Solubility control of Cu, Zn, Cd and Pb in contaminated soils

We developed a semiempirical equation from metal complextion theory which relates the metal activity of soil solutions to the soil's pH, organic matter content (OM) and total metal content (MT). The equation has the general form: where pM is the negative logarithm (to base 10) of the metal activity, and a, b and c are constants. The equation successfully predicted free Cu²⁺ activity in soils with a wide range of properties, including soils previously treated with sewage sludge. The significant correlation of pCu to these measured soil properties in long-contaminated soils suggests that copper activity is controlled by adsorption on organic matter under steady state conditions. An attempt was made from separate published data to correlate total soluble Cu, Zn, Cd and Pb in soils to soil pH, organic matter content and total metal content. For Cu, the total Cu content of the soil was most highly correlated with total soluble Cu. Similarly, total soluble Zn and Cd were correlated with total metal content, but were more strongly related to soil pH than was soluble Cu. Smaller metal solubility in response to higher soil pH was most marked for Zn and Cd, metals that tend not to complex strongly with soluble organics. The organic matter content was often, but not always, a statistically significant variable in predicting metal solubility from soil properties. The solubility of Pb was less satisfactorily predicted from measured soil properties than solubility of the other metals. It seems that for Cu at least, solid organic matter limits free metal activity, whilst dissolved organic matter promotes metal solubility, in soils well-aged with respect to the metal pollutant. Although total metal content alone is not generally a good predictor of metal solubility or activity, it assumes great importance when comparing metal solubility in soils having similar pH and organic matter content.     

The flux of Cd,Cu, Pb and Zn in mining polluted soils

The monitoring of heavy metal deposition onto soils surrounding old Pb-Zn mines in two locations in the UK has shown that relatively large amounts of Cd, Pb, Zn and, in one case, Cu are entering the soil annually. Small particles of ore minerals in windblown mine tailings were found to be contributing up to 1.46 g m^?2 yr^?1 of Pb, 1.41 g m^?2 yr^?1 of Zn and 0.027 g m^?2 yr^?1 of Cd. However, when these inputs from bulk deposition are compared with the concentrations of the same metals within the soil profiles it is apparent that relatively little long-term accumulation is occurring. Metals are being lost from the soil profiles, probably through leaching. A calculated relative retention parameter gave values that ranged from 0.01 to 0.17 for Cd, 0.11 to 0.19 for Zn, 0.32 to 0.63 for Cu and over 1 for Pb. These relative retention values were found to follow the order of electronegativity of the elements concerned: Pb>Cu>Zn>Cd. Distribution coefficient (Kd) values quantifying the adsorptive capacity of the mine soils for Cd and Pb showed marked differences for the two metals (12 to 69 cm³ g^?1 for Cd and 14 to 126 cm³ g^?1 for Pb) and may, in part, account for the two to one hundred-fold variation in the relative retention parameter for the different metals within these soils.     

Relation Between pH and Desorption of Cu,Cr, Zn,and Pb from Industrially Polluted Soils

Water, Air, & Soil Pollution - Desorption of Cu, Cr, Pb, and Zn from industrially polluted soils as a result of acidification is in focus. The eight soils of the investigation vary greatly in...     

Mobilization of Cu and Pb from multi-metal contaminated soils by dissolved humic substances extracted from leonardite and factors affecting the process

Journal of Soils and Sediments - The aim of the research was to determine the potential of dissolved humic substances extracted from leonardite to mobilize Cu and Pb from multi-metal contaminated...     

The effect of pH on the retention of Cu,Pb, Cd,and Zn by clay-fulvic acid mixtures

The addition of fulvic acid to clay suspensions (kaolinite, illite or montmorrillonite) resulted in increased uptake of Cu, Pb, Cd, and Zn ions over the pH range 3 to 6, due to the limited solubility of one of the metal-fulvate species formed. At higher pH values, residual metal ion was retained in solution, instead of precipitating as hydroxy species. The amount of total metal ion found in solution at equilibrium was determined by the quantity and type of clay added; the amount of organic acid present; and to a lesser extent, pH. The behavior of the clay-fulvic acid systems differed from that observed using other organic materials such as gelatine, tannic acid or a humic acid.     

低分子有机酸对土壤中重金属的解吸及影响因素

研究了柠檬酸、草酸、酒石酸和苹果酸对矿区土壤中重金属Pb、Cd、Cu和Zn的解吸行为,并探讨了介质pH值对其解吸土中重金属的影响。振荡解吸试验结果表明四种低分子有机酸对供试污染土壤中Pb、Cd、Cu和Zn都具有一定的解吸能力。由于土壤中重金属有效态含量较低,各重金属的解吸率都不高。在对Pb和Cd的解吸中,各低分子有机酸能力大小顺序为柠檬酸>酒石酸≈苹果酸>草酸;Cu的解吸顺序为柠檬酸>草酸>酒石酸≈苹果酸;Zn的解吸顺序为酒石酸>柠檬酸≈苹果酸>草酸。低分子有机酸随浓度的增加,其解吸能力提高。低分子有机酸对重金属的解吸量随pH值的降低而增加。     

Chemical speciation and bioavailability of Cd,Cu, Pb and Zn in Western Balkan soils

Abstract

Three thermal power plants in Serbia, Croatia and Bosnia of the Western Balkan region were expected to be metal polluting sources, and this study was performed to investigate the bioavailability and chemical speciation of trace metals in soils and soil water extracts, respectively. Surface (0–15 cm) soil samples along with maize and grass samples were collected at a gradient from the pollution source. The chemical speciation of metals was conducted using the Windereme Humic Aqueous Model (WHAM)/Model VI for water, whereas the Diffusion Gradient in Thin Films (DGT) technique was used to estimate plant availability. The chemical speciation indicated that more than 99% of all four metals in soil water extracts were complexed to fulvic acid. This is connected to relatively high soil pH (> 6.5) and high contents of soil organic matter in these soils. The accumulation of trace metals by DGT was not correlated to plant uptake. This is connected to the very low partitioning of free ions in solution, but also to the low variation in metal solubility and metal concentration in plant tissue between sites. In spite of active thermal power plants located in the areas, hardly any differences in concentration of soil metals between sites were seen and the partition of metals in soil waters was insignificant. The latter indicates that these soils have a large metal-retaining capacity. The only significant soil chemical variable affecting the variation in metal solubility was the soil pH. In a time with large infrastructure and industrial expansion in these areas, this investigation indicates the importance of protecting these high-quality soils from industrial use and degradation. High industrial activity has so far had insignificant effect on soil quality with respect to bioavailability of trace metals in these soils.     

The source of Pb,Cu, and Zn in fogwater

The variation in the concentrations of Zn, Pb, and Cu in water and acid extracts of airborne particulates and in fogwater collected in the rural northern San Joaquin Valley of California during the fall and winter of 1983–1984 was determined by anodic stripping voltammetry. There is a good correlation between water extracts of airborne particulates and fogwater for the concentrations of Cu and Pb and the concentration ratio (Cu/Pb), suggesting that the concentrations of these metals in fogwater is controlled by the concentration of extractable metal in the particulates on which the fog droplet forms. The major ion composition of the fogwater samples was measured by ion chromatography and compared with literature values for urban fogwater.     

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.     

Speciation of Zn,Cu, and Pb in the soil depending on soil texture and fertilization with sewage sludge compost

Background, aim, and scope  Heavy metal (HM) mobility in soil depends on the HM species in it. Therefore, knowledge of the HM speciation in soil allows the prediction of HM impact on the environment. HM speciation in soil depends on the metal chemical origin, soil texture, and other factors such as the origin and level of soil contamination. Recently, the problem of organic waste utilization is of great importance as the amount of this recyclable material is continually increasing. One of the possible ways of recycling is the use of processed organic wastes for agricultural needs. In this research, aerobically composted sewage sludge was used, the utilization of which is of essential importance. But one of the most serious restrictions is HM transfer from such material to the soil. Therefore, a prediction of HM mobility in soil and its migration in the environment is an important issue when using sewage sludge compost (SSC) in agriculture. Zn, Cu, and Pb speciation was performed according to the modified methodology of Tessier et al. (Anal Chem 51:844–851, 1979) in two different (sandy and clay) soils with background HM amounts and in soil samples amended with aerobically digested SSC to find out the predominant species of the investigated HM and to predict their potential availability. Materials and methods  The modified method of sequential extraction initially proposed by Tessier et al. (Anal Chem 51:844–851, 1979) is designed for HM speciation into five species where HM mobility decreases in the order: F1—exchangeable HM (extracted with 1 M MgCl₂ at an initial pH of 7 and room temperature), F2—carbonate-bound HM (extracted with 1 M CH₃COONa buffered to pH 5 at room temperature), F3—Fe/Mn oxide-bound HM (extracted with 0.04 M NH₂OH·HCl at an initial pH of 2 at 96°C), F4—organic matter-complexed or sulfide-bound HM (extracted with 0.02 M HNO₃ and 30% (v/v) H₂O₂ at a ratio of 1:1 and an initial pH of 2 at 85°C), and F5—the residual HM (digested with HNO₃, HF, and HCl mixture). After digestion, HM amounts in solution were determined by atomic absorption spectrometry (AAS ‘Hitachi’). Mixtures of uncontaminated soils of different textures (clay and sandy) with SSC in ratios 20:1, 10:1, and 5:1 were used to simulate the land application with SSC. During a period of 7 weeks, changes in Zn, Cu, and Pb content within species were investigated and compared weekly in soil–SSC mixtures with their speciation in pure soil and in the SSC. Results  Results in the SSC showed that more HM were found as mobile species compared to the soils, and in sandy soil, more were found in the mobile species than in clay soil. But the HM speciation strongly depended on the metal chemical origin. According to the potential availability, HM ranked in the following order: Zn>Pb>Cu. Zinc generally occurred in the mobile species (F1 and F3), especially in sandy soils amended with SSC, and changes of the Zn speciation were insignificant at the end of the experiment. Pb transfer to insoluble compounds (F5) was evident in the SSC–soil mixtures. This confirms that Pb is extremely immobile in the soil. However, the observed increase of Pb amounts in the mobile species (F1 and F2) during the course of experiment shows a critical trend of Pb mobilization under anthropogenic influence. Copper in the soil–SSC mixtures had a trend to form compounds of low mobility, such as organic complexes and sulfides (F4) and nonsoluble compounds (residual fraction F5). Initially, the amounts of mobile Cu species (F1 and F2) increased in the soils amended with SSC, probably due to the influence of SSC of anthropogenic origin with lower pH and high organic matter content, but Cu mobility decreased nearly to the initial level again after 3–4 weeks. Hence, the soil has a great specific adsorption capacity to immobilize Cu of anthropogenic origin. Discussion  Zn mobility and environmental impact was greater than that seen for Cu and Pb, while mobility of both Cu and Pb was similar, but variable depending on soil texture and contamination level. The effect on the shift of HM mobility and potential availability was greater in sandy SSC-amended soils than in clay soils and increased with an increasing amount of SSC. Conclusions  Usage of SSC for land fertilization should be strictly regulated, especially regarding Pb amounts. Recommendations and perspectives  The influence of SSC on Cu and Zn mobility and potential availability was more significant only in the case of sandy soil with a higher SSC ratio. Nevertheless, this waste product of anthropogenic origin increased Pb mobility in all cases in spite of only moderate Pb mobility in SSC itself. Therefore, aerobic processing of sewage sludge must be strictly regulated, especially regarding Pb amounts, and SSC ratios must be in control regarding HM amounts when using it for on-land application.     

Partition of Cd,Cu, Pb and Zn among mineral particles during their sorption in soils

Journal of Soils and Sediments - Heterogeneity of soil mineral particles may lead to the misinterpretation of bulk sorption data on their role in metal sorption, which may be resolved through the...     

Adsorption density,mobility and limit values of Cd,Zn, Cu and Pb in acid forest soils

To investigate Cd, Zn, Cu and Pb adsorption in acidified forest soils, six soil samples of the aluminium buffer range were selected and analyzed for their physical and chemical properties. Determination of the specific surface area using ethylene glycol monoethyl ether (EGME) adsorption yielded a characteristic value of the solid phases, which can parameterize the major properties of the various soil constituents with sufficient accuracy.

Traditional adsorption isotherms reveal the relation between the amount of a heavy metal adsorbed and the heavy metal concentration in the soil solution only for the soil under study and can therefore not be applied to other soils. To meet the aim of modelling heavy metal adsorption and mobility also for soils differing greatly in their properties, it was attempted to establish a generalizing adsorption isotherm for soils of entirely different composition of the solid phase. The generalizing adsorption density isotherms introduced in the following provide a useful mathematical model for the quantity/intensity relation of heavy metals in soils that differ greatly in their specific surface area and their composition.

It is also shown that limit values which take into account the major quantities influencing heavy metal adsorption and mobility in acid soils can be established from the regression equation between the adsorption density of a heavy metal (ions/m² specific surface area) and its concentration in the soil solution. In particular in view of the groundwater contamination to be expected if acid rain and, as a result, soil acidification continues, these limit values seem to provide considerably more information than the European limit values, given in mg heavy metal /kg soil, which are presently valid for any soil condition and property.     

不同肥料长期施用下稻田镉、铅、铜、锌元素总量及有效态的变化

以中国科学院桃源农业生态实验站的长期田间定位试验为基础,研究了16年长期定量施肥对土壤Cd、Pb、Cu和Zn积累及其有效性的影响。结果表明:单施化肥可使土壤Cd含量降低、Pb含量增加,对Cu和Zn的积累无显著影响,水稻收获时的移出效应可能是Cd含量降低的主要原因;与单施化肥相比,有机物料循环可提高土壤Cd和Pb的积累,但对Cu和Zn的积累无显著影响。试验期内单施化肥对土壤Cd、Pb、Cu和Zn的有效性无显著影响;有机物料循环可显著提高Cd和Zn的有效性,这与有机物料循环引起的土壤有机质含量增加和pH降低有关。     

用突变点检测方法预测木生境下污染土壤中的可提性镉、铅和锌

Accumulation of heavy metals in soils poses a potential risk to plant production, which is related to availability of the metals in soil. The phytoavailability of metals is usually evaluated using extracting solutions such as salts, acids or chelates. The purpose of this study was to identify the most significant soil parameters that can be used to predict the concentrations of acetic and citric acid-extractable cadmium (Cd), lead (Pb) and zinc (Zn) in contaminated woody habitat topsoils. Multiple linear regression models were established using two analysis strategies and three sets of variables based on a dataset of 260 soil samples. The performance of these models was evaluated using statistical parameters. Cation exchange capacity, CaCO3, organic matter, assimilated P, free Al oxide, sand and the total metal concentrations appeared to be the main soil parameters governing the solubility of Cd, Pb and Zn in acetic and citric acid solutions. The results strongly suggest that the metal solubility in extracting solutions is extractable concentration-dependent since models were overall improved by incorporating a change point. This change point detection method was a powerful tool for predicting extractable Cd, Pb and Zn. Suitable predictions of extractable Cd, Pb and Zn concentrations were obtained, with correlation coefficient (adjusted r) ranging from 0.80 to 0.99, given the high complexity of the woody habitat soils studied. Therefore, the predictive models can constitute a decision-making support tool for managing phytoremediation of contaminated soils, making recommendations to control the potential bioavailability of metals. The relationships between acetic and/or citric acid-extractable concentrations and the concentrations of metals into the aboveground parts of plants need to be predicted, in order to make their temporal monitoring easier.     

The effect of model soil contamination with Cr,Cu, Ni,and Pb on the biological properties of soils in the dry steppe and semidesert regions of southern Russia

Model soil contamination with Cr, Cu, Ni, and Pb in the dry steppes and semideserts of southern Russia has worsened the biological soil properties. With respect to the degree of deterioration of the biological properties, the soils can be arranged in the following sequence: dark chestnut soils > chestnut soils > light chestnut soils > brown semidesert soils > sandy brown semidesert soils. The sequence of metal oxides according to the adverse effect on the biological soil properties is as follows: CrO₃ > CuO ≥ PbO ≥ NiO.     

长春市城区土壤中Pb、Cu、Zn、Cd及Cr化学形态特征

为弄清长春市城市土壤中Pb、Cu、Zn、Cr及Cd的化学形态分布特征,系统采集了26件城市表层(0~20 cm)土壤样品,采用连续提取法对重金属各化学形态含量进行了测定。结果表明:Pb、Zn、Cu及Cr主要以残渣态存在,其次是铁锰氧化物结合态、腐殖酸结合态和强有机结合态占有次要地位,离子交换态和水溶态所占比例均较低;Cd则主要以碳酸盐结合态存在,同时,水溶态和离子交换态所占比例较高。残渣态Pb和Zn在城区表层土壤中所占比例较近郊土壤中略有下降,但幅度不大,除Cu外,其余各元素易迁移、高生物有效性的水溶态在城区表层土壤中所占比例略有上升。Pearson相关分析结果表明,各元素残渣态与全量均呈极显著正相关,其它各活性态与全量间的相关程度与重金属种类有关。土壤pH值和Fe、Mn含量对重金属的化学形态的影响也与重金属种类有关,而且,同一重金属的不同存在形态受土壤pH值和Fe、Mn含量的影响程度也不同。     

Mixed chelators of EDTA,GLDA, and citric acid as washing agent effectively remove Cd,Zn, Pb,and Cu from soils

Purpose

Soil washing with chelators is a viable treatment alternative for remediating multi-contaminated soils. The aim of this study was to investigate the removal efficiencies of Cd, Zn, Pb, and Cu in alkaline and acid multi-metal-contaminated soils by washing with the mixed chelators (MC).

Materials and methods

The batch experiments were carried out to evaluate the removal efficiencies of heavy metals in contaminated soils by the MC with different molar ratios of EDTA, GLDA, and citric acid, and evaluated the washing factors, including contact time, pH, MC concentration, and single and multiple washings at the same MC dose, on the removal efficiencies.

Results and discussion

Results showed that the removal efficiencies for Cd, Zn, Pb, and Cu by the MC (the molar ratio of EDTA, GLDA, and citric acid was 1:1:3) were as much as those of the only EDTA washing from both soil at the same application dose of total chelators; moreover, the application dose of EDTA decreased by 80%. For the alkaline-contaminated soil, the removal efficiencies of Cd, Zn, Pb, and Cu decreased with the increasing of the solution pH, which was opposite to acid-contaminated soil. This was attributed to that the metal-ligand complex could be obviously re-adsorbed on the soil surface sites, particularly in low pH values. The removal efficiencies of Cd, Zn, Pb, and Cu depended on MC concentration. A higher MC concentration led to a more effective removal of Cd, Zn, Pb, and Cu in alkaline-contaminated soil; however, their changes were slightly increased in acid-contaminated soil. At the same dose of MC, single washing with higher MC concentration might be favorable to remove heavy metals, moreover, with much less wastewater generation.

Conclusions

The MC (the molar ratio of EDTA, GLDA, and citric acid was 1:1:3) may be a useful, environmentally friendly, and cost-effective chelators to remediate heavily multi-metal-contaminated soil.

     

The determination of Zn,Cd, Pb and Cu in soil extracts by anodic stripping voltammetry

This work describes simultaneous determination of Zn, Cd, Pb and Cu in soil extract by d. c. anodic stripping voltammetry at the hanging mercury drop electrode. Soil samples were taken from six different areas characterized by different degrees of heavy metal pollution. The metals were extracted from the soil samples using 0.5 M HCI. The base electrolyte for ASV was 0.2 M acetic buffer at pH 5.0. These results are compared with those obtained by using atomic absorption spectrophotometric method. The accuracy and precision of the presented method are satisfactory (relative standard deviation is 3.5 to 11%). Iron, Al and Ti contained in the extract in the concentration of 1120, 5400, and 480 µg g^?1, respectively, do not present measurement difficulties.[/p]     

Predicting the solubility of Cd,Cu, Pb and Zn in uncontaminated Croatian soils under different land uses by applying established regression models

Soil pH, soil organic matter (SOM), dissolved organic carbon (DOC) and total trace metal concentration (M_(tot)) control the solubility of metals in the soil. Several regression models have included these soil chemical variables for the prediction of metal solubility and free metal ion (FMI) concentrations in contaminated soils. We hypothesize that models developed on contaminated soils (after optimization of the coefficients) can be used on samples from uncontaminated sites. Soil samples were collected from unpolluted agricultural and forest soils located in Eastern Croatia and extracted with water to determine the concentrations of Cd, Cu, Pb and Zn. We used these data to test the applicability of three regression models on existing conditions under different land uses. The same predictors issued in the three models and the same regression coefficients were utilized in the present study. The results showed a good correlation between the observed and predicted values of metal solubility. However, the models overestimate the total solution concentration (M_(sol)) and the concentrations of free metal ions (FMI) in solution, and therefore the same regression coefficients were optimized to fit our own observations. This was found to be very successful. The results showed that pH and DOC played a very important role in controlling metal solubility, while SOM and CEC were somewhat less significant. The impact of total soil concentration of metals (M_(tot)) was rather minor. However, we feel that to carry out good predictions of M_(sol) and FMI, the M_(tot) is needed in such regression models.