Control Technologies for Remediation of Contaminated Soil and Waste Deposits at Superf und Lead Battery Recycling Sites

This paper primarily addresses remediation of contaminated soils and waste deposits at defunct lead-acid battery recycling sites (LBRS) via immobilization and separation processes. A defunct LBRS is a facility at which battery breaking, secondary lead smelting, or both operations were performed for the primary purpose of reclaiming lead from spent lead-acid batteries. Metallic lead and lead compounds are generally the principal contaminants of concern in soils and waste deposits (i.e., buried, piled, landfilled waste) at these sites. Other metals (e.g., cadmium, copper, arsenic, antimony, and selenium) are often present at LBRS, but usually at much lower concentrations than lead and often present below hazardous concentrations. This article is primarily based on experience gained from: (1) Superfund site investigation, removal, and remedial actions, and (2) development and demonstration of control technologies under the Superfund Innovative Technology Evaluation (SITE) Program. The primary remedial options for lead contaminated soils and waste deposits include: (1) no action, (2) off-site disposal, (3) containment, (4) immobilization, (5) separation with resource recovery, and (6) separation without resource recovery. In spite of the toxicity of lead at low concentrations, the relative immobility of lead and site-specific risk assessments can still result in the selection of no action or containment remedies. Solidification/stabilization of lead-contaminated soils has been implemented at three Superfund sites and is the selected remedy at several others. Separation technologies (e.g., screening, extraction) are attractive because, if successful, they actually remove the contaminant from the environmental media. Separation technologies also offer the possibility that a valuable product (e.g., lead, plastic, energy) can be recovered, but careful consideration of economic and technical factors are required. Compared to the implementation of containment and solidification I stabilization remedies, separation technologies tend to be relatively novel, complex, and costly.     

A Modular Approach to A Microcomputer Monitoring System

Abstract

Under a cooperative agreement with the U.S. Environmental Protection Agency's (USEPA) Superfund Innovative Technology Evaluation (SITE) Emerging Technology Program, COGNIS, Inc. conducted bench-scale studies on the COGNIS TERRAMET® Lead Extraction Process. The process leaches, or extracts, lead from contaminated soil and consists of a lead leaching stage followed by recovery of the dissolved lead from the leachant. Prior to treatment, the soil is characterized, the type and extent of lead contamination is identified, and the soil is pretreated by physical separation methods to facilitate the extraction process. The physical pretreatment, for example, may include particle size separation to allow separate leaching of the sand and fines fractions and removal of larger lead particles by density separation techniques. As part of the SITE Program, COGNIS investigated seven different lead-contaminated soil samples in small bench-scale batch studies and three soils in larger bench-scale continuous-treatment studies. This bench-scale work led to the design, construction, and operation of a full-scale treatment plant by COGNIS at the Twin Cities Army Ammunition Plant (TCAAP), New Brighton, MN where lead and seven other heavy metals were extracted and recovered from over 20,000 tons of treated soil to meet cleanup criteria.     

Removal of PCBs from a Contaminated Soil Using CF-Systems® Solvent Extraction Process

ABSTRACT

The U.S. Environmental Protection Agency’s (EPA) Superfund Technical Assistance Response Team (START) in cooperation with EPA’s Superfund Innovative Technology Evaluation (SITE) program evaluated a pilot scale solvent extraction process developed by CF-Systems. This process uses liquefied propane to extract organic contaminants from soils, sludges, and sediments. A pilot-scale evaluation was conducted in Golden, CO at Hazen Research, Inc., using CF-Systems’ trailer-mounted organics extraction unit. Approximately 1,000 pounds of soil, with an average poly-chlorinated biphenyl (PCB) concentration of 260 mg/kg, was obtained from a remote Superfund site. Six 100-pound batches of the contaminated soil were extracted using multiple extraction sequences. Three of the six batch runs were subjected to three extraction sequences each, so that process variability could be evaluated. Results showed that PCB removal efficiencies varied between 91.4 and 99.4%, with the propane-extracted soils retaining low concentrations of PCBs (19.0–1.8 mg/kg). Removal efficiencies of oil and grease (O&G) were found to be 96.0 to 99.6% with propane-extracted soils retaining O&G concentrations from 279 to <20 mg/kg. Overall extraction efficiency was found to be dependant upon the numberof extraction cycles used.     

Remediation of cadmium contamination in paddy soils by washing with chemicals: selection of washing chemicals

The efficiencies of neutral salts, strong acids, and chelates were tested for extracting cadmium (Cd) from three paddy soils. The higher the selectivity of the cations of the added neutral salts toward soil adsorption sites, the lower the pH in the extracts and the more soil Cd could be extracted. In addition, soil carbon and nitrogen contents and mineral composition were closely associated with the amount of Cd extracted. Calcium chloride and iron(III) chloride were selected as wash chemicals to restore Cd-contaminated paddy soils in situ. Washing with calcium chloride led to the formation of Cd chloride complexes, enhancing Cd extraction from the soils. The washing also substantially decreased soil levels of exchangeable and acid-soluble Cd, which are the major forms of bioavailable Cd for rice (Oryza sativa L.). The optimum conditions for in situ soil washing were also determined for calcium chloride.     

Evaluation of the effect of small organic acids on phytoextraction of Cu and Pb from soil with tobacco Nicotiana tabacum

Phytoremediation, the use of plants to extract contaminants from soils and groundwater, is a promising approach for cleaning up soils contaminated with heavy metals. However its use is limited by the time required for plant growth, the nutrient supply and, moreover, by the limited metal uptake capacity. Synthetic chelators have shown positive effects in enhancing heavy metal extraction, but they have also revealed several negative side-effects. The objective of this study was to investigate the use of three natural low molecular weight organic acids (NLMWOA) (citric, oxalic, and tartaric acid) as an alternative to synthetic chelators. Slurry-, column-, toxicity- and phytoextraction experiments were performed. For the phytoextraction experiment the three NLMWOA were applied to a copper- and a lead-contaminated soil respectively. A significant increase in copper uptake was visible only in the citric acid treatment (67 mg kg-1) in comparison to the EDTA treatment (42 mg kg-1). The NLMWOA application showed no enhanced effect concerning the lead phytoextraction. A possible explanation for this lack of significance could be the rate of the degradation of NLMWOA. This rate might well be too high for these heavy metals with low mobility and bioavailability such as lead. The amounts of NLMWOA applied to the soil were very high (62.5 mmol kg-1 of soil) and the effect was too little. In this respect EDTA, which was applied in very small amounts (0.125 mmol kg-1) was more efficient. Thus making NLMWOA unsuitable to enhance phytoextraction of heavy metals from soil.     

Multi-step leaching of Pb and Zn contaminated soils with EDTA

The efficiency of multi-step leaching of heavy metal contaminated soils was evaluated in a laboratory scale study. Four different soils contaminated with Pb (1136+/-16-4424+/-313mgkg(-1)) and Zn (288+/-5-5489+/-471mgkg(-1)) were obtained from industrial sites in the Mezica Valley, Slovenia and Príbram district, Czech Republic. Different dosages (2.5-40mmolkg(-1)) of ethylenediamine tetraacetate (EDTA) were used to treat soils in 1-10 leaching steps. Higher EDTA dosages did not result in a proportional gain in Pb and Zn removal. EDTA extracted Pb more efficiently than Zn from three of four tested soils. The percentage of removed Zn did not exceed 75% regardless of the soil, EDTA dosage and leaching steps. Significantly more Pb (in three of four soils) and Zn were removed from soils when the same amount of EDTA was applied in several leaching steps. The interference of major soil cations Fe and Ca with EDTA complexation as a possible factor affecting Pb and Zn removal efficiency with multi-step heap leaching was examined and is discussed. The results of our study indicate that, for some soils, using multi-step leaching instead of the more traditionally used single dose EDTA treatment could improve heavy metal removal efficiency and thus the economics of soil remediation.     

The effect of operating variables on chelant-assisted remediation of contaminated dredged sediment

The paper shows the results from a number of lab-scale washing treatments using the four chelating agents EDTA, NTA, citric acid and [S,S]-EDDS aiming at the remediation of a real heavy metal-contaminated sediment. Investigation of the influence of chelant type and concentration as well as solution pH was the major focus of the work. The analysis of speciation of metals and chelating agents in solution was carried out through geochemical speciation modelling in order to identify the optimal conditions for the washing process as well as to evaluate the competition phenomena of metal-chelant complexes in solution. The major competing cations were found to be Ca above all and Mg under specific conditions. Among the investigated chelating agents, EDDS appeared to be less affected by competition by major cations while ensuring adequate heavy metal extraction efficiencies. For a 1:1 chelant/metal ratio, the following ranking was observed: EDDS>Cit>NTA>EDTA for As, EDDS>NTA congruent withEDTA>Cit for Cu, EDDS congruent withEDTA congruent withNTA>Cit for Zn, EDTA>NTA>EDDS>Cit for Pb at pH 5 and EDTA congruent withEDDS congruent withNTA>Cit for Pb at pH 8. For a 10:1 chelant/metal ratio geochemical modelling indicated that at the equilibrium the extracting solutions were dominated by the free form of the chelating agents, indicating the inability of such species to complex trace metals due the strong interactions existing between heavy metal ions and sediment constituents.     

Collateral benefits and hidden hazards of soil arsenic during abatement assessment of residential lead hazards

Abatement of soil-lead hazards may also reduce human exposure to other soil toxins, thereby achieving significant collateral benefits that are not accounted for today. This proposition was tested with the specific case of soil-arsenic, where 1726 residential soil samples were collected and analyzed for lead and arsenic. The study found that these two toxins coexisted in most samples, but their concentrations were weakly correlated, reflecting the differing sources for each toxin. Collateral benefits of 9% would be achieved during abatement of the lead-contaminated soils having elevated arsenic concentrations. However, a hidden hazard of 16% was observed by overlooking elevated arsenic concentrations in soils having lead concentrations not requiring abatement. This study recommends that soil samples collected under HUD programs should be collected from areas of lead and arsenic deposition and tested for arsenic as well as lead, and that soil abatement decisions consider soil-arsenic as well as soil-lead guidelines.     

Solvent Extraction Processes: A Survey of Systems in the SITE Program

Solvent extraction of contaminated soils, sludges and sediments has been successfully completed at a number of Superfund sites. Each commercialized process uses a unique operating system to extract organic contaminants from solids. These operating systems may be classified by the properties of the solvents each utilizes: (1) standard solvents, (2) near-critical fluids/liquified gases, and (3) critical solution temperature solvents. Pretreatment and post-treatment requirements vary depending upon the operating systems of the solvent extraction system. Future demonstrations of these technologies by the U.S. EPA’s Superfund Innovative Technology Evaluation Program will provide additional information regarding the efficacy of these processes.     

EDTA及其回收溶液治理重金属污染土壤的研究

试验结果表明,EDTA能够有效地萃取土壤重金属,由于其价格较贵和不易被降解等特点,限制了它的广泛运用.在运用MINTEQA2模型对萃取液中重金属离子形态分析的基础上,选用Na2S沉淀法将重金属从EDTA萃取液中有效分离.同时将回收的EDTA连续进行萃取土壤重金属,由于回收EDTA浓度下降的原因,其效果比新鲜EDTA的要稍微差一点,但从经济和效率上来说,仍旧可以用来治理重金属污染的土壤.     

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.     

Phytoextraction of lead from firing range soil by Vetiver grass

Phytoextraction techniques utilizing a sterile strain of Vetiver grass (Vetiveria zizanoides) along with soil amendments were evaluated for removing lead and other elements such as Zn, Cu, and Fe from the soil of a 50-year old active firing range at the Savannah River Site (SRS). Lead-contaminated soil (300-4500 ppm/kg) was collected, dried, placed in pots, fertilized, and used as a medium for growing transplanted Vetiver grass plants in a greenhouse. The uptake of metals by the plants was evaluated in response to various fertilization and pre-harvest treatment schemes. Baseline metal concentrations in the soil of all pots were measured prior to planting and when the plants were harvested. Plants grew better when fertilized with Osmocote fertilizer in comparison to plants fertilized with 10-10-10 (NPK) fertilizer. Application of a chelating agent, EDTA, one week prior to harvest significantly increased the amount of lead that was phytoextracted. Lead concentrations of up to 1390-1450 ppm/kg in tissue samples were detected. Maximum Pb levels were observed in root tissues. The addition of non-lethal doses of a slow-release herbicide in combination with EDTA did not appear to further enhance phytoextraction or the translocation of Pb into shoots. The study indicated that the use of Vetiver grass coupled with the use of chelating soil amendments has considerable potential for use as a remedial strategy for lead-contaminated soils such as those associated with firing ranges.     

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.     

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.     

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.     

Remediation of arsenic-contaminated soils and washing effluents

Laboratory experiments were conducted to determine the distribution of various arsenic species in tailings and soils. Other specific goal of the tests were to evaluate the extraction efficiency of arsenic using alkaline or acid washing, to determine optimum operational parameters of alkaline washing, and to evaluate the arsenic precipitation of washing effluents by pH adjustment or ferric chloride addition. Alkaline washing using sodium hydroxide was found to be favorable in removing arsenic from tailings or soils having a higher portion of arsenic in the operationally defined crystalline mineral fraction of crystalline oxide and amorphous aluminosilicates. This is due to the ligand displacement reaction of hydroxyl ions with arsenic species and high pH conditions that can prevent readsorption of arsenic because predominant negatively charged crystalline oxides do not attract the negatively charged oxyanions. For tailings, sodium hydroxide had 10-20 times higher extraction efficiencies than hydrochloric- or citric acid. The optimum concentration of sodium hydroxide for soil washing was determined to be 200 mM for all samples, while the optimum ratios were 10:1 and 5:1 for tailings and field/river sedimentary soils, respectively. The washing effluent of river soil was effectively treated by adjusting pH to 5-6 with hydrochloric acid, resulting in arsenic concentrations of <50 microgl(-1). In the case of field soil effluent, an addition of ferric chloride with a minimum mass ratio of 11 (Fe/As) was needed to reduce the arsenic below 50 microgl(-1).     

Removal of Pb and MDF from contaminated soils by EDTA- and SDS-enhanced washing

Heavy metal- and organic-contaminated sites are ubiquitous, but few studies have been conducted to address such an issue. EDTA- and SDS-enhanced washing was studied for remediation of Pb- and/or marine diesel fuel (MDF)-contaminated soils. The feasibility of recovery and reuse of EDTA and SDS, as well as the physicochemical interactions among the chemical agents, contaminants and soils were extensively investigated using batch experiments. The optimal washing sequence was then determined. The experimental results showed that EDTA could be recovered and reused for four cycles without significant loss of its chelating capacity, while the extraction capability of SDS was noticeably reduced after each reuse cycle. The free phase of marine diesel fuel (MDF) in soils physically isolated the sorbed Pb on soils and thus reducing its extraction by EDTA. The presence of SDS alone or together with low concentration of EDTA was found to enhance Pb removal probably via electrostatic interaction and dissolution of soil organic matter. However, it hindered Pb extraction by high concentration of EDTA, because of the potential formation of complexes between some strongly-bound Pb and SDS, that are more resistant to desorption. Therefore, EDTA washing followed by SDS achieved the highest Pb removal efficiency. On the other hand, MDF removal by SDS was significantly hindered by coexisting Pb in soils, probably because the formation of Pb-dodecyl sulfate (DS) complex would decrease the effective amount of SDS available for forming micelles in solution and enhance MDF sorption. EDTA alone or together with SDS could enhance MDF removal, but the residual MDF after EDTA-washing became more resistant to SDS removal. Consequently, SDS washing followed by EDTA is considered as the optimal washing sequence for MDF removal.     

1990 Thermal Remediation Industry Contractor Survey

The treatment of soil contaminated with organics and inorganics is becoming a major industry in the United States and Europe. The soil cleanup bill for the United States could run as high as $200 to $300 billion over the next 30 to 40 years. European soil cleanup costs could run as high as $130 billion.¹

The types of sites in the United States that will require soil treatment can be broken down into the following categories: ? CERCLA (Superfund) Actions

? RCRA Corrective Actions

? RCRA Closures

? Underground Storage Tanks

? Real Estate Transfers

? Spill Clean-ups.

The cleanup of sites in each of these categories, with the exception of the Real Estate Transfer category, is being driven by different sets of Federal regulations. Real Estate Transfer type regulations were first instituted in New Jersey and have now been promulgated in a number of other states.

The eventual cleanup cost for the Superfund sites will be close to $200 billion. Estimated costs for the industrial sector Superfund are $25 to $50 billion and the estimated cost for the Department of Energy sites is over $150 billion.2 An early RCRA Corrective Action cleanup estimate is $25 billion.3 This estimate may well be low, however, since the permitting, cleanup and delisting criteria are still not clearly defined. The EPA’s RCRA Corrective Action cost estimate is $7.4 billion. However, the Office of Management and Budget feels that this estimate is low.⁴

The potential magnitude of the cleanup costs has resulted in the development and implementation of many technologies for the decontamination of soils. Of the available remedial technologies, thermal treatment has perhaps had the most field testing. The purpose of this paper is to focus on the full scale site remediations which have been or are being conducted using thermal processing equipment. Projects which have been completed, are on-going, or have been contracted for, through January of 1990 are described.     

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.     

Comparison of a rhizosphere-based method with other one-step extraction methods for assessing the bioavailability of soil metals to wheat

There is no method recognized as a universal approach for evaluation of bioavailability of heavy metals in soil. Based on the simulation of the rhizosphere soil conditions and integration of the combined effects of root-soil interactions as a whole, a rhizosphere-based method has been proposed. Wet fresh rhizosphere soil was extracted by low-molecular-weight organic acids (LMWOAs) to fractionate metal fractions of soil pools, which were then correlated with the metal contents of wheat roots and shoots. The rhizosphere-based method was compared with other one-step extraction methods using DTPA, EDTA, CaCl2, and NaNO3 as extractants and the first step of the Community Bureau of Reference (BCR) method. Simple correlation and stepwise multiple regression analysis were used for the comparison. Simple correlation indicated that the extractable Cu, Zn, Cr, and Cd of soils by the rhizosphere-based method were significantly correlated with the metal contents of wheat roots. For DTPA, BCR1 and EDTA methods there was a relatively poor correlation between the extractable Cu, Zn and Cd of soil and metal contents of wheat roots. Stepwise multiple regression analysis revealed that the equation of the rhizosphere-based method was the simplest one, and no soil properties variables needed to be added. In contrast, the equations of other one-step extraction methods were more complicated, and soil properties variables needed to be entered. The most distinct feature of the rhizosphere-based method was that the recommended method was suitable for acidic, neutral and near alkaline soils. However, the DTPA and EDTA extraction methods were suitable for calcareous soils only-or-only for acidic soils. The CaCl2, and NaNO3 extraction methods were only suitable for exchangeable metals. In short, the rhizosphere-based method was the most robust approach for evaluation of bioavailability of heavy metals in soils to wheat.