太湖沉积物中重金属的测定及环境意义

通过对太湖地区水域湖泊沉积物中重金属含量的抽样测试，描述了太湖水域重金属（Ag、As、Cd、Cr、Cu、Hg、Ni、Pb、Zn等）元素的污染状及其分布，结果表明：太湖沉积物中重金属含量北部明显高于东部，来自太湖北岸城镇和工业区的未处理工业及生活污水，对太湖北部水域造成的重金属污染程度远高于以养殖业为主的东太湖及湖心水域。     

Environmental Assessments of Trace Metals in Sediments from Dongting Lake, Central China

INTRODUCTIONFresh water lakes are one of the planet’s mosti mportant freshwater resources.They support life invarious forms,develop tourism and provide uniquerecreational opportunities.It is also a good source ofthe provision of drinking-water for local communi-ties.Studies on trace elements in rivers,lakes,andsedi ments(Zhou et al.,2004;Gray et al.,2000;Grosheva et al.,2000;Klavins et al.,2000;Aucoinet al.,1999;Bortoli et al.,1998;Elbaz-Poulichet etal.,1996;Johansson et al.,1995;F r…     

太湖MS岩芯重金属元素地球化学形态研究

采用BCR三步提取法对太湖MS岩芯沉积物中Cu、Fe、Mn、Ni、Pb和Zn等6种重金属元素的化学形态进行了研究.结果表明,有效结合态的Cu、Ni和Pb主要以有机物及硫化物结合态、Fe-Mn氧化物结合态存在,Fe和Zn主要以Fe-Mn氧化物结合态存在,Mn主要以可交换态及碳酸盐结合态存在;Fe-Mn氧化物结合态的Ni、Pb和Zn与可还原态的Mn有较好的正相关关系,有机物及硫化物结合态的Cu、Mn、Ni、Pb和Zn与有机碳含量有较好的正相关关系;重金属形态分布体现了重金属元素地球化学性质的差异,以及重金属形态含量与沉积物理化性质的关系.沉积岩芯重金属元素形态垂向变化规律及次生相富集系数表明,Cu、Mn、Ni、Pb和Zn在沉积岩芯13～4 cm有效结合态含量较稳定,为自然沉积;4～0 cm有效结合态含量明显升高,存在一定程度的人为污染.根据137Cs测年结果判断,沉积岩芯Cu、Mn、Ni、Pb和Zn等重金属污染开始于20世纪70年代末期,主要污染元素及污染历史与太湖流域污染工业类型及经济发展阶段相吻合.     

太湖沉积物重金属及营养盐污染研究

通过太湖MS沉积岩芯元素地球化学指标的分析,对太湖沉积物污染历史进行了系统的讨论。根据化学元素的聚类分析结果、变化趋势,并与太湖流域经济发展进程对比,认为太湖沉积物铅、锌、锰、镍污染开始于20世纪70年代末期,砷、汞污染分别开始于30年代和40年代,随着底泥重金属污染程度的加重,沉积物表层磁化率明显升高;总磷自40年代以来含量不断增加,总氮、总有机碳含量增加开始于70年代末期,表明湖泊富营养化程度不断加重。太湖沉积物重金属及营养盐污染历史与该区经济发展阶段相吻合。     

Geochemical features of heavy metals in core sediments of northwestern Taihu Lake, China

Sequential core sediments from northwestern Taihu Lake in China were analyzed for grain size, organic carbon and heavy metal content. The sediments are composed of organic-poor clayey-fine silts. The chemical speciations of Cu, Fe, Mn, Ni, Pb, and Zn were also analyzed using the BCR sequential extraction procedure. Cu, Fe, Ni, and Zn are mainly associated with the residue fraction; Mn is concentrated mainly in exchangeable/carbonate fraction and residue fraction; and Pb mainly in Fe/Mn oxide fraction and organic/sulfide fraction. The exchangeable/carbonate fractions of Cu, Fe, Ni, Zn and Pb are lower. The fractions of Ni, Pb and Zn bound to the Fe/Mn oxide have significant correlations with reducible Mn; the organic/sulfide fractions of Cu, Mn, Ni, Pb, and Zn have significant correlations with TOC. The extractable fractions of Cu, Mn, Ni, Pb, and Zn are high at the top 4 cm of the core sediments as compared to those in the deeper layers, showing the anthropogenic input of heavy metals is due to rapid industrial development. The heavy metal pollution history of the sediments has been recorded since the late 1970s, determined by the result of ^137Cs dating.     

Environmental geochemistry of El Temsah Lake sediments, Suez Canal district, Egypt

The heavy metal contents of Mn, Ni, Cu, Zn, Cr, Co, Pb, Cd, Fe, and V in the surface sediments from five selected sites of El Temsah Lake was determined by graphite furnace atomic absorption spectrophotometer. Geochemical forms of elements were investigated using four-step sequential chemical extraction procedure in order to identify and evaluate the mobility and the availability of trace metals on lake sediments, in comparison with the total element content. The operationally defined host fractions were: (1) exchangeable/bound to carbonate, (2) bound to Fe/Mn oxide, (3) bound to organic matter/sulfides, and (4) acid-soluble residue. The speciation data reveals that metals Zn, Cd, Pb, Ni, Mn, Cu, Cr, Fe, and V are sink primarily in organic and Fe–Mn oxyhydroxides phases. Co is mainly concentrated in the active phase. This is alarming because the element is enriched in Al Sayadin Lagoon which is still the main site of open fishing in Ismailia. Average concentration of the elements is mostly above the geochemical background and pristine values of the present study. There is a difference on the elemental composition of the sediment collected at the western lagoon (Al Sayadin Lagoon), junction, the shoreline shipyard workshops, and eastern beach of the lake. Depending upon the nature of elements and local pollution source, high concentration of Zn, Pb, and Cu are emitted by industrial wastewater flow (shoreline workshops), while sanitary and agricultural wastewater (El Bahtini and El Mahsama Drains) emit Co and Cd in Al Sayadin Lagoon. On the other hand, there is a marked decrease in potentially toxic heavy metal concentrations in the sediments at the most eastern side of the lake, probably due to the successive sediment dredging and improvements in water purification systems for navigation objective. These result show that El Temsah receives concentrations in anthropogenic metals that risk provoking more or less important disruptions, which are harmful and irreversible on the fauna and flora of this lake and on the whole ecobiological equilibrium.     

湖南洞庭湖水系As和Cd等重金属元素分布特征及输送通量

土壤地球化学调查显示,长江沿岸,尤其湖南洞庭湖流域存在以镉为主的重金属高值带。为进一步确定As和Cd等重金属元素在河流中的存在形式、迁移方式和通量等地球化学特征,本研究在洞庭湖水系主要干支流的关键位置布置采样点,分夏季丰水期和冬季枯水期两次,采集了原水、0.45μm过滤水和0.20μm过滤水等水样品,以及悬浮物固体样品,分析了水和悬浮物样品中As和Cd、Pb等重金属元素含量。结果发现,As元素在湘江、资水、湘江上游支流西河和耒水中含量最高,耒水、西河及湘江的Pb、Zn含量相对偏高,Cd在湘江、耒水及汨罗江的含量也明显高于其他河流;研究区河水中As、Ni、Cd和Zn等元素在水中离子态比例较大,其溶解态含量受河水pH和温度的控制,湘江、西河、耒水和汨罗江中悬浮物As、Zn、Cu、Cd、Pb和Cu等元素含量远高于其他水系悬浮物,这与这些流域内存在多金属矿区密切相关;不同元素在河水中迁移途径有很大差别,As以溶解态和胶体态为主要迁移形式,Pb、Zn、Cu、Cd和Ni等重金属元素以悬浮物形式迁移的比例最大;主要入湖河流中,湘江输入洞庭湖的As、Zn、Cu和Cd总量最大,年通量分别为961.43 t、478.90 t、101.67 t、59.58 t。     

Application of equilibrium partitioning approach to derive sediment quality criteria for heavy metals in a shallow eutrophic lake, Lake Chaohu, China

In this study, the equilibrium partitioning approach was used to derive the sediment quality criteria (SQC) recommended values of eight heavy metals (Cr, Cu, Pb, Zn, Cd, As, Fe and Mn) for surface sediments taken from Lake Chaohu. The concentration of the heavy metal in the interstitial water (C _IW) was determined by the film diffusion gradient technology to obtain the metal partitioning coefficient (K _P). Moreover, the metal fractionation of the sediments were analyzed using European Community Bureau of Reference sequential extraction procedure and the partitioning of bound phases including total organic carbon (TOC), grain sizes and acid volatile sulfide (AVS) were also investigated. The values of K _P for Cr, Cu, Pb, Zn, Cd, As, Fe and Mn were 3,924.84, 2,276.23, 17,811.30, 738.35, 10,986.54, 718.74, 5,875.34 and 341.20 L/kg, respectively. Sediment quality criteria were normalized on the basis of fine materials, AVS, TOC and the residual metals (M _R). SQC values for Cr, Cu, Pb, Zn, Cd, As, Fe and Mn based on Chinese surface water quality criteria were derived with the values of 78.53, 56.95, 362.93, 74.68, 23.90, 71.84, 3,546.53 and 68.42 mg/kg, respectively. The suggested SQC values in this study were compared SQCs from different countries and areas, which indicated SQCs from different countries or regions appeared to have great discrepancies attributed to the difference of the physical and chemical characteristics of sediments.     

Heavy Metal Distributions and Source Tracing in the Lacustrine Sediments of Dongdao Island, South China Sea

The levels and depth distributions of As,Cd,Cu,Zn,Pb,Hg,Fe and Mn in two sediment cores DY2 and DY4 collected from the"Cattle Pond"of Dongdao Island,South China Sea,were determined and analyzed with the main objective to identify the sources of these elements and evaluate the corresponding sedimentological and geochemical processes.Lithological characters and sedimentary parameters such as LOI_(950℃),CaO,LOI_(550℃) and TOC indicate that the depth of 96 cm and 87 cm are the critical points for DY2 and DY4 cores,respectively.As,Cd,Cu,Zn,Hg and P are remarkably enriched in the ornithogenic sediments above the critical depth points;their concentration-versus-depth profiles are similar to those of TOC and LOIssooc;the ratios of As,Cd,Cu, Zn,Hg over Ca are significantly correlated with P/Ca.Statistical and comparative analyses of these elements' levels in the ornithogenic sediments of DY2 and DY4 strongly suggest that seabird droppings are the main source of these elements.Additionally,for the upper sediment layers of DY2 and DY4 cores,Fe oxide sorption mechanism,like organic matter,may also play an important role in the abundances of heavy metals.Heavy metal Pb has geochemical characteristics distinctly different from those of As,Cd,Cu,Zn,Hg and P,and its isotope composition indicates an origin of anthropogenic emissions from the surrounding countries.These geochemical characteristics in the orinithogenic sediments of Xisha Islands are compared with the studies in the remote Antarctic and Arctic regions.     

云蒙湖表层沉积物重金属分布特征及风险评价

为了解云蒙湖表层沉积物中重金属的污染状况,选取云蒙湖沉积物中6种重金属(Cu、Zn、Pb、Cr、Cd、As)作为研究对象,测定并分析其在云蒙湖表层沉积物中的分布、来源及生态风险,以期为云蒙湖沉积物中重金属污染治理及饮用水安全保障提供依据。采用富集系数法、相关性分析及聚类分析对重金属来源进行分析,并选用富集系数法、地累积指数法和潜在生态危害指数法对重金属污染程度及潜在生态危害进行了评价。结果表明:云蒙湖表层沉积物中6种重金属Cu、Zn、Pb、Cr、Cd、As平均含量分别为20.9、73.1、23.1、62.0、0.4和4.5 mg/kg;与临沂市土壤背景比较,Cd、Zn和Cr的含量超过临沂市土壤背景值,Cd污染最严重。重金属来源分析结果显示:Cd受人类活动影响较大,可能与区域农业和林业施肥有关;Cu、Zn、Pb、Cr和 As这几种重金属以自然来源为主。综合富集系数法、地累积指数法和潜在生态危害指数法3种评价方法的结果得出,云蒙湖表层沉积物中Cd 为最主要的污染元素,且具有较强的生态危害。     

Distribution and speciation of heavy metals in surface sediments from the Yangtze estuary and coastal areas

The concentrations and speciation of heavy metals (As, Cd, Cr, Cu, Hg, Ni, Pb and Zn) in the sediments of the nearshore area, river channel and coastal zones of the Yangtze estuary, China, were systematically investigated in this study. The concentrations of all heavy metals except Ni in the sediments of the nearshore area were higher than those of the river channel and coastal zones. In the nearshore area, the concentrations of most heavy metals except Hg in the sediments of the southern branch were higher than those of the northern branch because of the import of pollutants from the urban and industrial activities around. When compared with the threshold effect level (TEL) and geochemical background levels, Cr, Ni and As accumulated and posed potential adverse biological effects. The speciation analysis suggested that Cd, Pb and Zn in the sediments of the three zones showed higher bioavailability than the other heavy metals, and thus posed ecological risk. Significant correlations were observed among Cr, Cu, Ni and Zn (r > 0.77) in the nearshore area, Ni, Cu, Zn and Pb (r > 0.85) in the river channel and Ni, Cu, Cr, Pb and Zn (r > 0.75) in the coastal zone. Principal component analysis (PCA) indicated that the discharge of unban and industrial sewage, shipping pollution and the properties of the sediments (contents of Fe, Mn, Al, TOC, clay and silt) dominated the distribution of heavy metal in the nearshore area, river channel and coastal zones of the Yangtze estuary.     

武汉市墨水湖沉积物重金属污染特征与防治对策

武汉市墨水湖重金属污染严重,其污染特征在我国城市湖泊中具代表性。在对墨水湖不同湖区沉积物中重金属污染物空间分布特征进行分析的基础上,应用地积累指数法探讨不同重金属元素含量随深度变化的规律和原因,并对墨水湖沉积物中重金属的污染程度进行评价表明:墨水湖沉积物中重金属元素锌和汞污染最为严重,污染程度由高到低依次为:Zn>Hg>Cu>C r>Pb>A s;从整个湖区来看,分布有排污口的周边湖区污染严重,湖心污染程度较低;沉积物中主要重金属元素含量随深度增加而降低,其变化规律主要受污染状况的影响,沉积物颗粒粒径的变化和早期成岩作用的影响不大。为了改善墨水湖水质条件和重金属污染严重的现状,必须在截污、疏浚和引水工程等基本治理措施保护下,重建和恢复沉水植物系统,才能从根本上改善湖泊水质。     

Assessment of trace metal contents in water and bottom sediments from Eğirdir Lake,Turkey

The concentration of metals (Pb, As, Co, Cu, Ni, Zn, Fe and Mn) was investigated in water and sediment samples of E?irdir Lake. The Lake is the second largest fresh water lake of Turkey and it is used as drinking water in the region. The anthropogenic pollutants are primary sources of trace metals which are negatively affected lake water quality. These negative effects were observed in both lake water and bottom sediments. According to obtained data, Pb, Cu, Ni, Fe and Zn have significant enrichment in sediments samples. In addition, the hydrodynamic model of the lake was determined as effectively for Pb, Co, Cu, Ni, Zn, Fe and Mn accumulations. Also, the effect of anthropogenic pollutants was found to be more dominant than geogenic effect in metal accumulation of the lake bottom sediments. Therefore, anthropogenic pollutants within the lake basin should be consistently controlled for the sustainable usage of the lake.     

太湖沉积物中重金属的地球化学形态及特征分析

用连续提取法分析了太湖沉积物5种重金属的地球化学形态,对地球化学形态的组成和地理特征进行了分析研究.重金属地球化学形态配分的共同特点是可交换态最低,残渣态最高.两种形态中Cd的可交换态最高,Cr的残渣态最高,可交换态最低.Cd的碳酸盐态较高,Cr的最低;Pb、Cd的Fe-Mn氧化态较高,Cu的偏低;Cu的有机态最高,Cd的最低;Zn的地球化学形态比例大都处于中间.地域上变化较大的元素是Cd和Cu,变化不明显的元素有Pb和Zn.化学成分中Fe2O3、MnO与重金属地球化学形态的相关性最好,TOC与Cu的形态相关系数最高.综合对比分析表明,太湖沉积物重金属的生物有效性以Cd为最高,其次为Pb.     

Human Influence on Heavy Metal Distribution in the Upper Lake Nansi Sediments, Shandong Province, China

Core and surface sediment samples were collected from three sub-lakes ( Lake Nanyang, Lake Dushan and Lake Zhaoyang) in the Lake Nansi Basin, Shandong Province. In order to reveal the characteristics of spatial and historical distribution of heavy metals in different sublakes of the Upper Lake Nansi, heavy metal (As, Cr, Cu, Hg, K, Mn, Ni, Pb, Zn, Al, Fe, Ti and V) concentrations of sediment samples were investigated. Based on the activity of^137Cs in the sediments, the modem accumulation rate of Lake Nansi sediments is 3.5 mm/a. Our results show that the whole Upper Lake Nansi has been already polluted by heavy metals, among which Lake Nanyang has been polluted seriously by mercury, as well as by lead and arsenic, while Lake Dushan has been most seriously polluted by lead and arsenic. Historical variation of heavy metal (Cr, Cu, K, Ni, Zn, A1, Fe, Ti and V) concentrations shows an abrupt shift in 1962, resuiting in a division of two periods: from 1957 to 1962 when metal enrichment increased with time, and from 1962 to 2000 when it decreased with time, while that of some anthropogenic elements such as Hg, Pb and Mn tend to increase toward the surface. However, the variation trend of As in the sediments is different from that of Hg, Pb and Mn, with its maximum value appearing in 1982. Since 1982 the concentrations of As have decreased due to the forbidden use of arsenite pesticides. This variation trend revealed changes in manner of human activity (coal combustion, waste discharges from both industries and urban sewage ) within the catchment during different periods.     

湘江入湖河段沉积物重金属污染及其Pb同位素地球化学示踪

湘江是我国重金属污染最严重的河流之一.本次工作利用等离子质谱(ICP-MS)和多接收同位素质谱(MC-ICP-MS)等技术,对湘江入湖河段沉积物进行了系统的重金属微量元素和Pb同位素分析.结果表明,湘江河床沉积物明显富集Bi、Sc、V、Mn、Ni、Cu、Zn、Pb、Cd、Sn、Sb等多种重金属微量元素,而湖盆沉积物重金...     

Environmental assessment of heavy metal contamination in bottom sediments of Al-Kharrar lagoon,Rabigh, Red Sea,Saudi Arabia

In order to assess the pollution levels of selected heavy metals, 45 bottom sediment samples were collected from Al-Kharrar lagoon in central western Saudi Arabia. The concentrations of the heavy metals were recorded using inductively coupled plasma-mass spectrometer (ICP-MS). The results showed that the concentrations of Pb and Cd exceeded the environmental background values. However, the heavy metal contents were less than the threshold effect level (TEL) limit. The concentrations of heavy metals in lagoon bottom sediments varied spatially, but their variations showed similar trends. Elevated levels of metals were observed in the northern and southern parts of the lagoon. Evaluation of contamination levels by the sediment quality guidelines (SQG) of the US-EPA revealed that sediments were non-polluted-moderately to heavily polluted with Pb; non-polluted to moderately polluted with Cu; and non-polluted with Mn, Zn, Cd, and Cr. The geoaccumulation index showed that lagoon sediments were unpolluted with Cd, Mn, Fe, Hg, Mo, and Se; unpolluted to moderately polluted with Zn and Co; and moderately polluted with Pb, Cr, Cu, and As. The high enrichment factor values for Pb, As, Cu, Cr, Co, and Zn (>2) indicate their anthropogenic sources, whereas the remaining elements were of natural origins consistent with their low enrichment levels. The values of CF indicate that the bottom sediments of Al-Kharrar lagoon are moderately contaminated with Mn and Pb.     

Multivariate statistical techniques for evaluating and identifying the environmental significance of heavy metal contamination in sediments of the Yangtze River, China

The concentrations of heavy metals (Cr, Co, Ni, Cu, Zn, Pb, Cd, As, Hg, and Fe) in sediments of the Yangtze River, China, were investigated to evaluate levels of contamination and their potential sources. The lowest heavy metal concentrations were found in the source regions of the river basin. Relatively high concentrations of metals, except Cr, were found in the Sichuan Basin, and the highest concentrations were in the Xiangjiang and Shun’anhe rivers. All concentrations, except Ni, were higher than global averages. Principal component analysis and hierarchical cluster analysis showed that Zn, Pb, As, Hg, and Cd were derived mainly from the exploitation of various multi-metal minerals, industrial wastewater, and domestic sewage. Cu, Co, and Fe were derived mainly from natural weathering (erosion). Cr and Ni were derived mainly from agricultural activities, municipal and industrial wastewater. Sediment pollution was assessed using the geoaccumulation index (I _geo) and enrichment factor (EF). Among the ten heavy metals assessed, Cd and Pb had the highest I _geo values, followed by Cu, As, Zn, and Hg. The I _geo values of Fe, Cr, Co, and Ni were <0 in all sediments. EF provided similar information to I _geo: no enrichment was found for Cr, Co, and Ni. Cu, Zn, As, and Hg were relatively enriched at some sites while Cd and Pb showed significant enrichment.     

Distribution and immobilization of heavy metals in Pliocene aquifer sediments in Wadi El Natrun depression, Western Desert

The Pliocene aquifer receives inflow of Miocene and Pleistocene aquifer waters in Wadi El Natrun depression. The aquifer also receives inflow from the agricultural activity and septic tanks. Nine sediment samples were collected from the Pliocene aquifer in Wadi E1 Natrun. Heavy metal (Cu, Sr, Zn, Mn, Fe, Al, Ba, Cr, Ni, V, Cd, Co, Mo, and Pb) concentrations of Pliocene aquifer sediments were investigated in bulk, sand, and mud fractions. The determination of extractable trace metals (Cu, Zn, Fe, Mn, and Pb) in Pliocene aquifer sediments using sequential extraction procedure (four steps) has been performed in order to study environmental pathways (e.g., mobility of metals, bounding states). These employ a series of successively stronger chemical leaching reagents which nominally target the different compositional fractions. By analyzing the liquid leachates and the residual solid components, it is possible to determine not only the type and concentration of metals retained in each phase but also their potential ecological significance. Cu, Sr, Zn, Mn, Fe, and Al concentrations are higher in finer sediments than in coarser sediments, while Ba, Cr, Ni, V, Cd, Co, Mo, and Pb are enriched in the coarser fraction. The differences in relative concentrations are attributed to intense anthropogenic inputs from different sources. Heavy metal concentrations are higher than global average concentrations in sandstone, USEPA guidelines, and other local and international aquifer sediments. The order of trace elements in the bulk Pliocene aquifer sediments, from high to low concentrations, is Fe?>?Al?>?Mn?>?Cr?>?Zn?>?Cu?>?Ni?>?V?>?Sr?>?Ba?>?Pb?>?Mo?>?Cd?>?Co. The Pliocene aquifer sediments are highly contaminated for most toxic metals, except Pb and Co which have moderate contamination. The active soluble (F0) and exchangeable (F1) phases are represented by high concentrations of Cu, Zn, Fe, and Mn and relatively higher concentrations of Pb and Cd. This may be due to the increase of silt and clay fractions (mud) in sediments, which act as an adsorbent, retaining metals through ion exchange and other processes. The order of mobility of heavy metals in this phase is found to be Pb?>?Cd?>?Zn?>?Cu?>?Fe?>?Mn. The values of the active phase of most heavy metals are relatively high, indicating that Pliocene sediments are potentially a major sink for heavy metals characterized by high mobility and bioavailability. Fe–Mn oxyhydroxide phase is the most important fraction among labile fractions and represents 22% for Cd, 20% for Fe, 11% for Zn, 8% for Cu, 5% for Pb, and 3% for Mn. The organic matter-bound fraction contains 80% of Mn, 72% of Cu, 68% of Zn, 60% of Fe, 35% of Pb, and 30% of Cd (as mean). Summarizing the sequential extraction, a very good immobilization of the heavy metals by the organic matter-bound fraction is followed by the carbonate-exchangeable-bound fraction. The mobility of the Cd metal in the active and Fe–Mn oxyhydroxide phases is the highest, while the Mn metal had the lowest mobility.     

Study on effective species of heavy metals in lacustrine sediment core from Xijiu Lake,Taihu Lake catchment,China

The BCR sequential extraction procedure is applied to probe into the speciation distribution of heavy metals (Cd, Cr, Zn, Cu and Pb) in lake sediments of Core XJ2 in Xijiu Lake, Taihu Lake catchment, China. The results showed that the effective species concentration of this five heavy metal elements increased obviously during the past century, the proportions of organic/sulphide fractions of Zn, Cu and Pb decreased while the Fe–Mn oxide fractions increased, and the proportion of Fe–Mn oxide fractions of Cd decreased while the exchangeable and carbonate fractions increased. The concentrations of exchangeable and carbonate fractions of these five elements were increased in the past century, especially the proportions of these fractions of Cd, Zn, Cu and Pb increased prominently. These changes could be attributed to the anthropogenic pollution. Since the changes of the heavy metal concentrations were corresponding to the history of human activities, especially the industry development, within the catchment.