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]     

Binding of Cd,Cu, Pb and Zn in soil organic matter with different vegetational background

The influence of vegetational background on binding of selected heavy metals in humus was examined. For this purpose samples of terrestrial humus from surface soil layers with different vegetational background, such as spruce, pine and oak forests, and different types of mires were studied with respect to differences in binding of Cd, Cu, Pb and Zn. The metal binding capacity was examined at different pH using batch extractions. The results indicated that vegetational background influences the binding of metals in organic soil significantly. Drying and storage of the soil samples appeared not to affect the metal binding capacity of the soils. Neither did heating of the samples at 100 °C or incubation at constant temperature and moisture affect the binding significantly, indicating that any fungi or soil microorganisms present did not appreciably affect the metal binding 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...     

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.     

土壤中镉、铅、铜、锌复合污染生态效应的研究

本文着重研究了土壤中镉、铅、铜、锌复合污染对春小麦、水稻产生的生态效应。研究结果表明，土壤中隔、铅、铜、锌复合污染浓度达到一定程度时，会抑制作物生长，降低产量，并在作物体内累积。随着复合污染浓度的增加，作物生长量下降，而累积量上升，皆呈直线相关。复合污染中各元素的生态效应与他们单因子时不同，这是由于各元素间存在着多种作用机制。     

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.     

Accumulation of Zn, Cd, Cu, and Pb in Chinese cabbage as influenced by climatic conditions under protected cultivation

Accumulation of heavy metals from agricultural soils contaminated by low levels heavy metals has important implications in the understanding of heavy metal contamination in the food chain. Through field experiments (1994-1996), the influence of thermal regime under different treatments on the accumulation of zinc, cadmium, copper, and lead in Chinese cabbage [Brassica pekinensis (Lour) Rupr. cv. Nagaoka 50] grown in a Calcareous Fluvisol (Xerofluvent) in Granada (southern Spain) was examined. Two floating row covers were used: T(1) (perforated polyethylene, 50 microm thick) and T(2) (17 g m(-2) polypropylene nonwoven fleece). An uncovered cultivation (T(0)) served as control. Zn, Cd, Cu, and Pb levels in the whole tops of experimental plants were analyzed. Treatments T(1) and T(2) gave rise to differences in environmental conditions with respect to T(0). The influence of environmental factors manipulated by floating row covers (particularly under T(1)) increased total heavy metal accumulation in the above ground plant biomass with respect to the open-air crop. The total contents of Zn, Cd, Cu, and Pb were 30, 50, 90, and 40% higher in T(1), respectively, than in T(0). This technique could be used in contaminated zones for different plant species because the thermal effect favors the process of phytoextraction and thus reduces the contamination.     

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。     

Retention of Cd, Cu, Pb and Zn by Wood Ash, Lime and Fume Dust

Heavy metals are of interest due to their deleterious impacts on both human and ecosystem health. This study investigated the effectiveness of wood ash in immobilizing the heavy metals Pb, Cd, Cu and Zn from aqueous solutions. The effects of initial metal concentrations, solution pH, ash dose and reaction time on metal sorption, as well as the metal sorption mechanisms were studied. To investigate the effect of initial metal concentrations, solutions containing Cd, Zn (25, 50, 75, 100 or 125 mg L^?1), Cu (25, 50, 75, 100, 125, 150 or 175 mg L^?1) or Pb (250, 500, 750, 1000, 1250, or 1500 mg L^?1) were reacted with 10 g L^?1 ash for two hours. For the effect of pH, solutions containing 100 mg L^?1 of Cd, Cu or Zn or 1500 mg L^?1 of Pb were reacted with 15 g L^?1 ash over a pH range of 4 to 7. The wood ash was effective in immobilizing the four metals with a sorption range of 41–100 %. The amounts of metals retained by the ash followed the order of Pb > Cu > Cd > Zn. As expected, absolute metal retention increased with increasing initial metal concentrations, solution pH and ash dose. Metal retention by the ash exhibited a two-phase step: an initial rapid uptake of the metal followed by a period of relatively slow removal of metal from solution. Metal retention by the ash could be described by the Langmuir and Freundlich isotherms, with the latter providing a better fit for the data. Dissolution of calcite /gypsum minerals and precipitation of metal carbonate/sulfate like minerals were probably responsible for metal immobilization by the ash in addition to adsorption.     

Modelling of Cd, Cu, Ni, Pb and Zn uptake, by winter wheat and forage maize, from a sewage disposal farm

Abstract. A predictive model of metal concentrations in crops was developed to optimize soil liming and sludge application strategies at a dedicated sewage sludge disposal site. Predictions of metal concentrations in plant tissue were derived from measured values of soil metal concentration, humus content and soil pH. The plant and soil data used to parameterize the model were collected on site using quadrat sampling of mature crop and underlying topsoil. The uptake model was used to map predicted metal concentrations in wheat grain and forage maize based upon a database of soil characteristics (metal content, % humus and pH) measured as part of a routine geochemical survey of the site. The effect of a management strategy to modify uptake of Cd by wheat by changing soil pH was investigated. The effect of soil dust adhering to maize plants at harvest was also simulated to investigate the importance of this pathway for Cd transfer to animal feed such as silage.
The model gave satisfactory predictions for uptake of Cd and Zn but less useful simulations for Pb, Cu and Ni. The results for Cd uptake showed a greater dependence on soil pH in the case of wheat in comparison to maize. It is suggested that, for the study site, liming to pH 7.0 will reduce Cd concentrations in wheat grain to within EC legal standards. However the Cd content of maize may still exceed these guidelines, with a relatively minor contribution from contamination with soil dust.     

土法炼锌区大气沉降Pb、Zn、Cd及其对土壤质量的影响

Dust emissions from smelters, as a major contributor to heavy metal contamination in soils, could severely influence soil quality. Downwind surface soils within 1.5 km of a zinc smelter, which was active for 10 years but ceased in 2000, in Magu Town, Guizhou Province, China were selected to examine Pb, Zn, and Cd concentrations and their fractionation along a distance gradient from a zinc smelter, and to study the possible effects of Pb, Zn, and Cd accumulation on soil microorganisms by comparing with a reference soil located at a downwind distance of 10 km from the zinc smelter. Soils within 1.5 km of the zinc smelter accumulated high levels of heavy metals Zn (508 mg kg-1), Pb (95.6 mg kg-1), and Cd (5.98 mg kg-1) with low ratios of Zn/Cd (59.1--115) and Pb/Cd (12.4--23.4). Composite pollution indices (CPIs) of surface soils (2.52--15.2) were 3 to 13 times higher than the reference soils. In metal accumulated soils, exchangeable plus carbonate-bound fractions accounted for more than 10% of the total Zn, Pb, and Cd. The saturation degree of metals (SDM) in soils within 1.5 km of the smelter (averaging 1.25) was six times higher than that of the reference soils (0.209). A smaller soil microbial biomass was found more frequently in metal accumulated soils (85.1--438 μg C g-1) than in reference soils (497 μg C g-1), and a negative correlation (P < 0.01) of soil microbial biomass carbon to organic carbon ratio (Cmic/Corg) with SDM was observed. Microbial consumption of carbon sources was more rapid in contaminated soils than in reference soils, and a shift in the substrate utilization pattern was apparent and was negatively correlated with SDM (R = -0.773, P < 0.01). Consequently, dust deposited Pb, Zn, and Cd in soils from zinc smelting were readily mobilized, and weredetrimental to soil quality mainly in respect of microbial biomass.     

废旧电子产品拆解区农田土壤Cu、Zn、Pb、Cd污染特征及空间分布规律

信息技术产业的发展,带给人们生活便利和享受的同时也产生了新的环境问题———电子垃圾。电子垃圾具有资源再生性和潜在环境污染性的双重特点。它不仅具有金、铜、铝、银等多种贵金属以及塑料的回收利用的价值,还含有铅、汞、镉、六价铬、多溴联苯和多溴联苯醚等大量有害物质[1]。如果回收利用处置不当或者任意丢弃,则将成为重要的环境污染源而危害生态和人体健康及生命安全[2]。农田重金属污染在环境中难以降解并具有持久性,可通过食物链在动植物体内积累,从而对生物和人体健康构成威胁。长江三角洲某典型区拥有中国最大废旧金属回收产业,并具有完整的工业产业链。链的起端是源于20世纪70年代末的废旧拆解业,终端为电机、轴承等     

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.     

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。     

Changes in organic carbon and nitrogen in soil with metal pollution by Cd,Cu, Pb and Zn: a meta‐analysis

Organic carbon (OC) and nitrogen (N) storage in soil plays an important role in global climate change and in maintaining food security. Pollution of soil with heavy metals has occurred in many parts of the world, but their effects on soil OC and N have not been well addressed. Relevant data were extracted from peer‐reviewed journal papers and analysed by a meta‐analysis to determine how long‐term heavy metal pollution affected soil OC and N status. Plant biomass decreased significantly because heavy metals in soil decreased soil OC and N concentrations by 5.0 and 17.9%, respectively, but increased the C/N ratio by 5.1%. The largest reductions in soil OC and N concentrations were in soil more strongly polluted by metals. The changes in soil OC and N with metal pollution varied with climatic conditions. More substantial decreases in OC and N concentrations were likely to occur in polluted soil with large background contents of OC and low pH. Overall, heavy metals were linked to greater reductions in soil OC and N concentrations in natural ecosystems than in agro‐ecosystems. These results provided a quantitative evaluation of the effects of heavy metal pollution on the decrease in soil C and N concentrations and, therefore, on global climate change. Further consideration should be given to changes in the cycling of C and N in soil polluted with metals in natural and agro‐ecosystems.     

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 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.     

Toxicity of heavy metals (Zn,Cu, Cd,Pb) to vascular plants

The literature on heavy metal toxicity to vascular plants is reviewed. Special attention is given to forest plant species, especially trees, and effects at low metal concentrations, including growth, physiological, biochemical and cytological responses. Interactions between the metals in toxicity are considered and the role of mycorrhizal infection as well. Of the metals reviewed, Zn is the least toxic. Generally plant growth is affected at 1000 μg Zn L^?1 or more in a nutrient solution, though 100 to 200 µg L^?1 may give cytological disorders. At concentrations of 100 to 200 μg L^?1, Cu and Cd disturb metabolic processes and growth, whereas the phytotoxicity of Pb generally is lower. Although a great variation between plant species, critical leaf tissue concentrations affecting growth in most species being 200 to 300 μg Zn g^?1 dry weight, 15 to 20 μg Cu g^?1 and 8–12 μg Cd g^?1. With our present knowledge it is difficult to propose a limit for toxic concentrations of Zn, Cu, Cd and Pb in soils. Besides time of exposure, the degree of toxicity is influenced by biological availability of the metals and interactions with other metals in the soil, nutritional status, age and mycorrhizal infection of the plant.     

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.