Potentially toxic metal contamination of urban soils and roadside dust in Shanghai, China

A detailed investigation was conducted to understand the contamination characteristics of a selected set of potentially toxic metals in Shanghai. The amount of Pb, Zn, Cu, Cr, Cd and Ni were determined from 273 soil/dust samples collected within urban area. The results indicated that concentration of all metals except Ni in soils was significant, and metal pollution was even severer in roadside dust. A series of metal spatial distribution maps were created through geostatistical analysis, and the pollution hotspots tended to associate with city core area, major road junctions, and the regions close to industrial zones. In attempt of identifying the source of metals through geostatistical and multivariate statistical analyses, it was concluded as follows: Pb, Zn and Cu mainly originated from traffic contaminants; soil Ni was associated with natural concentration; Cd largely came from point-sourced industrial pollution; and Cr, Ni in dust were mainly related to atmospheric deposition.     

Characterizing the risk assessment of heavy metals and sampling uncertainty analysis in paddy field by geostatistics and GIS

For many practical problems in environmental management, information about soil heavy metals, relative to threshold values that may be of practical importance is needed at unsampled sites. The Hangzhou-Jiaxing-Huzhou (HJH) Plain has always been one of the most important rice production areas in Zhejiang province, China, and the soil heavy metal concentration is directly related to the crop quality and ultimately the health of people. Four hundred and fifty soil samples were selected in topsoil in HJH Plain to characterize the spatial variability of Cu, Zn, Pb, Cr and Cd. Ordinary kriging and lognormal kriging were carried out to map the spatial patterns of heavy metals and disjunctive kriging was used to quantify the probability of heavy metal concentrations higher than their guide value. Cokriging method was used to minimize the sampling density for Cu, Zn and Cr. The results of this study could give insight into risk assessment of environmental pollution and decision-making for agriculture.     

Heavy metals in soils from a typical industrial area in Sichuan,China: spatial distribution,source identification,and ecological risk assessment

Anthropogenic activities could result in increasing concentrations of heavy metals in soil and deteriorating in soil environmental quality. Topsoil samples from a typical industrial area, Shiting River Valley, Sichuan, Southwest China, were collected and determined for the concentrations of Cu, Zn, Cr, Cd, As, and Hg. The mean concentrations of these metals were lower than the national threshold values, but were slightly higher than their corresponding background values, indicating enrichment of these metals in soils in the valley, especially for Cu, Zn, and Hg. The topsoils in this area demonstrated moderate pollution and low potential ecological risk. Principal component analysis coupled with cluster analysis was applied to analyze the data and identified possible sources of these heavy metals; the results showed that soil Cd, Hg, As, Cu, and Zn were predominantly controlled by human activities, whereas Cr was mainly from the parent material. The spatial distribution of the heavy metals varied distinctly and was closely correlated to local anthropogenic activities. Furthermore, the concentrations of heavy metals in the industrial land demonstrated relatively higher levels than those of other land use patterns. Soil metal concentrations decreased with the distance increase from the traffic highway (0–1.0 km) and water system (0–2.0 km). Additionally, soil properties, especially pH and soil organic matter, were found to be important factors in the distribution and composition of metals.     

Geostatistical Assessment of the Impact of World War I on the Spatial Occurrence of Soil Heavy Metals

Previous research showed a regional Cu enrichment of 6 mg kg⁻¹ in the top soil of the Ypres war zone (Belgium), caused by corrosion of WWI shell fragments. Further research was required since in addition to Cu, also As, Pb, and Zn were used during the manufacturing of ammunition. Therefore, an additional data collection was conducted in which the initial Cu data set was tripled to 731 data points and extended to eight heavy metals (As, Cd, Cr, Cu, Hg, Ni, Pb, and Zn) which permitted (1) to evaluate the environmental impact of the heavy metals at a regional scale and (2) to assess their regional spatial occurrence by performing an optimized geostatistical modeling. The results showed no pollution at a regional scale, but sometimes locally concentrations exceeded the soil sanitation threshold, especially for Cu, Pb, and Zn. The spatial patterns of Ni and Cr were related to variations in soil texture whereas the occurrences of Cu and Pb were clearly linked to WWI activities. This difference in spatial behavior was confirmed by an analysis of coregionalization.     

Heavy metals contents in agricultural topsoils in the Ebro basin (Spain). Application of the multivariate geoestatistical methods to study spatial variations

In this work the content of seven heavy metals (Cd, Cr, Cu, Hg, Ni, Pb and Zn) and other parameters (the pH, organic matter, carbonates and granulometric fraction) in agricultural topsoil in the Ebro basin are quantified, based on 624 samples collected according to an 8 by 8 km square mesh. The average concentrations (mg/kg) obtained were: Cd 0.415+/-0.163, Cr 20.27+/-13.21, Cu 17.33+/-14.97, Ni 20.50+/-22.71, Pb 17.54+/-10.41, Zn 17.53+/-24.19 and Hg 35.6+/-42.05 microg/kg. The concentration levels are relatively low in areas of high pH and low organic matter content concentration. The results of factor analysis group Cd, Cu, Hg, Pb and Zn in F1 and Cr y Ni in F2. The spatial heavy metals component maps based on geostatistical analysis, show definite association of these factors with the soil parent material. The local anomalies (found in Cu, Zn and Pb) are attributed to anthropogenic influence.     

Multivariate statistical and GIS-based approach to identify heavy metal sources in soils

The knowledge of the regional variability, the background values and the anthropic vs. natural origin for potentially harmful elements in soils is of critical importance to assess human impact and to fix guide values and quality standards. The present study was undertaken as a preliminary survey on soil contamination on a regional scale in Piemonte (NW Italy). The aims of the study were: (1) to determine average regional concentrations of some heavy metals (Cr, Co, Ni, Cu, Zn, Pb); (2) to find out their large-scale variability; (3) to define their natural or artificial origin; and (4) to identify possible non-point sources of contamination. Multivariate statistic approaches (Principal Component Analysis and Cluster Analysis) were adopted for data treatment, allowing the identification of three main factors controlling the heavy metal variability in cultivated soils. Geostatistics were used to construct regional distribution maps, to be compared with the geographical, geologic and land use regional database using GIS software. This approach, evidencing spatial relationships, proved very useful to the confirmation and refinement of geochemical interpretations of the statistical output. Cr, Co and Ni were associated with and controlled by parent rocks, whereas Cu together with Zn, and Pb alone were controlled by anthropic activities. The study indicates that background values and realistic mandatory guidelines are impossible to fix without an extensive data collection and without a correct geochemical interpretation of the data.     

Influence of solution acidity and CaCl2 concentration on the removal of heavy metals from metal-contaminated rice soils

Soil washing is considered a useful technique for remediating metal-contaminated soils. This study examined the release edges of Cd, Zn, Ni, Cr, Cu or Pb in two contaminated rice soils from central Taiwan. The concentrations exceeding the trigger levels established by the regulatory agency of Taiwan were Cu, Zn, Ni and Cr for the Ho-Mei soil and Pb for the Nan-Tou soil. Successive extractions with HCl ranging from 0 to 0.2 M showed increased release of the heavy metals with declining pH, and the threshold pH value below which a sharp increase in the releases of the heavy metals was highest for Cd, Zn, and Ni (pH 4.6 to 4.9), intermediate for Pb and Cu (3.1 to 3.8) and lowest for Fe (2.1), Al (2.2) and Cr (1.7) for the soils. The low response slope of Ni and Cr particularly for the rice soils make soil washing with the acid up to the highest concentration used ineffective to reduce their concentrations to below trigger levels. Although soil washing with 0.1 M HCl was moderately effective in reducing Cu, Pb, Zn and Cd, which brought pH of the soils to 1.1+/-0.1 (S.D.), the concurrent release of large quantities of Fe and Al make this remediation technique undesirable for the rice soils containing high clay. Successive washings with 0.01 M HCl could be considered an alternative as the dissolution of Fe and Al was minimal, and between 46 to 64% of Cd, Zn, and Cu for the Ho-Mei soil and 45% of Pb in the Na-Tou soil were extracted after four successive extractions with this dilute acid solution. The efficacy of Cd extraction improved if CaCl2 was added to the acid solution. The correlation analysis revealed that Cr extracted was highly correlated (P < 0.001) with Fe extracted, whereas the Cu, Ni, Zn, Cd or Pb extracted was better correlated (P < 0.001) with Al than with Fe extracted. It is possible that the past seasonal soil flooding and drainage in the soils for rice production was conducive to incorporating Cr within the structure of Fe oxide, thereby making them extremely insoluble even in 0.2 M HCl solution. The formation of solid solution of Ni with Al oxide was also possible, making it far less extractable than Cd, Zn, Cu, or Pb with the acid concentrations used.     

重金属污染土壤的草酸和EDTA混合淋洗研究

采用不同浓度的草酸(oxalic acid,OX)和乙二胺四乙酸(EDTA)混合的淋洗方法研究重金属污染土壤的最佳混合淋洗方式,探讨了液固比、淋洗时间及pH对淋洗效果的影响,并分析了0.2 mol/L OX+0.2 mol/L EDTA处理前后土壤中重金属形态的变化。结果表明,采用0.2 mol/L OX+0.2 mol/L EDTA混合的淋洗法可同时去除多种重金属,且对Cu、Zn、Ni和Cr的去除率明显高于单用OX和EDTA,去除率分别为Cu 41.29%、Zn 84.73%、Ni 54.2%和Cr 66.01%。0.2mol/L OX+0.2 mol/L EDTA在液固比为5∶1、淋洗时间为4 h、pH为6时可分别达到最佳淋洗效果,且分别为Cu 62.59%、Zn 93.48%、Ni 55.95%和Cr 71.57%;Cu 50.47%、Zn 86.67%、Ni 61.53%和Cr 72.68%;Cu 44.40%、Zn 81.82%、Ni68.76%和Cr 74.93%。形态分析结果表明,0.2 mol/L OX+0.2 mol/L EDTA能较好地改变土壤中重金属形态的分布。     

A model for evaluation of the phytoavailability of trace elements to vegetables under the field conditions

Currently, several single extraction methods are used for the evaluation of the phytoavailability of metals using pot experiments. A systematic comparison, however, is lacking. It is especially true for the field studies. This study was to investigate the phytoavailability of trace elements to vegetables grown on metal-contaminated soils under the field conditions. All soils collected were typical calcareous soils in northern China. Four frequently used methods using CaCl2, diethylenetriaminepentaacetic acid (DTPA), CH3COOH, and water as extractants were compared for phyto-availability. The concentrations of metals extracted by these four extraction methods ranged from 3.42 to 815, 1.51- 6965, 0.732-24473, 0.688-7863, 0.246-685, 1.99-5337 0.203-4649 ng/g for Cr, Ni, Zn, Cu, Cd, Pb and REEs, respectively. Simple correlation analysis indicated that a significant correlation (Cr: r = 0.5411**; Zn: r = 0.6352**; Cd: r = 0.6979**; Pb: r = 0.5537** and REEs: r = 0.5185** -0.6684**) was observed between the CaCl2-extractable metals in soil solution and that in Chinese cabbage. In addition, soil pH, organic matter (OM), and cation exchange capacity (CEC) also affect the phytoavailability. An empirical model was developed to express the combined effect of soil properties on the phytoavailability. The stepwise multiple regression analysis demonstrated that the phytoavailability of trace elements strongly correlated with the extractable fraction by CaCl2, total metal concentration in soils, and soil pH, OM, CEC. This model can describe approximately 75-95% of the variability of metal uptake and the r2 values ranged from 0.741** to 0.954**, which were much better than the single correlation analysis. For celery and cole, a strong correlation was obtained for Cr, Ni, Zn, Cu, Cd, La, Ce, Pr and Nd. For spinach and Chinese cabbage, however, a positive correlation was only observed for 1 and 3 metals, respectively. Generally, the developed empirical model can integrate the combined effects of soil properties, extractable metal fractions in soil solutions and plant species on the phytoavailability of metals to vegetables in the field conditions.     

Accumulation and Chemical Fractionation of Heavy Metals in Andisols after a Different, 6-year Fertilization Management (8 pp)

Goal, Scope and Background Andisols are widespread in Japan and have some special properties such as high anion exchange capacity, low bulk density, and high organic matter content, which might influence the accumulation or chemical fractionation of heavy metals. However, few such data exist in Japanese andisols. The primary objective of this study was to investigate the distribution and chemical fractions of Cu, Zn, Ni, and Cr in the soil profiles and subsequently to assess their potential environmental hazard. Materials and Methods Soil samples were taken from a field experiment conducted on Japanese andisols, which had received either swine compost or chemical fertilizers for 6 years. Concentrations of Cu, Zn, Ni, and Cr were determined for all of the obtained extract solutions by ICP-AES. Results and Discussion Considerably higher total concentrations of Cu and Zn were observed in the top 20 cm layer of the compost-amended soil, relative to the unfertilized soil, while chemical fertilizers had little effect. Application of the swine compost increased the concentrations of Cu and Zn, but not Ni and Cr, in all fractions in the top 20 cm layer. The greatest increase in the organically bound fraction (OM) Cu and dilute acid-exchangeable fraction (DAEXCH) Zn was observed. This suggests that Cu and Zn are potentially bioavailable and mobile in the andisol profiles after 6-year consecutive applications of the swine compost. On the other hand, distribution of Cu, Zn, Ni and Cr among various soil fractions was generally unaffected by chemical fertilizers. Conclusions We observed that 6-year consecutive applications of the swine compost led to an increase in total metals of Cu and Zn, as well as their all-chemical fractions, in the top 20 cm soil layers. Potential hazard of heavy metals, especially of Cu and Zn, as a result of the use of swine compost on andisols, must be taken into account. Recommendations and Outlook The long-term effect of the accumulation of heavy metals, particularly Cu and Zn, in various plant tissues and soils, as well as their potential risk to surface water via runoff and groundwater via leaching, needs to be carefully considered. Further investigations in the long-term experiments are therefore necessary. - Abbreviations. EXCH, exchangeable fraction of metals; DAEXCH, dilute acid-exchangeable fraction of metals; FeMnOX, iron and manganese-oxide-bound fraction; OM, organically-bound fraction; RESD, residual fraction. COMPOST, SRNF, RANF, and CONTROL stand for compost (from swine wastes), slow-release nitrogen fertilizer (coated urea), readily available nitrogen fertilizer (including NH4-N, P, and K fertilizers), and no fertilizer application, respectively.     

Spatial distribution of heavy metals in urban soils of Naples city (Italy)

Concentrations of surface and sub-surface soil Cu, Cr, Pb and Zn in the Naples city urban area were measured in 1999. Contourmaps were constructed to describe the metals spatial distribution. In the most contaminated soil samples, metals were speciated by means of the European Commission sequential extraction procedure. At twelve sites, Cu, Pb and Zn levels in soil were compared with those from a 1974 sampling. Many surface soils from the urban area as well as from the eastern industrial district contained levels of Cu, Pb and Zn that largely exceeded the limits (120, 100 and 150 mg kg(-l) for Cu, Pb and Zn, respectively) set for soils of public, residential and private areas by the Italian Ministry of Environment. Chromium values were never above regulatory limits(120 mg kg(-1)). Copper apparently accumulates in soils contiguous to railway lines and tramway. Cu and Cr existed in soil mainly inorganic forms (-68%), whereas Pb occurs essentially as residual mineral phases (77%). The considerable presence of Zn in the soluble, exchangeable and carbonate bound fraction (23%) suggests this element has high potential bioavailability and leachability through the soil. Concentrations of Cu, Pb and Zn have greatly increased since the 1974 sampling, with higher accumulation in soils from roadside fields.     

Solubility of lead, zinc and copper added to mineral soils

Elevated levels of heavy metals in soils are a result of industrial activities, atmospheric deposition, and the land application of sewage sludges and industrial by-products. Their persistence in the soil environment has created interest in the possible changes in solubility. In this study, total dissolved concentrations of Pb, Zn, and Cu were monitored in seven metal-amended soils (a calcareous and six acid mineral soils). Single metal solutions were added to soils and equilibrated (aged) for 40 days. During the 40 days the soil was allowed to air-dry and was rewetted in cycles of about 5 days. At the end of this reaction period, metal solubility was measured (by atomic absorption spectrometry and direct current plasma spectrometry) at the initial soil pH and at decreased pH values which were induced by addition of small aliquots of acid. As expected, solubility of added Pb, Zn, and Cu increased with a decrease in pH. Furthermore, the results showed that the solubility relationship with pH was similar in all non-calcareous soils. This suggests that metal solubility may be controlled by similar soil components, presumably involving soil characteristics such as pH, organic matter content, and soil mineralogy. For each metal, an approximate pH value was found at which solubility deviated from the solubility of metals when they occur in soils at typical (natural) values. This pH was about (pH+/-0.2): 5.2 for Pb, 6.2 for Zn, and 5.5 for Cu. Thus, pH values below these thresholds may enhance metal mobility, biological availability and toxicity in soils. Metals dissolved at higher pH in the calcareous soil (18.8 g kg(-1) inorganic carbon, initial pH 8.2). In a calcareous soil, a significant fraction of these metals react with carbonates, and decreased pH results in much higher metal dissolution. Yet, metal solubility in soils is not determined by the formation and dissolution of single metal compounds.     

Tree species effect on the redistribution of soil metals

Phytostabilization of metals using trees is often promoted although the influence of different tree species on the mobilization of metals is not yet clear. Soil and biomass were sampled 33 years after planting four tree species (Quercus robur, Fraxinus excelsior, Acer pseudoplatanus, Populus 'Robusta') in a plot experiment on dredged sediment. Poplar took up high amounts of Cd and Zn and this was associated with increased Cd and Zn concentrations in the upper soil layer. The other species contained normal concentrations of Cd, Cu, Cr, Pb and Zn in their tissues. Oak acidified the soil more than the other species and caused a decrease in the concentration of metals in the upper soil layer. The pH under poplar was lower than expected and associated with high carbon concentrations in the top soil. This might be assigned to retardation of the litter decomposition due to elevated Cd and Zn concentrations in the litter.     

Electrokinetic remediation of a Cu-Zn contaminated red soil by controlling the voltage and conditioning catholyte pH

Electrokinetics is an innovative technique for treating heavy metals contaminated soil, especially low pH soils such as the Chinese red soil (Udic Ferrisols). In this paper, a Cu-Zn contaminated red soil is treated by electrokinetics. When the Cu-Zn contaminated red soil was treated without control of catholyte pH during the electrokinetic treatment, the soil pH in the soil sections near cathode after the experiment was high above 6, which resulted in accumulation of large amounts of Cu and Zn in the soil sections with such high pH values. Compared to soil Cu, soil Zn was more efficiently removed from the soil by a controlled electrokinetic method. Application of lactic acid as catholyte pH conditioning solution caused an efficient removal of Cu and Zn from the soil. Increasing the electrolyte strength (salt concentration) of the conditioning solution further increased Cu removal, but did not cause a significant improvement for soil Zn. Soil Cu and Zn fractions after the electrokinetic treatments were analyzed using sequential extraction method, which indicated that Cu and Zn precipitation in the soil section closest to the cathode in the treatments without catholyte pH control limited their removal from the soil column. When the catholyte pH was controlled by lactic acid and CaCl(2), the soil Cu and Zn removal percentage after 554 h running reached 63% and 65%, respectively. Moreover, both the residual soil Cu and Zn concentrations were lower than 100 mg kg(-1), which is adequate and meets the requirement of the Chinese soil environmental quality standards.     

Removal of heavy metals from anaerobically digested sewage sludge by isolated indigenous iron-oxidizing bacteria

The removal of heavy metals (Cr, Cu, Zn, Ni and Pb) from anaerobically digested sludge from the Yuen Long wastewater treatment plant, Hong Kong, has been studied in a batch system using isolated indigenous iron-oxidizing bacteria. The inoculation of indigenous iron-oxidizing bacteria and the addition of FeSO4 accelerated the solubilization of Cr, Cu, Zn, Ni and Pb from the sludge. pH of the sludge decreased with an increase in Fe2+ concentrations and reached a low pH of 2-2.5 for treatments receiving both bacterial inoculation and FeSO4. After 16 days of bioleaching, the following heavy metal removal efficiencies were obtained: Cr 55.3%, Cu 91.5%, Zn 83.3%, Ni 54.4%, and Pb 16.2%. In contrast, only 2.6% of Cr, 42.9% of Cu, 72.1% of Zn, 22.8% of Ni and 0.56% of Pb were extracted from the control without the bacterial inoculation and addition of FeSO4. The residual heavy metal content in the leached sludge was acceptable for unrestricted use for agriculture. The experimental results confirmed the effectiveness of using the isolated iron-oxidizing bacteria for the removal of heavy metals from sewage sludge.     

Use of sequential extraction to assess metal partitioning in soils

The state of heavy metal pollution and the mobility of Cd, Cu, Ni, Cr, Pb and Zn were studied in three texturally different agricultural soil profiles near a Cu-Ni smelter in Harjavalta, Finland. The pseudo-total concentrations were determined by an aqua regia procedure. Metals were also determined after division into four fractions by sequential extraction with (1) acetic acid (exchangeable and specifically adsorbed metals), (2) a reducing agent (bound to Fe/Mn hydroxides), (3) an oxidizing agent (bound to soil organic matter) and (4) aqua regia (bound to mineral structures). Fallout from the smelter has increased the concentrations of Cd, Cu and Ni in the topsoil, where 75-90% of Cd, 49-72% of Cu and 22-52% of Ni occurred in the first two fractions. Slight Pb and Zn pollution was evident as well. High proportions of mobile Cd, Cu and Ni also deeper in the sandy soil, closest to the smelter, indicated some downward movement of metals. The hydroxide-bound fraction of Pb dominated in almost all soils and horizons, while Ni, Cr and Zn mostly occurred in mineral structures. Aqua regia extraction is usefully supplemented with sequential extraction, particularly in less polluted soils and in soils that exhibit substantial textural differences within the profiles.     

Landscape ecology of the Guanting Reservoir, Beijing, China: multivariate and geostatistical analyses of metals in soils

Surface soil samples were collected from 52 sites around Guanting Reservoir in Beijing, China, and contents of 'total' metals (Cu, Zn, Pb, Cd, As, Ni and Cr) were determined. The results indicate that the degree of heavy metal pollution in the soils declines in the order of Cd>Cr>Zn>As>Cu>Ni>Pb. Based on the results of a combination of multivariate statistics and geostatiscal analyses, it was concluded that land application of phosphate fertilizer, wastewater and sludge were the primary sources of Cd and Zn in soils. Whereas As, Cu, Cr and Ni in some soils were due to natural rock weathering. The sources of Pb in soils only partially originated from land application of phosphate fertilizer, but mainly from vehicle exhaust. The greatest concentrations of all metals, except for Pb, were found in Huailai County and the towns of Yanghedaqiao and Guanting.     

Combining a finite mixture distribution model with indicator kriging to delineate and map the spatial patterns of soil heavy metal pollution in Chunghua County, central Taiwan

This study identifies the natural background, anthropogenic background and distribution of contamination caused by heavy metal pollutants in soil in Chunghua County of central Taiwan by using a finite mixture distribution model (FMDM). The probabilities of contaminated area distribution are mapped using single-variable indicator kriging and multiple-variable indicator kriging (MVIK) with the FMDM cut-off values and regulation thresholds for heavy metals. FMDM results indicate that Cr, Cu, Ni and Zn can be individually fitted by a mixture model representing the background and contamination distributions of the four metals in soil. The FMDM cut-off values for contamination caused by the metals are close to the regulation thresholds, except for the cut-off value of Zn. The receiver operating characteristic (ROC) curve validates that indicator kriging and MVIK with FMDM cut-off values can reliably delineate heavy metals contamination, particularly for areas lacking background information and high heavy metal concentrations in soil.     

A comparison of physiologically based extraction test (PBET) and single-extraction methods for release of Cu, Zn, and Pb from mildly acidic and alkali soils

In vitro digestion test can be applied to evaluate the bioaccessibility of soil metals by measuring the solubility of the metals in synthetic human digestive tract. Physiologically based extraction test (PBET), composed of sequential digestion of gastric and intestinal phase, is one of the frequently used in vitro digestion tests. In this study, the PBET was chosen to determine the bioaccessibility of Cu, Zn, and Pb in 14 mildly acidic and alkali (pH 5.87–8.30) soils. The phytoavailability of Cu, Zn, and Pb in the same soils was also measured using six single-extraction methods (0.1 M HNO₃, 0.4 M HOAc, 0.1 M NaNO₃, 0.01 M CaCl₂, 0.05 M EDTA, and 0.5 M DTPA). The extraction efficiencies of the methods were compared. The PBET had a strong ability to extract metals from soil, which was much greater than neutral salt extraction and close to dilute acid and complex extraction in spite of the last 2 h neutral intestinal digestion. The amounts of bioaccessible Cu, Zn, and Pb in the gastric phase and in the gastrointestinal phase were both largely determined by the total content of soil Cu, Zn, and Pb. But the results of gastrointestinal digestion reflected more differences resulting from element and soil types than those of gastric digestion did. It was noticed that most of variations in the amounts of soil Cu, Zn, and Pb extracted by EDTA were well explained by the total soil Cu, Zn, and Pb, as same as the PBET. Moreover, the solubility of Cu, Zn, and Pb in the gastric phase and gastrointestinal phase were all positively linearly correlated with the results of EDTA. It was suggested that EDTA extraction can be used to predict the bioaccessibility of Cu, Zn, and Pb in mildly acidic and alkali (pH?>?5.8) soils, and the PBET and EDTA could be applied to measure, in a certain extent, the bioaccessibility and phytoavailability of Cu, Zn, and Pb in mildly acidic and alkali (pH?>?5.8) soils at the same time.     

Solid speciation and mobility of potentially toxic elements from natural and contaminated soils: a combined approach

The study area (Szklary Massif, SW Poland) comprises three sites of different soil provenance: (1) natural serpentine Cambisol, (2) anthroposol situated on waste dump and (3) cultivated Inceptisol developed on glacial tills next to the dump. Potentially toxic elements (PTE) have either lithogenic or anthropogenic origins in these sites. The chemical partitioning of Co, Cr, Cu, Ni, Pb and Zn among solid forms was determined by sequential extractions coupled with direct mineral identifications (SEM, electron microprobe analysis - EMPA, and XRD). Examination of solid residues after several extraction steps was conducted in order to discuss the indirect speciation obtained by the extraction method. Total concentrations of PTE having anthropogenic origin greatly exceed those of lithogenic origin. Mobility of studied PTE is variable in the different environments except for Cr which is always mostly found in residual fractions of extractions. Cu and Pb are more mobile than Cr and Co in all soils. Zn is more stable (Cu>Pb>Ni>Co>Zn>Cr) in the serpentine soil and cultivated epipedon (Pb>Cu>Zn>Ni>Co>Cr) than in the anthroposol (Zn>CuPb>Ni>Co>Cr). PTE of lithogenic origin are generally less mobile than those from anthropogenic origin except Ni which is more mobile in the serpentine soil. Nonetheless, mineral forms of metals better determine their mobility than metal origin. Identification by direct methods of the PTE mineral form was not possible for metals present at low concentrations (Cu, Pb). However, direct mineralogical examinations of the solid residues of several extractions steps improved the assessment of the PTE solid speciation and mobility, particularly for Cr, Ni and Zn.