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.     

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.     

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.     

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。     

Microbial biomass and activity in urban soils contaminated with Zn and Pb

Summary The effects of heavy metals on microbial biomass and activity were investigated in 30 urban soils, contaminated mainly with Zn and Pb to different extents, in terms of the physicochemical and biological characteristics of the soils. Evaluated by simple and multiple regression analyses, the microbial biomass was not affected significantly by easily soluble Zn + Pb (extractable with 0.1 NHCI). The biomass was accounted for as a function of cation exchange capacity (CEC), total organic C and the numbers of fungal colonies present (R ² = 0.692). Carbon dioxide evolution from soils, which reflected microbial activity, was studied on soils incubated with microbial-promoting substrates (glucose and ammonium sulfate) or without. Carbon dioxide evolution was negatively related to Zn+Pb, and this inhibitory effect of the metals was greater in the soils incubated with substrates. Carbon dioxide evolution in soils with substrates was closely related to Zn+Pb, bacterial numbers and the numbers of fungal colonies (R ² = 0.718). Carbon dioxide evolution in soils without substrates was accounted for as a function of Zn + Pb, biomass and the C/N ratio (R ² = 0.511). Using these relationships, the effects of heavy metals on soil microorganisms are discussed in terms of metabolically activated and dormant populations.     

Changes in tolerance of soil microbial communities in Zn and Cd contaminated soils

Trace metals are present in the soil matrix in different forms, and this obscures the relationship between the amounts of metals, their biological availability and effects. Chemical methods have been devised to directly measure the biological available pools of trace metals, but such methods need to be validated against measured exposure of organisms in the soil. We studied acquired Zn- and Cd tolerance of the soil microbial community as a reporter of its exposure, and compared it with chemical determination of Zn and Cd in 10 soils differing in pH, organic matter content, texture, vegetation-/cultivation history and metal contamination. The tolerance was measured as LC₅₀ (i.e. the metal concentration which inhibits 50% of the activity) in suspensions of extracted soil bacteria, by measuring the incorporation rate of [³H] thymidine at different metal concentrations. Chemical determination of Cd and Zn in soils included total concentrations by aqua regia extractions (AR), and total concentrations in extracted pore water (PW). In addition was the ‘effective concentration’ (C_E) determined using the Diffusion Gradients in Thins films method (DGT). The LC₅₀ values correlated better with PW (r²=0.90 for Cd and r²=0.97 for Zn) and C_E (0.90 for Cd and 0.98 for Zn) compared to the correlation with AR (0.72 for Cd and 0.82 for Zn). After excluding a single extremely contaminated soil from the analysis, the correlation of LC₅₀ with AR was much poorer (r²=0.03 (ns) for Cd and r²=0.48 for Zn), whereas correlations remained significant for both PW (0.90 for Cd and 0.87 for Zn) and C_E (0.54 for Cd and 0.84 for Zn). In conclusion, PW fraction of Cd and Zn appear to be the best predictor of trace metal exposure of the soil microorganisms.     

Accumulation of As,Pb, Zn,Cd and Cu and arbuscular mycorrhizal status in populations of Cynodon dactylon grown on metal-contaminated soils

Metal(loid) accumulation and arbuscular mycorrhizal (AM) status of the dominant plant species, Cynodon dactylon, growing at four multi-metal(loid)s-contaminated sites and an uncontaminated site of China were investigated. Up to 94.7 As mg kg^?1, 417 Pb mg kg^?1, 498 Zn mg kg^?1, 5.8 Cd mg kg^?1 and 27.7 Cu mg kg^?1 in shoots of C. dactylon were recorded. The plant was colonized consistently by AM fungi (33.0–65.5%) at both uncontaminated site and metal-contaminated sites. Based on morphological characteristics, fourteen species of AM fungi were identified in the rhizosphere of C. dactylon, with one belonging to the genus of Acaulospora and the other thirteen belonging to the genus of Glomus. Glomus etunicatum was the most common species associated with C. dactylon growing at metal-contaminated sites. Spore abundance in the rhizosphere of C. dactylon growing at the metal-contaminated soils (22–82 spores per 25 g soil) was significantly lower than that of the uncontaminated soils (371 spores per 25 g soil). However, AM fungal species diversity in the metal-contaminated soils was significantly higher than that in the uncontaminated soils. This is the first report of AM status in the rhizosphere of C. dactylon, the dominant plant survival in metal-contaminated soils. The investigation also suggests that phytorestoration of metal-contaminated sites might be facilitated using the appropriate plant with the aid of tolerant AM fungi.     

Hg, Cu, Pb, Cd, and Zn Accumulation in Macrophytes Growing in Tropical Wetlands

The concentrations of Hg, Cu, Pb, Cd, and Zn accumulated by regional macrophytes were investigated in three tropical wetlands in Colombia. The studied wetlands presented different degrees of metal contamination. Cu and Zn presented the highest concentrations in sediment. Metal accumulation by plants differed among species, sites, and tissues. Metals accumulated in macrophytes were mostly accumulated in root tissues, suggesting an exclusion strategy for metal tolerance. An exception was Hg, which was accumulated mainly in leaves. The ranges of mean metal concentrations were 0.035?C0.953 mg g^?1 Hg, 6.5?C250.3 mg g^?1 Cu, 0.059?C0.245 mg g^?1 Pb, 0.004?C0.066 mg g^?1 Cd, and 31.8?363.1 mg g^?1 Zn in roots and 0.033?C0.888 mg g^?1 Hg, 2.2?C70.7 mg g^?1 Cu, 0.005?C0.086 mg g^?1 Pb, 0.001?C0.03 mg g^?1 Cd, and 12.6?C140.4 mg g^?1 Zn in leaves. The scarce correlations registered between metal concentration in sediment and plant tissues indicate that metal concentrations in plants depend on several factors rather than on sediment concentration only. However, when Cu and Zn sediment concentrations increased, these metal concentrations in tissues also increased in Eichhornia crassipes, Ludwigia helminthorriza, and Polygonum punctatum. These species could be proposed as Cu and Zn phytoremediators. Even though macrophytes are important metal accumulators in wetlands, sediment is the main metal compartment due to the fact that its total mass is greater than the corresponding plant biomass in a given area.     

洞庭湖区典型蔬菜土壤镉、铜、锌、铅含量状况及评价

采用单项污染指数和综合污染指数法对湖南洞庭湖区典型蔬菜土壤Cd,Cu,Zn,Pb含量状况进行了评价。结果表明,与湖南省潮土土壤背景值相比,土壤Cd,Cu和Zn含量明显富集,Pb含量总体不高。与国家土壤质量二级标准(GB15618-1995)相比,洞庭湖区蔬菜土壤以Cd污染为主,其次是Zn和Cu。Pb含量没有超标,其中湘阴县、沅江市、资阳区和赫山区蔬菜土壤环境质量为轻度污染,华容县处于警戒水平,需要修复治理或者改变土地利用方式。君山区和南县蔬菜土壤为清洁水平,适宜发展无公害蔬菜。污染风险高的区域土壤Cd,Cu和Zn之间存在极显著或显著正相关关系,但相关性弱。     

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.

     

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.     

Distribution of As, Cd, Pb, and Zn in redox features of mine-waste impacted wetland soils

Purpose

Wetland soils of the Coeur d??Alene (CdA) River Basin of northern Idaho, USA are contaminated with toxic elements released during mining activities. In this paper, we report results from a multi-scale investigation of total As, Cd, Pb, and Zn distributions along a transect of these contaminated soils.

Materials and methods

Four sites along an 80-m transect were established at the Black Rock Slough wetland in CdA River Basin. The elevation difference between the upslope and lowland site was 1.1?m. Soils were sampled from three depths, down to 45?cm. Redoximorphic features were isolated from the soils and categorized into five types of cemented particles, and Fe-enriched and depleted soil masses. Soils and isolated soil separates were analyzed for total elemental concentration.

Results and discussion

Within soil profiles, contaminants are enriched in surface horizons as compared to the original depositional profiles. Enrichment was more dramatic in the upland sites than the lowland sites. Fe-enriched masses that ranged in size from a few millimeters to several centimeters were also enriched in As, Pb, and Zn. At the smallest scale investigated, five different soil aggregate types ranging in size from 1 to 2?mm in diameter had distinct contaminant associations: Fe-cemented aggregates were elevated in As and Zn; Mn-cemented aggregates had more than five times as much Pb as the bulk soil; root channels were elevated in As; and charcoal particles were elevated in all contaminants, particularly Pb and Cd.

Conclusions

Results show that in wetland soils pedogenic processes differentially distribute contaminants amongst the redoximorphic features. The distribution is affected by landscape position and water table influence. At the pedon scale, there is an enrichment of As, Cd, Pb, and Zn in surface horizons, suggesting that upward flux of contaminants is occurring. This contaminant redistribution should be considered in design of management and remediation strategies.     

Distribution of Zn, Cd, Pb and Cu Metals in Groundwater of the Guadiamar River Basin

Traditionally, the Guadiamar River Basin (Seville, SouthwestSpain) has received pollution from two different sources. Inits upper course, from a pyrite exploitation and, in itslower reaches, from untreated urban and industrial wastes aswell as wastes from intensive agricultural activity. In 1998,the accidental release in the river of about 6 million m³ of acid water and sludge from mine tailings contributedto worsen the pollution of an already contaminated area. Themain polluting agents of the spill were heavy metals. Itaffected a large number of wells either directly or as a consequence of infiltration from polluted soils. Assessment of the pollution by total metal determination does not revealthe true environmental impact of the spill and speciation studies showing the distribution of the main pollutants are required. There is a direct association between the physicochemical speciation of an element and its bioavailability, toxicity and mobility. This article describesa distribution study of the metals Zn, Cd, Pb and Cu by speciation analysis of groundwater in six wells of the GuadiamarRiver Basin; the samples were taken several weeks after the spill. The speciation analysis resulted in the definition ofthree species categories: a) labile metal (H⁺ exchangeable),b) metal strongly associated to dissolved organic matter and c) metal associated with suspended material. Analysis was carried out by anodic stripping voltammetry (ASV). Metal speciation ingroundwater of the Guadiamar River Basin allows a differentiationbetween: on the one hand, metals from the mining spill, andon the other hand a less recent pollution from accumulatedinfiltration of either mining or agricultural origin, the last one due to an abuse of phytosanitary products.     

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.     

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]