Distribution and fractionation of heavy metals in the Tisa (Tisza) River sediments

Introduction In this work, sediments of the River Tisa (Tisza) are studied to assess their environmental pollution levels for some major heavy metals, as well as to predict the investigated elements’ mobility on the basis of their association type with the substrate. The Tisa River catchments area is a subbasin of the River Danube. Part of this river, 166 km long, belongs to the Serbian province of Vojvodina, before it flows into the Danube. It has been chosen for our investigation, because it has been exposed to intense pollution in the last decades. Materials and Methods The river sediment samples were collected at 32 locations. The proportions of sand, silt and clay fractions were determined. The sequential extraction procedure following a modified Tessier method was applied for speciation of the metal forms in the collected samples. The metal concentrations of Zn, Cd, Pb, Ni, Cu, Cr, Fe and Mn in extracts were determined by atomic absorption spectroscopy. Results and Discussion Granulometric analysis showed that some 50% of the Tisa River sediments were silt and clay, while the rest was sand with quartz, as the main constituent. The average metal content of the surface river sediment samples for every fraction of sequential extraction was presented and discussed in relation to pH, Eh and metal fractionation. The average metal content from the Tisa River sediments, obtained as an average of the metal’s concentration released in all five sequential extraction fractions was compared with: average metal contents of the Tisa River sediments in Hungary, metal content in soils formed on the Tisa River alluvium of Vojvodina, average metal content in soils of Vojvodina, and average metal content in soils of Hungary. An assessment of metal pollution levels in Tisa River sediments was made by comparing mean values for obtained results for the Tisa River sediments with the freshwater sediment’s Quality Guidelines as published by US EPA, Environment Canada and soil standards for Serbia. Conclusion According to US EPA and Canadian Quality Guidelines for freshwater sediments, the concentration of heavy metals in Tisa sediments were: (a) much higher than defined concentrations below which harmful effects on river biota are unlikely to be observed, (b) below defined concentrations above which harmful effects on river biota are likely to be observed. The concentration levels of Pb, Ni, Cu and Cr in Tisa River sediments are safe when compared with Serbian MAQ (Maximum Allowed Quantity) standards for soils, but they are unsafe in the case of Zn and Cd. Recommendations and Outlook The quality of sediments in the Tisa River was on the border line between potentially polluted and polluted. This line could very easily be exceeded since the quality of sediments in the Tisa River in Hungary was already worse than in Serbia. These results indicated the need for further monitoring of heavy metals in that locality.     

Analysis and assessment of heavy metal pollution in suspended solids and sediments of the river Danube

The Joint Danube Survey (JDS)--a comprehensive monitoring survey to assess the environmental pollution status of the river Danube--was carried out in 2001. Samples were taken at 74 positions along the river from Neu-Ulm (River-km 2589) down to the Danube Delta at the Black Sea (River-km 0) and in 24 main tributaries and anabranches. Besides other biological and chemical parameters, concentrations of Al, As, Cd, Cr, Cu, Fe, Pb, Mn, Hg, Ni, and Zn were determined in sediments and suspended solids. Lowest heavy metal concentrations were measured around River-km 1800. After an increase down to River-km 1000 (the Irongate Reservoir), a constant level or a slight decrease could be found down to and in the Danube Delta. Very high element concentrations were determined at only a few stations of the river Danube and in some tributaries. An evaluation of the pollution status of the river was carried out by enrichment factors (EFs) calculated using adapted background concentrations of heavy metals. Except single sampling sites and some tributaries, the pollution of the river Danube by As, Cr, Cu, Pb, Hg, Ni, and Zn can be regarded as rather low. However, elevated concentrations of Cd were found in both investigated matrices, particularly in the lower stretch of the river Danube beginning at the Irongate.     

Sequential extraction of heavy metals in river sediments of an abandoned pyrite mining area: pollution detection and affinity series

In this paper heavy metal pollution at an abandoned Italian pyrite mine has been investigated by comparing total concentrations and speciation of heavy metals (Fe, Cu, Mn, Zn, Pb and As) in a red mud sample and a river sediment. Acid digestions show that all the investigated heavy metals present larger concentrations in the sediment than in the tailing. A modified Tessier's procedure has been used to discriminate heavy metal bound to organic fraction from those originally present in the mineral sulphide matrix and to detect a possible trend of metal mobilisation from red mud to river sediment. Sequential extractions on bulk and size fractionated samples denote that sediment samples present larger percent concentrations of the investigated heavy metals in the first extractive steps (I-IV) especially in lower dimension size fractionated samples suggesting that heavy metals in the sediment are significantly bound by superficial adsorption mechanisms.     

Assessment of heavy metal contamination in Hindon River sediments: a chemometric and geochemical approach

The aim of this study was to assess the level of heavy metals (Cd, Cr, Cu, Fe, Mn, Ni, Pb, and Zn) in the surface sediments of the Hindon River, India that receives both treated and untreated municipal and industrial discharges generated in and around Ghaziabad, India. Mean metals concentrations (mg kg⁻¹) were in the range of; Cu: 21.70-280.33, Cd: 0.29-6.29, Fe: 4151.75-17318.75, Zn: 22.22.50-288.29, Ni: 13.90-57.66, Mn: 49.55-516.97, Cr: 17.48-33.70 and Pb: 27.56-313.57 respectively. Chemometric analysis was applied to identify contribution sources by heavy metals while geochemical approaches (enrichment factor and geo-accumulation index) were exploited for the assessment of the enrichment and contamination level of heavy metals in the river sediments. Chemometric analysis suggested anthropic origin of Cu, Cd, Pb, Zn, and Ni while Fe showed lithogenic origin. Mn and Cr was associated and controlled by mixed origin. Geochemical approach confirms the anthropogenic influence of heavy metal pollution in the river sediments. The study suggests that a complementary approach that integrates chemometric analysis, sediment quality criteria, and geochemical investigation should be considered in order to provide a more accurate appraisal of the heavy metal pollution in river sediments. Consequently, it may serve to undertake and design effective strategies and remedial measures to prevent further deterioration of the river ecosystem in future.     

Limited effects of heavy metal pollution on foraging and breeding success in the curlew (Numenius arquata)

We examined the effect of heavy metal pollution on the foraging success and breeding performance of the curlew (Numenius arquata) along a documented pollution gradient from a point source, and also by comparing foraging and breeding parameters between the polluted site and two non-polluted areas. Prey biomass and abundance, and foraging success did not vary along the pollution gradient, and were no less at the polluted site than in the non-polluted areas. Furthermore, there was no difference in adult weight during incubation between the polluted and non-polluted areas. There were also no differences in measures of breeding success along the pollution gradient, or between areas, which could be attributed to pollution per se. Egg shells from the polluted area had higher concentrations of heavy metals than in the non-polluted areas, and egg shells close to the pollution source were contaminated more than those further from it. However, there was no difference in calcium concentrations of egg shells or egg-shell thickness between areas. We conclude that in this study there were minimal immediate effects of heavy metal pollution on foraging and breeding success in the curlew.     

雷州半岛土壤重金属分布特征及其污染评价

在雷州半岛采集了106个土壤表层样品,分析了其中8种重金属元素(Cu、Pb、Zn、Cr、Ni、Cd、Hg和As)的全量.结果表明,雷州半岛土壤重金属污染由高到低排序为Ni＞Cr＞Hg＞Cu＞Zn＞Cd＞As＞Pb,Zn、Cd、As和Pb质量浓度均没有超标,Hg和Cu质量浓度超标率亦不高,但Ni和Cr平均质量浓度达49.81、87.13 mg/kg,高于国内外其他对照区域,超标率分别为25.47%和24.53%;重金属元素在雷州半岛各土壤利用类型中分布规律不明显,按4种主要土壤利用类型受重金属污染程度大小排序为甘蔗地＞果园土＞水田＞菜地;雷州半岛土壤综合污染指数总平均为0.970,土壤总体上尚清洁,重金属污染处于警戒水平;雷州半岛各区域中,徐闻、雷州两地土壤重金属质量浓度明显高于其他地区,其主要原因是徐闻、雷州两地成土母质主要为玄武岩,造成土壤Cr、Ni及其他重金属背景值较高.     

Determination of polybrominated diphenyl ethers in soil and sediment from an electronic waste recycling facility

In this study samples of ten species of fish were analyzed for concentrations of organochlorine pesticides, PCBs and heavy metals (Pb, Cd, and Cu). Fish were captured using electric fishing on ten sites along the Dr?me river (Rh?ne-Alpes region). Quantitative determination of the organochlorine and PCBs compounds was performed by gas chromatography-electron-capture detection (GC-ECD). The concentrations of heavy metals were determined by atomic absorption spectrophotometry. Samples contained detectable concentrations of lindane, PCBs, and heavy metals but at concentrations below the maximum residue limit (MRL). Non-parametric statistical analysis was performed to distinguish groups of sites with different levels of contamination. PCBs concentrations increased along the river with four groups of sites significantly different from each other. Cadmium concentrations were below the MRL. Lead contamination showed two groups significantly different and a repartition similar to PCBs. Copper contamination was correlated with the localization of vineyards. We assessed the potential effects of contamination the otter (Lutra lutra). The concentrations of all pollutants analyzed in fish sampled in this study are lower than the threshold values described in literature. The Dr?me river is relatively unpolluted river, and the establishment of otter populations should not be affected by pollution.     

Estimation of metal uptake efficiencies from precipitation in mosses in Lithuania

The main sources contributing to heavy metal content in mosses in Lithuania were examined by a comparison of heavy metal concentrations in moss and corresponding deposition levels calculated from bulk deposition analysis. Bulk deposition was collected in open areas as well as under the canopy of trees. Uptake efficiencies in moss were calculated for Cd, Cr, Cu, Fe, Mn, Ni, V and Zn. All elements in moss except Pb and Cd appeared to be more or less influenced by sources other than air pollution. The general order of this influence on the heavy metal content in moss was observed as follows: Ni < V < Cr < Zn < Fe < Mn. The contents of Mn and Zn in moss were greatly influenced by leaching from the canopy while Pb was the only element which showed a net metal retention by the canopy. Concentrations of Fe and Cr in moss were dominating due to contribution from soil dust.     

Informal e-waste recycling: environmental risk assessment of heavy metal contamination in Mandoli industrial area,Delhi, India

Nowadays, e-waste is a major source of environmental problems and opportunities due to presence of hazardous elements and precious metals. This study was aimed to evaluate the pollution risk of heavy metal contamination by informal recycling of e-waste. Environmental risk assessment was determined using multivariate statistical analysis, index of geoaccumulation, enrichment factor, contamination factor, degree of contamination and pollution load index by analysing heavy metals in surface soils, plants and groundwater samples collected from and around informal recycling workshops in Mandoli industrial area, Delhi, India. Concentrations of heavy metals like As (17.08 mg/kg), Cd (1.29 mg/kg), Cu (115.50 mg/kg), Pb (2,645.31 mg/kg), Se (12.67 mg/kg) and Zn (776.84 mg/kg) were higher in surface soils of e-waste recycling areas compared to those in reference site. Level exceeded the values suggested by the US Environmental Protection Agency (EPA). High accumulations of heavy metals were also observed in the native plant samples (Cynodon dactylon) of e-waste recycling areas. The groundwater samples collected form recycling area had high heavy metal concentrations as compared to permissible limit of Indian Standards and maximum allowable limit of WHO guidelines for drinking water. Multivariate analysis and risk assessment studies based on total metal content explains the clear-cut differences among sampling sites and a strong evidence of heavy metal pollution because of informal recycling of e-waste. This study put forward that prolonged informal recycling of e-waste may accumulate high concentration of heavy metals in surface soils, plants and groundwater, which will be a matter of concern for both environmental and occupational hazards. This warrants an immediate need of remedial measures to reduce the heavy metal contamination of e-waste recycling sites.     

Consequences and implication of heavy metal spatial variations in sediments of the Keelung River drainage basin, Taiwan

A great deal of effort was enforced to reduce the pollution of the Keelung River in the past 20 years. A set of sediments covering most of the Keelung River drainage basin was analyzed for bulk sediment heavy metal concentrations, grain size content and Pb-210 dating in order to understand the spatial variations of sediment heavy metal contents as well as to evaluate the effectiveness of pollution control. The results showed that anthropogenic pollution and grain size are two of the most important factors in controlling spatial variations of metals in the Keelung River sediments. In addition, little reduction of sediment heavy metal concentrations was observed in the Keelung River drainage basin. Large spatial variations of metals and grain size were observed. High concentrations of zinc, copper, lead and cadmium were found in sediments near the main outlets of the adjacent Da-Wu-Lun Industrial Park and municipal waste drainage systems. Anthropogenic sources of heavy metal have altered the natural sediment heavy metal distributions. Positive linear relationships between aluminum, iron and fine-grained sediments showed that spatial grain size variations controlled the natural aluminum and iron concentrations in sediments. Zinc, copper, lead and cadmium contents were much higher than those measured 15 years ago. The unusually high concentrations of heavy metals, high enrichment factors and their rapid increases with time in Pb-210 dated core showed that the efforts in heavy metal reduction were futile. A proper regulation to prevent further heavy metals from entering into the river is urgently needed.     

Risk assessment of heavy metal pollution for detritivores in floodplain soils in the Biesbosch, The Netherlands, taking bioavailability into account

Floodplains of the European rivers Rhine and Meuse are heavily polluted. We investigated the risk of heavy metal pollution (Cd, Cu, Pb, Zn) for detritivores living in a floodplain area, the Biesbosch, the Netherlands, affected by these rivers. Total soil, pore water and 0.01 M CaCl(2) extractable concentrations and concentrations in plant leaves, earthworms, isopods and millipedes were measured in two sites and compared with literature data to assess possible risks. Based on total metal concentrations in soil, serious effects on detritivores were expected. However, 0.01 M CaCl(2) extractable, pore water and plant leaf concentrations were similar to metal concentrations found in unpolluted areas. Concentrations of Cu and Cd in earthworms and Cu in millipedes were higher in the Biesbosch than in animals from reference areas. All other measured concentrations of heavy metals in earthworms, isopods and millipedes were similar to the ones found in reference areas. Despite high total soil concentrations, effects of Zn, Cu, Pb and Cd pollution on isopods are therefore not expected, while millipedes may only be affected by Cu. Since Cu and Cd levels in earthworms were increased compared to animals in unpolluted soils, this faunal group seems to be most at risk. Given the engineering role of earthworms in ecosystems, effects on the ecological functioning of floodplain soils therefore cannot be excluded.     

Distribution and accumulation of heavy metals in the sediments of Kaohsiung Harbor, Taiwan

The distribution, enrichment, and accumulation of heavy metals in the sediments, especially those at the vicinity of tributary estuaries of Kaohsiung Harbor, Taiwan were investigated. Sediment samples from six locations in the Kaohsiung Harbor were collected quarterly in the period from 2002 to 2005 and characterized for metal content (e.g., Hg, Pb, Cd, Cr, Cu, Zn and Al), water content, organic matter, total nitrogen, total phosphorous, total grease, and grain size. Results showed that metal concentrations varied from 0.58 mg kg(-1) for Cd to 596 mg kg(-1) for Zn. Metal concentrations at the vicinity of river mouths were higher than those at other locations. All heavy metals studied, except Cr, had relatively high enrichment factors and geo-accumulation indices in the estuaries. Moreover, metal concentrations correlated closely to the physical-chemical properties of the sediments, which strongly suggested the influence of industrial and municipal wastewaters discharged from the neighboring industrial parks and river basins. Results would help develop strategies for pollution control and sediment remediation of Kaohsiung Harbor.     

Exposure to heavy metals in blood and risk perception of the population living in the vicinity of municipal waste incinerators in Korea

Background, aim, and scope

The purpose of this study was to monitor and present the heavy metal concentrations in the blood of residents of areas near municipal waste incinerators (MWIs), who are more prone to environmental pollution. We also sought to compare and analyze the residents?? perception of environmental pollution as one of the factors affecting heavy metal concentrations in the blood using a survey about the perceived damage caused by the facilities. Since heavy metal levels in the blood can be affected not only by local environmental pollution but also by personal and occupational factors, heavy metal levels in the blood need to be verified and consistently monitored.

Methods

Residents who live within 300?m of MWIs in Seoul are acknowledged to be under indirect influence according to the Waste Disposal Act. A survey was given to 841 residents living within 300?m of a MWI from 2006 to 2009. The concentrations of heavy metals (lead, cadmium, and mercury) in the blood were measured in the 841 surveyed residents and in 105 residents in reference areas. Additionally, the perception of the damage caused by municipal waste incinerators was investigated using scores from 1 to 5 on a Likert scale.

Results

The measurements of the heavy metal concentrations in the blood showed that the mean concentrations of lead, cadmium, and mercury were 43.1, 1.7, and 1.3?ug/L, respectively. The blood levels of lead and cadmium were slightly higher in the group of the subjects who had resided the longest near the municipal waste incinerators. When compared with the domestic investigation by the Ministry of Environment, the concentrations of lead and cadmium were a little higher, while that of mercury was a little lower. Overall, there was no significant difference in the distribution of heavy metal levels in the blood among age groups. Additionally, the investigation of the perceived damage from municipal waste incinerators showed that the subjects     

Heavy metals and Pb isotopic composition of aerosols in urban and suburban areas of Hong Kong and Guangzhou,South China—Evidence of the long-range transport of air contaminants

Rapid urbanization and industrialization in South China has placed great strain on the environment and on human health. In the present study, the total suspended particulate matter (TSP) in the urban and suburban areas of Hong Kong and Guangzhou, the two largest urban centres in South China, was sampled from December 2003 to January 2005. The samples were analysed for the concentrations of major elements (Al, Fe, Mg and Mn) and trace metals (Cd, Cr, Cu, Pb, V and Zn), and for Pb isotopic composition. Elevated concentrations of metals, especially Cd, Pb, V and Zn, were observed in the urban and suburban areas of Guangzhou, showing significant atmospheric trace element pollution. Distinct seasonal patterns were observed in the heavy metal concentrations of aerosols in Hong Kong, with higher metal concentrations during the winter monsoon period, and lower concentrations during summertime. The seasonal variations in the metal concentrations of the aerosols in Guangzhou were less distinct, suggesting the dominance of local sources of pollution around the city. The Pb isotopic composition in the aerosols of Hong Kong had higher ²⁰⁶Pb/²⁰⁷Pb and ²⁰⁸Pb/²⁰⁷Pb ratios in winter, showing the influence of Pb from the northern inland areas of China and the Pearl River Delta (PRD) region, and lower ²⁰⁶Pb/²⁰⁷Pb and ²⁰⁸Pb/²⁰⁷Pb ratios in summer, indicating the influence of Pb from the South Asian region and from marine sources. The back trajectory analysis showed that the enrichment of heavy metals in Hong Kong and Guangzhou was closely associated with the air mass from the north and northeast that originated from northern China, reflecting the long-range transport of heavy metal contaminants from the northern inland areas of China to the South China coast.     

Effects of spatial and temporal variation in metal availability on earthworms in floodplain soils of the river Dommel, The Netherlands

Regarding impact on ecological soil functioning, metal pollution is often considered a constant factor for certain sampling sites. However, especially bioavailable concentrations may differ in space and time. This aspect was investigated on four sites along a metal-polluted river, differing in soil characteristics and metal concentrations. Every four weeks earthworm densities, soil characteristics, and metal concentrations in soil and earthworms were determined. Earthworm biomass and density fluctuated in time and increased with increasing metal contamination, indicating the presence of compensating factors. Multivariate analysis suggested organic matter and moisture content to be the main factors explaining earthworm biomass. Metal concentrations in the earthworms increased with increasing total or 0.01M CaCl(2) extractable soil concentrations, but no time-related trends were seen. Cadmium concentrations in the earthworms exceeded background values, suggesting a potential risk. The neutral red retention biomarker assay, however, did not show any signs of metal stress in the earthworms.     

Combination of beehive matrices analysis and ant biodiversity to study heavy metal pollution impact in a post-mining area (Sardinia, Italy)

Mining activities represent a major source of environment contamination. The aim of this study was to evaluate the use of bees and ants as bioindicators to detect the heavy metal impact in post-mining areas. A biomonitoring programme involving a combination of honeybee hive matrices analysis and ant biodiversity survey was conducted over a 3-year period. The experimental design involved three monitoring stations where repeated sampling activities focused on chemical detection of cadmium (Cd), chrome (Cr) and lead (Pb) from different matrices, both from hosted beehives (foraging bees, honey and pollen) and from the surrounding environment (stream water and soil). At the same time, ant biodiversity (number and abundance of species) was determined through a monitoring programme based on the use of pitfall traps placed in different habitats inside each mining site. The heavy metal content detected in stream water from the control station was always below the analytical limit of quantification. In the case of soil, the content of Cd and Pb from the control was lower than that of mining sites. The mean heavy metal concentrations in beehive matrices from mining sites were mainly higher than the control, and as a result of regression and discriminant analysis, forager bee sampling was an efficient environmental pollution bioindicator. Ant collection and identification highlighted a wide species variety with differences among habitats mostly associated with vegetation features. A lower variability was observed in the polluted landfill characterised by lack of vegetation. Combined biomonitoring with forager bees and ants represents a reliable tool for heavy metal environmental impact studies.     

Field effects of pollutants in dynamic environments. A case study on earthworm populations in river floodplains contaminated with heavy metals

In industrialized countries river floodplains can be strongly polluted with heavy metals. Published studies on effects of heavy metal pollution on soil invertebrates in floodplains, however, are inconclusive. This is unexpected since studies in other less dynamic environments reported clear effects at even lower levels of pollution. Flooding induces extra variation in invertebrate biomass and abundance which may reduce the probability to detect heavy metal effects. In this paper we combine reported data from studies on river floodplains in The Netherlands and Belgium and statistically analyze the effect of heavy metals on species composition, biomass, density and individual weight of earthworms. Interaction effects of heavy metal stress and flooding are also considered. The results suggest clear effects of zinc and copper on all variables and interaction of heavy metals and flooding for individual weight.     

Seasonal Fluctuation in Heavy Metal Pollution in Iran´s Siahroud River - A Preliminary Study (7 pp)

Background The management of its available water resources has become a key issue for Iran. During the last few decades, the water quality of Siahroud River in the coastal plain of the Caspian Sea in Gilan Province in Northern Iran has significantly degraded. The scarcity of water has been compounded by rapid population growth and increasing pollution from fertilizers, pesticides, and municipal and industrial wastes. One of the sources of this degradation is the movement of heavy metals from the river's watershed into the various water systems supported by the river, including the water system for Rasht City. Methods To study the magnitude of heavy metal pollution in the Siahroud River, seven heavy metals including Zn, Cu, Pb, Cd, Mn, Fe, and Ni were measured in duplicate from replicated water samples collected over five consecutive seasons and analyzed by Atomic Absorption Spectrometry. In situ measurements of pH were taken with the samples and total organic carbon (TOC) was analyzed by IR gas measurement. Results The results demonstrated that four of the seven heavy metals including Pb, Fe, Cd, and Mn exceeded permissible safe levels as established by the United States Environmental Protection Agency. Multivariate factor analysis suggested that industrial land-use was the main contributing factor for the high levels of Fe and Mn in the Siahroud River, whereas, Cd was principly from agricultural activities in the watershed. The data also suggested that pH and TOC had an important role in the behaviour of Pb and Mn, and that the elevated levels of these two heavy metals in Siahroud River was the consequence of other anthropogenic sources. Only negligible levels of Zn, Cu and Ni were detected. Finally, all the sampling stations were subjected to cluster analysis. The results indicated that three different zones could be distinguished according to the levels of pollution. In addition, it was shown that the urban areas did not have a significant impact on the heavy metal pollution in the river. This observation stems from the fact that the data from the sampling stations before and after Rasht City were not significantly different. Recommendation . Preventive measures need to be undertaken in the land-use systems and watersheds of the Siahroud River to reduce the pollution levels of Pb, Cd, Mn and Fe.     

Speciation as a screening tool for the determination of heavy metal surface water pollution in the Guadiamar river basin

The Guadiamar river basin has traditionally received pollutants from two main sources: in its northern section of mining origin, and in its southern section (next to Do?ana National Park) from urban-industrial and agricultural sources. In April 1998, the spill of 6 million m3 of mining wastes (acidic waters and sludge) severely polluted the Guadiamar river basin with heavy metals, which caused serious damage to the local ecosystem. There is a direct association between the physicochemical speciation of an element and its toxicity, biological activity, bioavailability, solubility, etc. This work describes a distribution study of the metals Zn, Cd, Pb and Cu by speciation analysis of surface waters in eleven sampling points of the Guadiamar river basin. Four metal fractions were determined using anodic stripping voltammetry: labile metal forms, H+ exchangeable metal forms, strongly inert forms (associated with organic and inorganic matter in solution), and forms associated with suspended matter. Total concentrations in surface waters followed the trend Zn > Cu > Pb > Cd. The speciation study showed that Zn and Cd were present to a large extent in available forms (labile and H+ exchangeable), while Pb and Cu were found mostly in the less available forms (strongly inert). Moreover, the available forms were found in the northern section (mining pollution) and the strongly inert forms in the southern section (urban, industrial and agricultural pollution). These results can illustrate the potential value of speciation to discern between different sources of pollution.