 0.00 0.04 0.39 0.77 0.64 0.46 0.38 0.20 0.12 0.20 2.96 0.45 1.88 1.26 1.16 1.11 0.92 3.51 5.36 1.08 3.64 0.79 0.21 4.38 Dry season 3.09 2.05 2.78 3.70 4.17 1.56 3.49 4.39 4.77 4.11 2.24 3.24 5.29 3.36 3.14 3.33 4.51 4.79 3.42 2.91 3.75 1.07 0.89 6.20 3.86 2.02 6.37 Eutrophication Index: E Flood season 0.22 0.17 0.13 0.17 0.00 0.00 0.00 0.00 0.18 0.16 0.16 0.23 0.15 0.18 0.55 1.99 2.08 2.92 2.08 2.69 10.60 9.00 3.69 1.51 2.37 0.94 4.95 Dry season 2.71 1.20 2.53 4.13 5.64 0.79 3.32 4.89 5.93 4.50 1.55 2.94 7.33 3.48 3.10 3.64 5.95 7.80 4.72 2.98 4.93 0.86 0.63 14.39 5.25 2.12 16.72

Pollution loads from the major pollution-emission outlets with concentrations exceeding the pollution standard in the corresponding water class in 2006 are given in Fig. 3. The highest concentrations of fecal coliform in most major pollutant-emission outlets are in July. Very few of them appear in April, June, September and October. The maximum of concentration of BOD5 in most major pollutant-emission outlets are in April and May. Some appear in June. The maximum concentrations of petroleum in most outlets are in May and September. The concentrations of mercury in most outlets are maximal in July and for few outlets it appears in September and October. In most major pollutant-emission outlets, maximum concentrations of arsenic occur in July and October. Volatile phenol concentration of most major pollutant-emission outlets is highest in May and July, and small amounts appear in April. The maximum cadmium concentrations occur in June and September. Only minority appear in May. In most outlets, plumbum concentrations are high in July, and low in April and October. The pollutants discharged by major pollutant-emission outlets are more serious to the ocean environment than the general sewages both in the amount and extent of pollution indexes. Seawater quality data sampling was conducted by National Marine Environmental Monitoring Center from July 21st to 27th and November 20th to December 1st in 2006 (National Marine Environmental Monitoring Center, 2009). Major water quality constituents include water temperature, salinity, DO, PH, COD, total nitrogen, phosphorus, reactive silicate, dissolved nitrogen, suspended matter, total organic carbon and other chemical indicators. The 27 stations in the coastal area of the Hebei Province are shown in Fig. 4. For the water quality constituents described in this paper, high uon water sampler was used as the sampling tool to take samples in the eld experiments. For sampling DO and COD, glass bottles were used. For other water quality samples, polyethylene bottles were used. Descriptions of measuring methods on water samples are given in Table 2.
A-Dry Season

7 5 3 1 -1

A-Flood Season

ZD

ZD

Qinhuangdao Waters

Fig. 8. Comparison of organic pollution and eutrophication indexes in ood and dry seasons, 2006.

H 052 BB H Z0 ZD BB 2 -B Z0 D 1 H 06 BD 4 0 B 5 H D0 ZD BB 6 -B Z0 D 3 H H 065 BB H Z04 BB H Z05 BB H Z0 ZD BB 6 -B Z0 D 7 ZD H07 -T 6 J H 077 BB H Z08 B ZD BZ0 -T 9 J0 86 TJ 16 T H J1 4 BB H Z10 BB H Z1 BN 1 H Z01 BN H Z02 BN H Z03 BN H Z04 BN H Z06 BN Z0 5
Tanshang Waters Tianjin Waters Cangzhou Waters

-B D

H 0 BB 5 2 H Z02 ZD BB -B Z0 D 1 H 06 BD 4 0 BD 5 H 06 ZD BB -B Z0 D 3 H H 065 BB H Z04 BB H Z05 BB H Z0 ZD BB 6 -B Z0 D 7 ZD H07 -T 6 J H 077 BB H Z08 B ZD BZ0 -T 9 J0 86 TJ 16 T H J1 4 BB H Z10 BB H Z11 BN H Z01 BN H Z02 BN H Z03 BN H Z04 BN H Z06 BN Z0 5
Qinhuangdao Waters

-B

Tanshang Waters

Tianjin Waters

Cangzhou Waters

E-Flood Season

E-Dry Season

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Fig. 5 has shown the vertical averaged concentration contours of COD and phosphate in coastal waters of the Hebei Province in the ood season (July 21st27th, 2006). It points out that the concentration of COD is the highest near the mouth of the Shahe River and Douhe River with the value of 4.45.2 mg/L. Estuaries of the Yanghe River and Luanhe River are also heavily polluted with the COD concentrations of 2.83.6 mg/L and 2.43.2 mg/L. COD concentrations in other waters are lower than 2 mg/L. Waters near the mouth of the Shahe River and Douhe River have the highest phosphate concentration of 0.0350.04 mg/L. Caofeidian waters is the secondary polluted area in phosphate concentration of 0.02 0.03 mg/L. Concentrations in other waters are relatively low. Phosphate concentration is higher in part of open sea than coastal waters. This indicates that the sources of phosphate are not only resulted from terrestrial sewages but also from the shing and harbor areas in open sea. Fig. 6 is about the vertical averaged concentration contours of COD and phosphate in coastal waters of Hebei Province in the dry season (November 20thDecember 1st, 2006). It presents that the concentration of COD is the highest near the mouth of the Shahe River and Douhe River with the value of 14 mg/L. The high concentration of COD results from excessive discharge of the Sanyou Chemical Industry. Near the Estuaries of the Luanhe River, there are also heavily polluted waters with COD concentrations of 68 mg/L. COD concentrations in other waters are lower than 2 mg/L. Waters near the mouth of the Shahe River and Douhe River have the highest phosphate concentration of 0.09 mg/L which is also caused by excessive discharge of the Sanyou Chemical Industry. Phosphate concentrations in Qinhuangdao and Tangshan waters are on the high side with the value of 0.04 mg/L. Phosphate concentration is higher in the open sea of Caofeidian and Huanghua Harbour than in the coastal area. Fig. 7 presents the comparison of pollutant concentration in ood and dry season. It shows that the COD concentration is higher in the dry season than that in the ood season near Qinhuangdao waters, which is contrary to the situation near Tangshan and Cangzhou waters. Phosphate concentration is higher in the dry season in most stations. Pollutant concentration is closely related to the ow rate of the runoff. In most of the waters, pollutant concentration decreases with the increasing ow rate in ood season. But in some other waters, ow of runoff carries more pollutants in ood season, which leads to higher pollutant concentrations in the receiving

waters. For most of the rivers in North China, the ow rate in ood season and dry season varies signicantly. Taking the Luanhe River in 2006 as an example, the average ow rate in ood season is 64.21 m3/s, while in dry season only 11.49 m3/s. In order to account for the effects of multiple water quality constituents on coastal waters of Hebei Province, index methods as described above are used for water quality assessment in Bohai Sea. Referring to Quan et al. (2005) and Wang et al. (2009), Organic Pollution Index and Eutrophication Index given below have been adopted. (1) Organic Pollution Index A is dened by:

COD DIN DIP DO CODs DINs DIPs DOs

where COD is chemical oxygen demand; DIN is dissolved inorganic nitrogen; DIP is the dissolved inorganic phosphorus; DO is dissolved oxygen; CODS, DINS, DIPS and DOS are the standard concentrations as dened in Sea Water Quality Standard of China, GB 3097-1997 (State Bureau of Environmental Protection, 1998). (2) Eutrophication Index E is dened by:

COD DIN DIP 106 4500

In order to make the conservative estimation, I-class standard in Sea Water Quality Standard of China is adopted: CODs = 2 mg/L, DINs = 0.2 mg/L, DIPs = 0.015 mg/L and DOs = 6 mg/L. As shown in Eq. (2), the Organic Pollution Index comprehensively account for the effects of COD, DIN, and DIP on water quality. Similarly, Eutrophication Index as shown in Eq. (3) indicates the multiple effects of COD, DIN, and DIP on eutrophication. Based on the previous research done by Quan et al. (2005), If A < 0, the water quality is classied as excellent; if 0 6 A < 1, it is good; If 1 < A < 2, water is beginning to be contaminated; If 2 < A < 3, it is lightly polluted; If 3 < A < 4, it is moderately polluted; If A > 4, it is heavily polluted waters. For Eutrophication Index, if E > 1, the water is in eutrophication situation. Higher E value indicates heavier eutrophication (as shown in Table 3). According to the measured data, DIN is substituted by the concentration of

Table 5 Water quality conditions based on the assessment by using Organic Pollution Index and Eutrophication Index in the coastal water of Hebei Province, Bohai Sea. Water quality zone Judged by Organic Polluted level (IIIVI are polluted water) I (%) Flood Season Flood season 33.33 0.00 II (%) 29.63 3.70 III (%) 18.52 7.41 IV (%) 3.70 18.52 V (%) 7.41 37.04 VI (%) 7.41 33.33 37.04 96.03 40.74 88.89 Organic Polluted stations, % Eutrophication stations, %

Fig. 9. Polluted coastal areas assessed by using Organic Pollution Index and Eutrophication Index in the coastal water of Hebei Province, Bohai Sea. The percentage of polluted areas was approximately estimated by the percentage of stations.

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dissolved nitrogen, and DIP is substituted by the concentration of Phosphate during the calculation. The results of Organic Pollution Index and Eutrophication Index in 27 stations are shown in Table 4 and Fig. 8. Organic Pollution Index A and Eutrophication Index E indicate that both organic pollution and eutrophication degree are much heavier in Tianjin and Cangzhou waters than that in Qinhuangdao and Tanshan waters in ood season. While in dry season the special distribution is

not evident, because most of the waters are polluted. Table 5 and Fig. 9 present the statistics of polluted coastal waters based on the pollution index. Results are based on the analysis of measured data in 27 stations which are almost evenly distributed in the coastal areas. Therefore, they can stand for the water quality status in the coastal waters to some degree. They present that, in ood season, 3.70% of the stations in coastal area is lightly polluted by organic pollution. Moderately and heavily polluted stations are in

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Fig. 10. Spatial distributions of Organic Index and Eutrophication Index in ood and dry season of 2006: (a) Organic Index in ood season, (b) Organic Index in dry season, (c) Eutrophication Index in ood season and (d) Eutrophication Index in dry season.

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the same percent 7.41%. And eutrophication station is in the proportion of 40.74%. It is obviously that the water quality is much worse in the dry season with 18.52% lightly polluted, 37.04% moderately polluted, 33.33% heavily polluted by organic pollution and 88.89% eutrophication station. Serious and widespread pollution is more likely to happen in dry season than ood season. The characteristic of temporal distribution is the same as that of pollutant source. There is a positive correlation between Organic Pollution Index A and Eutrophication Index E. Spatial distributions of Organic Index and Eutrophication Index in ood and dry season of 2006 are clearly explicated (in Fig. 10). High level of organic pollution is shown in Qinhuangdao waters (only stations BD05), Tangshan waters and Huanghua harbor waters. The eutrophication is much more serious in Qinhuangdao waters (only stations BD05), Tangshan waters (only station ZD-BDH076), Tianjin waters (only station HBBZ11), and Huanghua Harbour waters. Results indicate that Tangshan waters and Huanghua Harbor waters are heavily polluted, which agrees with the measured data. Through comparison and analysis in this study, Organic Pollution Index and Eutrophication Index were comprehensively used to assess water quality of the Bohai Sea. The result has shown that they can be used to reasonably quantify the level of temporal and spatial pollution in the coastal waters. It also shows that the Organic Pollution Index and Eutrophication Index are good representative indicators for water quality evaluation, which may be applied to other coastal areas for pollution assessment. The pollution index method has been used to assess water quality in the coastal waters in Hebei Province, China. Characteristics of water quality conditions are given below. (1) Pollutant loads from major pollutant-emission outlets of industrial sewages are more serious to the water environment than those from the general sewages. High concentration waters occur near the Shahe River, Douhe River, Yanghe River and Luanhe River on the aspect of COD and phosphate distribution. (2) Pollution of COD is mainly resulted from point pollutant sources at land, such as outfalls of river and sewage of industry directly discharged into the sea. For phosphate concentration, non-point source pollution from coastal ocean (shing and harbor areas) is an indispensable source. (3) The water quality condition is better in the Qinhuangdao water area than that in Tangshan and Cangzhou in 2006. In general, the pollution level is much higher in the dry season than in the ood season. (4) At present, controlling pollutant emission should be carried out based on the marine environment capacity. Especially, more attentions should be paid to the dispersion and distribution of pollutant under the typical hydrological conditions in the dry season. This study indicates that the pollution index method can be used as a useful and effective tool for the assessment of water quality in coastal environment. The case study presented in this paper may provide a good reference for coastal water quality assessment in other study sites. Acknowledgements This study was supported by Projects of the Integrated Coastal Investigation and Assessment of Hebei Province (908-SJ-HB-02-

04 and 908-SJ-HB-02-10). The authors appreciate the supports given by research collaborators in Marine Environment Monitoring Center of Hebei Province and National Marine Environmental Monitoring Center. The study was also partly supported by grants from the National Science Foundation of China (NSFC 50979071), and The National Keynote Research Program of China (2006BAJ27B04, 2008BAJ08B14, and 2007FY110300-03). Finally, the support from Guanghua Fund for the College of Civil Engineering of Tongji University has enabled the effective dissemination of this research. References
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