The Concentration and Partitioning of Heavy Metals in Surface Sediments of the Maharlu Lake,SW Iran

In this study, an assessment is made of the environmental impacts of heavy metal concentration and fractionation in bed sediments of the saline Maharlu Lake, SW Iran. Total elemental analysis indicated that sediments were highly enriched in Pb and Cd. Sequential extraction analysis revealed that salt of the lake is probably highly contaminated with Cd, Pb, and Co. Due to the oxidizing conditions of the lake, the organic matter fraction of the elements was not significant. In all sediments, Cd, Pb, Co, Mn, and Zn were strongly associated with exchangeable plus carbonate fractions, with mean percentage of 76.4%, 65.3%, 56%, 40.9%, and 34.3%, respectively. On average, the percentage of Ni associated with the sum of the exchangeable and carbonate fractions was 19.8%. Cr, Fe, and Cu fractionation indicated that these metals are environmentally inert and immobile. Statistical relationships among metal fractions and sediment properties showed that Cd, Pb, Zn, Ni, Co, and Mn were mainly from recent anthropogenic sources, while such sources were less important for Cr, Cu, and Fe. The latter metals represented natural geochemical levels.     

湘西河流表层沉积物重金属污染特征及其潜在生态毒性风险

花垣河和峒河是湘西地区受到锰矿和铅锌矿生产影响严重的两条河流。通过表层沉积物采样分析了Cd、Pb、Cu、Ni、Cr、Zn和Mn的总量,根据BCR连续提取程序分析沉积物样品中重金属的地球化学赋存形态,采用内梅罗指数法和地积累指数法评价了沉积物重金属污染特征,根据重金属的富集程度探讨了重金属污染来源,采用淡水生态系统沉积物质量基准(SQGs,TEL/PEL)和毒性单位评价了花垣河和峒河沉积物中重金属元素的生态毒性风险。结果表明,花垣河和峒河绝大多数位点的表层沉积物中Cd、Pb、Cu、Ni、Cr、Zn和Mn的总量高于参照点,形成严重的复合污染,花垣河沉积物中重金属的污染水平明显高于峒河,但沿程变化规律不明显,而峒河沉积物中重金属的沿程变化较有规律,即上游含量低,中下游含量较高。两条河流表层沉积物中富集程度居前列的均为Cd、Pb、Zn和Mn。花垣河和峒河沉积物重金属污染主要来源于矿业生产所产生废渣和废水的点排放。在花垣河和峒河的大多数位点,Cd、Pb和Mn的形态具有共同特征,其生物可利用态均较大程度地超过生物不可利用态,而且Mn和Cd的生物可直接利用态所占比例远高于其它重金属,而Cu和Cr的生物可直接利用态所占比例很低。花垣河沉积物中Cd、Pb和Zn在所有位点极大地超过PEL,在峒河中下游,Cd、Pb、Ni和Zn超过PEL,具有较大的潜在生物毒性。除上游S1位点外,花垣河的其余各位点都具有明显的急性毒性,峒河中下游各位点具有明显的急性毒性,这些河段需要重点治理。     

Cumulative Title Index

Abstract

Metal fractionation is a powerful tool for studying the mobility, bioavailability and toxicity of metals in sediments and soils. A seven-step sequential extraction technique was used to determine the potential mobility of selected heavy metals (Fe, Mn, Zn, Cu, Pb, Cd and Ni) in the sediments of Lake Naivasha. Results indicate that residual fraction was the most important phase for the elements Fe, Mn, Cu and Zn. However, Pb and Cd are highly enriched in the non-residual phases. Nickel on the other hand was distributed evenly between the non-residual and the residual fractions.

The total concentrations of the heavy metals suggested a decreasing order of iron ?> manganese ? zinc > nickel > copper ? lead > cadmium. However, the detailed sequential extraction data indicated an order of release or mobility of cadmium > lead ? nickel ? zinc > manganese > copper > iron. The high percentage of Cd and Pb in the mobile fractions suggests high bioavailability of these two elements in the study area and maybe a pointer to anthropogenic input of the two elements in the study area.     

Seasonal and spatial variations of heavy metals in surface sediments collected from the Baoxiang River in the Dianchi Watershed,China

To explore potential ecological hazards due to heavy metals in the Dianchi Lake Watershed, a three-stage European Community Bureau of Reference (BCR) sequential extraction procedure was applied to examine the spatial distributions and relative speciation ratios of Zn, Cu, Ni, Pb, and Cr in Baoxiang River sediments during wet and dry seasons. The metal species have similar spatial variations during different seasons. In the upstream reaches of the Baoxiang River, heavy metals reside primarily in the non-extractable residual fraction (72–90%). In the midstream, the residual fraction (35–89%) remains dominant, but the extractable fraction increases, featuring especially notable increases in the reducible fraction (5–40%). Downstream, the Cu, Ni, Pb, and Cr residual fractions remain high (46–80%) and the extractable fractions increase rapidly; the Zn extractable fraction is quite high (65.5%). Anthropogenic sources drive changes in heavy metal speciation. Changes in the river environment, such as pH and oxidation-reduction potential, also affect speciation. The reducible fraction of heavy metals in Baoxiang River sediments is most sensitive to pH. Potential ecological risk assessments for these five elements indicate that risks from Zn and Pb are mild to moderate in the middle and lower reaches of the river.     

铜锈环棱螺对沉积物中重金属的生物积累及其与重金属赋存形态的关系

以铜锈环棱螺（Bellamya aeruginosa）为测试生物,采用28 d沉积物生物积累试验研究铜锈环棱螺对污染河流沉积物中重金属的生物积累,并探讨其与重金属赋存形态的关系.结果表明：铜锈环棱螺肝胰脏对Cd、Pb、Cu、Cr、Zn和Mn均具有较强的积累作用.不同重金属的积累量存在较大差别,Zn的积累量最多,占重金属总积累量的84.32%±4.36%,其次为Cu,占7.67%±2.84%;Pb、Cr和Mn的比例相对较少,分别为3.62%±1.84%、2.22%±1.03%和1.33%±0.15%;Cd所占比例最少,为0.83%±0.53%.肝胰脏中重金属元素之间的相关性均不显著.肝胰脏金属污染指数与沉积物污染综合指数具有显著的正相关关系,铜锈环棱螺可以作为沉积物重金属污染的监测生物.不同沉积物Cd、Cr、Zn和Mn的生物-沉积物积累因子（BSAF）具有较大的差异,Cu和Pb的BSAF比较稳定.Cd的生物积累与沉积物中Cd的可交换的与酸可溶态及可氧化态显著相关;Pb的生物积累与Pb的可还原态显著相关;Cu的生物积累与Cu的可氧化态显著相关;Mn的生物积累与Mn的可交换的与酸可溶态和可还原态显著相关;Cr和Mn的生物积累与其不同形态和总量均不相关.BSAF不宜作为衡量铜锈环棱螺对沉积物中重金属生物积累能力的指标.     

Heavy Metals (Cd,Cu, Ni,Pb, and Zn) Fractionation in River Sediments,Hamedan, Western Iran

Five heavy metals (Cd, Cu, Ni, Pb, and Zn) in river sediments from Abshineh River, Hamedan, western Iran, were fractionated by a sequential extraction procedure. Cu, Ni, Pb, and Zn existed in sediments mainly in residual fraction (mean 92%, 86%, 77%, and 65%, respectively), whereas Cd occurred mostly as organic matter (mean 41%) and exchangeable (mean 25%) fractions. The mean percent of mobile fraction of Cd, Cu, Ni, Pb, and Zn in contaminated sediments was 25, 13, 4, 24, and 10, respectively, which suggests that the mobility and bioavailability of the five metals in sediments probably decline in the following order: Cd = Pb > Cu > Zn > Ni. The metal levels were also evaluated according to the contamination factor, which revealed significant anthropogenic pollution of Cd and Pb.     

Characterization of Heavy Metal Fractions in Agricultural Soils by Sequential Extraction Procedure: The Relationship Between Soil Properties and Heavy Metal Fractions

The present research was conducted to determine heavy metals in agricultural soils from Çanakkale, Turkey, using a sequential extraction procedure (acid soluble, reducible, oxidizable, and residual) as proposed by the Community Bureau of Reference (BCR) of the European Commission. Soil samples were taken from 12 different cultivated sites and analyzed for Cd, Co, Cr, Cu, Mn, Ni, Pb, and Zn concentrations. The results revealed an order of Mn > Cd > Pb > Co > Ni > Cu > Zn > Cr for the heavy metals based on the sum of the first three fractions (acid soluble + reducible + oxidizable). The relationships between soil properties and each metal fraction were identified through Pearsons's correlation analysis. Hierarchical cluster analysis was performed to determine the behaviors and similarities of metals in each fraction. While Mn, Pb, and Zn exhibited subjective behaviors in the acid-soluble fraction, Cd, Co, Cu, Cr, and Ni exhibited similar behaviors with each other.     

Multivariate analysis of heavy metal and nutrient concentrations in sediments of Taihu Lake, China*

Taihu Lake is one of the largest freshwater lakes in China. The Lake is very shallow with a mean depth of 1.9 m and an area of 2428 km². Nutrient concentrations (Org-C, Tot-N and Tot-P) and heavy metal concentrations (Ag, As, Cd, Co, Cr, Cu, Hg, Ni, Pb, Sr, Zn, etc.) in the lake's surface sediments were sampled at 13 locations. This was done to determine if industrialized areas along the lake's coastline were impacting the nutrient and heavy metal distribution of the lake's surface sediments. Principal Component Analysis (PCA) was used to assess the degree of contamination and spatial distribution of heavy metals and nutrients in different areas of Taihu Lake.A distinctive spatial distribution of heavy metals and nutrients was observed. Sediments from a large embayment of Taihu Lake called Lake Wulihu had significantly higher nutrient concentrations (Org-C, 2.05–3.83%; Tot-N, 0.28–0.54%; Tot-P, 0.10–0.33%) than any other area of Taihu Lake. These high nutrient levels were associated with the input of untreated domestic sewage from the large (circa one million people) City of Wuxi, which discharges its effluents into the Liangxi River. As a result, Lake Wulihu is the most eutrophic area of Taihu Lake. The nearby Meiliang Bay suffered from the worst heavy metal contamination in Taihu Lake (e.g. As, 64.0; Ag, 4.2; Cd, 0.93; Co, 14.2; Cr, 155.0; Cu, 144.0; Hg, 0.25; Ni, 79.8; Pb, 143.0 and Zn, 471 mg kg^–1). These high heavy metal concentrations were ascribed to the discharge of untreated and partially treated industrial waste water from Changzhou and Wujin via the Zhihugang River. Surface sediment samples from the east basin of Taihu Lake were characterized by high Org-C (1.0–2.3%) and Tot-N (0.18–0.37%) and low Tot-P (0.048–0.056%) concentrations. It is likely that macrophytes removal accounts for a major reduction of phosphorus in the sediments of the east basin of Taihu Lake.     

Bioavailability and Concentration of Heavy Metals in the Sediments and Leaves of Grey Mangrove, <Emphasis Type="BoldItalic">Avicennia marina</Emphasis> (Forsk.) Vierh,in Sirik Azini Creek,Iran

The concentration and bioavailability of Ni, Cu, Cd, Zn, and Pb in the sediments and leaves of grey mangrove, Avicennia marina, were studied throughout Sirik Azini creek (Iran) with a view to determine heavy metals bioavailability, and two methods were used. Results show that Zn and Ni had the highest concentrations in the sediments, while Cd and Cu were found to have the lowest concentrations in the sediments. Compared to the mean concentrations of heavy metals in sedimentary rock (shales), Zn and Cu showed lower concentration, possibly indicating that the origin of these heavy metals is natural. A geo-accumulation index (I _geo) was used to determine the degree of contamination in the sediments. I _geo values for Zn, Cu, Pb, and Ni showed that there is no pollution from these metals in the study area. As heavy metal concentrations in leaves were higher than the bioavailable fraction of metals in sediments, it follows that bioconcentration factors (leaf/bioavailable sediment) for some metals were higher than 1.     

Distribution of heavy metals in the geochemical phases of sediments from the Tietê River,Brazil

Abstract

The fractionation of heavy metals in riverbed sediments along the Tietê River basin, a highly polluted river in southeast region of Brazil, was investigated using a four-step sequential extraction procedure, in order to determine the concentration and distribution of Cu, Co, Cr, Cd, Zn, Ni and Pb, in the river bottom sediments, related to the potential mobility of geochemical phases. Around the metropolitan area of the City of São Paulo, which has 25 million people, the pollution is associated with municipal wastes and industrial effluents. Potentials of high mobility were observed for Cu and Zn along the entire river basin, associated mainly to the organic fraction, while at the Pirapora and Anhembi stations (upper and middle parts of the basin, respectively) the reactive forms of Ni and Pb were more associated to the Fe and Mn oxides. Near the mouth of the Tietê River, no significant contaminations caused by Cr and Ni in riverbed sediments was verified confirming the presence of these metals in the residual or lithogenous phase.     

Dissemination of heavy-metal contamination in surface sediments of the Uzunçayır Dam Lake,Tunceli, Turkey

The objective of this study was to determine the heavy-metal concentrations (Cu, Pb, Zn, Ni, Mn, Fe, As, Cd, Cr, and Hg), evaluate the pollution levels, and determine the concentration of chlorophyll-a and organic carbon in the surface sediments of the Uzunçay?r Dam Lake, Tunceli, Turkey, between 2015 and 2016. In order to evaluate the effect of the pollution level in the study area, the contamination factor (CF), enrichment factor, potential ecological risk index, and pollution load index were used. The concentrations of the studied heavy metals were ordered as follows: Fe > Mn > Ni > Cr > Zn > Cu > Pb > As > Cd > Hg. The highest CF value was found for the Ni element among the studied heavy metals in the Dam Lake. Moreover, the highest CF mean value was found for the As contamination level. According to the toxicity analyses in the study area, the potential toxic effect of sediments was not at a very serious level.     

Heavy metal distribution in superficial sedimenta ta Saco, Gulf of Cariaco, Sucre, Venezuela

The Gulf of Cariaco is a marine ecosystem with high primary productivity, which gives it an ecological and socioeconomic importance. Nevertheless, anthropogenic activities around the Gulf produce wastes that are deposited directly or by runoff into the sediments, and consequently, increases concentrations of metals in this ecosystem. The objective of this study was to determine the distribution of cadmium, copper, lead, manganese, nickel and zinc in geochemical fractions of surface sediments, using modified BCR sequential extraction procedure. The concentrations were measured using flame atomic absorption spectroscopy. In addition, the contents of soluble and exchangeable metals associated to carbonate fractions, determined by BCR, were compared with those determined by the method of Campanella. Samples were collected in 12 stations during June 2007. The applied methodologies were evaluated with a certified reference material of marine sediments (HISS-1) and the results indicated that these methods provide adequate accuracy and precision for the extraction of metals. The total metal concentrations (microg g(-1)) were, Cd: < limit of detection (LD)-5.0; Pb: 1.79-60.41; Cu: no detected (ND)-42.18; Zn: 25.13-104.57; Mn: 66.31-80.29 and Ni: 3.29-24.58. Cd, Cu, Ni and Pb at several stations, exceeded the Canadian Sediment Quality Guidelines of the Lowest Effect Levels (LEL). Cadmium was identified as being the most mobile of the elements, having the highest concentrations in soluble and exchangeable cations and carbonates. However, Pb, Cu, Mn and Zn levels were found highly associated to organic matter and sulfide fractions. The methods did not show significant statistical differences for the extraction of soluble and exchangeable cations and the metals associated to carbonate fraction. There are several significant correlations between heavy metals, which suggest their common origin.     

Geochemical distribution of heavy metals in sediments from sewage fed fish ponds from Kolkata Wetlands,India

Abstract

Kolkata wetlands are the largest sewage fed wetlands in the world. They have been used for aquaculture since 1960. Geochemical distribution of heavy metals (Cr, Cu, Mn, Fe, Zn, Pb, Ni and Al) has been studied in surface sediments using single and sequential extractions techniques. The metal concentrations in sediments were in the following order: Fe>Al> Mn>Zn>Cu> Pb>Cr> Ni, and the average concentrations were 29 μg g^?1, 54 μg g^?1, 328 μg g^?1, 32747 μg g^?1, 169 μg g^?1, 38 μg g^?1, 25 μg g^?1 and 23371 μg g^?1 dry weights for Cr, Cu, Mn, Fe, Zn, Pb, Ni and Al, respectively. Water-soluble percentages of the trace elements are quite low (<0.01–3.75%) but in the presence of chelating agents in the sediments increase the bioavailability of trace elements (2–58%). About 40% of trace elements are in the stable form as a residual fraction of the sediment and more than 50% (nonresidual fraction) metal contamination of the Kolkata wetland sediments were from anthropogenic inputs. The contamination risks of Cr, Mn, Zn, Pb, and Ni are high as their potential availabilities are 70.96%, 58.01%, 63.13%, 55.62%, and 52.15% respectively. The mean concentration of most of the heavy metals in sediments does not exceed the recommended reference values. Zinc and lead concentrations were greater than background level and Interim Sediment Quality Guidelines but lower than Probable Effect Level. Therefore a regular program for monitoring the distribution of heavy metals in water, sediments and biota should be imposed on sewage fed fish ponds of the Kolkata wetland ecosystem.     

Total and speciation analyses of heavy metals in the sand fraction of Nigerian oil sands for human and ecological risk assessment

Total metal analysis and metal speciation of sand fraction of Nigerian oil sands were done to extract and partition heavy metals into six operationally defined fractions in order to assess environmental and health implications of the oil sand development. Soxhlet extraction of bitumen from the oil sand was done using toluene. Traces of water and extracting solvent were removed at 70°C from the sand fraction using oven. Elemental analysis was performed by Atomic Absorption Spectrophotometry. The heavy metals except Cu have low Pollution index values. Negative geo-accumulation index was obtained for the metals except Cu, indicating that the oil sands were uncontaminated with the metals. Strong and significant positive correlations existed between Fe/Pb, Zn/Cu, Cd/Pb, Ni/Cd, Ni/Pb, Cd/Fe, Ni/Fe and Cr/Zn, while strong and significant negative correlations existed between Mn/Pb and As/Mn, indicating common sources or chemical similarities and vice versa. T-test results indicated significant differences between the concentrations of the metals. Cross-plot analysis showed strong positive correlation between the sand fraction and Nigerian bitumen. Speciation analysis indicated highest and lowest indices of metal mobility for Zn and Pb, respectively. This study concluded that the sand fraction may not pose any environmental risks from elemental point of view.     

Distribution and contamination pattern of heavy metals from surface sediments in the southern part of Caspian Sea,Iran

This study concentrates on the speciation and distribution patterns of some heavy metals (Pb, Ni, Cd, Zn, and Cu) in surface sediments in the southern part of the Caspian Sea, the biggest lake in the world, to obtain an overall classification for the origins of metals in the area using a sequential extraction technique. At all sampling stations, Pb, Ni, Zn, and Cu were mostly (>50%) accumulated in the resistant fraction, which indicated that there were no significant anthropogenic inputs of Pb, Ni, Zn, and Cu into the surface sediments of the south Caspian Sea. Guilan province on the west coast of Caspian Sea accumulated higher percentages of non-resistant fractions of Pb and Zn, while Mazandaran and Golestan provinces in the middle and western parts of the Caspian Sea, in the Iranian zone, accumulated higher percentages of non-resistant fractions of Ni and Cu. The present study revealed that the coastal area of the south Caspian Sea is still not seriously contaminated. Cadmium in Guilan and Golestan provinces were dominated by non-resistant fractions (55–69%), which indicated more anthropogenic inputs of Cd on the south coast of the Caspian Sea in comparison with other metals.     

渭河陕西段沉积物重金属空间分布及来源解析

为了了解渭河陕西段河道沉积物重金属空间分布特征,本研究对渭河陕西段干流及其支流17个采样点沉积物中的10种重金属元素(Cd、Sb、As、Co、Cu、Pb、Ni、Cr、Zn、Mn)含量进行测定及来源辨析。结果表明: 重金属元素Cd、Sb、As、Co、Cu、Pb、Ni、Cr、Zn、Mn的平均含量分别为0.10、1.24、11.73、11.95、24.90、24.91、29.31、54.18、72.74、626.85 mg·kg^-1, 除Cd的变异系数大于1以外,其他元素的变异系数均低于0.5。其中,Cd、Pb、Cr含量于灞河入渭处达到峰值,Co和Mn在黑河入渭处达到峰值,Cu和Zn在清姜河入渭处达到峰值, Sb、As和Ni分别于沙王渡、咸阳铁桥和林家村处达到峰值。相关性分析、主成分分析和聚类分析表明,Cd、Co、Cu、Pb、Ni、Cr、Zn、Mn主要来源于以工业源和生活源为主的污染源;Sb、As主要来源于农业和地球化学污染源。     

Bioaccumulation of heavy metals in two morphotypes of African large barb Labeobarbus intermedius (Osteichthyes: Cyprinidae) in Lake Hawassa,Ethiopia

Water and muscle tissue samples from two morphotypes of the African large barb Labeobarbus intermedius collected from three sites in Lake Hawassa in 2012–2013 were analysed for eight heavy metals, including Cd, Co, Cr, Cu, Mn, Ni, Pb and Zn. Five metals (Cr, Cu, Mn, Ni and Zn) were detected in fish muscle samples, whereas only Cr, Cu and Ni were detected in water samples. Of the five metals detected in the muscle samples, Cu and Zn were present in higher concentrations in the golden morphotype, whereas Cr, Mn and Ni were found in higher concentrations in the silver morphotype. Bioaccumulation factor (BAF) values indicated that Cr, Cu and Ni have a tendency to accumulate in fish muscle in amounts exceeding those in water. In both morphotypes the highest concentrations of Zn and Mn were detected at the Hospital site, whereas the concentrations of Cr, Cu and Ni were highest at the Tikur Wuha site. Chromium, Cu and Ni concentrations recorded in fish muscle at all sampling sites exceeded the safe limits recommended by FAO/WHO and UNESCO, suggesting that water and fish from Lake Hawassa are contaminated with heavy metals originating from factories, a hospital and agricultural activities in proximity to the lake.     

Geochemical distribution and fractionation of heavy metals in sediments of a freshwater reservoir of India

Abstract

Sediments of a polluted reservoir were evaluated for total contents of Cd, Cr, Cu, Ni, Pb and Zn along with their different geochemical forms (exchangeable, carbonate, Fe–Mn, organic matter and residual). Mineralogy of the sediments and physico-chemical parameters i.e. pH, OC and percentage of sand, silt and clay were also evaluated to see the dependency of heavy metals concentration on these parameters. The total concentration of heavy metals in the sediments varied according to sites and seasons. Except for station H1 which had moderately higher concentration of Cu (45.5 mg kg^-1), concentrations of all other metals at all the sites under study were below the standard shale value. Maximum proportions of all metals were associated with the carbonate and residual fractions. The Risk Assessment Code showed a low risk for Cr, Ni and Zn, and a medium risk for Cu at station H3 and H4. On the basis of freshwater sediment quality guidelines, there is a strong possibility of Cr and Cu toxicity for aquatic biota of the reservoir. The data were further processed using Pearson’s correlation and factor analysis to obtain more accurate information about the behaviour of these metals. A positive relationship among the metals confirmed the anthropogenic sources of pollution in the reservoir. Significant positive relationships of heavy metals with the texture of the sediment were also obtained.     

Assessment of Heavy Metal Enrichment,Bioavailability, and Controlling Factors in Sediments of Taihu Lake,China

Heavy metal distribution, bioavailability, and ecological risk in the surface sediment of Taihu Lake were evaluated. Samples were collected from eight representative sites in September 2011 and February 2012. In the surface sediment, average metal contents were in the order of Cr > Zn > Ni > Pb > Cu. Spatially, Zhushan Bay maintained higher Cu, Ni, and Zn contents and Xiaomeikou maintained higher Cr and Pb contents than other sites. Spatial and temporal variation were observed in the bioavailable metals determined by acid-soluble fraction of BCR extraction. The labile metals in Zhushan Bay and Xiaomeikou were quantified by diffusive gradients in thin films (DGT) and DGT-labile concentrations of Zn, Ni, Cu, Pb, and Cd were in descending order, indicating the inconsistence of labile concentrations of different heavy metals with the total metal contents and that the toxic effect of Cd in sediment should be given attention. The ecological risk assessed by Hakanson potential ecological risk index showed that Zhushan Bay suffered the most serious pollution and should be given special attention. Bioavailability of metals should be taken into account during risk assessment for more accurate estimation.     

Trace Metal Fractionation by the Sequential Extraction Method in Sediments from the Lis River (Portugal)

The extractable contents of Zn, Pb, Cu, Cr, Mn, Ni, Fe and Al were evaluated in sediments from the Lis River (Portugal) using the three-step sequential extraction procedure described by Community Bureau of Reference (BCR, now the Standards, Measurement and Testing Programme) of the European Union. The distribution of trace metals among the exchangeable, water and acid soluble, reducible, oxidizable and residual fractions was determined. The highest metal concentrations were observed in samples collected at the most polluted river sites (animal husbandry, domestic, industrial and agricultural wastes). Pb, Cu, Cr, Ni, Fe and Al were found mainly associated with the residual and organic fractions. High concentrations of Zn and Mn were found in the exchangeable/acid soluble fraction.