7
Baseline Heavy metals distribution and contamination in surface sediments of the coastal Shandong Peninsula (Yellow Sea) Guogang Li a , Bangqi Hu b,, Jianqiang Bi a , Qinuan Leng a , Chunqiao Xiao a , Zhongcheng Yang c a Beihai Offshore Engineering Survey Institute of the State Oceanic Administration, Qingdao 266061, China b Key Laboratory of Marine Hydrocarbon Resources and Environmental Geology, Qingdao Institute of Marine Geology, Ministry of Land and Resources, Qingdao 266071, China c Qingdao Bohai Construction Group Corporation, Qingdao 266001, China article info Keywords: Heavy metals contamination Sediment quality guidelines Environmental assessment Shandong Peninsula abstract Selected heavy metals (Cr, Cu, Ni, Pb and Zn) in surface sediments from the coastal Shandong Peninsula (Yellow Sea) have been determined to evaluate the spatial distribution and potential ecological risk. Results showed that heavy metal concentrations in the sediments generally met the criteria of China Marine Sediment Quality. However, both the enrichment factor (EF) and geoaccumulation index (I geo ) val- ues suggested the elevation of Pb concentration in the region. Based on the effect-range classification (TEL-PEL SQGs), Cr, Cu and Ni were likely to pose environment risks. Spatial distribution of ecotoxicolog- ical index (mean-PEL-quotient) suggested that most of the surface sediments have a 21% probability of being toxic. Similar results were also obtained by pollution load index (PLI). The spatial distribution pat- tern of heavy metal in surface sediments is a basis for undertaking appropriate action to protect marine sediment quality. Ó 2013 Elsevier Ltd. All rights reserved. Since 1980s, a rapid industrialization and economic develop- ment in China has brought a thriving economic success, accompa- nied with a series of severe environmental problems (Gao and Chen, 2012; Gu et al., 2012; Pan and Wang, 2012; Zhang et al., 2012b; Gan et al., 2013; Zhao et al., 2013). Toxic pollutants, such as heavy metals originating from human activities, are continuing to be introduced to aquatic environment through rivers, waste dumping and aeolian processes, then deposited in marine sedi- ments as a sink. One of the largest problems associated with the persistence of heavy metals is the potential for bioaccumulation and biomagnification, resulting in potential long-term implications on human health and ecosystem (Rainbow, 2007; Wang and Rain- bow, 2008). Due to the toxicity and persistence of heavy metal pol- lution, heavy metal research of estuarine and coastal area has attracted more public concerns recently (Christophoridis et al., 2009; Larrose et al., 2010; Feng et al., 2011; Liu et al., 2011; Sunda- ray et al., 2011; Varol, 2011; Gao and Li, 2012; Yang et al., 2012; Hu et al., 2013a; Hu et al., 2013b). It is necessary to investigate the dis- tribution and pollution degree of heavy metal, in order to interpret the mechanism of transportation and accumulation of pollutants and to provide basic information for coast utilization and supervi- sion (Long et al., 1998; Long et al., 2006). The Shandong Peninsula locates in the eastern China, west coast of the Yellow Sea, separates the South Yellow Sea (SYS) from the North Yellow Sea (NYS). Bedrocks of Shandong Peninsula are mainly igneous and metamorphic rocks. Small rivers (e.g. Dagu, Wulong, Rushan and Muzhu Rivers) originate from peninsula hills and flow into sea from both south and north banks of Shandong Peninsula (Xu et al., 2013a). As a spawning, feeding ground for a variety of marine life and traditional fishing ground, the coastal area around Shandong Peninsula is an important fishery and breeding area in eastern China (Jin and Tang, 1996; Gao et al., 2003). Several big cities (Qingdao, Yantai and Weihai Cities), with millions of population and prosperous economy, are located in the coastal area of Shandong Peninsula. It is part of Bohai economic rim and Yellow River economic belt, one of indispensable part of China’s coastal economic belt. Due to the rapidly expanding eco- nomic and industrial developments in these cities, anthropogenic pollutants increased obviously, resulting in heavy metal contami- nation occurring in Shandong Peninsula coastal area in recent dec- ades. For example, Jiaozhou Bay, located in south of Shandong Peninsula and surrounded by Qingdao city, was found heavily pol- luted for the Cu, Pb, Cd and Zn near estuaries of the east coast (Deng et al., 2010). Heavy metal pollution status of Shandong Pen- insula coastal area has attracted considerable attention of both sci- entific and regulatory communities. Recent studies mainly focused on assessment of heavy metal pollution of some estuaries and bays around Shandong Peninsula (Wang et al., 2007; Gao et al., 2008; Deng et al., 2010; Sun et al., 2012; Zhang et al., 2012a; Sheng 0025-326X/$ - see front matter Ó 2013 Elsevier Ltd. All rights reserved. http://dx.doi.org/10.1016/j.marpolbul.2013.08.032 Corresponding author. Address: Qingdao Institute of Marine Geology, Fuzhou South Road 62#, Qingdao, Shandong 266071, China. Tel.: +86 532 85718613; fax: +86 532 85720553. E-mail address: [email protected] (B. Hu). Marine Pollution Bulletin 76 (2013) 420–426 Contents lists available at ScienceDirect Marine Pollution Bulletin journal homepage: www.elsevier.com/locate/marpolbul

Heavy metals distribution and contamination in surface sediments of the coastal Shandong Peninsula (Yellow Sea)

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Marine Pollution Bulletin 76 (2013) 420–426

Contents lists available at ScienceDirect

Marine Pollution Bulletin

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

Baseline

Heavy metals distribution and contamination in surface sediments of thecoastal Shandong Peninsula (Yellow Sea)

0025-326X/$ - see front matter � 2013 Elsevier Ltd. All rights reserved.http://dx.doi.org/10.1016/j.marpolbul.2013.08.032

⇑ Corresponding author. Address: Qingdao Institute of Marine Geology, FuzhouSouth Road 62#, Qingdao, Shandong 266071, China. Tel.: +86 532 85718613; fax:+86 532 85720553.

E-mail address: [email protected] (B. Hu).

Guogang Li a, Bangqi Hu b,⇑, Jianqiang Bi a, Qinuan Leng a, Chunqiao Xiao a, Zhongcheng Yang c

a Beihai Offshore Engineering Survey Institute of the State Oceanic Administration, Qingdao 266061, Chinab Key Laboratory of Marine Hydrocarbon Resources and Environmental Geology, Qingdao Institute of Marine Geology, Ministry of Land and Resources, Qingdao 266071, Chinac Qingdao Bohai Construction Group Corporation, Qingdao 266001, China

a r t i c l e i n f o

Keywords:Heavy metals contaminationSediment quality guidelinesEnvironmental assessmentShandong Peninsula

a b s t r a c t

Selected heavy metals (Cr, Cu, Ni, Pb and Zn) in surface sediments from the coastal Shandong Peninsula(Yellow Sea) have been determined to evaluate the spatial distribution and potential ecological risk.Results showed that heavy metal concentrations in the sediments generally met the criteria of ChinaMarine Sediment Quality. However, both the enrichment factor (EF) and geoaccumulation index (Igeo) val-ues suggested the elevation of Pb concentration in the region. Based on the effect-range classification(TEL-PEL SQGs), Cr, Cu and Ni were likely to pose environment risks. Spatial distribution of ecotoxicolog-ical index (mean-PEL-quotient) suggested that most of the surface sediments have a 21% probability ofbeing toxic. Similar results were also obtained by pollution load index (PLI). The spatial distribution pat-tern of heavy metal in surface sediments is a basis for undertaking appropriate action to protect marinesediment quality.

� 2013 Elsevier Ltd. All rights reserved.

Since 1980s, a rapid industrialization and economic develop-ment in China has brought a thriving economic success, accompa-nied with a series of severe environmental problems (Gao andChen, 2012; Gu et al., 2012; Pan and Wang, 2012; Zhang et al.,2012b; Gan et al., 2013; Zhao et al., 2013). Toxic pollutants, suchas heavy metals originating from human activities, are continuingto be introduced to aquatic environment through rivers, wastedumping and aeolian processes, then deposited in marine sedi-ments as a sink. One of the largest problems associated with thepersistence of heavy metals is the potential for bioaccumulationand biomagnification, resulting in potential long-term implicationson human health and ecosystem (Rainbow, 2007; Wang and Rain-bow, 2008). Due to the toxicity and persistence of heavy metal pol-lution, heavy metal research of estuarine and coastal area hasattracted more public concerns recently (Christophoridis et al.,2009; Larrose et al., 2010; Feng et al., 2011; Liu et al., 2011; Sunda-ray et al., 2011; Varol, 2011; Gao and Li, 2012; Yang et al., 2012; Huet al., 2013a; Hu et al., 2013b). It is necessary to investigate the dis-tribution and pollution degree of heavy metal, in order to interpretthe mechanism of transportation and accumulation of pollutantsand to provide basic information for coast utilization and supervi-sion (Long et al., 1998; Long et al., 2006).

The Shandong Peninsula locates in the eastern China, west coastof the Yellow Sea, separates the South Yellow Sea (SYS) from theNorth Yellow Sea (NYS). Bedrocks of Shandong Peninsula aremainly igneous and metamorphic rocks. Small rivers (e.g. Dagu,Wulong, Rushan and Muzhu Rivers) originate from peninsula hillsand flow into sea from both south and north banks of ShandongPeninsula (Xu et al., 2013a). As a spawning, feeding ground for avariety of marine life and traditional fishing ground, the coastalarea around Shandong Peninsula is an important fishery andbreeding area in eastern China (Jin and Tang, 1996; Gao et al.,2003). Several big cities (Qingdao, Yantai and Weihai Cities), withmillions of population and prosperous economy, are located inthe coastal area of Shandong Peninsula. It is part of Bohai economicrim and Yellow River economic belt, one of indispensable part ofChina’s coastal economic belt. Due to the rapidly expanding eco-nomic and industrial developments in these cities, anthropogenicpollutants increased obviously, resulting in heavy metal contami-nation occurring in Shandong Peninsula coastal area in recent dec-ades. For example, Jiaozhou Bay, located in south of ShandongPeninsula and surrounded by Qingdao city, was found heavily pol-luted for the Cu, Pb, Cd and Zn near estuaries of the east coast(Deng et al., 2010). Heavy metal pollution status of Shandong Pen-insula coastal area has attracted considerable attention of both sci-entific and regulatory communities. Recent studies mainly focusedon assessment of heavy metal pollution of some estuaries and baysaround Shandong Peninsula (Wang et al., 2007; Gao et al., 2008;Deng et al., 2010; Sun et al., 2012; Zhang et al., 2012a; Sheng

G. Li et al. / Marine Pollution Bulletin 76 (2013) 420–426 421

et al., 2013; Xu et al., 2013a, 2013b) or the offshore area of SouthYellow Sea (He et al., 2008; Yuan et al., 2012). So far, there are lim-ited works focused on large-scale and thoroughly sampled investi-gation for the coastal area of Shandong Peninsula.

In this study, a total of 208 surface sediment samples, collectedaround the coastal area of Shandong Peninsula, were analyzed forsediment types and chemical composition. Our main objectivesare: (1) to reveal the spatial distribution of heavy metals (Cr, Cu,Ni, Pb and Zn) in the study area, (2) to assess potential ecologicalrisk using mean-PEL-quotients (M-PEL-Q), (3) to evaluate the me-tal contamination using the enrichment factor (EF), geoaccumula-tion index (Igeo) and pollution load index (PLI).

Based on Chinese Offshore Investigation and Assessment Pro-ject, a total of 208 surface sediment samples (0–2 cm depth) werecollected from the coastal Shandong Peninsula (Fig. 1) in 2007. Allsamples were obtained by a stainless steel grab sampler. Afterdetermining general sediments characteristics onboard, sedimentsamples were then frozen in cold store until further laboratoryanalysis. Bulk sediment sample was divided into three subsamplesfor the determinations of heavy metals, total organic carbon (TOC)and grain size. Grain size analysis was performed using MalvernMastersizer 2000 laser particle size analyzer. Before analysis, about1 g samples were pre-treated with 30% H2O2 and 0.5 N HCl for 24 hto remove organic matter and biogenic carbonate.

Fig. 1. Map showing the Yellow Sea in North China (a) and the s

Prior to elements analyses, about 20 g of the sub-samples wereoven-dried at 45 �C for 24 h, then ground to pass a 0.125 mm sieveand stored in clean plastic bags at room temperature. An X-rayfluorescence spectrometer (XRF, Axios PW4400) was used fordetermining Al and Fe and inductively coupled plasma mass spec-trometry (ICP-MS, Thermo X series) for Cr, Cu, Ni, Pb and Zn. Blanksand China Stream Sediment Reference Materials (GSD9, GSD4 andGBW07345) were included in the analyses as part of the qualityassurance and quality control (QA/QC) (see Dou et al., 2013 for de-tail). The differences of the concentrations between the deter-mined and certified values were less than 5%, and the analyticalprecision for replicate samples was within ±10%. Prior to total or-ganic carbon (TOC) analysis, sub-samples were freeze-dried andpulverized. After that, about 1 g sediments were treated with 10%HCl for 3 h to remove inorganic carbon, then dried and determinedwith a Carlo-Erba™ element analyzer. The measurement error waswithin 5% based on replicate sediment analysis.

The statistical summary and other comparisons of the heavymetal contents are summarized in Table 1. The ranges of heavymetal contents and TOC were: 35.0–99.6 mg/kg for Cr, 6.7–46.2 mg/kg for Cu, 19.0–56.8 mg/kg for Ni, 19.0–42.2 mg/kg forPb, 37.0–181.1 mg/kg for Zn and 0.26–1.58% for TOC. Based onthe mean content, the components in surface sediments were ar-ranged in the following decreasing order: Zn > Cr > Ni > Pb > Cu.

urface sampling sites in the coastal Shandong Peninsula (b).

Table 1Summary of heavy metal concentrations in surface sediments of the coastal Shandong Peninsula (unit: mg kg�1).

Regions Cr Cu Ni Pb Zn Reference

Coastal Shandong Peninsula 35.0–99.6 6.7–46.2 19.0–56.8 19.0–42.2 37.0–181.1 This study(57.8 ± 10.7) (20.0 ± 7.2) (31.2 ± 6.5) (28.4 ± 3.7) (74.7 ± 22.4)

Bohai Bay, Bohai Sea 10.2–84.3 7.8–38.6 16.5–43.7 8.7–53.6 40.5–126 Hu et al. (2013a)(33.5) (22.7) (30.5) (21.7) (71.7)

Liaodong Bay, Bohai Sea 8.0–75.8 5.7–37.1 7.0–40.5 18.9–61.2 14.5–145 Hu et al. (2013b)(46.4) (19.4) (22.5) (31.8) (71.7)

Changjiang Estuary 36.9–173 6.9–49.7 17.6–48.0 18.3–44.1 47.6–154 Zhang et al. (2009)(78.9) 30.7 (31.8) (27.3) (94.3)

Pearl River Estuary 58.1–118 11.2–75.7 18.1–72.7 49.3–78.9 28.4–237 Zhou et al. (2004)(89.0) (46.2) (41.7) (59.3) (150)

South Yellow Sea n.d. 6.0–32.9 n.d. 6.2–39.3 24.6–244 Yuan et al. (2012)(16.9) (17.8) (93.7)

East China Sea Inner Shelf 45.1–142 18.8–49.2 n.d. 24.4–53.0 80.2–140 Liu et al. (2011)(93.5) (37.4) (34.1) (116)

Izmit Bay, Turkey 74.3 67.6 n.d. 102 930 Pekey, 2006 Hamer and Karius, 2002Bremen Bay, Germany 131 87.0 60.0 122 790Masan Bay, Korea 30.5–99.8 13.5–90.7 10.2–40.4 13.0–82.2 80.0–379 Hyun et al. (2007)

(67.1) (43.4) (28.8) (44.0) (206.3)Average upper crust of East China 99 27 37 15 66 Gao et al. (1998)MSQ-1a 80 35 n.d. 60 150 CSBTS (2002)MSQ-2a 150 100 n.d. 130 350 CSBTS (2002)

a MSQ-1 and MSQ-2 are the Marine Sediment Quality standard criteria (GB 18668-2002) issued by the China State Bureau of Quality and Technical Supervision (CSBTS).

422 G. Li et al. / Marine Pollution Bulletin 76 (2013) 420–426

For the comparison purpose, the average upper continental crust(UCC) values of East China (Gao et al., 1998) and other regionsthroughout the world are listed in Table 1.

In surface sediments from the coastal Shandong Peninsula, themean contents of Cu, Ni and Cr (Pb and Zn) were lower (higher)with respect to their corresponding average values in the UCC ofEast China (Table 1). Among all the coastal areas chosen for com-parison, the average content of Cr for coastal Shandong Peninsulawas higher than that of Bohai and Liaodong Bay (Hu et al.,2013a; Hu et al., 2013b) in the Bohai Sea, but much lower thanother regions. For the other four selected metals (Cu, Ni, Pb andZn), the mean contents of coastal Shandong Peninsula were com-parable with those of Bohai and Liaodong Bay, but lower than thosefound in the Changjiang Estuary (Zhang et al., 2009) and Pearl RiverEstuary (Zhou et al., 2004), where their surrounding areas are theother two most heavily urbanized zones in China. In addition, theaverage concentrations of Cr, Cu, Ni, Pb and Zn in the study areawere significantly lower than those found in sediments of the IzmitBay in Turkey (Pekey, 2006), Bremen Bay in Germany (Hamer andKarius, 2002) and the Masan Bay in Korea (Hyun et al., 2007).

In general, the spatial distribution of heavy metals and TOCshow similar patterns (Fig. 2). In the southern Shandong Penin-sula, high content zones of heavy metals and TOC are located inthe offshore area extending towards northwest, while relativehigher content zone are distributed along the nearshore area ofthe north Shandong Peninsula. Low values of heavy metals andTOC are found nearby the east end of Shandong Peninsula(Chengshan Cape). It is well known that organic matter has a highaffinity through adsorption or complexion for heavy metals in theaquatic environment (Dou et al., 2013; Hu et al., 2013a; Hu et al.,2013b). Significant positive correlations between TOC and heavymetals are established (Table 2), suggesting that TOC is an impor-tant factor controlling the abundance of heavy metals. Sedimentgrain size is another controlling factor affecting the abundanceof heavy metals in sediments. Due to surface adsorption and ionicattraction, fine-grained sediments tend to have relatively highmetal contents. In this study, mean grain size (Mz) was foundto be positive correlated with most metals (Table 2), with Pear-son’s correlation coefficients (r) as 0.51 for Cr, 0.56 for Cu, 0.49for Pb, 0.38 for Zn, 0.51 for Ni (p < 0.01, n = 208). This suggeststhat heavy metals contents were influenced by grain size to a cer-tain extent.

It is important to determine whether the concentrations of hea-vy metals in sediments pose a threat to aquatic life. The extent ofmetal pollution was assessed by comparing metal concentrationsin surface sediments to the China Marine Sediment Quality (GB18668-2002) (CSBTS, 2002) and the TEL/PEL SQGs (Macdonaldet al., 1996; Long et al., 1998; MacDonald et al., 2000).

Marine Sediment Quality (GB 18668-2002), established by Chi-na State Bureau of Quality and Technical Supervision (CSBTS,2002), contains three standard criteria for marine sediments. Theprimary sediment standard criteria is applied to protecting thehabitats for marine life including natural, rare and endangered spe-cies as well as the areas for human recreation and sports, while thesecond sediment standard criteria is applied to regulating generalindustrial use and coastal tourism. Referring to Marine SedimentQuality (GB 18668-2002), the overall average concentrations ofall selected heavy metals in the coastal Shandong Peninsula surfacesediments are below or close to the primary standard criteria (Ta-ble 1). However, the metal concentrations at several sampling sitesexceeded the primary criteria (MSQ-1). Among the 208 samplingsites, there were eight sites exceeding the primary criteria for Cr,six sites for Cu, and four sites for Zn, but below the secondary cri-teria (MSQ-2). Because there are no Ni standards available in GB18668-2002, we cannot evaluate the sediment quality with respectto Ni. In general, the studied five heavy metal concentration sug-gested that the overall sediment quality in the coastal ShandongPeninsula has not been significantly impacted by heavy metalpollution.

The TEL/PEL SQGs are also applied to assess the degree to whichthe sediment-associated chemical status might adversely affectaquatic organisms and are designed to assist in the interpretationof sediment quality (Macdonald et al., 1996; Long et al., 1998; Mac-Donald et al., 2000). The threshold effects level (TEL) were inter-preted to present chemical concentrations below which adversebiological effects rarely occur, and the probable effects level (PEL)were intended to present chemical concentrations above which ad-verse biological effects frequently occur (Macdonald et al., 2000).When compared to the TEL-PEL SQGs, the concentrations of Cr,Cu, Ni, Pb and Zn are below TEL with 36%, 45%, 0%, 96% and 73%of sample sites, respectively, and 64% for Cr, 55% for Cu, 95% forNi, 4% for Pb and 27% for Zn fall in the range between TEL andPEL. There are also 5% of sample sites for Ni slightly exceeds PEL,which indicated a potential harm for aquatic organisms (Table 3).

Fig. 2. Spatial distribution of total organic carbon (%TOC) and heavy metal concentrations (Cr, Cu, Ni, Pb and Zn, mg kg�1) of surface sediments in the coastal ShandongPeninsula.

Table 2Pearson’s correlation matrix for the heavy metals and major elements, TOC and meangrain-size (Mz).

TOC Mz Cr Cu Pb Zn Ni Al

Mz 0.486Cr 0.835 0.506Cu 0.735 0.560 0.865Pb 0.726 0.492 0.553 0.488Zn 0.618 0.384 0.650 0.627 0.437Ni 0.870 0.506 0.903 0.841 0.665 0.610Al 0.829 0.590 0.884 0.903 0.573 0.678 0.863Fe 0.741 0.575 0.830 0.857 0.692 0.628 0.796 0.843

Correlation is significant at the 0.01 level (two-tailed).

Table 3Comparison between heavy metals concentration (mg/kg) in the study area and theTEL and PEL-SQGs (MacDonald et al., 2000).

Sediment quality guidelines Metal concentration (mg/kg)

Cr Cu Ni Zn Pb

TEL 52.3 18.7 15.9 124 30.2PEL 160 108 42.8 271 112

Compared with TEL and PEL (% of sample in each guideline)

<TEL (%) 36 45 0 96 73PTEL and < PEL (%) 64 55 95 4 27PPEL (%) 0 0 5 0 0

G. Li et al. / Marine Pollution Bulletin 76 (2013) 420–426 423

In order to combine metal-specific SQG values and then todetermine the possible biological effect of combined metals, the

mean PEL quotients (m-PEL-Q) for the five measured heavy metals(Cr, Cu, Ni, Pb and Zn) were calculated as following (Long et al.,1998):

m� PEL� Q ¼

Xn

i¼1

ðCi=PELiÞ

nð1Þ

where Ci is the concentration of measured metal (i), PELi is the PELvalues of metal (i) and n is the number of metal. Several classes oftoxicity probability for biota were defined as: m-PEL-Q < 0.1: 8%probability of toxicity; 0.11–1.5: 21% probability of toxicity;1.51–2.3: 49% probability of toxicity; and >2.3: 73% probabilityof toxicity (Long et al., 1998). The m-PEL-Q in surface sedimentsof the coastal Shandong Peninsula varied from 0.22 to 0.62 (meanvalue of 0.36), indicating that the combination of the five studiedmetals may have a 21% probability of being toxic. Based on the m-PEL-Q data, a contour map of multi-metals ecological risk poten-tial of east Shandong Peninsula was presented (Fig. 3a). The high-est potential ecological risk zone was found in southeast area andrelatively high potential was found in the nearshore area of northShandong Peninsula.

The enrichment factor (EF) is widely used to estimates the me-tal source (anthropogenic or natural) and the degree of anthropo-genic influence based on the use of a normalization element inorder to alleviate the variations produced by heterogeneous sedi-ments (Adamo et al., 2005). In this study, the crustal average metalconcentrations in eastern China (Gao et al., 1998) were used as thebackground metal values shown in (Table 1). We defined the EF asthe sample metal (Me) to aluminum (Al) ratio divided by the base-line metal/Al ratio, and expressed as:

Fig. 3. Spatial distribution of m-PEL-Q (a) and PLI (b) in the coastal ShandongPeninsula.

0

1

2

3

EF

Cr Cu Ni Pb Zn

-3

-2

-1

0

1

Igeo

Cr Cu Ni Pb Zn

0

1

2

3

CF

Cr Cu Ni Pb Zn

(a)

(b)

(c)

Fig. 4. Box-and-whisker plots for (a) EF, (b) Igeo and (c) CF of heavy metals in thesurface sediments of coastal Shandong Peninsula.

424 G. Li et al. / Marine Pollution Bulletin 76 (2013) 420–426

EF ¼Me=Alð Þsample

Me=Alð Þbaselineð2Þ

where (Me/Al)sample and (Me/Al)baseline represent the ratio of heavymetal to Al concentrations in this study and in background sample,respectively. Generally, an EF value of 0.5–1.5 suggests the givenmetal may be entirely provided from crustal contribution or naturalweathering processes, while the EF value greater than 1.5 indicatesa significant proportion of non-crustal metal composition comingfrom either natural processes or anthropogenic influence (Zhangand Liu, 2002). The EF values of heavy metals in the study area var-ied as follow: 0.44–0.75 (mean of 0.57) for Cr, 0.30–1.43 (mean of0.72) for Cu, 0.62–1.15 (mean of 0.84) for Ni, 1.53–2.67(mean of1.9) for Pb and 0.74–2.64 (mean of 1.12) for Zn (Fig. 4a). As shownin box and whisker plot (Fig. 4a), the EF values of Cr, Cu, Ni and Znwere less than 1.5, suggesting a primary natural source in the studyarea, whereas the EF values of Pb were all greater than 1.5, indicat-ing a notably non-crustal origin. This suggests that Pb was the mostcontaminated element among the five studied heavy metals, andthe major source of Pb was anthropogenic input such as gasolineand industrial activities (Cheng and Hu, 2010).

The geoaccumulation index (Igeo) is another parameter to assessthe heavy metal contamination (Müller, 1979), is defined as thefollowing equation:

Igeo ¼ log2Cn

1:5Bn

� �ð3Þ

where Cn is the concentration of metal (n) and Bn is the geochemicalbackground concentration of metal (n). The factor of 1.5 is a back-ground matrix correction factor that includes possible variations

of the background values due to lithogenic effects (Müller, 1979).A seven-level classification of Igeo is defined as: unpolluted (Igeo 6 0),unpolluted to moderately polluted (0 < Igeo 6 1), moderately pol-luted (1 < Igeo 6 2), moderately to strongly polluted (2 < Igeo 6 3),strongly polluted (3 < Igeo 6 4), strongly to extremely polluted(4 < Igeo 6 5), and extremely polluted (Igeo > 5) (Müller, 1981). TheIgeo values of surface sediments from the coastal Shandong Penin-sula are �2.08 to �0.58 (average �1.39) for Cr, �2.29 to 0.19 (aver-age �1.12) for Cu, �1.55 to 0.03 (average �0.86) for Ni, �0.24 to0.91 (average 0.32) for Pb and �1.42 to 0.87 (average �0.46) forZn, respectively (Fig. 4b). The averaged pollution degree of thesemetals decreased in the following order: Pb > Zn > Ni > Cu > Cr,which is similar with that observed from EF values. According tothe Müller scale (Müller 1981), the Igeo values indicates no pollutionof the investigated metals in the study area as a whole, althoughsome deviation is observed depending on each metal and samplinglocation. The Igeo values for Pb were between 0 and 1 generally, indi-cating that slight to moderate Pb pollution occurred around Shan-dong Peninsula.

The contamination factor (CF) and pollution load index (PLI) arealso introduced to assess the degree of anthropogenic metal con-tamination. The CF for each metal is the ratio of measured concen-tration in the sediment to the background value, which is definedas follows:

CF ¼ Mesample

Mebaselineð4Þ

G. Li et al. / Marine Pollution Bulletin 76 (2013) 420–426 425

If CF < 1, it means no or low contamination exists; 1 < CF < 3 ismoderate contamination; 3 < CF < 6 is considerable contamination;and CF > 6 is very high contamination (Hakanson, 1980). The PLI isdetermined as the nth root of the n contamination factors (CFn)multiplied together and calculated using the following equation:

PLI ¼ ðCF1 � CF2 � CF3 � . . .� CFnÞ1=n ð5Þ

This empirical index provides a simple, comparative means forassessing the level of heavy metal pollution. The PLI value >1 indi-cates a polluted condition, while PLI <1 means no metal pollutionexisting (Tomlinson et al., 1980). The results of CFs are 0.35 to1.01 (average 0.58) for Cr, 0.25 to 1.71 (average 0.74) for Cu, 1.27to 2.81 (average 1.89) for Pb, 0.56 to 2.74 (average 1.13) for Zn,0.51 to 1.53 (average 0.84) for Ni, respectively (Fig. 4c), with thesame decreasing order as EF and Igeo: Pb > Zn > Ni > Cu > Cr. ThePLI values are between 0.56 and 1.62, with mean of 0.94. Amongall sampling sites, 69 of 208 values are greater than 1, which means33% of sites are metal contaminated to some extent. As shown inthe contour map of PLI values (Fig. 3b), the distribution of pollutionare the same as that observed from m-PEL-Q index (Fig. 3a).

This field study demonstrated that the sediment quality in thecoastal Shandong Peninsula (Yellow Sea) generally met the pri-mary sediment criteria of Chinese Marine Sediment Quality (GB18668-2002). Both the EF and Igeo values showed a moderate to sig-nificant Pb contamination in the study area. In compared with con-sensus-based SQGs, Cr, Cu and Ni were likely to result inoccasionally adverse biological effects on the aquatic ecosystems.Spatial distribution of the ecotoxicological index (mean-PEL-quo-tients) suggests that the combination of the five studied metalsmay have a 21% probability of being toxic. Both of the m-PEL-Qand PLI shown that the highest ecotoxicological potential zonesare located in southeast area, and relatively high potential wasfound in the nearshore area of north Shandong Peninsula. Thiswork represents the current state of sediment quality in the coastalShandong Peninsula that will be a useful tool to authorities incharge of sustainable estuarine and coastal zone management.

Acknowledgments

This work was jointly supported by Project of State OceanicAdministration, China (908-01-CJ05), National Natural ScienceFoundation of China (41206049) and Marine Science & TechnologyProgram of North China Sea Branch of the State Oceanic Adminis-tration (2013B11).

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