西南涌及支流大塱涡涌表层底泥重金属污染特征与潜在生态风险研究
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摘要
河流污染主要有内源污染和外源污染两部分,而内源污染则以底泥污染为主要代表,底泥是重金属等污染物的源与汇,会对河流造成二次污染。西南涌是连接广州和佛山两地重要的地表水体,近年来西南涌流域工农业和城镇化进程发展比较迅猛,污染物排放量大增,环境保护设施建设滞后,导致西南涌受到了严重的污染。因此本论文开展了西南涌及其污染较为严重支流大塱涡涌表层底泥重金属污染特征与赋存形态的基础研究,拟为制定西南涌及大塱涡涌污染治理与控制规划提供重要的科学依据。
本论文以西南涌流域11个采样断面和重点支流大塑涡涌7个采样断面的表层底泥样品为研究对象,选取部分底泥样品用X射线荧光光谱仪进行元素分析,应用微波消解——原子吸收分光光度法测定了底泥中重金属Cu、Zn、Pb、Cd、Cr、Mn和Fe的总量,采用Tessier五步连续提取法对底泥中Cu、Zn、Pb、Cd和Cr的形态进行逐级提取,在此基础上,对西南涌流域和支流大望涡涌底泥中重金属的来源、污染状况、沿程分布规律、赋存形态特征进行了研究,最后采用基于重金属总量和赋存形态两个体系不同方法对研究区域的重金属污染水平及潜在生态危害进行了评价。主要研究结果如下：
1.西南涌底泥中Cu的含量为58.53-4522.65mg/kg；Zn的含量为114.18-1322.43mg/kg；Pb的含量为54.53-550.00mg/kg；Cd的含量为1.01～5.81mg/kgCr的含量为10.54-2535.64mg/kg；Mn的含量为95.45-949.40mg/kg；Fe的含量为22264.18-54044.36mg/kg。Cu、Zn、Pb、Cd、Cr的平均含量分别是国家土壤质量三级标准的1.39倍、0.91倍、0.31倍、2.45倍、0.84倍,因此西南涌底泥重金属污染程度为Cd>Cu>Zn>Cr>Pb,西南涌底泥重金属的平均值分别超过珠三角土壤重金属背景值的1.81倍(Pb)到19.45倍(Cd),可见西南涌底泥重金属污染比较严重,位于工业区的大望涡涌上游S2断面重金属污染最为严重。
大塱涡涌底泥中Cu的含量为52.95-2168.95mg/kg,Zn的含量为415.00-3743.75mg/kg；Pb的含量为7.05-1884.60mg/kg；Cd的含量为0.97-8.72mg/kg；Cr的含量为82.30-762.40mg/kg；Mn的含量为73.85-240.05mg/kg；Fe的含量为22544.64-43191.96mg/kg。底泥中重金属Cu、Zn、Cd的平均含量超过土壤环境质量三级标准,Cu、Zn、Cd、Cr含量均远远超出广东土壤背景值,分别超出8.52-75.14倍,且Cu、Zn、Pb含量的平均值超过农用污泥中污染物控制标准,因此该河段疏浚出的底泥不宜作为肥料直接施用于农田,必须经过对底泥重金属进行处理才能使用。
2.西南涌底泥中重金属Cu、Zn、Cd、Cr在0.01显著性水平下呈显著正相关,表明沿岸农业污水、生活污水和工业污水有可能是它们共同的污染来源；有机质与Cu、Zn、Cr、Cd在0.01显著水平下呈显著正相关,说明沉积物中有机物和粘土矿物对重金属的分布与富集起着重要的作用。
3.西南涌和大塱涡底泥重金属的赋存形态分布趋势相似,底泥中Cu都是主要以有机结合态为主,Zn主要以碳酸盐结合态为主,Pb主要以残渣态和铁锰结合态为主,Cd主要以可交换态和有机结合态为主,Cr主要以铁锰结合态为主。
4.从基于重金属总量和赋存形态两种体系7种评价方法的结果可以看出,西南涌和大塱涡底泥中Cd、Cu和Zn的潜在生态风险及生物有效性均比较高,对环境影响比较大,西南涌污染较严重的为上游的S1与S2断面及下游的S9、S10与S11断面,大塱涡涌污染较严重的为上游的W1与W2断面及中游的W5与W6断面。
The main river pollution including internal pollution and external pollutions, and sediment pollution were investigated as the main representative in the internal pollution. As sources and sinks of heavy metals and other pollutants, sediment would cause secondary pollution. Xinan River was an important surface water bodies connecting Guangzhou and Foshan. In recent years, with the rapid development of industry and agriculture and the urbanization process in the Xinan River basin, and pollution emissions growth and the environmental protection facilities construction lags behind, resulting in serious pollution to Xinan River. In order to provide important scientific basis for pollution treatment and control planning of the Xinan River and its serious polluted branch Dalangwo Stream, the pollution characteristics and chemical speciation of heavy metals in surface sediments were carried out.
Samples of the surface sediment were taken at11positions along the Xinan River basin and7positions from the key tributary Dalangwo Stream. Parts of the sediment samples were analysed by X-ray fluorescence spectrometer method for elemental analysis, while the contents of heavy metals of Cu, Zn, Pb, Cd, Cr, Mn and Fe in the surface sediments were carried out by microwave digestion-atomic absorption spectrophotometry, and the chemical speciations of heavy metals of Cu, Zn, Pb, Cd and Cr in surface sediment were determined by the Tessier sequential extraction method. Bassed on which, the source, pollution state, distribution rule and chemical speciation characteristics of heavy metals in the surface sediment from the Xinan River basin and its branch Dalangwo Stream were studied. The pollution level and potential ecological risk of the heavy metals in surface sediments were evaluated on the basis of analysis of the total amount and chemical speciations of heavy metals. The main findings were as follows:
1. The heavy metal concentration (mg/kg) of Xinan River sediment ranged as flowings: Cu,58.53-4522.65; Zn,114.18-1322.43; Pb,54.53-550.00; Cd,1.01-5.81; Cr,10.54-2535.64; Mn,95.45-949.40; and Fe,22264.18-54044.36in the surface sediments. The average Cu, Zn, Pb, Cd and Cr were1.39,0.91,0.31,2.45and0.84times higher than Environmental Quality Standard for Soils Ⅲ, and the pollution degree of heavy metals was established as the following orders:Cd>Zn>Cu>Cr>Pb. The contents of heavy metal were1.81(Pb) to19.45(Cd) times higher than the Pearl River Delta soil background values, respectively. Obviously, the pollution of heavy metals in Xinan River sediment was serious, and the most serious pollution section was S2located in the industrial zone.
Dalangwo Stream sediment heavy metal concentration (mg/kg) were:Cu,52.95-2168.95; Zn,415.00-3743.75; Pb,7.05-1884.60; Cd,0.97-8.72; Cr,82.30-762.40; Mn,73.85-240.05; and Fe,22544.64-43191.96in the surface sediments. Compared with Environmental Quality Standard for Soils Ⅲ, Cu, Zn and Cd were out of limits badly. The average contents of Cu, Zn, Cd and Cr were far beyond the Guangdong soil background values, were higher than8.52-75.14times, respectively. The sediment dredging out form Dalangwo River could not be directly used in farmland as fertilizer because the average concentration of Cu, Zn and Pb exceed the control standards for pollutants in sludges from agricultural use.
2. The heavy metals Cu, Zn, Cd and Cr in the Xinan River sediment showed a very significant positive correlation(p<0.01), which indicated that the agricultural wastewater, domestic sewage and industrial wastewater along the river bank may be their common sources of pollution. The correlation of organic matter and heavy metals Cu, Zn, Cd and Cr reached an outstanding level(p<0.01), which showed that organic matter and clay minerals in sediment played an important role in the distribution and concentration of heavy metals.
3. The speciation distribution trends of heavy metals in Xinan River and Dalangwo Stream sediments were similar. Cu mainly existed in the organic fraction; Zn mainly in carbonate adsorbed fraction; Pb mainly in residual fraction and Fe-Mn oxide fraction; Cd mainly existed in exchangeable fraction and organic fraction; Cr mainly existed in Fe-Mn oxide fraction.
4. Seven kinds of evaluation methods based on total concentration and sequential extraction of heavy metals in sediment were employed to assess the degree of contamination and potential ecological risk of heavy metals in sedimens from Xinan River and its tributary Dalangwo Stream, The results of comprehensive assessment indicated that the potential ecological risk and bioavailability of Cd, Cu and Zn in Xinan River and its tributary Dalangwo Stream were very high, and had great impact on the local environment. Additionally, the more serious pollution sections of Xinan River were S1and S2in the upstream, S9, S10and S11in the downstream, but the more serious pollution sections of Dalangwo Stream were W1and W2in the upstream, W5and W6in the midstream.
本论文以西南涌流域11个采样断面和重点支流大塑涡涌7个采样断面的表层底泥样品为研究对象,选取部分底泥样品用X射线荧光光谱仪进行元素分析,应用微波消解——原子吸收分光光度法测定了底泥中重金属Cu、Zn、Pb、Cd、Cr、Mn和Fe的总量,采用Tessier五步连续提取法对底泥中Cu、Zn、Pb、Cd和Cr的形态进行逐级提取,在此基础上,对西南涌流域和支流大望涡涌底泥中重金属的来源、污染状况、沿程分布规律、赋存形态特征进行了研究,最后采用基于重金属总量和赋存形态两个体系不同方法对研究区域的重金属污染水平及潜在生态危害进行了评价。主要研究结果如下：
1.西南涌底泥中Cu的含量为58.53-4522.65mg/kg；Zn的含量为114.18-1322.43mg/kg；Pb的含量为54.53-550.00mg/kg；Cd的含量为1.01～5.81mg/kgCr的含量为10.54-2535.64mg/kg；Mn的含量为95.45-949.40mg/kg；Fe的含量为22264.18-54044.36mg/kg。Cu、Zn、Pb、Cd、Cr的平均含量分别是国家土壤质量三级标准的1.39倍、0.91倍、0.31倍、2.45倍、0.84倍,因此西南涌底泥重金属污染程度为Cd>Cu>Zn>Cr>Pb,西南涌底泥重金属的平均值分别超过珠三角土壤重金属背景值的1.81倍(Pb)到19.45倍(Cd),可见西南涌底泥重金属污染比较严重,位于工业区的大望涡涌上游S2断面重金属污染最为严重。
大塱涡涌底泥中Cu的含量为52.95-2168.95mg/kg,Zn的含量为415.00-3743.75mg/kg；Pb的含量为7.05-1884.60mg/kg；Cd的含量为0.97-8.72mg/kg；Cr的含量为82.30-762.40mg/kg；Mn的含量为73.85-240.05mg/kg；Fe的含量为22544.64-43191.96mg/kg。底泥中重金属Cu、Zn、Cd的平均含量超过土壤环境质量三级标准,Cu、Zn、Cd、Cr含量均远远超出广东土壤背景值,分别超出8.52-75.14倍,且Cu、Zn、Pb含量的平均值超过农用污泥中污染物控制标准,因此该河段疏浚出的底泥不宜作为肥料直接施用于农田,必须经过对底泥重金属进行处理才能使用。
2.西南涌底泥中重金属Cu、Zn、Cd、Cr在0.01显著性水平下呈显著正相关,表明沿岸农业污水、生活污水和工业污水有可能是它们共同的污染来源；有机质与Cu、Zn、Cr、Cd在0.01显著水平下呈显著正相关,说明沉积物中有机物和粘土矿物对重金属的分布与富集起着重要的作用。
3.西南涌和大塱涡底泥重金属的赋存形态分布趋势相似,底泥中Cu都是主要以有机结合态为主,Zn主要以碳酸盐结合态为主,Pb主要以残渣态和铁锰结合态为主,Cd主要以可交换态和有机结合态为主,Cr主要以铁锰结合态为主。
4.从基于重金属总量和赋存形态两种体系7种评价方法的结果可以看出,西南涌和大塱涡底泥中Cd、Cu和Zn的潜在生态风险及生物有效性均比较高,对环境影响比较大,西南涌污染较严重的为上游的S1与S2断面及下游的S9、S10与S11断面,大塱涡涌污染较严重的为上游的W1与W2断面及中游的W5与W6断面。
The main river pollution including internal pollution and external pollutions, and sediment pollution were investigated as the main representative in the internal pollution. As sources and sinks of heavy metals and other pollutants, sediment would cause secondary pollution. Xinan River was an important surface water bodies connecting Guangzhou and Foshan. In recent years, with the rapid development of industry and agriculture and the urbanization process in the Xinan River basin, and pollution emissions growth and the environmental protection facilities construction lags behind, resulting in serious pollution to Xinan River. In order to provide important scientific basis for pollution treatment and control planning of the Xinan River and its serious polluted branch Dalangwo Stream, the pollution characteristics and chemical speciation of heavy metals in surface sediments were carried out.
Samples of the surface sediment were taken at11positions along the Xinan River basin and7positions from the key tributary Dalangwo Stream. Parts of the sediment samples were analysed by X-ray fluorescence spectrometer method for elemental analysis, while the contents of heavy metals of Cu, Zn, Pb, Cd, Cr, Mn and Fe in the surface sediments were carried out by microwave digestion-atomic absorption spectrophotometry, and the chemical speciations of heavy metals of Cu, Zn, Pb, Cd and Cr in surface sediment were determined by the Tessier sequential extraction method. Bassed on which, the source, pollution state, distribution rule and chemical speciation characteristics of heavy metals in the surface sediment from the Xinan River basin and its branch Dalangwo Stream were studied. The pollution level and potential ecological risk of the heavy metals in surface sediments were evaluated on the basis of analysis of the total amount and chemical speciations of heavy metals. The main findings were as follows:
1. The heavy metal concentration (mg/kg) of Xinan River sediment ranged as flowings: Cu,58.53-4522.65; Zn,114.18-1322.43; Pb,54.53-550.00; Cd,1.01-5.81; Cr,10.54-2535.64; Mn,95.45-949.40; and Fe,22264.18-54044.36in the surface sediments. The average Cu, Zn, Pb, Cd and Cr were1.39,0.91,0.31,2.45and0.84times higher than Environmental Quality Standard for Soils Ⅲ, and the pollution degree of heavy metals was established as the following orders:Cd>Zn>Cu>Cr>Pb. The contents of heavy metal were1.81(Pb) to19.45(Cd) times higher than the Pearl River Delta soil background values, respectively. Obviously, the pollution of heavy metals in Xinan River sediment was serious, and the most serious pollution section was S2located in the industrial zone.
Dalangwo Stream sediment heavy metal concentration (mg/kg) were:Cu,52.95-2168.95; Zn,415.00-3743.75; Pb,7.05-1884.60; Cd,0.97-8.72; Cr,82.30-762.40; Mn,73.85-240.05; and Fe,22544.64-43191.96in the surface sediments. Compared with Environmental Quality Standard for Soils Ⅲ, Cu, Zn and Cd were out of limits badly. The average contents of Cu, Zn, Cd and Cr were far beyond the Guangdong soil background values, were higher than8.52-75.14times, respectively. The sediment dredging out form Dalangwo River could not be directly used in farmland as fertilizer because the average concentration of Cu, Zn and Pb exceed the control standards for pollutants in sludges from agricultural use.
2. The heavy metals Cu, Zn, Cd and Cr in the Xinan River sediment showed a very significant positive correlation(p<0.01), which indicated that the agricultural wastewater, domestic sewage and industrial wastewater along the river bank may be their common sources of pollution. The correlation of organic matter and heavy metals Cu, Zn, Cd and Cr reached an outstanding level(p<0.01), which showed that organic matter and clay minerals in sediment played an important role in the distribution and concentration of heavy metals.
3. The speciation distribution trends of heavy metals in Xinan River and Dalangwo Stream sediments were similar. Cu mainly existed in the organic fraction; Zn mainly in carbonate adsorbed fraction; Pb mainly in residual fraction and Fe-Mn oxide fraction; Cd mainly existed in exchangeable fraction and organic fraction; Cr mainly existed in Fe-Mn oxide fraction.
4. Seven kinds of evaluation methods based on total concentration and sequential extraction of heavy metals in sediment were employed to assess the degree of contamination and potential ecological risk of heavy metals in sedimens from Xinan River and its tributary Dalangwo Stream, The results of comprehensive assessment indicated that the potential ecological risk and bioavailability of Cd, Cu and Zn in Xinan River and its tributary Dalangwo Stream were very high, and had great impact on the local environment. Additionally, the more serious pollution sections of Xinan River were S1and S2in the upstream, S9, S10and S11in the downstream, but the more serious pollution sections of Dalangwo Stream were W1and W2in the upstream, W5and W6in the midstream.
引文
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