Heavy metal species,mobility and availability in soils

The ecological effects of heavy metals in soils are closely related to the content and speciation of the elements in the solid and liquid phases of soils. Methods for the determination of metal species in both phases are described and critically evaluated. In connection with the possible binding mechanisms of heavy metals in soils the concept of specific and non-specific adsorption is discussed. Recent results indicate that the adsorption of heavy metals on soil particles is not only restricted to the formation of surface complexes but can also take place in the interior of minerals. Diffusion processes of heavy metals into soil minerals are described for goethite. In order to assess metal mobility and availability in soils, the concentration and speciation of metals in the soil solution or in comparable aeqeous equilibrium solutions of soil samples and the transfer of metals from solid pools to the liquid phase and vice versa have to be assessed. Methods for the determination of the amount of plant available heavy metals are described and the associated problems discussed.     

Simultaneous Sorption of Cd,Cu, Ni,Zn, Pb,and Cr on Soils Treated with Sewage Sludge Supernatant

Disposal of sewage sludge creates the potential for heavy metal accumulation in theenvironment. This study assessed nine soils currently used as Dedicated Land Disposal units(DLDs) for treatment and disposal of municipal sewage sludge in the vicinity of Sacramento,California. Adsorption characteristics of these soils for Cd, Cu, Ni, Zn, Pb, and Cr were studiedby simultaneously mixing these elements in the range of 0-50 µmol L-1 with sludgesupernatant and reacting with the soil using a soil:supernatant ratio of 1:30, pH = 4.5 or 6.5, andconstant ionic strength (0.01 M Na-acetate). The concentration of metals in the supernatant wasdetermined after a 24 hr equilibration period. Adsorption isotherms showed that metal sorptionwas linearly related to its concentration in the supernatant solution. The distribution coefficientKd (Kd = concentration on solid phase/concentration in solution phase) was computed as theslope of the sorption isotherm. The distribution coefficients were significantly correlated to soilorganic matter content for Ni, Cu, Cd, and Pb at pH 4.5 and for Ni, Cu, Zn, and Cd at pH 6.5.There was also a correlation between Kd and soil specific surface area but no relationship to othersoil properties such as CEC, clay content, and noncrystalline Fe and Al materials. Therefore, soilorganic carbon and surface area appear to be the most important soil properties influencing metaladsorption through formation of organo-metal complexes. The Kd values for all elements werehigher at pH 6.5 than at 4.5. Selectivity between metals resulted in the following metal affinitiesbased on their Kd values: Pb>Cu>Zn>Ni>Cd≈Cr at pH 4.5 andPb>Cu≈Zn>Cd>Ni>Cr at pH 6.5.     

Urban soil pollution in Damascus,Syria: concentrations and patterns of heavy metals in the soils of the Damascus Ghouta

The objective of the study was to assess the extent and severity of heavy metal contamination of arable soils of the Damascus Ghouta, an area with intensive agricultural production. We examined the present degree and spatial distribution of heavy metal concentrations in 51 soil profiles and in 22 topsoil samples in the Damascus Ghouta. The soils were digested with aqua regia for heavy metal analysis. Pb, Cu and Zn concentrations in the topsoils exhibited anthropogenic increased values. The major sources for the heavy metal contamination in Damascus city are most possibly emissions from vehicles. These emissions transported by air and sewage water together with household and industrial sewage effluents have been considered to be responsible for the increased heavy metal concentrations found in the soils of the central Barada area. However, the values were in most cases below tolerable values of soil for agricultural use. Cr concentrations up to 1800 mg kg⁻¹ were found near a tannery industrial estate. Concerning the health risk of the population bioavailability and mobility of heavy metals seems to be of minor importance, based on the soil properties found in the study area. However, direct ingestion of soil, e.g., by children and inhalation of dust may contribute largely to the accumulation of heavy metal in human and livestock.     

热带地区强风化土壤表面的化学反应以及土壤管理的合理建议

Highly weathered soils are distributed in the humid and wet-dry tropics, as well as in the humid subtropics. As a result of strong weathering, these soils are characterized by low activity clays, which develop variable surface charge and related specific properties. Surface reactions regarding base exchange and soil acidification, heavy metal sorption and mobility, and phosphorus sorption and availability of the tropical highly weathered soils are reviewed in this paper. Factors controlling surface reactivity towards cations and anions, including ion exchange and specific adsorption processes, are discussed with consideration on practical implications for rational management of these soils. Organic matter content and pH value are major basic factors that should be controlled through appropriate agricultural practices, in order to optimise favorable effects of colloid surface properties on soil fertility and environmental quality.     

Influence of copper on the adsorption and desorption of paraquat, diquat, and difenzoquat in vineyard acid soils

Retention of the cationic herbicides paraquat (PQ), diquat (DQ), and difenzoquat (DFQ) in two vineyard soils with a different management history and retention capacity was examined. The influence of copper on the ability of the soils to retain the herbicides was determined by comparing the results of adsorption and desorption tests on untreated and Cu-enriched soil samples, and also on soils that were previously treated with EDTA to extract native copper. The three herbicides were strongly adsorbed by both soils. Soil 1 exhibited linear adsorption isotherms for PQ and DFQ with partition coefficients, KD, of 1.28 x 103 and 1.37 x 103 L kg-1, respectively, and a Freundlich-type isotherm for DQ with a linearized partition coefficient, KD*, of 1.01 x 103 L kg-1. On the other hand, soil 2 exhibited curved isotherms and smaller KD* values (viz. 106, 418, and 28 L kg-1 for PQ, DQ, and DFQ, respectively). Using EDTA to extract copper from the soils released new sites for the herbicides to bind. The three herbicides exhibited strong hysteresis in the adsorption-desorption process. Extracting copper decreased the percent desorption of PQ and DQ; on the other hand, it decreased the affinity of DFQ for the resulting vacant adsorption sites. Similarly, competitive adsorption tests with copper and the herbicides revealed that the metal was only capable of displacing DFQ from adsorption sites. The behavior of this herbicide in the soils was consistent with a specific adsorption model. The disparate behavior of the two soils toward the herbicides was a result of the adsorption sites in soil 1 being less extensively occupied than those of soil 2 in the adsorption tests. The effect of copper on the adsorption of DFQ in the two soils was acceptably reproduced by an adsorption model involving Coulombic and specific sorption with competition from the metal.     

Parameterization of Freundlich adsorption isotherms for heavy metals in soils from an area with intensive livestock production

Adsorption coefficients are valuable tools used to estimate the environmental relevance of heavy metal contamination. However, their determination with batch experiments is laborious. Thus, attempts have been made to deduce these coefficients from soil parameters. However, the application of the resulting parameterized equations to different sets of samples has often yielded poor results. Hence, the objectives of the present study were (1) to deduce basic soil properties governing the coefficients of Freundlich adsorption isotherms for Cd, Cu, Ni, Pb, and Zn, and (2) to derive parameterized isotherms and examine their accuracy. For this purpose, 30 topsoil and nine subsoil samples were investigated which represented one Podzol‐Cambisol‐Gleysol soilscape in an area with intensive livestock production in Lower Saxony, Germany. Total background concentrations (aqua regia digestion) of heavy metals in topsoils ranged from 0.290 (Cd) to 19.2 mg kg^—1 (Zn) and exhibited elevated mobilizable proportions (NH₄EDTA pH 4.6 extract) of 17 (Ni) — 66 % (Zn) from the total concentration. Background concentrations were higher in topsoils than in subsoils by factors of 1.7 (Ni) — 28 (Zn). These differences were assigned to the special situation of heavy metal input mostly originating from animal excrements. The isotherms obtained by batch experiments showed larger coefficients K_F for partition among soil solid phase and soil solution in topsoils than in subsoils by a factor of 3.5. The coefficients of the isotherms were significantly correlated with routinely determined soil properties such as cation exchange capacity and pH (R = 0.36—0.89). Parameterized isotherms were calculated for each metal by inserting the relevant parameters in multiple linear regression equations. Among these parameters were the soil pH, cation exchange capacity, total metal concentration, and the concentrations of organic carbon, clay, fine silt, and various pedogenic oxides. The K_F values, separately calculated for topsoils and subsoils, agreed well with those determined by batch experiments (R = 0.63—0.97). Therefore, parameterized isotherms are valuable tools for the prediction of heavy metal partition in soils from one soilscape and for a risk assessment in the investigated, densely stocked area and similar areas.     

Comparison of fractal dimensions of soils estimated from adsorption isotherms,mercury intrusion,and particle size distribution

The values of the surface fractal dimensions were determined for several samples of Cambisols and Luvisols from analysis of nitrogen and water vapor adsorption isotherms and from mercury intrusion data. Moreover, the values of fractal dimension characterizing the particle size distributions of soil samples were calculated by using a number‐based method. For almost all investigated soils the values of the surface fractal dimension, obtained from water vapor isotherms were lower than those obtained from nitrogen isotherms. Largest were the surface fractal dimensions evaluated form mercury intrusion data. No significant correlations between different kinds of surface fractal dimensions were found, and the reasons of this finding are discussed. However, the values of the surface fractal dimensions calculated from mercury intrusion data correlate with those characterizing the texture of soils. The paper also reports on correlations between of the values of surface area, fractal dimensions and some selected physico‐chemical characteristics of soils.     

Effect of long-term irrigation with untreated sewage effluents on soil properties and heavy metal adsorption of leptosols and vertisols in Central Mexico

The effect of long-term irrigation with untreated sewage effluents from Mexico City on soil properties and heavy metal adsorption behaviour of soils at Irrigation District 03 in the Mezquital Valley, Central Mexico, was studied. General soil parameters of 25 samples from Ap-horizons of Mollic Leptosols and Eutric Vertisols taken at sites which have been under irrigation for different periods of time were compared with samples from fields under rainfed agriculture. The adsorption of Pb, Cd, Cu and Zn was analysed in 8 selected samples by batch experiments. The long-term irrigation of soils with untreated sewage effluent has increased the contents of total (TOC) and dissolved (DOC) organic carbon in Ap-horizons of Leptosols and Vertisols, and diminished the contents of manganese oxides in Vertisols. This influences the heavy metal adsorption behaviour of both soils, since DOC enhances metal solubility at low loading rates and TOC improves metal adsorption capacities at high loading rates. The possibility of an increase in the chloride content in soils due to wastewater irrigation and its relation to higher Cd mobility are discussed, as is the importance of humus balance control through oriented management practices in order to minimize heavy metal mobility in soils, which have been under irrigation with wastewater during long periods.     

Characterization of Pterocarpus macrocarpus (pradoo wood) biochar and its effect on the retention properties of sandy soils in Northeast Thailand

Pradoo wood biochar has been tested in order to explore sustainable solutions to the development of agriculture on poor sandy soils in marginal areas in Northeast Thailand. Some basic physicochemical properties of biochar, for example pore size distribution, cation exchange capacity (CEC), specific surface area (SSA), and water and nutrient adsorption, were determined and compared to soil properties in order to determine appropriate biochar application to soil. Pradoo wood biochar showed important adsorption properties with high SSA, CEC and nutrient adsorption. The water retention properties were also improved on the dry end of the water retention curve. Phosphorous and ammonium adsorption–desorption isotherms were established and their respective affinity for the biochar surface was quantified, by the means of a retention index and thermodynamical parameters. We found that despite excellent retention properties, biochar needs to be added in large amounts (between 10 and 70 kg m⁻²) to soil to be able to modify noticeably the resulting soil properties.     

不同土地利用方式土壤对铜、镉离子的吸附解吸特征

采用一次平衡法对Cu²⁺、Cd²⁺在城市及城郊农田、林地、草地3种土地利用方式土壤中的吸附解吸过程进行比较研究, 结果表明: Cu²⁺、Cd²⁺在3种土地利用方式土壤中的吸附量均随平衡液浓度的增加而增大, Cu²⁺、Cd²⁺在农田土壤上的吸附量均高于林地和草地土壤。分别用Langmuir和Freunlich两种等温吸附方程对吸附过程进行拟合, 3种土壤对Cu²⁺的吸附过程运用Langmuir方程拟合效果好, 而对Cd²⁺的吸附过程运用Freunlich方程拟合效果更好。Cu²⁺在3种土壤的解吸量大小顺序为农田>林地>草地, Cd²⁺在3种土壤的解吸量大小顺序为农田>草地>林地。两种离子在3种土壤中的动态吸附是个快速反应的过程, 随时间延长, 吸附反应趋于平衡。运用双常数函数方程和Elovich方程能较好地拟合重金属在土壤上的吸附动力学过程。Cu²⁺、Cd²⁺的吸附与土壤黏粒含量、有机质含量、CEC和pH均有关。     

THE CONTENTS AND SORPTION OF CADMIUM IN SOME AGRICULTURAL SOILS OF ENGLAND AND WALES

Cadmium sorption was measured in 10 agricultural soils with pH ranging from 4.5 to 7.9, and total Cd content from 0.27 to 1.04 μg g^?1 dry soil. With initial Cd concentrations of 0.5 to 100.0 μM, sorption from 0.002 M CaCl₂ was described by the Freundlich adsorption equation but the gradients of the isotherms increased when the initial concentrations were below 0.5 μm. This indicates that there are specific sites of differing sorption energy; differences between soils in the gradients of the isotherms at low initial concentration could largely be accounted for by their contents of ‘free’ Fe₂O₃. When initial concentrations were below 0.5 μm there was a linear relationship between the quantity of Cd sorbed and the final concentration in solution. This relationship held with all soils except that of lowest pH from which there was a net loss of Cd to the solutions. Desorption was measured from three soils with contrasting pH. With the soil of lowest pH, over 80 per cent of sorbed Cd was desorbed to 0.002 m CaCl₂ and up to 30 per cent to 100 or 500 μm solutions of heavy metal chlorides. In contrast, only very small proportions (<1.25 per cent) were desorbed from the other soils with pH 6.7 and 7.8. The results indicate that Cd is strongly sorbed by soils of pH of above 6.0 when added in amounts comparable to additions in sewage sludges or phosphatic fertilizers, and illustrate the importance of liming as a means of reducing the mobility of this metal in soils.     

金属离子在铁(氢)氧化物与腐殖质微界面上的吸附机理和模型研究进展

铁(氢)氧化物和腐殖质是广泛分布在土壤中的重要天然活性物质,因其具有较大的比表面积并且铁(氢)氧化物表面的-OH与腐殖质表面的-COOH、-OH等活性官能团可通过静电作用、配体交换等多种机制对重金属离子产生较强吸附,从而影响重金属离子在环境中的迁移、转化和生物效应。深入了解重金属离子在铁(氢)氧化物-腐殖质复合体微界面相互作用的分子机理,对于阐明重金属离子在环境中的迁移、转化过程具有重要意义。本文综述了金属离子在铁(氢)氧化物与腐殖质上吸附机理和模型的研究进展,为重金属污染土壤的风险评估和控制提供理论依据。     

Electrokinetic properties of soil minerals and soils modified with polyelectrolytes

The formation features of nanoadsorption polyelectrolyte (PE) layers with the formation of a mineral-organic matrix on the surface of clay minerals and soils (kaolinite, montmorillonite, quartz sand, gray forest soil, and chernozemic soil) have been elucidated by direct adsorption measurements. It has been found that the experimental values for the limit adsorption of polyacrylamide (PAM) and polyacrylic acid (PAA) on all the minerals are significantly higher than the calculated values for the formation of a monolayer. This indicates adsorption on the surface of not only separate macromolecules but also secondary PE structures as packets or fibrils determining the cluster-matrix structure of the modified surface. The study of the electro-surface properties (electrophoretic mobility, electrokinetic potential, pH, and electroconductivity) of mineral and soil particles adsorption-modified with PEs has confirmed the differences in the adsorption mechanisms (from physical sorption to chemisorption) with the formation of surface compounds depending on the different polar groups of PEs and the mineral type.     

Parameters of selective sorption of Co,Cu, Zn,and Cd by a soddy-podzolic soil and a chernozem

The adsorption and ion-exchange behavior of Co, Cu, Zn, and Cd were studied in two soils of different genesis. The sorption parameters and selectivity coefficients of the Me-Ca ion exchange were determined using the Langmuir and Freundlich adsorption isotherms and two models of ion-exchange sorption based on the mass action law (a polyfunctional ion exchanger and a mixture of two ideal exchangers) for describing the relationships between the dissolved and sorbed metal forms. It was shown that simple models provided information for better understanding of the behavior of metals in sorption and ion-exchange processes, but the conclusions about the sorption of different metals in a specific soil or a specific metal in different soils based on these models can be different.     

Adsorption of emerging sodium p-perfluorous nonenoxybenzene sulfonate (OBS) onto soils: Kinetics, isotherms and mechanisms

The widespread use of sodium p-perfluorous nonenoxybenzene sulfonate(OBS), a typical alternative to perfluorooctane sulfonate, has resulted in potential threats to the environment, but the adsorption behavior of OBS in soils has not yet been reported. In this study, the adsorption behaviors of OBS on five soils with different physicochemical properties were investigated. The rate of OBS adsorption was fast, and most of the OBS uptake was completed within 12 h. The good model fit of OBS adsorption to the pseudo-second-order and Elovich models indicated the occurrence of chemical adsorption. The adsorption isotherms of OBS on the soils were better described by the Freundlich model than by the Langmuir model, suggesting that the OBS adsorption sites on the soils were heterogeneous. This is possibly associated with various adsorption mechanisms including hydrophobic, π-π, hydrogen bonding, and electrostatic interactions,further confirmed by the good model fit to the D-R isotherm. Adsorption of OBS occurred on the soils, and the adsorption process was spontaneous and endothermic. In addition, the soils were more suitable for OBS adsorption at lower pH values due to the stronger electrostatic adsorption. The OBS adsorption on the soils decreased with the increase of soil depth from 0 to 30 cm. Moreover, the presence of organic matter and ammonia nitrogen in the soils was favorable for OBS adsorption, and these parameters decreased with increasing soil depth, making OBS adsorption less prominent in the deeper soil. This study indicates that OBS is easily enriched in surface soils, and that soil organic matter and ammonia nitrogen significantly affect OBS migration in soil.     

Response of the sorption behavior of Cu,Cd, and Zn to different soil management

This study investigated the effect of different farming practices over long time periods on the sorption‐desorption behavior of Cu, Cd, and Zn in soils. Various amendments in a long‐term field experiment over 44 y altered the chemical and physical properties of the soil. Adsorption isotherms obtained from batch sorption experiments with Cu, Cd, and Zn were well described by Freundlich equations for adsorption and desorption. The data showed that Cu was adsorbed in high amounts, followed by Zn and Cd. In most treatments, Cd ions were more weakly sorbed than Cu or Zn. Generally, adsorption coefficients K_F increased among the investigated farming practices in the following order: sewage sludge ≤ fallow < inorganic fertilizer without N ≈ green manure < peat < Ca(NO₃)₂ < animal manure ≤ grassland/extensive pasture. The impact of different soil management on the sorption properties of agricultural soils for trace metals was quantified. Results demonstrated that the soil pH was the main factor controlling the behavior of heavy metals in soil altered through management. Furthermore, the constants K_F and n of isotherms obtained from the experiments significantly correlated with the amount of solid and water‐soluble organic carbon (WSOC) in the soils. Higher soil pH and higher contents of soil organic carbon led to higher adsorption. Carboxyl and carbonyl groups as well as WSOC significantly influenced the sorption behavior of heavy metals in soils with similar mineral soil constituents.     

可变电荷土壤中特殊化学现象及其微观机制的研究进展

综述了近年来可变电荷土壤化学研究的进展,着重总结了可变电荷土壤中的盐吸附、铁铝氧化物对土壤自然酸化的抑制作用和离子强度对离子专性吸附的影响等特殊化学现象及其微观机制的研究进展。用颗粒表面扩散层重叠导致有效电荷数量减小的原理解释了盐吸附现象和铁铝氧化物对土壤自然酸化的抑制作用。阐明了可变电荷土壤和矿物中介质离子强度影响离子专性吸附的机制,用四层吸附模型解释了离子专性吸附随离子强度增大而增加的现象,并根据胶体zeta电位随离子强度改变而变化的趋势进一步证明了离子强度增大使胶体专性吸附面上静电电位的绝对值减小,是离子专性吸附随离子强度增大而增加的主要原因。带电颗粒表面双电层结构和双电层相互作用的深入研究,有助于阐明可变电荷土壤中一些特殊化学现象的微观机理,从而进一步完善土壤化学理论。     

Fluxes of Cu,Zn, Pb,Cd, Cr,and Ni in temperate forest ecosystems

The literature on the fluxes of six heavy metals in temperate forest ecosystems is reviewed. Special attention is given to wet and dry deposition and internal flux, to metal budgets for ecosystems and soils, to concentrations in aqueous compartments of the ecosystem and to speciation in soil solutions. Metal fluxes are discussed in relation to pollution load, soil type, tree species and land use. The mobility of Cu and Pb is strongly dependent on the solubility of organic matter. These metals are commonly accumulated in forest soils. Zinc, Cd and Ni are greatly influenced by soil acidity and are often lost in considerable amounts from acidified soils. Chromium is often at balance in forest ecosystems. Implications for metal solubility and budgets in forest soils are discussed in connection with an increase in soil acidification.     

Modelling the effects of ageing on Cd,Zn, Ni and Cu solubility in soils using an assemblage model

Ageing reactions can reduce trace metal solubility and can explain natural attenuation of contaminated soils. We modelled ageing reactions in soil with an assemblage model that considers slow reactions in Fe‐oxyhydroxides and reversible sorption on organic matter and clay minerals. Metal adsorption kinetics on Fe‐oxyhydroxides was obtained from data with synthetic oxyhydroxides. Metal solubility and isotopic exchangeability data were obtained from 28 soils amended with Ni, Zn, Cu and Cd metal salts and monitored for 850 days. The assemblage model was constructed in WHAM 6.0 and used soil properties and dissolved organic matter as input data. The model was first validated to predict dissolved metal concentrations, based on the concentration of isotopic exchangeable metals. The model overestimated metal solubility without parameter adjustment by mean factors of 4–7, and successful fits were obtained by increasing the specific surface area of Fe‐oxyhydroxides from measured values of synthetic systems to a value of 600 m² g^?1 recommended by other authors. The effect of ageing on the isotopic exchangeable metal fraction was subsequently modelled starting from the predicted fraction of metals present on Fe‐oxyhydroxides immediately after soil spiking. The observed isotopic exchangeable metal fractions of Ni, Zn and Cd agreed reasonably well with predicted values. The model predicts that ageing reactions are more pronounced at higher pH because metal sorption is increasingly directed to oxyhydroxide surfaces with increasing soil pH. Modelling fixation of Cu requires more information on fixation of that metal in organic matter.