Figure
1.
Locations of Dongting Lake and sediment sampling points.
| Citation: | Majid Abrehdary, Lars E. Sjöberg, Mohammad Bagherbandi. Combined Moho parameters determination using CRUST1.0 and Vening Meinesz-Moritz model. Journal of Earth Science, 2015, 26(4): 607-616. doi: 10.1007/s12583-015-0571-6
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Fresh water lakes are one of the planet's most important freshwater resources. They support life in various forms, develop tourism and provide unique recreational opportunities. It is also a good source of the provision of drinking-water for local communities. Studies on trace elements in rivers, lakes, and sediments (Zhou et al., 2004; Gray et al., 2000; Grosheva et al., 2000; Klavins et al., 2000; Aucoin et al., 1999; Bortoli et al., 1998; Elbaz-Poulichet et al., 1996; Johansson et al., 1995; Förstner and Wittmann, 1979) have become a major environmental focus especially in the last decades because of their toxicity, persistence, and bio-accumulative nature. Sediments are not only important sinks for various pollutants like pesticides and trace metals but also they play a significant role in the remobilization of contaminants in aquatic system under favorable conditions and in the interactions between water and sediment. The release of trace metals from sediments into the water body and consequently to the aquatic organisms depends on the speciation (i.e. metals may be precipitated, complexed, adsorbed, or solubi-lized) of metals. It also depends on some other fac-tors such as sediment pH and the physical and chemical characteristics of the aquatic system (Morgan and Stumm, 1991).
Dongting Lake lies south of the middle Yangtze River in Hunan Province, China and its area is 2 691 km2 (Lu et al., 2003). It is the second largest fresh-water lake, and it serves as the important reservoir for Yangtze River valley. This lake is a source of drinking water and serves as a tourism spot and provides unique recreational opportunities. Yangtze River pours flows from northwest and joins the lake through three river channels named Songzi, Hudu and Ouzi river channels (ab. Song-Ou channels). Other four major tributaries, namely, Xiangjiang, Zishui, Yuanjiang, and Lishui rivers discharge water into the lake from south, west, and northwest, respectively. Northeastward water flows out of Dongting Lake through Chenglingji back into Yangtze River and finally discharges into East China Sea (Fig. 1). Dongting Lake mainly consists of East Dongting Lake, South Dongting Lake (including Wanzi Lake and Hengling Lake) and West Dongting Lake. This lake serves as a remarkable habitat for animal and plant life, especially for waterfowl, and is wetlands of international importance, protected by the Ramsar Convention (Sitelist of Wetlands of International Importance, 2004). During the last decade, researchers have mainly focused on the water pollution of Dongting Lake (Mao and Xia, 2002; Bu and Chai, 2001; tu, 2001; Dai et al., 2000), and they assumed that the overall water quality in the lake region was within the third class of water quantity of surface water and belongs to the middle-degree eutrophic type (by environment quantity standards for surface water by China State Bureau of Environment Protection and Quality and Technical Supervision, GHZB 1-1999). However, few studies have dealt with the aspect of pollution and distribution of trace metals in the sediment of Dongting Lake. The major objective of this research is: (1) to investigate the contamination levels of trace metals in sediments from the Dongting Lake area; (2) to study the speciation of trace metals (Cd, Cr, Cu, Ni, Pb and Zn) in the lake sediments because of their environmental implication; (3) to assess the risk of Dongting Lake water contamination by analyzing the lake sediment.
To study the status quo of trace metal pollution, lake and stream sediment samples were mainly collected from the places, where tributaries joined Dongting Lake and the centre belt of Dongting Lake and this study was made in November, 2004 (Fig. 1). Sediment samples within the 0-25 cm surface layer were collected using a precleaned stainless dredge (10"×6"×5") and immediately placed in plastic zipped-bags. Those samples were transported to the laboratory and air-dried at room temperature, and sieved into 2 mm grain size. It was then disaggregated by mortar and pestle and quartered and finally those samples less than 0.074 mm grain size were taken for analysis. The local sampling points were calibrated using GPS (Global Position System).
The sediment fractions were subjected to a modified BCR sequential extraction technique (Mossop and Davidson, 2003). Extractions were carried out using the reagents given in Table 1.The various stages of extraction in this study are described as follows.
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Step 1: Extraction of exchangeable metals, water and acid soluble metals: a total of 40 mL of acetic acid was added to 1 g of the air-dried sediment and was shaken overnight. The mixture was centrifuged to separate the extract from the residue.
Step 2: Extraction of reducible metals: a total of 40 mL of hydroxylammonium chloride at pH 1.5 was added to the residue obtained from step 1 in a centrifuge tube and then extraction was performed as above.
Step 3: Extraction of oxidizable metals: the residue obtained from step 2 was treated twice with 8.8 mol/L hydrogen peroxide and evaporated to near dryness, followed by the addition of 50 mL of ammonium acetate, adjusted to pH 2 with nitric acid, and then the extraction was performed as above.
Step 4: Extraction of residual fraction: the material remaining after step 3 was digested with aqua acid using microwave-assisted digestion procedure by Mars-5 microwave labstation (CEM Company, USA). The residues were placed in a PTFE reactor with 65% HNO3 4 mL and 37% HCl 12 mL.
Then they were heated followed a three-stage digestion programmer in Mars-5 microwave labstation: step 1, 250 W, 2 min; step 2, 400 W, 2 min; step 3, 500 W, 8 min. The concentrations of the trace metals were determined by AAS on a Perkin-Elmer 800. Duplicate measurements showed that concentrations of elements are reproducible with an analytical precision better than 10%.
Total element concentrations were determined by the analysis of digested sediments. Lake sediments were digested with 30 mL of HCl∶HNO3∶H2O mixture (3∶1∶2 volume to volume) at 95 ℃ for 1 h and analyzed for Cd, Cr, Cu, Ni, Pb and Zn by ICP-MS (Thermoelemental X7, made in USA). Validation of instrument accuracy and precision was carried out through the analysis of GBW07401, GBW07402, and GBW07403 reference samples (the State Primary Reference Material, SPRM, China) (Table 2). Also the analysis of elements using blanks is reproducible with an analytical precision better than 10%. These results were applicable for each metal and sample in almost all cases.
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The concentrations of 6 trace metals (Cd, Cr, Cu, Ni, Pb and Zn) in sediments collected from Dongting Lake, and other global published values for lake sediments are listed in Table 3. Considering the whole Dongting Lake, the average values of copper, lead, zinc, cadmium, chromium, and nickel are higher compared with the corresponding values obtained for water sediments, Quaternary red soil, and carbonate rock from Yangtze River drainage area, China (Zhu and Zang, 2001; Zhang et al., 1995), especially the average concentration of Cd in sediments collected from Dongting Lake is up to 2.7 mg/kg, which is 20 times or more compared with other sediment samples. It shows that Cd added is highly pollutant. In addition to cadmium, the average values of copper, lead, zinc, chromium, and nickel in this study are also higher compared with the corresponding values of the samples obtained from Poyang Lake (the biggest fresh-water lake in China) (lu, 1994), Taihu Lake (the third fresh-water lake in China) (Qu et al., 2001), Tuskegee Lake (Ikem et al., 2003), Lake Pontchartrain (Byrne and Deleon, 1986), and Siberian Pond (Gladyshev et al., 2001). Additionally, the results in this study for copper, lead, zinc, and cadmium are higher than the background levels of soil (Ⅰ soil, national standards of soil environment quality by China State Bureau of Environment Protection and Quality and Technical Supervision, GB 15618-1995), while those of Cr and Ni are 86.8 and 39.8 mg/kg, respectively, which are similar toⅠ soil. However, with the exception of the higher concentration of Cd, the average concentrations of copper, lead, zinc, and nickel in this study are lower compared with the threshold values for severely polluted soil (Ⅲ soil, GB 15618-1995). According to the results of Canadian fresh-water sediment analysis, the concentrations of copper, lead, zinc, cadmium, and chromium in this study are higher compared with the Canada EPA (Environment Protect Agency) Interim Sediment Quality Guideline (ISQG) Threshold Effect Level (TEL) and are lower compared with the Probable Effect Level (PEL) for the above metals (Table 3); Only the effect of nickel is slightly higher than the PEL value, which may be resulted from the regional higher Ni-background. The TEL indicates the threshold levels of sediment contamination by various elements that can be tolerated by the majority of benthic organisms; whereas the PEL shows the probable levels of sediment contamination by various elements that cannot be tolerated by the majority of benthic organisms (smith, 1996). It is obvious that Dongting Lake area has suffered from heavy metal pollution, especially due to Cd to some extent. The relatively higher values obtained for Dongting Lake sediments with respect to other lake sediments and regional background levels already discussed may bebecause of the heavier impact anthropogenic sources on pollution by anthropogenic sources in the Dongting Lake drainage area.
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In this study, the authors used the modified BCR three-step sequential extraction technique to determine the chemical association of these trace elements (Cu, Pb, Zn, Cd, Cr and Ni) with major sedimentary phase. The metals associated with the sediment in the most labile manner are obtained in the first step, which are called soluble species and carbonates phases. The metals bouned to iron and manganese oxhydroxides phases are obtained in the second step and the metals associated with the organic matter and sulphides are released in the third step and the residual fraction is obtained in the final step. Speciation is very useful to determine the degree of association of the metals in the sedimentand to find the extent of remobilization of these metals into the environment (Förstner, et al., 1990). Also this method is useful for distinguishing those metals with a lithogenic origin from those with an anthropogenic origin. Table 4 shows the mean trace element concentrations in sediments, collected from Dongting Lake, and calculated using BCR sequential extraction procedure. Figure 2 shows the results of chemical
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Considering the Dongting Lake sediments, all the 6 trace elements, except Pb and Cd, were extracted from the residual fraction (step 4) at an average percentage higher than 60%; especially, 80% for Cr and 90% for Ni. According to Rubio et al. (1991) and Samanidou and Fytianos (1987), the residual phase represents those metals, which are largely embedded in the crystal lattice of the sediment fraction with a lithogenic origin, and they are not remobilized into the aquatic medium in the nature's conditions, except under very harsh situations. Therefore, it is assumed that, heavy metals Cu, Zn, Cr, and Ni mainly originate during the production of parent rock weathering and are transported and deposited in mineral substances of natural rock debris.
In the sediments of the Dongting Lake district, the presence of exchangeable and carbonate-bandedmetals (step 1) is very low, approximately 9% of Zn, 5% of Cu and Ni, 2% of Pb and 0.4% of Cr, with an exception of Cd, which occupies approximately 50%. According to Pérez et al. (1991), the metals associated with exchangeable ions and carbonates are extremely important because it represents the proportion of heavy metals that can be easily remobilized by the changes in environmental conditions such as pH, salinity, etc.. Therefore the Cd in sediments poses the biggest potential environmental risk. For Fe/Mn oxhydroxides phases (step 2), the average percentage of Pb in the reducible fraction is approximately 60%, followed by 25% for Cu and Cd, 20% for Zn, 4% for Cr, and 8% for Ni. Fe/Mn oxides exist as nodules, concretions, cement between particles or as a coating on particles, and these are excellent trace element scavengers (jenne, 1968). In the sediments of Dongting Lake, the redox-sensitive Fe/Mn hydroxides/oxides constitute significant sinks of heavy metals in the aquatic systems, especially Pb. The average percentages of 6 trace elements in sulfides and organic matter phases (step 3) are similar and range from 7% to 10%. The interaction of organic complexes and sorbing agents with trace elements in the sediments is a chelation, which is a biochemical process. Comparing with the result of the speciation analysis, it can be concluded that co-precipitation with iron sulfides and the chelation with organic matter are less effective in concentrating trace metals than incorporating into Fe/Mn hydroxides. Under oxidizing conditions, metals present in natural organic matter and sulfides (due to complexation and peptization) and living organisms (as a result of bioaccumulation of metals) may be remobilized into the aquatic environment.
Irrespective of sampling point, the distribution of metals in the Dongting Lake sediment samples generally follows the order given below: for Cu and Zn, residual fraction > Fe/Mn oxhydroxides > organic matter and sulphides > exchangeable and carbonate bound; for Pb, Fe/Mn oxhydroxides > residual fraction > organic matter and sulphides > exchangeable and carbonate bound; for Cd, exchangeable and carbonate bound > Fe/Mn oxhydroxides > residual fraction > organic matter and sulphides; and for Cr and Ni, the order is residual fraction > organic matter and sulphides > Fe/Mn oxhydroxides > exchangeable and carbonate bound.
A quantitative measure of metal pollution in aquatic sediments has been introduced by Müller (1979), which is called the "index of geoaccumulation", and developed in Europe. It is widely used to study the levels of pollution of the trace metals in sediments, especially, it is used recently to study the trace metal pollution assessments in sediments (Förstner, 1989; Müller, 1979). The formula of geoaccumulation index is as follows
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(1) |
where Cn represents the concentration of the measured element "n" in the sediment, and its unit is mg/kg; Bn is the geochemistry background value of the elements "n" in sediments; its unit also is mg/kg. The factor k is used because of the possible variations of the background data due to lithogenic effects (in general, k is 1.5). Here, approximately 79.5% of Dongting Lake sediments come from Yangtze River, while the sediments from Xiangjiang River, Zishui River, Yuanjiang River, and Lishui River are only 18.0%, and other sources provide 2.5% (Jiang and Do, 2003). This distribution is seemed to be similar to the trace element concentrations of the soil of Dongting alluvia plain (ab., SDTAP). Therefore the concentrations of STDAP are taken as Bn: Cu, 45.86 mg/kg; Pb, 27.75 mg/kg; Zn, 99.67 mg/kg; Cd, 0.23 mg/kg; Cr, 83.92 mg/kg; Ni, 41.8 mg/kg (tong, 2005). As the possible variations of the background data due to lithogenic effects are also considered, k is taken as 1 in this study. The index of geo-accumulation consists of 7 grades (Table 4) (Förstner et al., 1990).
Table 5 shows that the index values for the whole Dongting Lake lie at a maximum of 4 for Cd, while the indices for Cu, Pb, and Zn attain grade 1. Cadmium reaches the highest grade 5 in East Dongting Lake and Chenglingji. From Lujiao to Chenglingji within East Dongting Lake, the degree of pollution of cadmium achieves strong to very strong, and the polluted levels of Cu, Pb and Zn are higher compared with other lakes. In whole Dongting Lake, the order of Cd pollution is: East Dongting Lake > Chenglingji > West Dongting Lake > Hengling Lake > Wanzi Lake > Datong Lake > Song-Ou channels > Caisang Lake; the decreasing order of indices for Cu is: East Dongting Lake > Datong Lake, but other lakes are unpolluted by Cu. East Dongting attains moderate pollution by Pb and Zn, while other lakes remain unpolluted. Cr and Ni do not cause pollution in these lakes.
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To evaluate the mobility and bioavailability of trace elements in sediments from Dongting Lake, individual (Cfi) and global (Cf=ΣCfi) contamination factors were calculated. The individual contamination factor (Cfi) was defined as the sum of heavy metal concentration in the mobile phases (from step 1 to step 3) of the sample divided by the residual phase content. The global contamination factor Cf was determined as the sum of the individual factors (fernardes, 1997). These methods have been used by other authors (Marguí et al., 2004; Ikem et al., 2003; Barona et al., 1999). The lower the values, the smaller the relative metal mobility; and the higher the Cf values, the stronger the overall potential risks posed by the toxic elements. The Cfi value shows the risk of contamination of water body by a pollutant. The number of toxic elements determined in a sediment sample and their respective calculated Cfi value influences the Cf value. Table 7 shows the individual (Cfi) and global (Cf=ΣCfi) contamination factors for six elements analyzed in the sediments from Dongting Lake.
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East Dongting Lake and Chenglingji have the highest individual and global contamination factors compared with other sites, and this indicates that both these pose the highest environmental risk. Cr and Ni have the lowest Cfi values ranging from 0.1 to 0.3; for Pb, from 1.4 to 3.5; and for Zn these values range from 0.4 to 1.2; whereas Cd values are in the range of 3.4 to 30.6. Based on the calculated individual contamination factors, a decreasing order, which posed the highest risk to lake water contamination, is as follows: Cd > Pb > Zn > Cu > Ni > Cr. According to the Cf values, the decreasing order of contamination and environmental risk in the study is: Chenglingji>East Dongting Lake>Datong Lake>Hengling Lake>Wanzi Lake>West Dongting Lake>Caisang Lake. These results are consistent with those of the geo-accumulation index. Therefore, the index of geoaccumulation method is considered as a fast, economical, and effective tool to assess the heavy metal contamination in lake sediment.
The 6 trace metals' concentrations of surface sediment samples collected from the Dongting Lake area were analyzed. The results are shown as follows: (1) The worst affected district of cadmium pollution in Dongting Lake area is the part from Lujiao to Chenglingji within East Dongting Lake, which may do harm to the location and the downstream areas of Yangtze River; (2) From the assessment of geo-accumulation index, Cd is found to be the heavy metal pollutant, followed by Pd, Cu, and Zn in the sediment of Dongting Lake, and the contamination of Cd in the whole lake has already reached strongly polluted level; (3) From the fractionation study, water contamination risk is the highest in East Dongting Lake and Chenglingji based on the calculated individual contamination factors and global contamination factors obtained from the Lake sediments. Therefore, there is an urgent need to protect Dongting Lake from anthropogenic sources of pollution to reduce environmental risks, and this study may provide valuable database for future research on Dongting Lake.
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Zhigang YAO, Zhengyu BAO, Pu GAO. Environmental Assessments of Trace Metals in Sediments from Dongting Lake, Central China. Journal of Earth Science, 2006, 17(4): 310-319.
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