Measuring bioavailable trace metals by diffusive gradients in thin films (DGT): soil moisture effects on its performance in soils

Conventional methods of measuring labile chemical species of trace metals in soil solutions, such as chemical competition following centrifuging, are inadequate if the speciation changes during sampling and extraction. A new technique, diffusive gradients in thin films (DGT), measures labile species of trace metals in natural waters and sediments in situ. A well-defined diffusive gel layer distinguishes it from other resin-based techniques. It perturbs the soil in a controlled way by introducing an in situ local sink for metal ions. Resulting fluxes to the device are quantitatively measured, allowing assessment of re-supply kinetics and in some cases measurement of in situ soil solution concentrations. We used DGT to measure fluxes of Cd, Co, Cu, Ni, Pb and Zn in a sludge-treated soil at various moisture contents (27–106%). Replicate measurements showed that the precision of DGT-measured fluxes was within 10%. For moisture contents exceeding the field capacity (42%), the DGT response reflected soil water concentrations. At smaller moisture contents, changes related to tortuosity and dilution were reflected in the measurements. This technique has the potential for in situ measurements in the field where it should provide quantitative flux data on individual soils and provide a good surrogate for bioavailable metal.     

The Monitoring of Cr(III) and Cr(VI) in Natural Water and Synthetic Solutions: An Assessment of the Performance of the Dgt and Dpc Methods

The technique of diffusive gradients in thin films or diffusive gradient in thin films (DGT) has been used in this work for the in situ measurement of labile Cr(III) and Cr(VI) species. Direct measurement of Cr(VI) was also carried out in parallel with a field-based colourimetric technique based on the EPA 7196 diphenyl-carbohydrazide (DPC) method. The efficiency of the DGT and DPC methods were tested (a) in the laboratory, using synthetic solutions in the presence of realistic concentrations of Cr, humic substances (HS), and ethylenediaminetetraacetic acid (EDTA), and (b) in the field, in river water affected by effluents discharged by the tannery industry. The main advantage of the DGT method is that it allows the in situ separation of labile species of Cr(III) and Cr(VI), though there are still uncertainties about its performance in field conditions. The DPC method proved to be a fast, accurate, and relatively economical option for the field-based determination of Cr(VI). Sample acidification and ageing of unacidified samples from contaminated aquatic environments, produced significant errors in the determination of ‘dissolved’ Cr. The concentration of Cr(VI) determined by either the DGT or the DPC method exceeds recommended international guidelines.     

A Study of Diffusive Gradients in Thin Films for the Chemical Speciation of Zn(II), Cd(II), Pb(II), and Cu(II): The Role of Kinetics

The lability and mobility of Zn(II)–, Cd(II)–, Pb(II)–, and Cu(II)–humic acid complexes were studied using diffusive gradients in thin films (DGT). A unique feature of this research was (1) the use of DGTs with diffusive layer thicknesses ranging from 0.4 to 2.0 mm to study lability and mobility of Zn(II)–, Cd(II)–, Pb(II)–, and Cu(II)–humic acid complexes, combined with (2) the application of a competing ligand exchange (CLE) method using Chelex 100, the same chelating resin that is used in DGT, to study the kinetic speciation. The CLE experiments were run immediately after the completion of the DGT experiments, thereby allowing effects of the competing ligand to be separated from the effects introduced by the use of the polyacrylamide gel that is used in DGT. The results indicate that Zn(II) and Cd(II) tend to form more labile and more mobile complexes with humic acid than Pb(II) or Cu(II). The dissociation rate constants of Zn(II), Cd(II), and Pb(II) were found to increase with the ionic potential of the metal, suggesting that the binding between some trace metals and humic acid has a significant covalent component. Furthermore, the results suggest that the Eigen mechanism may not be strictly obeyed for metals such as Cu(II) which have high rate constants of water exchange, k _w. Consequently, the markedly slow kinetics of Cu(II)-HA species suggests that the usual equilibrium assumption may not be valid in freshwaters.     

Determination of High Resolution Pore Water Profiles of Trace Metals in Sediments of the Rupel River (Belgium) using Det (Diffusive Equilibrium in Thin Films) and DGT (Diffusive Gradients in Thin Films) Techniques

The techniques of diffusional equilibrium in thin films (DET) and diffusional gradients in thin films (DGT) were used to obtain high resolution pore water profiles of total dissolved and labile trace (mobilizable) metals in the sediments of the Rupel River, Belgium. DGT measures labile metal species in situ by immobilizing them on a resin gel after diffusion through a diffusive gel whereas for DET an equilibrium is established between the DET gel and the pore water. Concentrations of Pb and Zn obtained by DGT were in good agreement with the results obtained by centrifugation, and thus were well buffered by rapid equilibrium with the solid phase, whereas Fe, Mn and Cd were very tightly bound to the sediment phase and large differences were observed between the labile and the total metal concentrations. Cu, Zn, Co and Ni show intermediated behavior. Good correlations were found between the profiles of As and Fe and Mn and Co for DET as well as DGT showing a close link between the geochemical behavior of these elements. Cu, Zn, Pb and Cd are also influenced by the reductive mobilization of Fe and Mn oxides but are also closely linked to the bacterial degradation of organic matter in the surface sediments as to the precipitation of metal sulfides in the deeper layers.     

Bioavailability of Metals at a Southeastern Brazilian Coastal Area of High Environmental Concern Under Anthropic Influence: Evaluation Using Transplanted Bivalves (<Emphasis Type="Italic">Nodipecten nodosus</Emphasis>) and the DGT Technique

Metals are commonly determined in aquatic organisms, primarily using bivalves to provide important data on their bioavailability. The technique of diffusive gradients in thin films (DGTs) has also been employed to assess the concentration of metals in freshwater and marine environments, determining their lability. The present work evaluated and compared the labile and bioavailable concentrations of Cd, Co, Cu, Mn, Ni and Pb in seawater from Ilha Grande Bay, RJ, using DGT and transplanted bivalves (Nodipecten nodosus), respectively. The scallops and DGTs were immersed in water at three sampling locations within the bay from July to September 2012 (winter campaign) and from December 2012 to February 2013 (summer campaign). The metals were determined by inductively coupled plasma-mass spectrometry (ICP-MS) and optical emission spectrometry (ICP-OES). DGT technique was successfully used to determine the concentrations of metals in waters, except for Pb when short deployment times were used. All metals were determined using transplanted bivalves (N. nodosus), but pre-exposure to Cd was evident, which made the interpretation of the data for this analyte difficult. The data on metal lability in Ilha Grande Bay waters obtained from the DGT technique were correlated with the metal bioavailability determined in the soft tissues of the transplanted N. nodosus for Co, Cu, Mn, Ni and Pb. This is the first evaluation of this type for this area of high environmental concern. Both techniques revealed that Náutico was the location with the highest concentration of metals in the study area.     

Stabilized Liquid Membrane Device (SLMD) for the Passive, Integrative Sampling of Labile Metals in Water

A stabilized liquid membrane device (SLMD) is described forpotential use as an in situ, passive, integrative samplerfor cadmium (Cd), cobalt (Co), copper (Cu), nickel (Ni), lead(Pb), and zinc (Zn) in natural waters. The SLMD (patent pending)consists of a 2.5-cm-wide by 15-cm-long strip of low-density polyethylene (LDPE) layflat tubing containing 1 mL of an equalmixture (v/v) of oleic acid (cis-9-octadecenoic acid) and EMO-8Q (7-[4-ethyl-1-methyloctyl]-8-quinolinol). The reagentmixture continuously diffuses to the exterior surface of the LDPE membrane, and provides for sequestration of several divalent metals for up to several weeks. Depending on samplerconfiguration, concentration factors of several thousand canbe realized for these metal ions after just a few days. In addition to in situ deployment, the SLMD may be useful for laboratory determination of labile metal species in grab samples. Methods for minimizing the effects of water flow onthe sampling rate are currently under investigation.     

Evaluation of Different Extraction Methods for the Assessment of Heavy Metal Bioavailability in Various Soils

The main objective of this study was to compare the effectiveness of different methods (heavy metals in pore water (PW), diffusive gradients in thin films (DGT), diethylene triamine pentaacetic acid (DTPA) extraction, and total heavy metals (THM) in soil) for the assessment of heavy metal bioavailability from soils having various properties and heavy metal contents. The effect of soil heavy metal pollution on shoot yield and sulfatase enzyme activity was also studied. Wheat (Triticum aestivum) was grown in different soils from Spain (n?=?10) and New Zealand (n?=?20) in a constant environment room for 25 days. The bioavailabilities of Cd, Cr, Cu, Ni, Pb, and Zn were assessed by comparing the metal contents extracted by the different methods with those found in the roots. The most widely applicable method was DGT, as satisfactory Cu, Ni, Pb, and Zn root concentrations were obtained, and it was able to distinguish between low and high Cr values. The analysis of the metal concentrations in PW was effective for the determination of Cr, Ni, and Zn content in root. Copper and Pb root concentrations were satisfactorily assessed by DTPA extraction, but the method was less successful with determining the Ni and Cr contents and suitable just to distinguish between high and low concentrations of Zn. The THM in soil method satisfactorily predicted Cu and Pb root concentrations but could only be used to distinguish between low and high Cr and Zn values. The Cd root concentration was not successfully predicted for any of the used methods. Neither shoot yield nor sulfatase enzyme activity was affected by the metal concentrations.     

皖南茶园土壤重金属化学形态及其生物有效性

以皖南茶园为研究对象,通过Tessier连续提取分级法对茶园土壤重金属(Zn,Cu,Pb,Ni)全量及其化学形态进行了分析,利用活性态重金属占全量之比来评价其生物有效性。结果表明,皖南茶园土壤中Zn,Cu,Pb,Ni含量均未超过国家标准;除Zn外,其他元素均高出背景值,存在较明显的富集现象;土壤中4种重金属在5种形态上表现出不同的分布规律,Zn,Cu,Ni以残渣态为主,分别占总量的72.55%,90.00%和81.79%,而Pb以铁锰氧化物结合态为主,占总量的70.09%;Zn,Cu,Pb,Ni的活性态部分占全量比例分别为5.04%,1.51%,0.97%和0.23%,土壤重金属活性态部分与茶叶中重金属含量之间呈现正相关关系,且皖南茶区的茶叶重金属含量在限量值的安全范围内。     

水稻子实对不同形态重金属的累积差异及其影响因素分析

在分析成都平原核心区土壤重金属(Cd、Cr、Pb、Cu、Zn)全量、各形态含量及相应点位种植的水稻子实重金属含量的基础上,通过统计分析、空间插值及线性回归方程的模拟,研究了土壤Cd、Cr、Pb、Cu、Zn全量的空间分布状况、各形态重金属含量统计特征,以及水稻子实对重金属各形态的累积差异及其影响因素。结果表明,成都平原水稻土重金属污染较轻,除Cd外,均低于国家土壤环境质量二级标准。土壤中重金属的可交换态含量均较低,Cd主要以铁锰氧化态存在,Cr、Cu、Zn、Pb主要以残渣态存在。水稻子实对5种重金属的累积效应顺序为:Cd>Zn>Cu>Pb>Cr。与水稻重金属累积关系密切的重金属活性形态(可交换态、碳酸盐结合态、铁锰氧化物结合态和有机物结合态)主要有:Cd的碳酸盐结合态、Cr的可交换态、Pb的有机物结合态和Cu的碳酸盐结合态含量;Zn各活性形态对水稻子实含量的影响不明显。土壤理化性质对不同活性形态重金属元素的影响效应各不相同。活性态Cd主要受有机质、pH和容重的影响;活性态Cr与pH、有机质、CEC和容重密切相关;活性态Pb与有机质、容重、中细粉粒、砂粒等均有密切的关系;Cu的活性主要受粘粒、有机质含量的影响;Zn的有效性主要受pH、有机质、砂粒、容重的影响。总的看来,对土壤Cd、Cr、Pb、Cu、Zn各活性形态含量影响效应较强的是有机质、pH、容重,而与土壤吸附性能密切相关的颗粒组成、CEC的影响不甚明显。     

Effect of biosolid application to Mollisol Chilean soils on the bioavailability of heavy metals (Cu,Cr, Ni,and Zn) as assessed by bioassays with sunflower (Helianthus annuus) and DGT measurements

Purpose

This study assessed the effect of biosolid application on the bioavailable fraction of some trace elements (Cu, Cr, Ni, and Zn) using a bioassay with sunflower (Helianthus annuus) and a chemical assay, diffusion gradient in thin films (DGT).

Materials and methods

Five surface soil samples (0–20 cm) were collected from an agricultural zone in Central Chile where biosolids are likely to be applied. Municipal biosolids were mixed with the soil at concentrations of 0, 30, 90, and 200 Mg ha^?1. The experiment to determine the bioavailability of metals in the soil using the bioassay was performed using sunflower. The DGT technique and Community Bureau of Reference (BCR) sequential extraction were used to determine the bioavailable fractions of the metals.

Results and discussion

The application of biosolids increased the phytoavailability of Zn, Ni, and Cr in most of the soils, as indicated by the increasing concentrations in sunflower plants as the biosolid application rate increased. In two of the soils, Codigua and Pelvín, this increase peaked at an application rate of 90 Mg ha^?1. Decreases in the bioavailable fractions of Zn, Ni, and Cr were observed with higher biosolid application rates. The bioavailability of metals was estimated through multiple linear regression models between the metals in the sunflower plants and the different chemical fractions of metals in the soils treated with different biosolid rates, which displayed a positive contribution of the labile (water soluble, carbonate, and exchangeable), oxide, and organic metal forms in the soil, particularly with respect to Ni and Zn at application rates of 30 and 90 Mg ha^?1. The bioavailable fraction of metals was determined in soils using the DGT technique. The effective concentration (C _E) results were compared with those in sunflower plants. The DGT technique could effectively predict the bioavailable fractions of Cr, Ni, and Zn in the Taqueral soil but only that of Zn in the Polpaico soil.

Conclusions

The application of biosolids significantly increased the labile fraction of most of the metals in the studied soils, particularly at the highest biosolid application rate. C _E increased as the concentration of biosolids increased for most of the metals. The effectiveness of the DGT technique for predicting the bioavailability of metals was dependent on the soil type and the metal. However, the C _E for soil Cu was not related to plant Cu for all soils studied.     

泉州走马埭典型土壤重金属的赋存形态分析

采用改进的Tessier连续萃取方法研究了泉州走马埭国家农田示范保护区典型土壤中重金属(Cr、Ni、Cu、Zn、Cd、Pb)的化学形态分布,通过土壤重金属的赋存形态分析比较了6种重金属的生物可利用性。研究结果表明,土壤中不同重金属元素化学形态分布具有不同的特点:Cr和Ni主要以残渣态存在,其余形态所占的比例很小;Cu以残渣态含量最高,碳酸盐结合态含量最低;Zn以残渣态为主,可交换态含量最低;Cd以可交换态和碳酸盐结合态为主,水溶态含量最低;Pb以残渣态和铁锰氧化物结合态为主,水溶态含量最低。土壤中除Cd外,Zn、Cu、Cr、Pb、Ni在正常自然条件下相对比较稳定。     

Modelling trace metal extractability and solubility in French forest soils by using soil properties

Soil/solution partitioning of trace metals (TM: Cd, Co, Cr, Cu, Ni, Sb, Pb and Zn) has been investigated in six French forest sites that have been subjected to TM atmospheric inputs. Soil profiles have been sampled and analysed for major soil properties, and CaCl₂‐extractable and total metal content. Metal concentrations (expressed on a molar basis) in soil (total), in CaCl₂ extracts and soil solution collected monthly from fresh soil by centrifugation, were in the order: Cr > Zn > Ni > Cu > Pb > Co > Sb > Cd , Zn > Cu > Pb = Ni > Co > Cd > Cr and Zn > Ni > Cu > Pb > Co > Cr > Cd > Sb , respectively. Metal extractability and solubility were predicted by using soil properties. Soil pH was the most significant property in predicting metal partitioning, but TM behaviour differed between acid and non‐acid soils. TM extractability was predicted significantly by soil pH for pH < 6, and by soil pH and Fe content for all soil conditions. Total metal concentration in soil solution was predicted well by soil pH and organic carbon content for Cd, Co, Cr, Ni and Zn, by Fe content for Cu, Cr, Ni, Pb and Sb and total soil metal content for Cu, Cr, Ni, Pb and Sb, with a better prediction for acidic conditions (pH < 6). At more alkaline pH conditions, solute concentrations of Cu, Cr, Sb and Pb were larger than predicted by the pH relationship, as a consequence of association with Fe colloids and complexing with dissolved organic carbon. Metal speciation in soil solutions determined by WHAM‐VI indicated that free metal ion (FMI) concentration was significantly related to soil pH for all pH conditions. The FMI concentrations of Cu and Zn were well predicted by pH alone, Pb by pH and Fe content and Cd, Co and Ni by soil pH and organic carbon content. Differences between soluble total metal and FMI concentrations were particularly large for pH < 6. This should be taken into account for risk and critical load assessment in the case of terrestrial ecosystems.     

渭河(咸阳段)表层沉积物中重金属形态分布特征

采用欧共体修正BCR四步连续提取法对渭河(咸阳段)的表层沉积物的重金属(Pb,Cr,Cu,Ni,Mn和Zn)形态进行了研究.结果表明,Cr,Ni和Zn主要以残渣态的形式存在,分别为97.91%,66.36%和73.68%,表现出很高的稳定性.而Pb和Mn仅在乙酸提取态含量分别达27.66%和38.49%时表现出一定的生物有效性和潜在危害性."非稳定态"重金属的空间分布特征是沣河渭河交汇处上游位含量最高,其次为渭河3号桥下,沣河渭河交汇处下游含量最低.     

Bioconcentration factors for metals in humic waters at different pH in the Rönnskär area (N. Sweden)

The metal content of bryophytes (Fontinalis antipyretica), invertebrates (Asellus aquaticus, Sialis lutaria, Libellulidae) and fish (Perca fluviatilis, Esux lucius) was measured along an aquatic concentration gradient of Zn, Cu, Cd, Pb, As, Hg, generated by air emissions from the Rönnskär smelters. The separation of pH effects on metal uptake, was facilitated by metal and pH vectors being mostly well separated from each others. The interpretation was facilitated by seasonal small variations in water metal content, which improved the calculation of bioconcentration factors (BCF) as a strict measure of bioavailability. It was found that BCF varied as function of element and taxon. When pH decreased, BCF also did so for Zn, Cd, Ni, Co in bryophytes, while BCF increased for Pb, Cu in in fish. We conclude and agree that one-sided focusing on total concentrations may overlook shifts in speciation due to pH in moderately acidified waters for elements like Cu and Pb.     

Monitoring of subaqueous depots with active barrier systems for contaminated dredged material using dialysis samplers and DGT probes

Background, Aims and Scope  Disposal of dredged material in subaqueous depots is increasingly considered an economic and ecologically sound option in managing contaminated dredged material. The concept of subaqueous disposals capped with active barrier systems has been developed to minimize this risk of contaminant release. As such a depot represents a permanent installation within a sensitive ecosystem, it requires a thorough monitoring concept. It is the goal of this work to develop such a concept regarding general considerations and results of laboratory and field investigations. Methods  In addition to the state-of-the-art techniques developed for other under-water constructions, this monitoring concept is developed with particular respect to the chemical isolation of the dredged material from the overlying water body. It comprises the use of seepage meters, dialysis samplers, and DGT gel probes for determining the migration of selected target solutes. The capability of the dialysis samplers is demonstrated by comparing field results with model calculations. The appropriateness of DGT probes to assess the impact of humic substances on trace metal speciation and on copper toxicity is demonstrated with the aid of laboratory experiments. Results and Discussion  The experimental results show that, by using dialysis samplers, the temporal changes in concentration-depth-profiles of heavy metals in the pore solution can be monitored. Additionally, the application of DGT probes facilitates the in situ detection of labile species of a metal in the presence of dissolved humic substances, which serves to reflect its toxicity. Conclusions. Three subsequent monitoring phases are distinguished on the basis of both general considerations and the findings from field results: A hydraulic phase that is characterized by compaction and pore water expulsion, a geochemical phase in which the demobilization of pollutants can occur due to substantial changes in the physico-chemical conditions (pH, EH), and a steady-state-phase where pore water flow and geochemical conditions are approaching their minimum. Recommendations and Outlook  The monitoring concept suggested here provides a versatile tool to assess the chemical isolation of subaqueous sediment depots and other contaminated sediment sites. This is of great importance as subaqueous disposal is increasingly considered a future management strategy as space for upland disposal is limited and treatment, in general, proves to be too costly.     

Bioavailability as a Factor in Risk Assessment of Metal-Contaminated Soil

To accurately assess the risks of metal contaminants in soil, the bioavailability of the metals need to be considered. The bioavailable concentrations determined from homogenized, dried soils are not necessarily representative of in situ conditions of undisturbed field soils. In this study, we investigated the accumulation of metals in wheat (Triticum aestivum) grown in undisturbed contaminated (Pb, Zn, Cu, and Cd) soil cores, in relation to total soil, leachate, and diffusive gradients in thin films (DGT)-labile metal concentrations. Despite the fact that many of the samples contained metal concentrations above guideline values, no significant effects were observed on wheat growth. The bioavailability of metals in the most contaminated samples was estimated to be medium to low, possibly explaining why few effects were observed in the bioassay. For Cu, Zn, and especially for Pb, leachate and DGT-labile concentrations were better predictors of uptake by wheat than total concentrations based on correlations. It is suggested that DGT and leachate concentrations in combination with bioassays in undisturbed soil cores can be used to account for metal bioavailability in soil. These tests could be used during the ecological risk screening stage, in conjunction with total concentrations and guideline values to better estimate receptor exposure.     

Sediment management and the renewability of floodplain clay for structural ceramics

Background, aim, and scope  

The Netherlands has vast resources of clay that are exploited for the fabrication of structural ceramic products such as bricks and roof tiles. Most clay is extracted from the so-called embanked floodplains along the rivers Rhine and Meuse, areas that are flooded during high-discharge conditions. Riverside clay extraction is—at least in theory—compensated by deposition. Based on a sediment balance (deposition versus extraction), we explore the extent to which clay can be regarded as a renewable resource, with potential for sustainable use. Beyond that, we discuss the implications for river and sediment management, especially for the large engineering works that are to be undertaken to increase the discharge capacities of the Rhine and Meuse.     

Speciation of Metals in Sewage Sludge and Sludge-amended Soils

This study is aimed at ascertaining the chemical partitioning ofCu, Zn, Pb, Ni, Cr and Cd in sewage sludge and agricultural soils repeatedly amended with sludge. The operationally determined speciation was investigated by using selective five steps sequential extraction method for partitioning these metals into different chemicalforms, likely to be released in solution under various environmental conditions. It provides qualitative evidence regarding the form of the association of metals and indirectly of their bioavailability. It can help to explain the process by which metals are eliminated from sewagesludge and also indicate the impact of the use of sludge on agriculturalsoils, as amendments. Data obtained by extraction procedure showed different metal distribution trend among the fractions in sewage sludgeand sludge-amended soils. Comparison of distribution pattern of metals in sludge and sludge-applied soils shows that there is possible redistribution of metals among the different phases. The sum of the metal content in the fractions compared well with the total metal content in sewage sludge, the ratios averaging 1.02, 1.04, 1.07, 0.94, 1.06, and 1.12 for Cu, Zn, Pb, Ni, Cr, and Cd, respectively. The metal recovery efficiency in sludge-amended soils was found to be: 108±6%, 102±5%, 115±8%, 111±4%, 104±7%and 124±28% for Cu, Zn, Pb, Ni, Cr and Cd, respectively.     

包头市铜厂周边土壤中重金属垂直分布特征与形态分析

为了解包头市铜厂周边地区土壤剖面中重金属污染状况,采用火焰原子吸收分光光度法和Tessier连续提取法,对土壤中6种重金属（Cu,Zn,Mn,Ni,Pb和Cd）的垂直分布特征、形态及潜在生物可利用性进行了分析。结果表明:研究区土壤剖面各层土壤中6种重金属含量均超过内蒙古土壤背景值,Cu,Pb和Cd为主要污染物。随采样深度的增加,Cu,Zn,Pb和Mn的含量呈现下降趋势,且由相关性系数可知重金属Cu,Zn和Pb可能有相同人为或自然污染源;土壤剖面中6种重金属均主要以残渣态存在,含量均在50%以上,对生物危害较小;潜在生物可利用性分析结果为:Cu（32.61%） > Mn（31.85%） > Ni（24.90%） > Zn（16.60%） > Cd（15.23%） > Pb（14.87%）,Cu和Mn的潜在生物可利用性较大,其次为Ni,Zn,Cd和Pb潜在生物可利用性较小。     

Speciation in metal contaminated soils as revealed by an ion exchange resin membrane fractionation procedure

Abstract

Ion exchangers have proven to be a useful tool in the study of metal speciation in aquatic environments, but have seen little application in the study of metal behavior in soil environments. The labile metal species in polluted soils were evaluated by equilibrating soil suspensions with ion exchange resin membranes of different types at pH values ranging from 3 to 9. The total soluble metal content of cadmium (Cd), chromium (Cr), nickel (Ni), and lead (Pb) contaminated Western Canadian soils was subdivided into (i) low‐pH labile, (ii) weak‐acid labile, (iii) weak‐base labile, (iv) high‐pH labile, and (v) non‐adsorbable forms using cation and anion exchange membranes. Soil suspension is mixed overnight with different types of resin membranes and the cations transferred from the soil are subsequently eluted from the membranes using 1N HCl. The HCl extract is then analyzed for Cd, Cr, Ni, and Pb. The aqueous phase remaining in contact with the soil residue is considered the amount of released non‐labile, non‐adsorbable species. The low‐pH labile fraction constituted the largest proportion of the added metal in poorly buffered (sandy) soils. Weak‐acid and base labile fractions were typically highest in highly buffered soils. Clearly, metal contaminated soils most likely to cause environmental damage are sandy textured soils subject to acidification, although the production of chelating substances by roots and microorganisms may also mobilize considerable quantities of metal in soils of high clay content.