Characterization of zinc in contaminated soils: complementary insights from isotopic exchange,batch extractions and XAFS spectroscopy

Isotopic exchange (IE) of trace metals is an established method for characterizing metal reactivity in soils, but it is still unclear which metal species are isotopically exchangeable. In this study, we used IE to quantify ‘labile’ zinc (Zn) in 51 contaminated soils that were previously studied by Zn K‐edge X‐ray absorption fine structure (XAFS) spectroscopy and sequential extraction (SE). All soils had been contaminated by runoff water from 17‐ to 74‐year‐old galvanized power‐line towers. They covered a wide range in pH (4.0–7.7), organic carbon (0.9–10.2%), clay (3.8–45.1%) and Zn concentrations (251–30 090 mg kg^?1). Isotopic exchange was also performed on selected Zn minerals used as references for linear combination fitting of XAFS spectra. The isotopically exchangeable fraction (%E) of Zn generally decreased with increasing pH, but small %E values were also observed for acidic soils with a large fraction of Zn in hydroxy‐interlayered minerals (Zn‐HIM). The fraction of Zn identified by XAFS spectroscopy as (tetrahedrally and octahedrally coordinated) ‘sorbed Zn’ agreed reasonably well with the isotopically exchangeable fraction but was in many cases larger than the %E, indicating that some ‘sorbed Zn’ may be isotopically non‐exchangeable, such as Zn sorbed in micropores of Fe oxyhydroxides. Zinc identified by XAFS spectroscopy as Zn precipitates (Zn phyllosilicates, Zn‐layered double hydroxide (Zn‐LDH) or hydrozincite) or as Zn‐HIM was largely isotopically non‐exchangeable (‘non‐labile’). Comparison between IE and extraction results suggested that the isotopically exchangeable Zn was mainly extracted in the first two fractions of the SE. However, non‐labile Zn was also extracted in these first two fractions for some soils, including a hydrozincite‐containing soil. Despite the presence of Zn‐LDH and/or Zn phyllosilicates in almost all soils, the Zn concentrations in solution and labile Zn increased with increasing soil total Zn at a given pH, which contradicts the concept of precipitation control by a single phase. Solution Zn was well predicted from the labile Zn following a sorption model.     

化学萃取修复尾渣土壤的金属形态变化特征

The efficiency of EDTA, HNO3 and CaCl2 as extractants to remove Pb, Zn and Cu from tailing soils without varying soil pH was investigated with distributions of Pb, Zn and Cu being determined before and after extraction using the sequential extraction procedure of the optimized European Community Bureau of Reference （BCR）. Results indicated that EDTA and HNO3 were both effective extracting agents.The extractability of extractants for Pb and Zn was in the order EDTA 〉 HNO3 〉 CaCl2, while for Cu it was HNO3 〉 EDTA 〉 CaCl2. After EDTA extraction, the proportion of Pb, Zn and Cu in the four fractions varied greatly, which was related to the strong extraction and complexation ability. Before and after extraction with HNO3 and CaCl2, the percentages of Pb, Zn and Cu in the reducible, oxidizable and residual fractions changed little compared to the acid-extractable fraction. The lability of metal in the soil and the kinds of extractants were the factors controlling the effects of metal extraction.     

Determination of labile Cu in soils and isotopic exchangeability of colloidal Cu complexes

Measurement of labile (isotopically exchangeable) pools of metals (E values) in soil is required to assess the size of metal pools potentially available to soil organisms, from both a micronutrient deficiency and metal toxicity viewpoint. In this paper, E values of soil Cu were measured by an isotope dilution technique using different solution extracts – water with and without resin purification, water coupled with Donnan dialysis (free ion determination) and 0.01 m CaCl₂. Using these techniques, the isotopic exchangeability of Cu species in water extracts was investigated. The results showed that the specific activity of ⁶⁴Cu in the water‐soluble fraction was less than in the free metal ion fraction or in the fraction that adsorbed to resin. The isotopically non‐exchangeable Cu in water extracts ranged between 4% and 40% of water‐soluble Cu (16% on average), and appeared to be associated with dispersed colloids. The existence of isotopically non‐exchangeable Cu in water extracts led to overestimation (17.7% on average) of isotopically exchangeable Cu in soils when based on the specific activity in water extracts. The method of isotope dilution coupled with resin extraction is recommended for the determination of isotopically exchangeable Cu in soils when water extracts are used.     

Multi‐element stable isotopic dilution and multi‐surface modelling to assess the speciation and reactivity of cadmium and copper in soil

Chemical extraction, multi‐element stable isotopic dilution (ID) and multi‐surface modelling were used to investigate the lability of cadmium (Cd) and copper (Cu) in nine types of soil with different properties and contaminated or not with Cd and Cu. The chemical extraction and ID analyses both showed that Cd was more labile than Cu in all the soil types studied. From the ID results, 32.8–93.3% of total Cd and 14.7–71.8% of total Cu were isotopically exchangeable after 3 days of equilibration. A single extraction in 0.43 m HNO₃ gave similar results to the 3‐day ID assay for Cu in most of the soils and for Cd in the non‐calcareous soils. However, an eight‐step selective sequential extraction (SSE) procedure gave different results from the ID assay for both metals. Predictions of the multi‐surface model for the amounts of Cd and Cu adsorbed, based on measured metal ion activities in the soil solution and the concentrations of reactive surfaces in the soil, agreed with the ID results. The model predicted that soil organic matter was the predominant sorbent for Cd and Cu in the soils and that manganese oxide was the least important sorbent. The contributions of iron oxides to sorption were predicted to be small except in soil with a high pH and little organic matter. The predicted sorption on different soil components did not match SSE measurements.     

Retention Capacity and Environmental Mobility of Pb in Soils along Highway Corridor

Although lead (Pb) emissions have dropped drastically with the phase-out of tetra-ethyl lead (TEL) as a fuel additive, Pb deposited along highway corridors continues to be of concern because of its toxicity. This paper provides comprehensive data on the extent and distribution of Pb in roadside soils, Pb interaction with soils as a function of soil composition, the retention capacity of soil based on batch adsorption tests, the retention mechanism of Pb using selective sequential extraction, the potential for mobility using batch desorption tests with simulated rain and winter road salt, and column leach tests. Highway soils on high-traffic sections near Burnaby, Canada were found to have Pb accumulations up to 1628mg/kg soil. Contamination was mainly in the top 0.3m, with concentrations rapidly decreasing to the background level at a depth of 0.6m. The top layer contained more organic material and had a high adsorption capacity. Highway soils were found to have 3–10 times higher Pb adsorption capacities than the amount currently deposited. Selective sequential extraction indicated low exchangeable Pb in highway soils. Batch desorption tests with leaching solutions of H₂O (pH 5.5), HNO₃ solution (pH 4.0) and aqueous NaCl solution (0.17M) indicate low likelihood of significant leaching. Selective sequential extraction, leachate extraction and desorption tests show that Pb has limited mobility in highway soil.     

Estimating total Pb,Cd, and Zn in contaminated soils from NH4HCO3‐DTPA‐extractable levels

Abstract

Twenty‐six garden soils from Aspen, Colorado, contaminated with old silver mine dumps, were extracted with diethylenetriamine pentaacetic acid (DTPA) and NH₄HCO₃‐DTPA (AB‐DTPA). Total soil digests (HNO₃‐HClO₄‐HF) were carried out on 21 highly contaminated soils. All soil extracts and digests were analyzed for Pb, Cd, and Zn using inductively‐coupled plasma atomic emission spectrometry (ICPS). Linear regression equations for DTPA versus AB‐DTPA values gave 0.96, 0.99 and 0.99 “r”; values for Pb, Cd, and Zn, respectively. Linear regression equations for total Pb, Cd, and Zn levels versus their respective AB‐DTPA extractable levels were developed with “r”; values of 0.92, 0.93, and 0.89, respectively. It was concluded that AB‐DTPA test can be used to screen soils contaminated with the above‐mentioned elements.     

Comparison of Prewashing Procedures for the Assessment of Phosphate Rock Dissolution in Soils

When evaluating phosphate rock (PR) dissolution, previous to the extraction with sodium hydroxide (NaOH), dry soil samples with PR were extracted with three solutions to remove exchangeable and solution calcium (Ca) [sodium chloride (NaCl) 1 M, buffered NaCl with ethylenediaminetetraacetic acid (EDTA) (NaCl–EDTA), and NaCl buffered at pH 7 with triethanolamine (TEA) (NaCl–TEA)] for comparison with the extraction of soil samples without any prewash. In acidic soils, up to 51% of applied P was recovered during the NaCl extraction because of the high exchangeable acidity released during the extraction. In soils with exchangeable Ca>2 cmol₍₊₎kg^?1, high EDTA quantities also promoted PR dissolution. The NaCl–TEA solution efficiently removed Ca, avoiding PR dissolution and P retention by calcium hydroxide [Ca(OH)₂] during the NaOH extraction. Thus, when evaluating PR dissolution we recommend the use of NaCl–TEA to remove Ca. We also recommend the same procedure when applying the Chang and Jackson fractionation to calcareous soils and soils submitted to PR application.     

Evaluation of certain Ni soil tests for an initial estimation of Ni sufficiency critical levels

Although Ni is officially recognized as an essential micronutrient for all higher plants, the majority of the published research on soil availability of Ni focuses on its hazardous role as a heavy metal. The objective of the study was to evaluate certain Ni soil tests in uncontaminated soils for an initial estimation of its sufficiency critical levels. Nickel was extracted from 30 cultivated soils employing the following extraction methods: DTPA, AB‐DTPA, AAAc‐EDTA, Mehlich‐3, 0.1 M HCl, and 0.1 M HNO₃. Ryegrass (Lolium perenne L.) was grown in pots containing the soils, harvested five times, certain plant parameters were determined, and the Cate–Nelson procedures were used for Ni critical levels determination. Among the six methods, HCl was the least reliable extractant for the evaluation of soil available Ni, whereas the most significant (p ≤ 5%) relationships between Ni concentration or Ni uptake by ryegrass and Ni soil tests were consistently obtained for AAAc‐EDTA or Mehlich‐3 extractable Ni. In many cases, > 80% of the variability of Ni concentration or uptake by ryegrass was explained by these two soil tests without the inclusion of other soil properties that affect Ni bioavailability. Sufficiency critical levels of Ni in soil were ≈ 2 mg kg^–1 for both methods. Consequently, as an initial approach, concentrations of AAAc‐EDTA or Mehlich‐3 extractable Ni < 2 mg kg^–1 are probably a good guide to indicate soils that will respond to Ni fertilization.     

A rapid method to determine cation exchange capacity and exchangeable bases in calcareous,gypsiferous, saline and sodic soils

Summary

A simple, single‐step extraction with LiEDTA for the estimation of CEC and exchangeable bases in soils has been developed. Multivalent cations are stripped from the soil adsorption sites by the strongly chelating agent EDTA, and are replaced by Li. In soils without CaCO₃ or water soluble salts, exchangeable divalent cations (Ca, Mg) are chelated by EDTA and exchangeable monovalent cations (Na, K) are replaced in a single extraction step using 0.25–2.5 g of soil and 10.0 ml of extractant.

In calcareous soils the CEC can be determined in the same way, but for the extraction of exchangeable Ca and Mg, another separate extraction is needed because dissolution of calcite by EDTA is unavoidable. This extraction is done with as much NaEDTA as needed to extract only exchangeable Ca and Mg in a 1:2 (m/V) soil/alkaline‐50% (V/V) aethanolic solution to minimize dissolution of calcite.

In gypsiferous soils gypsum is transformed into insoluble BaSO₄ and soluble CaEDTA by LiBaEDTA thus avoiding interference of Ca from dissolution of gypsum, which renders the traditional methods for determining CEC unsuitable for such soils. To determine exchangeable Ca and Mg, Na₄EDTA is used as for calcareous soils.

In saline/sodic soils replacement of Na by Li is incomplete but the Na/Li‐ratio at the complex after extraction is proportional to the molar Na/Li‐ratio in the extracts, so that the CEC and original exchangeable sodium (ESP) content can be calculated. Additional analysis of Cl and, if necessary, SO₄ in the extracts of saline soils can be used to correct for the effect of dissolution of the salts on the sum of exchangeable cations.

This new method is as convenient as the recently developed AgTU (silverthiourea), but is better suitable for calcareous and gypsiferous soils.     

Evaluation of universal extractants for determining plant available potassium in intensively cultivated soils

Abstract

Eighteen soils from northwestern Switzerland were used to study the value of seven universal extractants (CaCl₂; DB‐DTPA; Mehlich 1, 2, and 3; Morgan‐Wolf; and NH₄OAc‐EDTA) for predicting plant available potassium (K) as compared to a bioassay (a modified Neubauer test with winter rye). These extractants were evaluated on the basis of K uptake by the bioassay test and the soil K status. In order to create the sufficiency level of exchangeable K for plant growth, soils were treated with 0, 20, 40, 80, and 160 mg K/kg of soil. The range of K uptake by the bioassay tests was between 89.2 and 403.0 mg/kg of soil for the control pots, and 136.6 to 495.8 for the K treatments with optimal conditions for plant growth. The average amounts of K extracted by the seven universal extractants, in ascending order, were: CaCl₂ < Morgan‐Wolf < Mehlich 1 < Mehlich 2 < NH₄OAc‐EDTA < Mehlich 3 < DB‐DTPA. The highest simple correlation with K uptake versus the bioassay test was obtained with the DB‐DTPA (r = 0.89) extractant and the lowest with the Mehlich 1 (r = 0.53) extractant. The DP‐DTPA, NH₄OAc‐EDTA and Mehlich 3‐K procedures showed an advantage over K procedures based on water soluble and exchangeable K pools in the investigated soils in order to predict the amount of plant‐available K. A simple regression and the Cate‐Nelson graphic method offer the possibility of assessing the soil‐K status using K values obtained by these universal extractants and to calibrate them against K forms as follows: exchangeable, water soluble, and non‐exchangeable.     

Use of Single Extraction Methods to Predict Bioavailability of Heavy Metals in Polluted Soils to Rice

Human exposure to toxic heavy metals via dietary intake is of increasing concern. Heavy-metal pollution of a rice production system can pose a threat to human health. Thus, it was necessary to develop a suitable extraction procedure that would represent the content of metal available to rice plants (Oryza sativa L.). The aim of this study was to predict, on the basis of single extraction procedures of soil heavy metals, the accumulation of heavy metals (cadium, lead, copper, and zinc) in rice plants. Six extracting agents [Mehlich 1, Mehlich 3, EDTA (ethylenediaminetetraacetic acid), DTPA–TEA (diethylenetriaminepentaacetic acid–triethanolamine), ammonium acetate (NH₄OAc), and calcium chloride (CaCl₂)] were tested to evaluate the bioavailability of heavy metals from paddy soils contaminated with lead–zinc mine tailings to rice. The extraction capacity of the metals was found to be of the order EDTA > Mehlich 3 > Mehlich 1 > DTPA–TEA > NH₄OAc > CaCl₂. The correlation analysis between metals extracted with different extractants and concentrations of the metals in the grain and stalk of the plant showed positive correlations with all metals. The greatest values of correlation coefficients were determined between the NH₄OAc- and CaCl₂-soluble fractions of soil and contents in plants in all four metals studied. Therefore, NH₄OAc and CaCl₂ were the most suitable extractants for predicting bioavailability of heavy metals in the polluted soils to rice. The results suggested that uptake of heavy metals by rice was mostly from exchangeable and water-soluble fractions of the metals in the soils. Soil-extractable metals were more significantly correlated with metal accumulation in the stalk than in the grain. The pH had more significant influence on availability of heavy metals in the soils than total content of metals and other soil properties. The bioavailability of metals for rice plants would be high in acidic soils.     

Mehlich‐1‐ and DTPA‐extractable lead in soils in relation to soil properties

Abstract

Mehlich‐1 and DTPA extractants are frequently used to predict metal availability in soils. Metal extractability by the acid or chelate extractant reflects the metal characteristics and metal‐soil interactions. In this study, samples of eight topsoils from the southeastern United States were incubated with added lead (Pb) at the rate of 40 mg#lbkg^‐1. After five months in the greenhouse, Mehlich‐1 and DTPA extractants were employed to extract Pb in both metal‐amended and natural soils. For the natural soils, Pb concentration in the DTPA extractant was always higher than that in the Mehlich‐1 extractant. This indicates that the DTPA chelate extractant is able to dissolve some Pb in soils which is not solubilized by protons. The negative correlation found between Mehlich‐1‐extractable Pb and soil clay content might result from two mechanisms: i) strong association between Pb and soil surfaces, or ii) readsorption of Pb during extraction. None of the correlations between DTPA‐extractable Pb and soil properties was significant, suggesting that the DTPA‐extractable Pb is not heavily dependent on soil properties. The DTPA extractant showed a high ability to solubilize Pb in the natural soils possibly due to a high affinity of Pb for soil organic matter.     

Labile lead in polluted soils measured by stable isotope dilution

It is well known that lead (Pb) is strongly immobilized in soil by adsorption or precipitation. However, the reversibility of these reactions is poorly documented. In this study, the isotopically exchangeable Pb concentration in soils (E‐value) was measured using a stable isotope (²⁰⁸Pb). Soils were collected at three industrialized sites where historical Pb emissions have resulted in elevated Pb concentrations in the surrounding soil. Lead concentrations ranged from background values, in the control soils collected far from the emission source, to highly elevated concentrations (5460–14440 mg Pb kg^?1). The control soil of each site was amended in the laboratory with Pb(NO₃)₂ to the same total Pb concentrations as the field‐contaminated soils. The %E values (E‐value relative to total Pb content) were greater than 84% in the laboratory‐amended soils, and ranged from 45% to 78% (mean 58%) in the field‐contaminated soils. The relatively large labile fractions of Pb in the field‐contaminated soils show that the majority of Pb is reversibly bound despite the fact that the binding strength is large. The Pb concentrations in soil solution were up to 3500‐fold larger for the laboratory‐amended soils than for field‐contaminated soils at corresponding total Pb concentrations. These differences cannot be explained by differences in labile fractions of Pb but are attributed to the decrease in soil solution pH upon addition of Pb²⁺‐salt.     

Comparison of four extractants and chemical fractions for assessing available zinc and copper in soils of India

Abstract

Relative suitability of different extraction procedures for estimating available zinc (Zn) and copper (Cu) in soils was assessed using DTPA, 0.1 N HCl, ammonium acetate+EDTA, and double acid (HCl+ H₂SO₄) as extractants and rice as a test crop in Neubauer experiment. The relationships between Zn concentration and uptake of Zn by rice plants and Zn extracted by the different methods showed that DTPA‐TEA, pH 7.3, could very suitably be used to assess Zn availability in soils. However, 0.1 N HCl was better for assessing the Cu availability in soils to the rice plants. Water‐soluble and exchangeable fractions of Zn and Cu had significant positive correlations with Zn and Cu concentrations, respectively obtained by all the four extractants tested. The results also showed that DTPA and ammonium acetate+EDTA extracted organically bound Zn, whereas DTPA, 0.1 N HCl and ammonium acetate+EDTA extracted organically bound Cu. Water‐soluble, exchangeable and organic matter bound fractions exhibited significant relationships with Zn and Cu concentrations, their uptake and rice dry matter yield.     

Effect of soil microorganisms on the sorption of zinc and lead compounds by goethite

The objectives of this study were (1) to determine the effect of microorganisms during in‐vitro incubation on the amount of Zn and Pb from solution retained on goethite precipitated as coatings on a sand matrix and (2) to evaluate accumulation of heavy metals in the biomass of soil microorganisms in the fresh soil samples using an extractive approach. A mixture of colonies of cultivated microorganisms extracted from a Haplic Luvisol (Russia) and an Antropi‐urbic Regosol (Germany) were used to prepare the cell and the microbial‐debris suspensions. The concentrations of Zn and Pb in the studied solutions supplied with microbial suspensions and/or goethite coated sand were 0.1 mM (130.8 and 414 mg kg^–1 of sand, respectively). Exchangeable forms of metals were determined by extraction with 10 mL of 1.0 M KNO₃. Nonexchangeable forms of Zn and Pb were recovered using 40 mL of 0.3 M NH₂OH‐HCl in 1 M HNO₃. Concentrations of Pb increased in the solutions and decreased on the surface of the Fe‐mineral due to living microorganisms. In comparison to incubation of heavy‐metal solutions with goethite only, the absolute concentrations of nonexchangeable forms of metal were reduced by microbial suspension to a greater extent than those of the exchangeable forms, whereas the relative content of both fractions decreased by a factor of almost two. Sorption of Pb by goethite was inversely correlated with the concentration of organic C in the solution. Microorganisms clearly influenced the Zn sorption by goethite at concentrations of C_org > 400 mg L^–1. The amount of Zn retained was decreased primarily due to decreasing Zn portions in the exchangeable fraction. Microbial debris prepared by autoclaving reduced the Pb sorption by goethite similar to the results for living cells. Living microorganisms accumulated more Zn than did microbial debris. The data of this paper show that a direct determination of heavy‐metal accumulation in soil microorganisms by extraction with 2.0 M KCl as well as by extraction with 1 M CH₃COONH₄ at the natural pH of the soils after chloroform fumigation of fresh soils samples with different concentrations of organic C was not possible.     

Concentrations and forms of heavy metals in Slovak soils

The risk assessment of heavy‐metal contamination in soils requires knowledge of the controls of metal concentrations and speciation. We tested the relationship between soil properties (pH, CEC, C_org, oxide concentrations, texture) and land use (forest, grassland, arable) and the partitioning of Al, Cd, Cr, Cu, Fe, Mn, Ni, Pb, and Zn among the seven fractions of a sequential extraction procedure in 146 A horizons from Slovakia. Using a cluster analysis, we identified 92 soils as representing background metal concentrations while the remaining 54 soils showed anthropogenic contamination. Among the background soils, forest soils had the lowest heavy‐metal concentrations except for Pb (highest), because of the shielding effect of the organic layer. Arable soils had the highest Cr, Cu, and Ni concentrations suggesting metal input with agrochemicals. Grassland soils had the highest Cd and Zn concentrations probably for geogenic reasons. Besides the parent material (highest metal concentrations in soils from carbonatic rock, lowest in quartz‐rich soils with sandy texture), pedogenic eluviation processes controlled metal concentrations with podzols showing depletion of most metals in E horizons. Partitioning among the seven fractions of the sequential extraction procedure was element‐specific. The pH was the overwhelming control of the contributions of the bioavailable fractions (fractions 1–4) of all metals and even influenced the contributions of Fe oxide‐associated metals (fractions 5 and 6) to total metal concentrations. For fractions 5 and 6, Fe concentrations in oxides were the most important control of contributions to total metal concentrations. After statistically separating the pH from land use, we found that the contributions of Cu in fractions 1–4 and of NH₄NO₃‐extractable Al, Cd, Pb, and Zn to total metal concentrations were significantly higher under forest than under grassland and in some cases arable use. Our results confirm that metal speciation in soils is mainly controlled by the pH. Furthermore, land use has a significant effect.     

Verhalten von Schwermetallen in Böden 1. Untersuchungen zur Schwermetallmobilität

Behaviour of heavy metals in soils. 1. Heavy metal mobility 158 soil samples with widely varying composition were analysed for their total, EDTA, DTPA and CaCl₂ extractable contents of Cd, Zn, Mn, Cu and Pb. By means of single and multiple regressions the relations between the different heavy metal fractions and the pH, organic carbon and clay content were considered. The correlations between the total, EDTA and DTPA extractable contents are very close, whereas the CaCl₂ extractable contents are not or only weakly correlated with these fractions. According to these statistical results the former fractions are considered to be the total quantity (total content) and the reactive quantity (EDTA and DTPA extractable contents) of the heavy metals, whereas the CaCl₂ extractable fraction represents the mobile fraction of the heavy metals in soils. The multiple regressions show that the mobile content of heavy metals is closely correlated with each of the quantity fractions and with soil pH. In the same way the proportion of the mobile fraction (in %) of the total, EDTA and DTPA extractable heavy metal content of the soil samples is closely related to the soil pH. Hereby the proportion of the mobile content of the various elements increases in the pH range 6,5 - 3 below element-specific threshold pH values (in brackets) in the order Cd (6,5) > Mn (5,7) > Zn (5,3) > Cu (4,5) > Pb (3,5). In the pH range 6,5 - 7,5 mainly Cu and to a lesser degree also Pb show an increasing mobility due to the influence of soluble organic substances.     

The effect of EDTA on the extractability of Zinc (Zn), Cadmium (Cd) and Nickel (Ni) in Vertisol and Alluvial soils

Ethylendiamintetraacetic acid (EDTA) is persistent in the environment. The presence of EDTA in soil may alter the mobility and transport of Zn, Cd and Ni in soils because of the formation of water soluble chelates, thus increasing the potential for metal pollution of natural waters. Mobility of metals is related to their extractability. To investigate metal extractability affected by EDTA, Zn, Cd and Ni were added to Vertisol and Alluvial soil at rates of 50, 2 and 5 mg kg^-1, respectively. Both natural and metal amended soils were treated with Na₂EDTA at rates of 0; 0.2 and 0.5 mg kg^-1. After five months of incubation soil samples were extracted with 0.1 N HCl, 0.005 M DTPA + 0.01 M CaCl₂ + 0.1 M TEA (0.005 M Diethylenetriaminepentaacetic acid + 0.01 M Calcium cloride + 0.1 M Triethanolamine) and 1 M Mg(NO₃)₂, the latter of which extracts the exchangeable from of metald (Zn, Cd and Ni).

According to experiment results, Zn, Cd and Ni in all extraction increased with increasing rates of EDTA in the natural and metal amended soils.     

Comparative evaluation of residual and total metal analyses in polluted soils

Abstract

Two digestion procedures, employing aqua regia‐HF (ARHF) and HNO₃‐HCIO4‐HF (HHH), were used to analyze residual metals (following a chemical fractionation scheme) and total metal content of two soils, one moderately polluted by municipal sludge applications and the other a grossly‐contaminated sample (20.8% Pb) from a battery recycling site. Although commonly used in sequential extraction analyses, the ARHF method solubilized only 53% (significant at p = 0.05) of the HHH‐determined residual Pb in the battery soil. For the sludge‐amended soil, residual Cd, Pb, and Zn were not statistically different by the two methods. For the battery soil, a single ARHF extraction also underestimated total Pb and Cu relative to HHH, but both methods gave statistically‐similar total Cd, Cu, Pb, and Zn for the sludge‐amended soil. As the sample metal concentration increased, the ability of ARHF to solubilize HHH‐equivalent metal quantities generally decreased. Since the degree of contamination is often unknown for environmental samples, the HHH method is more reliable for assessing residual and total metals in polluted soils     

Sequential fractionation of chromium and nickel from some serpentinite‐derived soils from the eastern Transvaal

Abstract

Soils derived from ultramafic serpentinitic rocks are inherently infertile. These soils support plant species that are able to hyperaccumulate both chromium (Cr) and nickel (Ni). This study was conducted to determine the efficacy of a sequential extraction technique in explaining sources of Cr and Ni that are taken up by plant species growing on these soils. The sequential extraction of soil samples obtained from the eastern Transvaal involved the following reagents: H₂O and 0.5M KNO₃, 0.5M NaOH, 0.05M Na₂EDTA, and 4M HNO₃. More than 95% of the total Cr was extracted by HNO₃ while the remaining extractants fell into the order NaOH > EDTA ? KNO₃ + H₂O. There would appear to be a loose correlation between easily soluble Cr (KNO₃ + H₂O) and the uptake of Cr by the plant. A somewhat higher proportion of Ni was extracted prior to the HNO₃ treatment although amounts removed by KNO₃ + H₂O were all less than 1% of the total. It would appear that plant species growing on these soils are able to accumulate these elements from sources other than those considered easily available. A highly significant coefficient of determination was obtained between Ni extracted by oxalate and EDTA extractable. The fraction extracted by the steps in the sequential procedure can be related to exchangeable and sorbed (KNO₃ and H₂O) and an easily acid soluble inorganic fraction (HNO₃). The NaOH and EDTA fractions are probably related to the Cr and Ni bound in the form of organic complexes and associated with iron oxides.