Leaching of heavy metals from contaminated soils using EDTA

Ethylenediaminetetraacetic acid (EDTA) extraction of Zn, Cd, Cu and Pb from four contaminated soils was studied using batch and column leaching experiments. In the batch experiment, the heavy metals extracted were virtually all as 1:1 metal-EDTA complexes. The ratios of Zn, Cd, Cu and Pb of the extracted were similar to those in the soils, suggesting that EDTA extracted the four heavy metals with similar efficiency. In contrast, different elution patterns were obtained for Zn, Cd, Cu and Pb in the column leaching experiment using 0.01 M EDTA. Cu was either the most mobile or among the most mobile of the four heavy metals, and its peak concentration corresponded with the arrival of full strength EDTA in the leachate. The mobility of Zn and Cd was usually slightly lower than that of Cu. Pb was the least mobile, and its elution increased after the peaks of Cu and Zn. Sequential fractionations of leached and un-leached soils showed that heavy metals in various operationally defined fractions contributed to the removal by EDTA. Considerable mobilisation of Fe occurred in two of the four soils during EDTA leaching. Decreases in the Fe and Mn oxide fraction of heavy metals after EDTA leaching occurred in both soils, as well as in a third soil that showed little Fe mobilisation. The results suggest that the lability of metals in soil, the kinetics of metal desorption/dissolution and the mode of EDTA addition were the main factors controlling the behaviour of metal leaching with EDTA.     

Optimizing the molarity of a EDTA washing solution for saturated-soil remediation of trace metal contaminated soils

Three experiments were conducted to optimize the use of ethylenediaminetetraacetic acid (EDTA) for reclaiming urban soils contaminated with trace metals. As compared to Na(2)EDTA, (NH(4))(2)EDTA extracted 60% more Zn and equivalent amounts of Cd, Cu and Pb from a sandy loam. When successively saturating and draining loamy sand columns during a washing cycle, which submerged it once with a (NH(4))(2)EDTA wash and four times with deionised water, the post-wash rinses largely contributed to the total cumulative extraction of Cd, Co, Cr, Cu, Mn, Ni, Pb and Zn. Both the washing solution and the deionised water rinses were added in a 2:5 liquid to soil (L:S) weight ratio. For equal amounts of EDTA, concentrating the washing solution and applying it and the ensuing rinses in a smaller 1:5 L:S weight ratio, instead of a 2:5 L:S weight ratio, increased the extraction of targeted Cr, Cu, Ni, Pb and Zn.     

Influence of ozonation on extractability of Pb and Zn from contaminated soils

The effect of soil ozonation on Pb and Zn extraction with EDTA, bioavailability (Ruby's Physiologically Based Extraction Test, PBET) and mobility (Toxicity Characteristic Leaching Procedure, TCLP) of Pb was studied on contaminated soils taken from 7 different locations in the Mezica Valley, Slovenia. EDTA extraction (40 mmol kg(-1)) removed from 27.4+/-1.5% to 64.8+/-1.5% of Pb, and from 1.9+/-0.2% to 22.4+/-2.0% of Zn from tested soils, and significantly reduced soil Pb bioavailability (PBET) and mobility (TCLP). Pretreatment of tested soils with ozone before EDTA extraction enhanced EDTA extractability of Pb for 11.0 to 28.9%, but had no effect on the extractability of Zn. In most of the soils, ozonation had no statistically significant effect on bioavailability and mobility of Pb, residual after EDTA extraction. Using linear regression analysis we found a significant increase (p<0.01) in EDTA extractability of Pb after soil ozonation in soils with a higher initial Pb content. EDTA extractability of Pb after soil ozonation was also significantly higher for soils with a lower Pb extractability when treated with EDTA alone. We found no correlation between soil organic matter content and the percentage of the Pb fraction bound to soil organic matter (where from 25.6+/-1.3% to 73.2+/-0.6% of Pb reside in tested soils) and Pb extractability with EDTA after soil ozonation.     

The use of poplar during a two-year induced phytoextraction of metals from contaminated agricultural soils

The efficiency of poplar (Populus nigra L.xPopulus maximowiczii Henry.) was assessed during a two-year chemically enhanced phytoextraction of metals from contaminated soils. The tested metal mobilizing agents were EDTA (ethylenediaminetetraacetic acid) and NH4Cl. EDTA was more efficient than chlorides in solubilizing metals (especially Pb) from the soil matrix. The application of chlorides only increased the solubility of Cd and Zn. However, the increased uptake of metals after the application of higher concentrations of mobilizing agents was associated with low biomass yields of the poplar plants and the extraction efficiencies after the two vegetation periods were thus comparable to the untreated plants. Additionally, the application of mobilizing agents led to phytotoxicity effects and increased mobility of metals. Higher phytoextraction efficiencies were observed for Cd and Zn compared to Pb and Cu. Poplars are therefore not suitable for chemically enhanced phytoextraction of metals from severely contaminated agricultural soils.     

Isotherms and sequential extraction procedures for evaluating sorption and distribution of heavy metals in soils

Heavy metals are potentially toxic to human life and the environment. Their contaminating effect in soils depends on chemical associations. Hence, determining the chemical form of a metal in soils is important to evaluate its mobility and bioavailability. We utilized a sequential extraction procedure and sorption isotherms (monometal and competitive) to evaluate the mobility and distribution of Cd, Cu, Ni, Pb, and Zn in four soils differing in their physicochemical properties: Calcixerollic Xerochrepts (Cx1 and Cx2), Paralithic Xerorthent (Px) and Lithic Haplumbrept (Lh). Most of the metals retained under point B conditions of sorption isotherms were extracted from the more mobile fractions: exchangeable and carbonates, in contrast with the profiles of the original soils where metals were preferently associated with the residual fraction. In soils having carbonate concentration under 6% (Cx1 and Lh), the exchangeable fraction was predominant, whereas in calcareous soils (Cx2 and Px) metals extracted from carbonates predominated. Partitioning profiles were in accordance with the affinity sequences deduced from the initial slope of isotherms and showed that the soils had a greater number of surface sites and higher affinity for Pb and Cu than for Cd, Ni, or Zn. In general, the simultaneous presence of the cations under study increased the percentages of metals released in the exchangeable fraction. The tendency towards less specific forms was more noticeable in Cx2 and Px soils and for Ni, Zn, and Cd. The affinity of inorganic surfaces was larger for Zn than for Cd or Ni, but the affinity of organic surfaces was larger for Cd or Ni than for Zn.     

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.     

Microbial indicators of heavy metal contamination in urban and rural soils

Urban soils and especially their microbiology have been a neglected area of study. In this paper, we report on microbial properties of urban soils compared to rural soils of similar lithogenic origin in the vicinity of Aberdeen city. Significant differences in basal respiration rates, microbial biomass and ecophysiological parameters were found in urban soils compared to rural soils. Analysis of community level physiological profiles (CLPP) of micro-organisms showed they consumed C sources faster in urban soils to maintain the same level activity as those in rural soils. Cu, Pb, Zn and Ni were the principal elements that had accumulated in urban soils compared with their rural counterparts with Pb being the most significant metal to distinguish urban soils from rural soils. Sequential extraction showed the final residue after extraction was normally the highest proportion except for Pb, for which the hydroxylamine-hydrochloride extractable Pb was the largest part. Acetic acid extractable fraction of Cd, Cu, Ni, Pb and Zn were higher in urban soils and aqua regia extractable fraction were lower suggesting an elevated availability of heavy metals in urban soils. Correlation analyses between different microbial indicators (basal respiration, biomass-C, and sole C source tests) and heavy metal fractions indicated that basal respiration was negatively correlated with soil Cd, Cu, Ni and Zn inputs while soil microbial biomass was only significantly correlated with Pb. However, both exchangeable and iron- and manganese-bound Ni fractions were mostly responsible for shift of the soil microbial community level physiological profiles (sole C source tests). These data suggest soil microbial indicators can be useful indicators of pollutant heavy metal stress on the health of urban soils.     

Bioaccumulation in Porcellio scaber (Crustacea, Isopoda) as a measure of the EDTA remediation efficiency of metal-polluted soil

Leaching using EDTA applied to a Pb, Zn and Cd polluted soil significantly reduced soil metal concentrations and the pool of metals in labile soil fractions. Metal mobility (Toxicity Characteristic Leaching Procedure), phytoavailability (diethylenetriaminepentaacetic acid extraction) and human oral-bioavailability (Physiologically Based Extraction Test) were reduced by 85-92%, 68-91% and 88-95%, respectively. The metal accumulation capacity of the terrestrial isopod Porcellio scaber (Crustacea) was used as in vivo assay of metal bioavailability, before and after soil remediation. After feeding on metal contaminated soil for two weeks, P. scaber accumulated Pb, Zn and Cd in a concentration dependent manner. The amounts of accumulated metals were, however, higher than expected on the basis of extraction (in vitro) tests. The combined results of chemical extractions and the in vivo test with P. scaber provide a more relevant picture of the availability stripping of metals after soil remediation.     

Mobility of Zn, Cd and Pb in soils as affected by poultry litter extract--II. Redistribution among soil fractions

The application of poultry litter to metal-contaminated soils may influence metal leaching and distribution of metals among soil fractions. Soil columns (one uncontaminated control, one metal-amended, and two metal-contaminated soils) were leached with H2O, CaCl2, EDTA, and poultry litter extract (PLE) solutions. After leaching, the soil samples in the columns were sequentially extracted for water soluble (WS), exchangeable (EXC), organic matter (OM), Mn oxide (MNO), amorphous Fe oxide (AFEO), crystalline Fe oxide (CFEO) and residual (RES) fractions. The OM fraction showed high retention for Zn from the PLE. The EDTA redistributed Zn, Cd and Pb from the EXC, OM and MNO fractions to the WS fraction. The PLE usually solubilized more Zn and Cd from the EXC fraction than CaCl2. Neither PLE nor CaCl2 mobilized Pb. The application of poultry litter on metal-contaminated soils might cause Zn and Cd redistribution from the EXC to the WS fraction and enhance metal mobility.     

Estimating the extractability of potentially toxic metals in urban soils: a comparison of several extracting solutions

Metals released by the extraction with aqua regia, EDTA, dilute HCl and sequential extraction (SE) by the BCR protocol were studied in urban soils of Sevilla, Torino, and Glasgow. By multivariate analysis, the amounts of Cu, Pb and Zn liberated by any method were statistically associated with one another, whereas other metals were not. The mean amounts of all metals extracted by HCl and by SE were well correlated, but SE was clearly underestimated by HCl. Individual data for Cu, Pb and Zn by both methods were correlated only if each city was considered separately. Other metals gave poorer relationships. Similar conclusions were reached comparing EDTA and HCl, with much lower values for EDTA. Dilute HCl extraction cannot thus be recommended for general use as alternative to BCR SE in urban soils.     

The EDTA effect on phytoextraction of single and combined metals-contaminated soils using rainbow pink (Dianthus chinensis)

Rainbow pink (Dianthus chinensis), a potential phytoextraction plant, can accumulate high concentrations of Cd from metal-contaminated soils. The soils used in this study were artificially added with different metals including (1) CK: original soil, (2) Cd-treated soil: 10 mg Cd kg(-1), (3) Zn-treated soil: 100 mg Zn kg(-1), (4) Pb-treated soil: 1000 mg Pb kg(-1), (5) Cd-Zn-treated soil: 10 mg Cd kg(-1) and 100 mg Zn kg(-1), (6) Cd-Pb-treated soil: 10 mg Cd kg(-1) and 1000 mg Pb kg(-1), (7) Zn-Pb-treated soil: 100 mg Zn kg(-1) and 1000 mg Pb kg(-1), and (8) Cd-Zn-Pb-treated soil: 10 mg Cd kg(-1), 100 mg Zn kg(-1), and 1000 mg Pb kg(-1). Three concentrations of 2Na-EDTA solutions (0 (control), 2, and 5 mmol kg(-1) soil) were added to the different metals-treated soils to study the influence of applied EDTA on single and combined metals-contaminated soils phytoextraction using rainbow pink. The results showed that the Cd, Zn, Pb, Fe, or Mn concentrations in different metals-treated soil solutions significantly increased after applying 5 mmol EDTA kg(-1) (p<0.05). The metal concentrations in different metals-treated soils extracted by deionized water also significantly increased after applying 5 mmol EDTA kg(-1) (p<0.05). Because of the high extraction capacity of both 0.005 M DTPA (pH 5.3) and 0.05 M EDTA (pH 7.0), applying EDTA did not significantly increase the Cd, Zn, or Pb concentration in both extracts for most of the treatments. Applying EDTA solutions can significantly increase the Cd and Pb concentrations in the shoots of rainbow pink (p<0.05). However, this was not statistically significant for Zn because of the low Zn concentration added into the contaminated soils. The results from this study indicate that applying 5 mmol EDTA kg(-1) can significantly increase the Cd, Zn, or Pb concentrations both in the soil solution or extracted using deionized water in single or combined metals-contaminated soils, thus increasing the accumulated metals concentrations in rainbow pink shoots. The proposed method worked especially well for Pb (p<0.05). The application of 2 mmol EDTA kg(-1) might too low to enhance the phytoextraction effect when used in silty clay soils.     

Is an adjusted rhizosphere-based method valid for field assessment of metal phytoavailability? Application to non-contaminated soils

Previously recommended rhizosphere-based method (RHIZO) applied to moist rhizosphere soils was integrated with moist bulk soils, and termed adjusted-RHIZO method (A-RHIZO). The A-RHIZO and RHIZO methods were systematically compared with EDTA, DTPA, CaCl2 and the first step of the Community Bureau of Reference (BCR1) methods for assessing metal phytoavailability under field conditions. Results suggested that moist bulk soils are equally suited or even better than rhizosphere soils to estimate metal phytoavailability. The A-RHIZO method was preferred to other methods for predicting the phytoavailability of Ni, Cu, Zn, Cd, Pb and Mn to wheat roots with correlation coefficients of 0.730 (P<0.001), 0.854 (P<0.001), 0.887 (P<0.001), 0.739 (P<0.001), 0.725 (P<0.001) and 0.469 (P<0.05), respectively. When including soil properties, other extraction methods were also able to predict phytoavailability reasonably well for some metals. Soil pH, organic matter and Fe-Mn oxide contents, and cation-exchange capacity mostly influenced the extraction and phytoavailability of metals.     

Metal contamination and solid phase partitioning of metals in urban roadside sediments

This study was undertaken to assess the anthropogenic impact on metal concentrations of urban roadside sediments (N = 633) in Seoul city, Korea and to estimate the potential mobility of selected metals (Zn, Cu, Pb, Cr, Ni, and Cd) using sequential extraction. Comparison of metal concentrations in roadside sediments with mean background values in sediments collected from first- or second-order streams in Korea shows that Zn, Cu and Pb are most affected by anthropogenic inputs. The 206Pb/207Pb ratios of roadside sediments (range = 1.1419-1.1681; mean 1.1576 +/- 0.0068) suggest that Pb is mainly derived from industrial sources rather than from leaded gasoline. A five-step sequential extraction of roadside sediments showed that Zn, Cd and to a lesser degree Ni occur predominantly in the carbonate bound fraction, while Pb is highest in the reducible fraction, Cu in the organic fraction, and Cr in the residual fraction. It was found that the concentrations in the readily available exchangeable fraction were generally low for most metals examined, except for Ni whose exchangeable fraction was appreciable (average 15.2%). Considering the proportion of metals bound to the exchangeable and carbonate fractions, the comparative mobility of metals probably decreases in the order of Zn > Ni > Cd > Pb > Cu > Cr. As potential changes of redox state and pH may remobilize the metals bound to carbonates, reducible, and/or organic matter, and may release and flush them through drain networks into streams, careful monitoring of environmental conditions appears to be very important. With respect to ecotoxicity, it is apparent the Zn and Cu pollution is of particular concern in Seoul city.     

Electrokinetic enhancement removal of heavy metals from industrial wastewater sludge

An enhanced electrokinetic process for removal of metals (Cr, Cu, Fe, Ni, Pb, Zn) from an industrial wastewater sludge was performed. The electrokinetic experiments were conducted under a constant potential gradient (1.25 V cm(-1)) with processing fluids of tap water (TW), sodium dodecylsulfate (SDS) and citric acid (CA) for 5 days. Results showed that metal removal efficiency of heavy metals for EK-TW, EK-SDS and EK-CA systems are 11.2-60.0%, 37.2-76.5%, and 43.4-78.0%, respectively. A highest metal removal performance was found in EK-CA system. The removal priority of investigated metals from sludge by EK process was found as: Cu > Pb > Ni > Fe > Zn > Cr. The results of sequential extraction analysis revealed that the binding forms of heavy metals with sludge after electrokinetic process were highly depend upon the processing fluid operated. It was found that the binding forms of metals with sludge were changed from the more difficult extraction type (residual and sulfate fractions) to easier extraction types (exchangeable, sorbed, and organic fraction) after treatment by electrokinetic process. Results imply that if a proper treatment technology is followed by this EK process to remove metals more effectively, this treated sludge will be more beneficial for sludge utilization afterwards. Before it was reused, the risk associated with metals of more mobile forms to the environment need to be further investigated. The cost analysis was also evaluated for the investigated electrokinetic systems.     

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.     

Simultaneous mobilization of heavy metals and polychlorinated biphenyl (PCB) compounds from soil with cyclodextrin and EDTA in admixture

This study evaluated the efficacy of a washing process with cyclodextrin in combination with ethylenediaminetetraacetate (EDTA) for the simultaneous mobilization of heavy metals and PCBs from a field contaminated soil. Ultrasonically aided mixing of the field contaminated soil with a combination of cyclodextrin solution (10%, w/v) and a sparing quantity (2 mmol) of EDTA, simultaneously mobilized appreciable quantities of PCBs and much of the analyte metal (Cd, Cr, Cu, Mn, Ni, Pb, Zn) burdens. Relative to the action of individual reagents, a combination of randomly methylated (RAMEB) or hydroxypropyl beta-cyclodextrin (HPCD) with EDTA did not alter the PCB extraction efficiency nor did the presence of cyclodextrin change the efficiency of mobilization of most heavy metals (Al, Cd, Cr, Fe, Mn, Ni, and Zn) but did increase the recovery of Cu and Pb modestly. Three sonication-washes with the same charge of reagents mobilized appreciable quantities of PCBs (40-76%) and quantitatively extracted the labile fraction of Cd, Cu, Mn, and Pb. RAMEB proved to be more efficient than HPCD for PCB extractions. Three successive extractions with a single charge of cyclodextrin mobilized almost as much PCB (RAMEB, 76%; HPCD, 40%) as did the companion extractions that used fresh reagents each time (RAMEB, 78%; HPCD, 42%). Collectively, these studies demonstrated that PCB compounds and selected heavy metals can be co-extracted efficiently from soil with three successive washes with the same washing suspension containing EDTA and cyclodextrin.     

The study of metal contamination in urban soils of Hong Kong using a GIS-based approach

The study of regional variations and the anthropogenic contamination by metals of soils is very important for environmental planning and monitoring in urban areas. An extensive survey was conducted in the highly urbanized Kowloon area (46.9 km(2)) of Hong Kong, using a systematic sampling strategy with a sampling density of 3-5 composite soil samples (0-15 cm) per km(2). Geochemical maps of 'total' metals (Cd, Cr, Cu, Ni, Pb and Zn) from strong acid extraction in the surface soils were produced based on geographical information system (GIS) technology. A significant spatial relationship was found for Ni, Cu, Pb and Zn in the soils using a GIS-based analysis, suggesting that these metal contaminants in the soils of the Kowloon area had common sources. Several hot-spot areas of metal contamination were identified from the composite metal geochemical map, mainly in the old industrial and residential areas. A further GIS analysis revealed that road junctions, major roads and industrial buildings were possible sources of heavy metals in the urban soils. The Pb isotope composition of the contaminated soils showed clear anthropogenic origins.     

Heavy metal levels and solid phase speciation in street dusts of Delhi,India

Street dust samples were collected from three different localities (industrial, heavy traffic and rural) situated in the greater Delhi area of India. The samples analyzed for Cd, Zn, Pb, Ni, Cu, and Cr indicated remarkably high levels of Cr, Ni, and Cu in the industrial area, whilst Pb and Cd did not show any discernible variations between the three localities. A multivariate statistical approach (Principal Component Analysis) was used to define the possible origin of metals in dusts. The street dusts were sequentially extracted so that the solid pools of Cd, Zn, Pb, Ni, Cu, Cr could be partitioned into five operationally defined fractions viz. exchangeable, bound to carbonates, bound to Fe-Mn oxides, bound to organic matter and residual. Metal recoveries in sequential extractions were +/- 10% of the independently measured total metal concentrations. Cd was the only metal present appreciably (27.16%) in the exchangeable fraction and Cu was the only metal predominantly associated (44.26%) with organic fraction. Zn (45.64%) and Pb (28.26%) were present mainly in the Fe-Mn oxide fraction and the residual fraction was the most dominant solid phase pool of Cr (88.12%) and Ni (70.94%). Assuming that the mobility and bioavailability are related to the solubility of geochemical forms of the metals and decrease in order of extraction, the apparent mobility and potential metal bioavailability for these highly contaminated street dust samples is: Cd>Zn approximately equal Pb>Ni>Cu>Cr.     

Process evaluation for optimization of EDTA use and recovery for heavy metal removal from a contaminated soil

This study aimed to establish an optimized, closed loop application of ethylenediaminetetraacetic acid (EDTA) in heavy metal removals from a contaminated soil through integrating EDTA recovery/regeneration and metal precipitation processes in the treatment train. Three divalent heavy metals were investigated, namely, Pb, Cd, and Ni. The extractability of the metals by EDTA followed the decreasing order of CdPb>Ni. The first part of this study was to search for the optimal use of the fresh EDTA in removing these heavy metals from the contaminated soil. The second part of this study was devoted to the recovery/regeneration of the spent EDTA which followed the sequential processes involving (1) complex destabilization by adding ferric ion (Fe(III)) to liberate Pb, Cd, and Ni, (2) precipitation of the liberated Pb, Cd, and Ni in phosphate (PO4(3-)) forms, and (3) precipitation of the excess Fe(III) which eventually produced free EDTA for reuse. The process variables were dosages of Fe(III) and PO4(3-), pH and reaction times. Laborious trial experiments would be needed in searching for the optimum conditions for the above processes. To expedite this exercise, a geochemical equilibrium model, MINTEQA2, was used to find the thermodynamically favorable conditions for recoveries of both EDTA and heavy metals. This was then followed by experimental examination of the process kinetics to observe for the optimal reaction time for each thermodynamically favorable process. This study revealed that 2 h of reaction time each for the complex destabilization reaction and the metal phosphate precipitation reaction was sufficient to achieve equilibrium. With the optimized process condition identified in this study, a total of 95%, 89% and 90% of the extracted Pb, Cd and Ni, respectively, could be precipitated from the spent EDTA solution, with 84% EDTA recovery. The reused EDTA maintained more than 90% of its preceding extraction power in each cycle of reuse.     

Effect of biosolid incorporation to mollisol soils on Cr, Cu, Ni, Pb, and Zn fractionation, and relationship with their bioavailability

Biosolid application to soil may be a supply of nutrients and micronutrients but it may also accumulate toxic compounds which would be absorbed by crops and through them be incorporated to the trophic chain.

The present study deals with the effect of biosolid application on Cr, Cu, Pb, Ni, and Zn in agricultural soils. The procedure used is sequential extraction so that the availability of those metals may be estimated and related to their bioavailability as determined through two indicator plants grown in greenhouse: ryegrass (Lolium perenne L.) and red clover (Trifolium pratense). Results showed that biosolid application to soil increased total Cu and Zn content. Sequential extraction showed that the more labile Zn fractions increased after biosolid application to soil. This was confirmed when assessing the total content of this metal in shoot and root of the plants under study, since a higher content was found in plant tissues, while no significant differences were found for Cu, Cr, Ni, and Pb.