Fingernails as biological indices of metal exposure

Metal determination in human tissues is the most common application of biological monitoring for screening, diagnosis and assessment of metal exposures and their risks. Various biopsy-materials may be used. This paper deals with the quantitative determination of Cd, Pb, Cr, Mn, Fe, Ni, Cu, and Zn concentrations in nails of male subjects exposed to these metals alongwith their respective controls, while working in locomotive, carriage and roadways workshops, and lead battery factories. The levels of Cd, Pb, Cr, Mn, Fe, Ni, Cu and Zn in fingernails, assayed by atomic absorption spectrophotometry, were compared with their respective controls by student ‘t’ test. All the obtained values were correlated to the personal and medical history of the subjects under study. Significantly high levels of Cd, Pb, Cr, Fe, Ni, Cu and Zn were present in smokers, compared to nonsmokers. The concentrations of Cd, Pb, Cr, Mn and Fe were not significantly high in vegetarian subjects. It was also observed that there is no contribution of liquor towards nail-metal concentration. Significant correlations were observed between skin disease and Cr, Mn, Fe, Cu; hypertension and Cd, Mn, Cu; mental stress and Cd, Pb, Mn, Ni, Cu, Zn; diabetes and Cr, Mn, Ni; chest pain and Pb; respiratory trouble and Cr, Mn, Fe, Ni, Zn; tuberculosis and Zn; acidity and Cd; and ophthalmic problems and Mn, Fe, Ni, and Zn     

Accumulation of metals and metalloids in radish (Raphanus sativus L.) and spinach (Spinacea oleracea L.) irrigated with domestic wastewater in the peri-urban areas of Khushab City,Pakistan

Accumulation of different metals and metalloids was assessed in two vegetables radish (Raphanus sativus L.) and spinach (Spinacea oleracea L.) irrigated with domestic wastewater in the peri-urban areas of Khushab City, Pakistan. In general, the metal and metalloid concentrations in radish and spinach were higher at site-II treated with sewage water than those found at site-I treated with canal water. In case of radish at both sites the levels of metals (Cr, Mn, Fe, Co, Ni, Cu, Zn, As, Se, Mo, Cd, and Pb) were below the permissible level except those of Mn, Ni, Mo, Cd, and Pb. At both sites, the transfer factor ranged from 0.047–228.3 mg kg^?1 with Cr having the highest transfer factor. The metal pollution index in soil was in the following order: As > Fe > Ni > Zn > Cd > Mo > Se > Co > Pb > Mn > Cr > Cu, respectively. While in case of spinach at both sites, the concentrations of metals and metalloids in vegetable samples irrigated with canal and sewage water were observed below the permissible level except Mn, Ni, Zn, Mo, and Pb. At both sites, the transfer factor ranged from 0.038–245.4 mg kg^?1 with Cr having the highest transfer factor. The metal pollution index in soil was in the following order: Cd > Ni > Co > Se > Mn > Zn > Mo > Pb > Fe > Cr > As > Cu, respectively.     

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.     

Heavy metal contamination in vegetables grown around peri-urban and urban-industrial clusters in Ghaziabad,India

Heavy metal contamination of agricultural soils resulting from rapid industrialization and urbanization is of great concern because of potential health risk due to dietary intake of contaminated vegetables. The present study aims to evaluate the status of heavy metals contamination of agricultural soils and food crops around an urban-industrial region in India. Transfer factor values of Cu, Cr, Pb, Cd, Zn, and Ni from soil to vegetable was estimated. The mean heavy metal concentrations (mg/kg) in agricultural soils (Cu: 17.8, Cr: 27.3, Pb: 29.8, Cd: 0.43, Zn: 87, Mn: 306.6, Fe: 16984, and Ni: 53.8) were within allowable concentrations for Indian agricultural soil. The concentrations of Pb, Cd, Zn, and Ni in crops/vegetables exceeded the World Health Organization/Food and Agriculture Organization safe limits. Relative orders of transfer of metals from soil to edible parts of the crops/vegetables were Cd > Pb > Ni > Zn > Cu > Cr. The enrichment factors of heavy metals in soil indicated minor to moderately severe enrichment for Pb, Cd, and Ni; minor to moderate enrichment for Zn; no enrichment to minor enrichment for Mn; and no enrichment to moderate enrichment for Cu at different sites. Ecological risk index of soil showed considerable contamination in one of the wastewater irrigated sites.     

Comparative Evaluation of Trace Metal Distribution and Correlation in Human Malignant and Benign Breast Tissues

Selected trace metals were analyzed in human malignant and nonmalignant (benign) breast tissue samples by the flame atomic absorption spectrophotometric method. In malignant tissues, dominant mean concentrations were revealed by Na, K, Ca, Mg, Fe, Zn, and Al at 927, 552, 231, 61.7, 36.5, 18.3, and 8.94 microg/g, respectively, while the mean metal levels in benign tissues were 903, 435, 183, 63.3, 24.7, 14.5, and 10.1 microg/g, respectively. Average concentrations of Cd, Co, Cr, Cu, Fe, Mn, K, Ca, and Zn were noted to be significantly higher in the malignant tissues compared with the benign tissues. Significantly strong correlations (r > 0.50) in malignant tissues were observed between Mn and Co, Mn and Cd, Cd and Cr, Fe and Mn, Cd and Co, Fe and Co, Mg and Pb, Cd and Fe, Mg and Ni, Pb and Ni, Ni and Sr, and Fe and Pb, whereas, Cd and Co, Cd and Mn, Co and Mg, Co and Mn, Cu and Mn, Co and Ni, Mg and Ni, Cd and Cu, Cd and Ni, Ca and Mg, Mn and Pb, Cu and Ni, Fe and Ni, Cd and Mg, Co and Cu, Cr and Na, and Cd and Cr revealed strong and significant relationships in benign tissues at p < 0.001. Principal component analysis of the metals data yielded six principal components for malignant tissues and five principal components for benign tissues, with considerably different loadings, duly supported by cluster analysis. The study revealed a considerably different pattern of distribution and mutual correlations of trace metals in the breast tissues of benign and cancerous patients.     

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.     

Heavy Metal Contamination in Roadside Soil and Their Mobility in Relations to pH and Organic Carbon

Concentrations of Pb, Zn, Cd, Ni, Cu, Cr, and Mn were determined to assess the impact of automobiles on heavy metal contamination of roadside soil. Soil samples at four polluted sites and a control site were collected at a depth of 0, 2, 5, 10, 15, 20, 30?cm. A comparison of elemental levels between polluted and control sites exhibited exceptionally higher concentrations at the former sites. The Pb levels in polluted sites varied from 70 to 280.5?µgg^?1and it rapidly decreased with depth. Similarly, mean concentrations of Zn, Cd, Ni, Cu, Cr, and Mn were significantly higher at polluted sites and followed a decreasing trend with the increase in depth. Correlation coefficients between heavy metals and traffic density were positively significant except for nickel. Profile samples showed that Pb, Zn, Cd, Cu, and Mn were largely concentrated in the top 5?cm confirming airborne contamination. The vertical movement and partitioning of metals, except Ni and Cr, exhibited predominant association with soil pH and organic carbon. The results have been presented using Heavy Metal Index.     

Bioaccumulation and rhizofiltration potential of Pistia stratiotes L. for mitigating water pollution in the Egyptian wetlands

The bioaccumulation and rhizofiltration potential of P. stratiotes for heavy metals were investigated to mitigate water pollution in the Egyptian wetlands. Plant and water samples were collected monthly through nine quadrats equally distributed along three sites at Al-Sero drain in Giza Province. The annual mean of the shoot biomass was 10 times that of the root. The concentrations of shoot heavy metals fell in the order: Fe < Mn < Cr < Pb < Cu < Zn < Ni < Co < Cd, while that of the roots were: Fe < Mn < Cr < Pb < Zn < Ni < Co < Cu < Cd. The bio-concentration factor (BCF) of most investigated heavy metals, except Cr and Pb, was greater than 1000, while the translocation factor (TF) of most investigated metals, except Pb and Cu, did not exceed one. The rhizofiltration potential (RP) of heavy metals was higher than 1000 for Fe, and 100 for Cr, Pb and Cu. Significant positive correlations between Fe and Cu in water with those in plant roots and leaves, respectively were recorded, which, in addition to the high BCF and RP, indicate the potential use of P. stratiotes in mitigating these toxic metals.     

Heavy metals distribution in the coral reef ecosystems of the Northern Red Sea

Concentrations of seven heavy metals (Cu, Zn, Pb, Cd, Ni, Co and Fe) were measured in the seawater, sediments, common scleractinian reef-building corals and soft corals (Octocorallia : Alcyonacea) at seven reef sites in the Northern Red Sea: I (Hurghada), II (Ras Za’farana), III (El-Ain Al-Sukhna), IV (El-Tur), V (Sha’b Rashdan), VI (Sharm El-Sheikh) and VII (Dahab). Levels of heavy metals were considerably elevated in seawater, sediments and corals collected from reef sites exposed to increased environmental contamination, as a result of diversified natural and anthropogenic inputs. Soft corals of genera Lithophyton, Sarcophyton and Sinularia showed higher concentrations of Zn, Pb, Cd and Ni than hard coral genera Acropora and Stylophora. Soft coral Sarcophyton trocheliophorum collected from El Ain Al-Suhkna (Gulf of Suez) had greater concentration of Cu, followed by hard corals Acropora pharaonis and Acropora hemprichi. The elevated levels of Zn, Cd and Ni were reported in the dry tissue of soft coral Sinularia spp. On the other hand, the soft coral Lithophyton arboreum displayed the highest concentration of Pb at Sha’b Rashdan (Gulf of Suez) and elevated concentration of Zn at Sharm El-Sheikh. Sediments showed significantly higher concentration of Fe than corals. The higher levels of Fe in hard corals than soft corals reflected the incorporation of Fe into the aragonite and the chelation with the organic matrix of the skeleton. The greater abundance of soft corals in metal-contaminated reef sites and the elevated levels of metals in their tissue suggesting that the soft corals could develop a tolerance mechanism to relatively high concentrations of metals. Although the effects of heavy metals on reef corals were not isolated from the possible effects of other stresses, the percentage cover of dead corals were significantly higher as the concentrations of heavy metals increased.     

Geochemical cycling of heavy metals in a marine coastal area: benthic flux determination from pore water profiles and in situ measurements using benthic chambers

Concentrations of the heavy metals Cd, Co, Cr, Cu, Fe, Mn, Ni, Pb and Zn were measured in sea water, suspended matter, sediments and pore water samples collected in a coastal area of the middle Tyrrhenian Sea. Concentration factors between pore water (extracted from the first centimeter of the sediments) and the overlying sea water (taken 30 cm above the sea bed) were less than 1 for Cr, Cu and Pb, 1–10 for Cd and Ni, 10–100 for Fe and Co, 100–1000 for Mn, and 1–100 for Zn.The benthic fluxes of heavy metals at the sediment-water interface were measured directly using in situ benthic chambers and calculated using Fick's first law during two experimental periods, one in 1986 and the other in 1988. The fluxes of Cu, Ni, Pb and Zn varied significantly over time; this appeared to be related to their relatively low ( 10) concentration factors. From the benthic chamber experiments, metals with positive fluxes were in the order: Mn > Fe > Co > Cd, while those with negative fluxes were: Zn > Pb > Ni Cu. Fluxes calculated using Fick's Law were: positive – Mn > Fe > Zn (or Zn > Fe) > Ni > Co > Cd, negative fluxes Pb > Cu > Cr.Measured (benthic chamber) and calculated (Fick's first law) fluxes for Co, Cd, Mn, Pb and Fe were comparable within an order of magnitude, although less agreement was found for Cu, Ni and Zn. Removal of Ni and Zn at the sediment-water interface has been proposed to explain the fact that the measured and calculated fluxes have opposite directions for these metals.     

Use of the green alga Ulva rigida C. Agardh as an indicator species to reassess metal pollution in the Thermaikos Gulf, Greece, after 13 years

The concentrations of metals (Mn, Pb, Fe, Zn, Cu, Cd,Co, Ni, Cr, Na, K, Ca, Mg) were determined in thegreen alga Ulva rigida, in the sediment andseawater of Thermaikos Gulf (Greece) during monthlysamplings in 1994–1995. This Gulf is the recipientof domestic and industrial effluents. Pb, Fe, Cu, Coand Cr concentrations in U. rigida at the studyarea were higher than those 13 years earlier andapparently came from different sources than those forZn, Cd and Ni. The relative abundance of metals inthe alga decreased in the order: Mg > Na > K >Ca > Pb > Fe > Mn > Zn > Cr, Cu > Ni >Co > Cd. Only Cu concentrations in the alga fromKalochori and Cd ones from Viamyl showed significantseasonal changes. Cu and Cd concentrations ingeneral followed the same pattern of variation, withminimum values in winter-spring. This pattern isdiscussed in relation to growth dynamics and tissueage. Only Pb concentrations in the alga showed asignificant positive correlation with concentrationsin the seawater. There were both positive andnegative correlations among some metals in the alga. It is concluded that U. rigida can be used as anindicator species, especially for Pb.     

Metal concentrations in Sargassum algae from coastal waters of Nha Trang Bay (South China Sea)

The concentrations of metals, viz., Fe, Mn, Cu, Zn, Cd, Pb, and Ni, were investigated in brown algae of the genus Sargassum collected in the coastal waters of Nha Trang Bay (South China Sea). Metal concentrations in algae growing in the zone of influence of the city of Nha Trang were higher than those in macrophytes collected to the south and north of the city. Similar levels of Cu and Fe concentrations were observed in macrophytes from the urbanized coastal areas of Nha Trang Bay and in algae from the Peter the Great Bay (Sea of Japan). This is suggestive of comparable metal inputs from the anthropogenic sources of the cities of Nha Trang and Vladivostok (Peter the Great Bay). However, the concentrations of Pb, Ni, and Cd in algae from the coastal waters of Nha Trang Bay were lower than in macrophytes from the inshore zone of Vladivostok. The high level of pollution of sea water with Zn compounds near Nha Trang was local. The metal levels in macrophytes from background areas reflect the geochemical features of the environment. Sargassum algae from Nha Trang Bay had lower concentrations of Zn, Cd, and Ni and higher concentrations of Mn than algae from Peter the Great Bay. The background concentrations of Cu, Pb, and Fe in macrophytes from both bays were virtually the same.     

Contents of Cd,Fe, Mn and Zn in the tissue ofKatelysia hiantina collected from Tolo Harbour,an almost land-locked sea

Summary Samples ofK.hiantina and sediments were collected from iron ore tailings and other nearby sites within Tolo Harbour for heavy metal analysis. It was found that sediments as well as the clams at the tailings contained higher concentrations of Cd, Fe, Mn and Zn. Positive correlations between the metals in the sediments and clam tissues were found. The clams collected from the tailings showed a bustantial loss of Fe, Mn and Zn when reared in clean filtered seawater for a period of 8 days.     

浙江油茶产地土壤和果实金属元素含量特征

为探讨油茶(Camellia oleifera)产地土壤和油茶果实中金属元素分布和富集特征,在油茶果实成熟期,对浙江5个油茶产地土壤及油茶果实中金属元素进行污染分析和富集能力评价.结果表明,浙江油茶产地土壤中Pb、Cr、Cd、As、Hg、Ni、Cu和Zn含量低于农用地土壤污染风险筛选值,综合污染等级为安全.个别产区常山...     

Anthropogenic impacts on heavy metal concentrations in surface soils from the typical polluted area of Bengbu,Anhui province,Eastern China

A total of 30 surface soil samples were collected from the typical polluted area of Bengbu, Anhui province, Eastern China. The content characteristics, source identification, and risk assessment of heavy metals (Cd, Cu, Mn, Ni, Pb, and Zn) were studied based on the field investigation, sampling, indoor test, and statistical analysis. Results showed that the concentrations of Cd, Cu, Mn, Ni, Pb, and Zn showed different spatial variation and ranged from 0.48 to 1.84, 12.78 to 239.07, 287.14 to 491.96, 15.29 to 52.99, 13.28 to 68.82, and 28.83 to 184.79 mg/kg, respectively. Besides Mn, the contents of other metals have exceeded the local background value to a certain extent, and the higher concentrations recorded were found in the east of Bali channel. Source analyses indicated that Cd, Cu, Pb, and Zn were attributed to industrial emissions, vehicle exhaust pollution, and phosphate uses in agriculture, whereas Ni and Mn were mainly of natural origin. Among the six heavy metals, Cd posed the highest ecological risk with the proportion of 3.3% at a considerable level, 36.7% at a high level, and 60% at a very high level, Cu presented a low-to-moderate ecological risk, while others presented a relatively low risk in surface soils, suggesting that Cd and Cu, especially for Cd, should draw environmental concern.     

Comparison of Trace Elements in the Scalp Hair of Malignant and Benign Breast Lesions Versus Healthy Women

Trace elements including Al, Ca, Cd, Co, Cr, Cu, Fe, K, Mg, Mn, Na, Ni, Pb, Sb, Sr, and Zn were analyzed in the scalp hair samples of women with malignant breast lesions, women with benign breast lesions, and healthy donors using atomic absorption spectrophotometric method. In the scalp hair of malignant-tumor patients, the highest average concentration was shown by Ca (1,187 μg/g), followed by Na (655 μg/g), Mg (478 μg/g), Zn (391 μg/g), Sr (152 μg/g), Fe (114 μg/g), and K (89.8), while in the case of benign-tumor patients, the average estimated element levels were 1,522, 1,093, 572, 457, 217, 80.4, and 74.7 μg/g, respectively. Most of the elements exhibited non-normal distribution evidenced by large spread, standard error, and skewness values. Mean concentrations of Ca (634 μg/g), Zn (206 μg/g), Mg (162 μg/g), Fe (129 μg/g), and Na (82.1 μg/g) were noteworthy in the scalp hair of healthy women. Average levels of Na, Sr, K, Cd, Co, Pb, Mg, Ca, Zn, Ni, Sb, and Mn were revealed to be significantly higher in the hair of malignant and benign patients compared to the healthy women; however, Fe, Cu, Al, and Cr were not significantly different in the scalp hair of the three groups. The quartile distributions of Ca, Cd, Co, Cr, K, Mg, Mn, Na, Ni, Pb, Sb, and Sr revealed maximum spread in the scalp hair of malignant and benign groups; nevertheless, Al, Cu, Fe, and Zn exhibited almost comparable quartile levels in the three groups. Strong correlation coefficients were found between Fe and Cd, Al and Na, Mn and Sr, Co and Cr, Cd and Cr, Pb and K, Pb and Mn, Cu and Na, and Al and Fe in the scalp hair of malignant-tumor patients, while Fe and K, Cd and Co, Na and Co, and Cr and Pb showed strong correlations in the scalp hair of benign-tumor patients, both of which were significantly different compared with the healthy subjects. Multivariate cluster analysis also revealed divergent clustering of the elements in the scalp hair of malignant and benign patients in comparison with the healthy women.     

Accumulation of Heavy Metals in Potatoes Grown on Calcareous Soils of the Hamedan,Western Iran

This study was conducted to investigate heavy metal contamination in agricultural soils and their transfer in a soil-potato system. A total of 59 pairs of potato and soil samples, representing different locations were collected from Hamedan, western Iran and subjected to heavy metals analysis. Average concentrations of Cd, Cu, Fe, Mn, Ni, Pb, and Zn were 1.2, 13.1, 161.4, 13.2, 3.2, 19.5, and 41.5 mg kg^?1 dry weight in potato tubers, respectively. A sequence of decreasing plant transfer factors values: Cd > Pb > Cu > Zn > Ni ≥ Mn > Fe was obtained. Furthermore, the health risk index (HRI) values were within the safe limit (<1) except for Cd and Pb. HRI values for Cd and Pb were higher than 1, indicating potential health risk, especially for children. The results indicated that daily intakes of Cd and Pb in potato in the study area may present a future hazard.     

Characterization and human health risk assessment of trace metal in PM10 in Bac Giang,short-term study in a developing province in Vietnam

Abstract

This study investigated the airborne concentration of PM₁₀ and 20 trace elements (Al, As, Ba, Ca, Cd, Co, Cr, Cu, Fe, K, Mg, Mn, Mo, Na, Ni, Na, Pb, Ti, V, Zn) in residential, industry, traffic road, coal mining, thermal power plant area of Bac Giang province. The average PM₁₀ concentration was highest at coal site, followed by traffic 1 sites, industrial sites and traffic 2 sites, the residential sites, and lowest at the power plant site located in mountain area. While Al, Ca, Fe, K, Mg, Na were the most abundant elements in all sampling sites, accounting for 73–96% of total obtained elements, the concentration of As, Cd, Cr, Cu, Mn, Ni, Pb, V, and Zn occupied from 2.9 to 23.2%. Noticeably, the concentrations of Cd were from 7 to 65 times higher than the concentration limit for Cd (0.1?ng/m³) according the World Health Organization (WHO). Although, the Hazard Index (HI values) of all metals were found to be within the safe level for both children and adults, the Carcinogenic Risk (CR) of Cr and As in all sites were closed to the acceptable levels for children, implying a potential carcinogenic risks of these metals.     

The use of the three-ridge clam (Amblema perplicata) to monitor trace metal contamination

The three-ridge clamAmblema perplicata was used to monitor two streams for the presence of zinc (Zn) and cadmium (Cd) derived from an industrial source. Clams were collected from a relatively uncontaminated area in one river and transported to four study sites in the two contaminated streams. The clams were placed into polyethylene cages and left in these streams for one week. Control clams were treated in a similar manner and left in the uncontaminated river.The highest mean concentration of Zn (956 µg/g dry wt) was found in the gill tissue of clams from the most contaminated site. The highest mean Cd concentration (18.6 µg/ g dry wt) was found in digestive glands of clams, also from the most contaminated site. Mean concentrations at contaminated sites were significantly higher than background and control levels; the findings suggest that these particular organs of clams may be useful in monitoring levels of Zn and Cd in other freshwater systems.     

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.