Enrichment of marsh soils with heavy metals by effect of anthropic pollution

The impact of waste disposal on marsh soils was assessed in topsoil samples collected at eight randomly selected points in the salt marsh in Ramallosa (Pontevedra, Spain) at 4-month intervals for 2 years. Polluted soil samples were characterized in physico-chemical terms and their heavy metal contents determined by comparison with control, unpolluted samples. The results revealed a marked effect of waste discharges on the soils in the area, which have low contents in heavy metals under normal environmental conditions. In fact, the studied soils were found to contain substantial amounts of total and DTPA-extractable Cd, Cu, Pb and Zn. Based on the relationship of the redox potential with the DTPA-extractable Cd, Cu, Pb, and Zn contents of the soils, strongly reductive conditions raised the total contents in these elements by effect of their remaining in the soils as precipitated sulphides. Such contents, however, decreased as oxidative conditions gradually prevailed. The contents in DTPA-extractable metals increased with increasing Eh through the release of the metals in ionic form to the soil solution under oxidative conditions. The contents in heavy metals concentrating in the polluted soils were several times higher than those in the control soils (viz. 2 vs. 6 for Cd, 4 vs. 6 for Cu, 4 vs. 20 for Pb, and 2 vs. 15 for Zn, all in mg kg⁻¹). This can be expected to influence the amounts of available heavy metals present in the soils, and hence the environmental quality of the area, in the near future. Based on its geoaccumulation index (Class ≥3 for Cd and Cu, and 1–4 for Pb and Zn), the Ramallosa marsh is highly polluted with Cd and moderately to highly polluted with Cu, Pb and Zn. The enrichment factors obtained confirm that the salt marsh is highly polluted (especially with Cd) as the primary result of anthropic activity.     

Sorption processes and XRD analysis of a natural zeolite exchanged with Pb(2+), Cd(2+) and Zn(2+) cations

In this study the Pb(2+), Cd(2+) and Zn(2+) adsorption capacity of a natural zeolite was evaluated in batch tests at a constant pH of 5.5 by polluting this mineral with solutions containing increasing concentrations of the three cations to obtain adsorption isotherms. In addition X-ray powder diffraction (XRD) was used to investigate the changes of zeolite structure caused by the exchange with cations of different ionic radius. The zeolite adsorption capacity for the three cations was Zn>Pb>Cd. Moreover a sequential extraction procedure [H(2)O, 0.05 M Ca(NO(3))(2) and 0.02 M EDTA] was applied to zeolite samples used in the adsorption experiments to determine the chemical form of the cations bound to the sorbent. Using this approach it was shown that low concentrations of Pb(2+), Cd(2+) and Zn(2+) were present as water-soluble and exchangeable fractions (<25% of the Me adsorbed), while EDTA extracted most of the adsorbed cations from the zeolite (>27% of the Me adsorbed). The XRD pattern of zeolite, analysed according to the Rietveld method, showed that the main mineralogical phase involved in the adsorption process was clinoptilolite. Besides structure information showed that the incorporation of Pb(2+), Cd(2+) and Zn(2+), into the zeolite frameworks changed slightly but appreciably the lattice parameters. XRD analysis also showed the occurrence of some isomorphic substitution phenomena where the Al(3+) ions of the clinoptilolite framework were replaced by exchanged Pb(2+) cations in the course of the ion exchange reaction. This mechanism was instead less evident in the patterns of the samples doped with Cd(2+) and Zn(2+) cations.     

Heavy metals distribution in soils surrounding an abandoned mine in NW Madrid (Spain) and their transference to wild flora

The present work concerns the distribution and mobility of heavy metals (Fe, Mn, Cu, Zn and Cd) in the surrounding soils of a mine site and their transfer to wild flora. Thus, soils and plants were sampled from a mining valley in NW Madrid (Spain), and total and extractable heavy metals were analysed. Soils affected by mining activities presented total Cd, Cu and Zn concentrations above toxic thresholds. The percentage of extractable element was highest for Cd and lowest for Cu. A highly significant correlation was observed between the total and extractable concentrations of metals in soils, indicating that, among the factors studied, total metals concentration is the most relevant for heavy metals extractability in these soils. (NH(4))(2)SO(4)-extractable metal concentrations in soils are correlated better with metal concentrations in several plant species than total metals in soils, and thus can be used as a suitable and robust method for the estimation of the phytoavailable fraction present in soils. Twenty-five vascular plant species (3 ferns and 22 flowering plants) were analysed, in order to identify exceptional characteristics that would be interesting for soil phytoremediation and/or reclamation. High Cd and Zn concentrations have been found in the aerial parts of Hypericum perforatum (Cd), Salix atrocinerea (Cd, Zn) and Digitalis thapsi (Cd, Zn). The present paper is, to the best of our knowledge, the first report of the metal accumulation ability of the two latter plant species. The phytoremediation ability of S. atrocinerea for Cd and Zn was estimated, obtaining intervals of time that could be considered suitable for the phytoextraction of polluted soils.     

Chelant extraction of heavy metals from contaminated soils.

The current state of the art regarding the use of chelating agents to extract heavy metal contaminants has been addressed. Results are presented for treatability studies conducted as worst-case and representative soils from Aberdeen Proving Ground's J-Field for extraction of copper (Cu), lead (Pb), and zinc (Zn). The particle size distribution characteristics of the soils determined from hydrometer tests are approximately 60% sand, 30% silt, and 10% clay. Sequential extractions were performed on the 'as-received' soils (worst case and representative) to determine the speciation of the metal forms. The technique speciates the heavy metal distribution into an easily extractable (exchangeable) form, carbonates, reducible oxides, organically-bound, and residual forms. The results indicated that most of the metals are in forms that are amenable to soil washing (i.e. exchangeable+carbonate+reducible oxides). The metals Cu, Pb, Zn, and Cr have greater than 70% of their distribution in forms amenable to soil washing techniques, while Cd, Mn, and Fe are somewhat less amenable to soil washing using chelant extraction. However, the concentrations of Cd and Mn are low in the contaminated soil. From the batch chelant extraction studies, ethylenediaminetetraacetic acid (EDTA), citric acid, and nitrilotriacetic acid (NTA) were all effective in removing copper, lead, and zinc from the J-Field soils. Due to NTA being a Class II carcinogen, it is not recommended for use in remediating contaminated soils. EDTA and citric acid appear to offer the greatest potential as chelating agents to use in soil washing the Aberdeen Proving Ground soils. The other chelating agents studied (gluconate, oxalate, Citranox, ammonium acetate, and phosphoric acid, along with pH-adjusted water) were generally ineffective in mobilizing the heavy metals from the soils. The chelant solution removes the heavy metals (Cd, Cu, Pb, Zn, Fe, Cr, As, and Hg) simultaneously. Using a multiple-stage batch extraction, the soil was successfully treated passing both the Toxicity Characteristics Leaching Procedure (TCLP) and EPA Total Extractable Metal Limit. The final residual Pb concentration was about 300 mg/kg, with a corresponding TCLP of 1.5 mg/l. Removal of the exchangeable and carbonate fractions for Cu and Zn was achieved during the first extraction stage, whereas it required two extraction stages for the same fractions for Pb. Removal of Pb, Cu, and Zn present as exchangeable, carbonates, and reducible oxides occurred between the fourth- and fifth-stage extractions. The overall removal of copper, lead, and zinc from the multiple-stage washing were 98.9%, 98.9%, and 97.2%, respectively. The concentration and operating conditions for the soil washing extractions were not necessarily optimized. If the conditions had been optimized and using a more representative Pb concentration (approximately 12000 mg/kg), it is likely that the TCLP and residual heavy metal soil concentrations could be achieved within two to three extractions. The results indicate that the J-Field contaminated soils can be successfully treated using a soil washing technique.     

The influence of EDTA application on the interactions of cadmium, zinc, and lead and their uptake of rainbow pink (Dianthus chinensis)

Soil used in this study was artificially contaminated with Cd, Zn, Pb, or applied in combinations (Cd-Zn, Cd-Pb, Zn-Pb, or Cd-Zn-Pb) to study the interactions of metals in soil contaminated with multiple metals. After planting rainbow pink (Dianthus chinensis) in these soils for 21 days, three different concentrations of ethylenedinitrilotetraacetic acid (EDTA) solutions were added to study the effect of applying EDTA on the interactions among these metals. The concentrations of Cd, Zn, and Pb in the soil solutions of different metals-treated soils increased significantly after applying 5 mmol EDTA kg(-1) soil (p<0.05). The potential of groundwater contamination will increase after applying EDTA and it is not recommended to be in situ used or have to use very carefully. The existence of Pb in the Cd-contaminated soil enhanced the uptake of Cd in rainbow pink in the treatments of control and 2 mmol EDTA kg(-1) soil. Cadmium inhibited the concentration of Zn without applying EDTA. However, whether the application of EDTA or not and the applied EDTA concentration had the greatest effect on the uptake of Pb when compared to Cd and Zn. After applying 5 mmol EDTA kg(-1) soil, Cd or Zn in the Pb-contaminated soil inhibited the uptake of Pb in rainbow pink, but there were no effect in other treatments.     

Monitoring of electrokinetic removal of heavy metals in tailing-soils using sequential extraction analysis

This research focused on the monitoring of the electrokinetic removal of heavy metals from tailing-soils, and emphasizes the dependency of removal efficiencies upon their physico-chemical states, as demonstrated by the different extraction methods adopted, which included aqua regia and sequential extraction. The tailing-soils examined contained high concentrations of target metal contaminants (Cd=179mgkg(-1), Cu=207mgkg(-1), Pb=5175mgkg(-1), and Zn=7600mgkg(-1)). The removal efficiencies of the different metals were significantly influenced by their speciations, mobilities and affinities (adsorption capacities) in the soil matrix. The removal efficiencies of mobile and weakly bound fractions, such as the exchangeable fraction were more than 90% by electrokinetic treatment, but strongly bound fractions, such as the organically bound species and residual fraction were not significantly removed (less than 30% removal efficiencies). In accordance with the general sequence of mobilities of heavy metals in soils, the removal efficiencies of more mobile heavy metals (Cd, Cu, and Zn) were higher than that of less mobile heavy metal (Pb).     

Solubility of heavy metals added to MSW

This paper aims to investigate the six heavy metal levels (Cd, Cr, Cu, Pb, Ni and Zn) in municipal solid waste (MSW) at different pHs. It intends to provide the baseline information of metals solubility in MSW co-disposed or co-digested with MSW incinerator ashes in landfill or anaerobic bioreactors or heavy metals contaminated in anaerobic digesters. One milliliter (equal to 1mg) of each metal was added to the 100ml MSW and the batch reactor test was carried out. The results showed that higher HNO3 and NaOH were consumed at extreme pH of 1 and 13 compared to those from pH 2 to 11 due to the comparably higher buffer capacity. Pb was found to have the least soluble level, highest metal adsorption (%) and highest partitioning Kd (lg(-1)) between pH 3 and 12. In contrast, Ni showed the highest soluble level, lowest metal adsorption (%) and lowest Kd (lg(-1)) between pH 4 and 12. Except Ni and Cr, other four metals seemed to show the amphibious properties as comparative higher solubility was found in the acidic and basic conditions.     

Removal and recovery of lead(II) from single and multimetal (Cd, Cu, Ni, Zn) solutions by crop milling waste (black gram husk)

The study reports removal of heavy metals when present singly or in binary and ternary systems by the milling agrowaste of Cicer arientinum (chickpea var. black gram) as the biosorbent. The biosorbent removed heavy metal ions efficiently from aqueous solutions with the selectivity order of Pb>Cd>Zn>Cu>Ni. The biosorption of metal ions by black gram husk (BGH) increased as the initial metal concentration increased. Biosorption equilibrium was established within 30 min, which was well described by the Langmuir and Freundlich adsorption isotherms. The maximum amount of heavy metals (qmax) adsorbed at equilibrium was 49.97, 39.99, 33.81, 25.73 and 19.56 mg/g BGH biomass for Pb, Cd, Zn, Cu and Ni, respectively. The biosorption capacities were found to be pH dependent and the maximum adsorption occurred at the solution pH 5. Efficiency of the biosorbent to remove Pb from binary and ternary solutions with Cd, Cu, Ni and Zn was the same level as it was when present singly. The presence of Pb in the binary and ternary solutions also did not significantly affect the sorption of other metals. Breakthrough curves for continuous removal of Pb from single, binary and ternary metal solutions are reported for inlet-effluent equilibrium. Complete desorption of Pb and other metals in single and multimetal solutions was achieved with 0.1 M HCl in both shake flask and fixed bed column studies. This is the first report of removal of the highly toxic Pb, Cd, and other heavy metals in binary and ternary systems based on the biosorption by an agrowaste. The potential of application for the treatment of solutions containing these heavy metals in multimetal solutions is indicated.     

Heavy metal contamination in soils and vegetables near an e-waste processing site, South China

Environmental pollution due to uncontrolled e-waste recycling activities has been reported in a number of locations of China. In the present study, metal pollution to the surrounding environment from a primitive e-waste processing facility was investigated. Soils at sites where e-waste is burned in the open air, those of surrounding paddy fields and vegetable gardens, as well as common vegetable samples were collected and analyzed for heavy metals. The results showed that the soils of former incineration sites had the highest concentrations of Cd, Cu, Pb, and Zn with mean values of 17.1, 11,140, 4500, and 3690 mg kg(-1), respectively. The soils of nearby paddy fields and vegetable gardens also had relatively high concentrations of Cd and Cu. In the edible tissues of vegetables, the concentrations of Cd and Pb in most samples exceeded the maximum level permitted for food in China. Sequential leaching tests revealed that the Cu, Pb, and Zn were predominantly associated with the residual fraction, followed by the carbonate/specifically adsorbed phases with the exception of Cd, which was mainly in the extractable form in paddy fields and vegetable soils. The data showed that uncontrolled e-waste processing operations caused serious pollution to local soils and vegetables. The cleaning up of former incineration sites should be a priority in any future remediation program.     

Potential risks of metal toxicity in contaminated sediments of Deûle river in northern France

The aim of this paper was to evaluate the potential sediment cumulative damage and toxicity due to metal contamination in a polluted zone of De?le river (in northern France) from nearby two smelters. Metal-enrichment factors and geoaccumulation indices measured with sediment depth revealed that--compared to background levels either in local reference soils or in world rivers sediments/suspended particulate matter--Cd contributed to the highest pollution levels, followed by Zn, Pb and to a much lesser extent Cu and Ni. A comparison of the vertical distribution of AVS (acid volatile sulfides), SEM (simultaneously extracted metals), TMC (total metal concentrations), TOC (total organic carbon) and interstitial water-metal concentrations in the sediment allowed us to highlight the extent of toxicity caused by Cd, Pb, Zn, Ni and Cu and to raise the possibility of their association with certain geochemical phases. To assess the actual environmental impacts of these metals in De?le river, numerical sediment quality guidelines were further used in the present work. Sedimentary Pb, Zn, and Cd contents largely exceeded PEC (probable effect concentration) values reported as consensus-based sediment quality guidelines for freshwater ecosystems. As for risks of toxicity from pore waters, metal concentrations reached their maxima at the surficial layers of the sediment (1-3 cm) and IWCTU (Interstitial Water Criteria Toxicity Unit) observed for Pb and to a lesser extent Cd, violated the corresponding water quality data recommended by USEPA.     

Heavy metal sorption and desorption capacity of soils containing endogenous contaminants

Soils on serpentinites in some regions of northwestern Spain have been the subject of agricultural management practices involving the use of fertilizers and various types of organic waste containing heavy metals. Although such practices have facilitated crop growth, they have also raised the natural contents in heavy metals of the soils. In this work, three ferralic Cambisols and another three mollic Leptosols with high Cr and Ni contents were used to study competitive sorption and desorption of six heavy metals via K(d100), which was employed as a measure of the ability of the soils to adsorb and retain each metal. Lead was found to be the metal sorbed and retained to the greatest extent, and Cd, Ni and Zn those sorbed and retained in the smallest amounts. Although the ferralic Cambisols were found to contain greater amounts of natural heavy metals, they exhibited an increased ability to adsorb and retain the body of metals relative to the mollic Leptosols by effect of their increased contents in clay and Fe, Mn and Al oxides, in addition to their higher ion-exchange capacity. Based on the results, Pb and Cu are strongly bound, and Zn, Cd and Ni weakly bound, to the soils. The ferralic Cambisols exhibited an increased capacity to adsorb and retain Cd, Ni, Zn and--especially--Cr than the mollic Leptosols; the latter, however, proved more effective in adsorbing and retaining Cu and Pb by virtue of their increased organic matter contents. Copper sorption and retention, and Pb retention, were found to be correlated with the content in organic matter and that in vermiculite--which was only present in the mollic Leptosols--in the clay fraction.     

Biosorption of heavy metals and uranium by starfish and Pseudomonas putida

Biosorption of heavy metals and uranium from contaminated wastewaters may represent an innovative purification process. This study investigates the removal ability of unit mass of Pseudomonas putida and starfish for lead, cadmium, and uranium by quantifying the adsorption capacity. The adsorption of heavy metals and uranium by the samples was influenced by pH, and increased with increasing Pb, Cd, and U concentrations. Dead cells adsorbed the largest quantity of all heavy metals than live cells and starfish. The adsorption capacity followed the order: U(VI)>Pb>Cd. The results also suggest that bacterial membrane cells can be used successfully in the treatment of high strength metal-contaminated wastewaters.     

Investigation of the transport and fate of Pb, Cd, Cr(VI) and As(V) in soil zones derived from moderately contaminated farmland in Northeast, China

Some farmland in Shenyang had been irrigated with industrial wastewater since 1962. Although wastewater irrigation was ceased in 1992, soil had been heavily polluted by heavy metals, especially by Cd. For better understanding processes of soil-heavy metal interactions, in particular, the mobility and retention mechanism of heavy metal in soil, a study on the transport and fate of heavy metals in soil zones from Shenyang suburb was carried out by column leaching tests in laboratory. Breakthrough curves of Pb, Cd, Cr(VI) and As(V) fitted by Thomas model and Yoon–Nelson model. The results of fitted breakthrough curves showed that transport rates of the four heavy metals in the soil zones followed the order: Cr(VI) > As(V) > Cd > Pb, which indicated that Cr(VI) was much more mobile, and Pb was comparatively unmovable. Cr in effluents and As were almost entirely Cr(VI) and As(V), respectively, and no Cr(III) and As(III) was ever detected during the leaching tests. The contents of Pb, Cd, Cr and As in leached soils decreased in the order of Pb > Cd > Cr > As, which suggested that adsorption ability of soil to Pb was greatest and to As was least. The methods of selective sequential extraction and solvent extraction were used to determine the fractions of Pb, Cd, Cr, As and the valent states of Cr, As [Cr(VI) or Cr(III), As(V) or As(III)] in original soils and in leached soils. After leaching tests, the relative and absolute concentrations of exchangeable, carbonate, Fe–Mn oxide and organic fraction of each element were all increased, which enhanced the potential mobility and risk of Pb, Cd, Cr and As to soil/groundwater system. The relative concentrations of Cr(III) and As(III) in different depth of the soil zones after leaching tests were increased by about 6.0% and 5.6%, respectively. Cr(III) and As(III) tended to be adsorbed by soils, which reduced the mobility of them into groundwater.     

Assessment of single extraction methods for the prediction of bioavailability of metals to Brassica juncea L. Czern. (var. Vaibhav) grown on tannery waste contaminated soil

Various single extractant (DTPA, EDTA, NH(4)NO(3), CaCl(2), and NaNO(3)) was used to evaluate the bioavailability of heavy metals from tannery wastewater contaminated soil and translocation of metals to the plant of Brassica juncea L. Czern. (var. Vaibhav). The extraction capacity of the metals was found in the order: EDTA>DTPA>NH(4)NO(3)>CaCl(2)>NaNO(3). Cluster analysis between different extractants showed close relationship between DTPA, CaCl(2), NH(4)NO(3) except EDTA and NaNO(3), which showed dispersed relationship. Principal components analysis (PCA) applied to metals extracted with EDTA showed different grouping of metals (i) Na, Co, Pb, Ni and (ii) K, Mn, Zn, Cr, in the loading plot which showed similar availability from contaminated soil. PCA applied on metals accumulation data in the plants also exhibited different grouping of variables (i) Cu, Co, Ni, Cd and (ii) Mn, Zn, Pb, Fe showed almost similar accumulation pattern in the plants. The data displayed positive loading for Mn and negative loading for Cr with PC(2). Cd and Zn have shown high loadings in PC(1) and PC(2), respectively. The translocation of most of the tested metals (Pb, Mn, Cd, Ni, Fe) in the shoot of the plant was found better except Cr, Cu, Co and K. The correlation analysis between different extractable metals and metal accumulation in the shoot of the plant showed significant positive correlation with Pb and Cr. Overall, extraction capacity and cluster analysis augmented that EDTA was found suitable extractant for tannery wastewater contaminated soil to B. juncea.     

Simultaneous sorption and desorption of Cd, Cr, Cu, Ni, Pb, and Zn in acid soils I. Selectivity sequences

The sorption and desorption of six heavy metals by and from the surface or immediately subsurface horizons of eleven acid soils of Galicia (N.W. Spain) were characterized by means of batch experiments in which the initial sorption solution contained identical mass concentrations of each metal. Concentration-dependent coefficients K(d) were calculated for the distribution of the metals between the soil and solution phases, and the values obtained for initial sorption solution concentrations of 100mgL(-1) of each metal (K(d100)) were used, for each soil, to order the metals as regards their sorption and retention. Pb and Cu were sorbed and retained to a greater extent than Cd, Ni or Zn, which had low K(d100) values. Pb was sorbed more than any other metal. Cr was generally sorbed only slightly more than Cd, Ni or Zn, but was strongly retained, with K(d100) (retention) values greater than those of Pb and Cu in soils with very low CEC (<3cmol((+))kg(-1)). The sorption of Pb and Cu correlated with organic matter content, while the retention of these and the other metals considered appeared to depend on clay minerals, especially kaolinite, gibbsite, and vermiculite.     

Accumulation of Cd, Pb and Zn by 19 wetland plant species in constructed wetland

Uptake and distribution of Cd, Pb and Zn by 19 wetland plant species were investigated with experiments in small-scale plot constructed wetlands, into which artificial wastewater dosed with Cd, Pb and Zn at concentrations of 0.5, 2.0 and 5.0mgl(-1) was irrigated. The results showed that the removal efficiency of Cd, Pb and Zn from the wastewater were more than 90%. Generally, there were tens differences among the 19 plant species in the concentrations and quantity accumulations of the heavy metals in aboveground part, underground part and whole plants. The distribution ratios into aboveground parts for the metals absorbed by plants varied also largely from about 30% to about 90%. All the plants accumulated, in one harvest, 19.85% of Cd, 22.55% of Pb and 23.75% of Zn that were added into the wastewater. Four plant species, e.g. Alternanthera philoxeroides, Zizania latifolia, Echinochloa crus-galli and Polygonum hydropiper, accumulated high amounts of Cd, Pb and Zn. Monochoria vaginalis was capable for accumulating Cd and Pb, Isachne globosa for Cd and Zn, and Digitaria sanguinalis and Fimbristylis miliacea for Zn. The results indicated that the plants, in constructed wetland for the treatment of wastewater polluted by heavy metals, can play important roles for removal of heavy metals through phytoextraction. Selection of plant species for use in constructed wetland will influence considerably removal efficiency and the function duration of the wetland.     

Investigation of the potential mobility of Pb, Cd and Cr(VI) from moderately contaminated farmland soil to groundwater in Northeast, China

The adsorption/desorption of Pb, Cd and Cr(VI) on moderately contaminated farmland soils in Northeast China and the effect of pH value on adsorption/desorption were investigated. Soil column leaching experiment was also carried out to further understand the mobility of the three metals in aeration zone of soil. Both Langmuir and Freundlich model gave good fits to the adsorption data of Pb and Cd, while the adsorption data of Cr(VI) followed linear adsorption isotherm. The adsorption/desorption of Pb, Cd and Cr(VI) obtained equilibrium in a few hours. Adsorption amounts of the three metals decreased in the order: Pb>Cd>Cr(VI). Desorption of the metals was insignificant at pH 5.0. Pb and Cd adsorption increased with pH, while Cr(VI) decreased. The effect of pH on desorption was contrary to that of adsorption. Leaching experiment showed that the mobility of these metals followed the order of Cr(VI)>Cd>Pb, which was consistent with the adsorption/desorption study. The results suggest that once soil is polluted by wastewater containing Pb and Cd, Pb and Cd tend to accumulating in topsoil and move downward very slowly, while the mobility of Cr(VI) in soil/groundwater system is much high because only limited amount of Cr(VI) were adsorbed by soil.     

The use of municipal sewage sludge for the stabilization of soil contaminated by mining activities

The ability of municipal sewage sludge to immobilize Pb, Zn and Cd contained in contaminated soil originating from a former mining area in Lavrion, Greece was investigated. The soil was cured with sewage sludge in various proportions. The stabilization was evaluated primarily by applying chemical tests and complemented by the performance of additional biological tests. Application of the U.S. EPA Toxicity Characteristic Leaching Procedure (TCLP) on the stabilized mixtures proved that Pb, Zn and Cd solubility was reduced by 84%, 64% and 76%, respectively, at 15% w/w sludge addition, while a 10% w/w addition was sufficient to reduce Pb solubility below the U.S. EPA TCLP regulatory limit. The results of the extraction using EDTA solution showed the same trend, resulting in 26%, 36% and 53% reduction in the Pb, Zn and Cd extractable fractions, respectively. Speciation analysis of the treated soils revealed a significant decrease in the mobile fractions of heavy metals, which was attributed to their retention in sewage sludge by adsorption and organic complexation mechanisms. For the assessment of possible phytotoxicity, experiments including growing dwarf beans in the treated soil was carried out. It was found that sewage sludge addition had a positive effect on plant growth. Furthermore, the Pb and Zn uptake of plant leaves and roots was reduced, while Cd uptake was unaffected by the sludge treatment. The results of this study support the hypothesis that municipal sewage sludge is a potential effective stabilizing agent for contaminated soil containing Pb, Zn and Cd.     

Stabilization of an elevated heavy metal contaminated site

Heavy metal contamination is a common problem that is encountered at many uncontrolled sites. Immobilization is seen as a promising technology for heavy metal remediation. Here, we report a remediation case study of an elevated and multi-metal contaminated site containing Cd, Cu, Ni, Pb, and Zn. In a laboratory test, when the soil was stabilized with reagent grade stabilizers (CaHPO(4) and CaCO(3)), the toxicity characteristic leaching procedure (TCLP) extractable concentrations of Cd, Cu, Pb, and Zn were reduced by more than 87%. The greatest reduction was shown with Pb (99.8%). In the field, Ca(H(2)PO(4))(2) due to lower cost and higher solubility replaced CaHPO(4). The TCLP results of the field treatment showed that the extractable concentrations of Cd, Cu, Pb, and Zn were significantly reduced after 30 days of stabilization. The reduction ratios were 98% (Cd), 97% (Cu), 99% (Pb), and 96% (Zn). Although, the reduction ratio of Ni was only 65%, the average extractable concentration was still less than 4.0mg/l. The percent reduction can, therefore, be considered reasonable. The significant reduction of extractable metal concentrations showed that the stabilizers, a combination of Ca(H(2)PO(4))(2) and CaCO(3), successfully immobilized heavy metals on the site.     

Application of EDTA decontamination on soils affected by mining activities and impact of treatment on the geochemical partition of metal contaminants

Two soil samples were collected at mining areas located in southern Hunan Province, China. EDTA extraction of Pb, Zn, Cu and Cd from these two tailing soils was studied using column leaching experiments. The redistributions of heavy metals (HMs) were determined using the modified BCR (Community Bureau of Reference) sequential extraction procedure, before and after EDTA extraction. The results indicated that EDTA was an effective extractant because of its strong chelating ability for various HMs. The proportions of Pb, Zn, Cu and Cd in the four fractions varied largely after EDTA extraction. The extraction efficiency of EDTA of the acid-extractable fraction (AEX) was significant in shallow soil column, while in deeper soil column, decrease of the extraction efficiency of reduced (RED), oxidizable (OX) and residual fractions (RES) was obtained, which was mainly due to the decrease of EDTA concentration.