Non-enhanced phytoextraction of cadmium,zinc, and lead by high-yielding crops

Heavy metal soil contamination from mining and smelting has been reported in several regions around the world, and phytoextraction, using plants to accumulate risk elements in aboveground harvestable organs, is a useful method of substantially reducing this contamination. In our 3-year experiment, we tested the hypothesis that phytoextraction can be successful in local soil conditions without external fertilizer input. The phytoextraction efficiency of 15 high-yielding crop species was assessed in a field experiment performed at the Litavka River alluvium in the P?íbram region of Czechia. This area is heavily polluted by Cd, Zn, and Pb from smelter installations which also polluted the river water and flood sediments. Heavy metal concentrations were analyzed in the herbaceous plants’ aboveground and belowground biomass and in woody plants’ leaves and branches. The highest Cd and Zn mean concentrations in the aboveground biomass were recorded in Salix x fragilis L. (10.14 and 343 mg kg^?1 in twigs and 16.74 and 1188 mg kg^?1 in leaves, respectively). The heavy metal content in woody plants was significantly higher in leaves than in twigs. In addition, Malva verticillata L. had the highest Cd, Pb, and Zn concentrations in herbaceous species (6.26, 12.44, and 207 mg kg^?1, respectively). The calculated heavy metal removal capacities in this study proved high phytoextraction efficiency in woody species; especially for Salix × fragilis L. In other tested plants, Sorghum bicolor L., Helianthus tuberosus L., Miscanthus sinensis Andersson, and Phalaris arundinacea L. species are also recommended for phytoextraction.     

Reactions of compost-derived humic substances with lead, copper, cadmium, and zinc

Thermodynamic stability constants of the formation of complexes from the reactions of humic substances with various metals are usually used as parameters to judge the reactivities of both humic substances and metals. However, in calculating the thermodynamic stability constants, complicated processes for the acquisition of activities of components in reactions are absolutely inevitable. In this study, we investigated the average conditional concentration quotients of the complexes formed from the reaction of metals with humic substances and the relations of these quotients to thermodynamic stability constants. The characterized humic substances including HA (MW>1,000), FA (MW>1,000), and FA (MW<1,000) extracted from a swine compost were prepared to react with Pb, Cu, Cd, and Zn at 25 degrees C and at pH 4.00 and 6.50. Reactions of HA (MW>1,000), FA (MW>1,000), and FA (MW<1,000) with the four metals were carried out at 1:0.1, 1:0.5, 1:1, 1:5, and 1:10 ligand:metal stoichiometry. The concentrations of the free ions of Pb, Cu, Cd, and Zn in the reaction systems of metal-HA suspensions and metal-FA solutions were measured by anodic stripping voltammetry (ASV). The sequence of the average conditional concentration quotients of the formed complexes from the reaction of humic substances with metals was FA(MW<1,000)>FA(MW>1,000)>HA(MW>1,000), showing the relative reactivities of the fractions of swine compost-derived humic substances. The sequence of reacting metals with humic substances was Pb>Cu>Cd>Zn, which is in good agreement with the sequence reported by judging the thermodynamic stability constants. The average conditional concentration quotients of the formed complexes from the reaction of humic substances with metals were thus useful parameters that can be directly related to thermodynamic stability constants and other parameters.     

Multi-generation toxicity of zinc, cadmium, copper and lead to the potworm Enchytraeus albidus

In standard chronic terrestrial toxicity tests with invertebrates, adult organisms are exposed to the contaminants and the number of offspring is quantified. These procedures do not allow the assessment of possible effects on all life stages of the organism, which may lead to an underestimation of the toxicity of the test substance. To evaluate the importance of this issue, the potworm Enchytraeus albidus was exposed to zinc, cadmium, copper and lead for two subsequent generations. Juvenile production was assessed for both generations. Considering the variability of metal toxicity data reported in the literature, it is concluded that the two generation assay did not markedly increase the sensitivity of the standard E. albidus test for the tested metals. Therefore, toxicity data obtained with the proposed test guideline with E. albidus are protective for all life stages.     

Computational spectroscopic study of copper, cadmium, lead and zinc interactions in the environment

Molecular modelling has been used to investigate the interactions of various heavy metals, in order to understand and possibly to control the nature and behaviour of metals, especially in the aquatic environment. The interactions of copper, cadmium, lead and zinc with organic acids were studied using density functional theory (DFT) calculations. Carboxylic acid was used as a model molecule. The structure of each metal carboxylate was optimized and the vibrational spectrum calculated. The results indicate that there is a shift in the calculated v_S(C=O) of metal carboxylates compared with that of carboxylic acid. It was also found that hexaaqua structures of both cadmium and zinc are stable whereas those of copper and lead are not. Furthermore, dipole moment calculations indicate that cadmium carboxylate dihydrate is more representative of cadmium interactions in the aquatic environment. Moreover, hexaaquo cadmium could further interact with surrounding molecules in the aquatic environment.     

柴河铅锌尾矿中重金属铅、锌、镉的迁移特征

采用柱状淋滤实验模拟降水,研究柴河铅锌尾矿中重金属铅(Pb)、锌(Zn)、镉(Cd)的迁移特征。结果表明:无覆土层的尾矿柱(柱1)与含50cm覆土层的尾矿柱(柱2)淋滤液pH均在30d分别出现最低值5.86和6.67;在180d分别出现最高值7.85和7.89。柱1淋滤液中Pb、Zn、Cd最高质量浓度分别为0.053 0、5.980 0、0.009 4mg/L,均超过《地表水环境质量标准》(GB 3838—2002)的Ⅳ类标准规定的限值。柱2淋滤液中Pb、Cd最高浓度符合GB 3838—2002的Ⅳ类标准,Zn最高浓度超过GB 3838—2002的Ⅳ类标准规定的限值。随着淋滤时间延长,柱2淋滤液中Pb、Zn、Cd浓度均低于柱1,说明表层覆土措施可减少尾矿中重金属淋失。经过柱状淋滤实验,柱2中40cm处Pb、Zn、Cd全量相比原覆土分别增加17.47%、23.37%、26.09%,表明下部尾矿层中的重金属可向上部覆土层迁移。     

Evaluation of surrogate measures of cadmium, lead, and zinc bioavailability to Eisenia fetida

We evaluated weak-electrolyte (0.1 M Ca(NO3)2) soil extractions and ion-exchange membranes coated with a metal chelator as measures of Cd, Pb, and Zn bioavailability in spiked artificial soil by comparing their metal availability estimates to acute lethal toxicity in the earthworm Eisenia fetida. Ca(NO3)2 extractions were precisely related to toxicity in all toxicity tests, and enabled the development of time-independent LC50S (incipient lethal-levels, ILLs) calculated using exposure levels based on extraction data. ILLs with 95% CIs for the Cd, Pb, and Zn toxicity tests were 9.8 (9.4-10.3), 1.16 (1.11-1.22), and 6.33 (6.18-6.49) Ca(NO3)2-extractable mmol metal/kg soil, respectively. Mixture toxicity of Cd, Pb, and Zn, assessed using the toxic unit (TU) approach, was 1.35 TU, suggesting additivity. Chelating ion-exchange membrane uptake was variable, and not well related to toxicity. Weak-electrolyte extractions show promise as precise, inexpensive surrogate measures of Cd, Pb, and Zn bioavailability in soil.     

Earthworms as biological monitors of cadmium, copper, lead and zinc in metalliferous soils

Earthworms (Lumbricus rebellus and Dendrodrilus rubidus) were sampled from one uncontaminated and fifteen metal-contaminated sites. Significant positive correlations were found between the earthworm and 'total' (conc. nitric acid-extractable) soil Cd, Cu, Pb and Zn concentrations (data log1) transformed). The relationships were linear, and the accumulation patterns for both species were similar when a single metal was considered, even though there were species difference in mean metal concentrations. Generally, the earthworm Cd concentration exceeded that of the soil; by contrast, the worm Pb concentration was lower than the soil Pb concentration in all but one (acidic, low soil Ca) site. Our observations suggest that Cu and Zn accumulation may be physiologically regulated by both species. Total-soil Cd explained 82-86% of the variability (V2) in earthworm Cd concentration; 52-58% of worm Pb and worm Zn concentrations were explained by the total-soil concentrations of the respective metals. Total-soil Cu explained only 11-32% of the worm Cu concentration. The effect of soil pH, total Ca concentration, cation-exchange capacity (CEC) and organic carbon on metal accumulation by L. rubellus and D. rubidus was investigated by multiple regression analysis. Soil pH (coupled with CEC) and soil Ca had a major influence on Pb accumulation (V2 of worm Pb increased to 77-83%), and there was some evidence that Cd accumulation may be suppressed in extremely organic soils. The edaphic factors investigated had no effect on Cu or Zn accumulation by earthworms. In the context of biomonitoring, it is proposed that earthworms have a potential in a dual role: (1) as 'quantitative' monitors of total-soil metal concentrations (as shown for Cd); and (2) as estimators of 'ecologically significant' soil metal, integrating the effects of edaphic factors (as shown for Pb).     

Comparison of the adsorption of lead,cadmium, copper,zinc and barium to freshwater surface coatings

Measurements were made regarding the adsorption of lead, cadmium, copper, zinc and barium to freshwater surface coatings (biofilms and associated minerals), which were collected in Nanhu Lake in Jilin Province, PR China, in order to investigate the variability of adsorption capacities of these heavy metals mentioned in the above surface coatings. The adsorption of lead and other heavy metals to the biofilms was observed to decrease in the following order: copper, lead, zinc, cadmium, and barium. Generally, the values of Gamma(max) (the maximum adsorption, micromol/m(2)) increased with the standard electrode potential of metal elements used and were recorded as 166.7, 40.0, 29.4, 10.8, and 1.8 for copper, lead, zinc, cadmium and barium, respectively. The values of 1/Gamma(max) increased linearly with the decrease in values of the standard electrode potential of metal elements with a significant correlation (n=5, p=0.01) and increased linearly with the increase in values of covalent radius of metal elements with a significant correlation (n=5, p=0.05). This indicates that standard electrode potential and covalent radius were two of the principal characteristics of metals employed, causing the variation of lead and other heavy metal adsorption to the surface coatings.     

Loading estimates of lead, copper, cadmium, and zinc in urban runoff from specific sources

Urban stormwater runoff is being recognized as a substantial source of pollutants to receiving waters. A number of investigators have found significant levels of metals in runoff from urban areas, especially in highway runoff. As an initiatory study, this work estimates lead, copper, cadmium, and zinc loadings from various sources in a developed area utilizing information available in the literature, in conjunction with controlled experimental and sampling investigations. Specific sources examined include building siding and roofs; automobile brakes, tires, and oil leakage; and wet and dry atmospheric deposition. Important sources identified are building siding for all four metals, vehicle brake emissions for copper and tire wear for zinc. Atmospheric deposition is an important source for cadmium, copper, and lead. Loadings and source distributions depend on building and automobile density assumptions and the type of materials present in the area examined. Identified important sources are targeted for future comprehensive mechanistic studies. Improved information on the metal release and distributions from the specific sources, along with detailed characterization of watershed areas will allow refinements in the predictions.     

Distribution of copper, lead, cadmium and zinc concentrations in soils around Kabwe town in Zambia

The extent of pollution of the environment as a result of mining activities in Kabwe, the provincial capital of Central province in Zambia has not yet been evaluated. Mining of lead and zinc were the core activities of Kabwe mine while cadmium and silver were produced as by-products. The smelting processes produced a significant amount of copper. The spatial distribution of four heavy metals in soils in the northern, eastern, southern and western directions of the mine was analyzed using atomic absorption spectrometry (AAS). Samples were collected up to 20 km in each direction from the mine. Results were consistent with the wind flow patterns in the town. Results ranged between 0.08 and 28 mg kg(-1) (Cd); 0.20 and 0.61 mg kg(-1) (Cu); 0.10 and 758 mg kg(-1) (Pb) and 0.40 and 234 mg kg(-1) (Zn) suggesting high precipitation of metals from the core mining activities. These concentrations were for only the fractions of metals extractable by 0.5M nitric acid and that could be available for plant uptake in the environment. The distribution of metals indicated a decrease of metal concentrations with distance from the mine, which confirmed that precipitation due to mining activities was the main cause of soil contamination.     

Response of kidney bean to concentration and chemical form of cadmium, zinc, and lead in polluted soils

Seven soils which had been polluted with heavy metals from a zinc smelter were sequentially extracted so that Cd, Zn, and Pb could be partitioned into five operationally defined geochemical fractions: exchangeable, carbonate, Fe-Mn oxide, organic, and residual fractions. Kidney beans were planted in the soils to examine the effect of concentration and chemical form of the metals in soil on the growth and metal uptake of the plants. The growth of kidney bean was restricted in heavy metal polluted soils compared with controls. Metal concentration and metal uptake by plants were correlated. The highest relationship was found between amount of metal uptake and the metal concentration in exchangeable + carbonate forms. The uptake of metals was according to their solubility sequence, i.e. Cd > Zn > Pb. The uptake rate of exchangeable + carbonate forms was the same for the three elements.     

Effects of chronic exposure to lead,copper, zinc,and cadmium on biomarkers of the European eel,Anguilla anguilla

Exposure to specific metallic compounds can cause severe deleterious modifications in organisms. Fishes are particularly prone to toxic effects from exposure to metallic compounds via their environment. Species that inhabit estuaries or freshwater environments can be chronically affected by persistent exposure to a large number of metallic compounds, particularly those released by industrial activities. In this study, we exposed yellow eels (European eel, Anguilla anguilla) for 28 days to environmentally relevant concentrations of four specific metals; lead (300, 600, and 1,200 μg/l), copper (40, 120, and 360 μg/l), zinc (30, 60, and 120 μg/l) and cadmium (50, 150, and 450 μg/l). The selected endpoints to assess the toxicological effects were neurotransmission (cholinesterasic activity in nervous tissue), antioxidant defense, and phase II metabolism (glutathione-S-transferase [GST] activity, in both gills and liver tissues), and peroxidative damage. The results showed an overall lack of effects on acetylcholinesterase for all tested metals. Lead, copper, and cadmium exposure caused a significant, dose-dependent, increase in GST activity in gill tissue. However, liver GST only significantly increased following zinc exposure. No statistically significant effects were observed for the thiobarbituric acid reactive substances assay, indicating the absence of peroxidative damage. These findings suggest that, despite the occurrence of an oxidative-based response after exposure to lead, copper, and cadmium, this had no consequence in terms of peroxidative membrane damage; furthermore, cholinergic neurotoxicity caused by lead, copper, and cadmium did not occur. The implications of these results are further discussed.     

Transfer of cadmium, lead, and zinc from industrially contaminated soil to crop plants: a field study

The documeneed adverse health effects of soil Cd and Pb have led to public concern over soil contamination with metals. A 4-year field experiment was conducted to study the transfer of Cd, Pb, and Zn from soil contaminated by smelter flue-dust to crop plants grown in a rotation. The soil was amended with Pb?Zn smelter flue-dust (2-66.8 kg per 10 m(2) plot) to simulate the long-term effect that the smelting of non-ferrous metal ore has on arable soils. The treated soil became strongly contaminated with metals (Cd 3.2-106 mg/kg, Pb 146-3452 mg/kg, Zn 465-11 375 mg/kg). Concentrations of Cd, Pb, and Zn in barley grain, barley straw meadow bluegrass, red clover, and potatoes were generally low. The highest metal concentrations were found in potato tubers (intact), meadow bluegrass, and barley straw. The observed reduction in crop yield was probably the result of possible nutrient imbalances rather than of metal (Zn, Cu) phytotoxicities. Zn and Cd uptake by the plants can be described by the saturation (plateau) model (y = ax(b), b < 1). The relationship between Pb in the soil and plants was linear with an extremely low slope (0.0001-0.0003). No excessive dietary intake of Cd is expected when Cd concentrations in barley grain and potato tubers grown on the contaminated soil are not higher than 0.6 and 1.0 mg/kg, respectively. Based on the risk analysis and taking into account the saturation model of the soil-plant metal relationship, it was concluded that, under the conditions of this experiment (neutral soil pH), soil with Cd concentrations of up to 30 mg/kg is still safe for production of these crop plants.     

Effects of EDTA on solubility of cadmium, zinc, and lead and their uptake by rainbow pink and vetiver grass

Rainbow pink (Dianthus chinensis), a potential phytoextraction plant, can accumulate high concentrations of Cd from contaminated soils. Vetiver grass (Vetiver zizanioides) has strong and long root tissues and is a potential phytostabilization plant since it can tolerate and grow well in soils contaminated with multiple heavy metals. Soil was moderately artificially contaminated by cadmium (20 mg/kg), zinc (500 mg/kg), and lead (1000 mg/kg) in pot experiments. Three concentrations of Na2-EDTA solution (0, 5, and 10 mmol/kg soil) were added to the contaminated soils to study the influence of EDTA solution on phytoextraction by rainbow pink or phytostabilization by vetiver grass. The results showed that the concentrations of Cd, Zn, and Pb in a soil solution of rainbow pink significantly increased following the addition of EDTA (p < 0.05). The concentrations of Cd and Pb in the shoots of rainbow pink also significantly increased after EDTA solution was applied (p < 0.05), but the increase for Zn was insignificant. EDTA treatment significantly increased the total uptake of Pb in the shoot, over that obtained with the control treatment (p < 0.001), but it did not significantly increase the total uptake of Cd and Zn. The concentrations of Zn and Pb in the shoots of rainbow pink are significantly correlated with those in the soil solution, but no relationship exists with concentrations in vetiver grass. The toxicity of highly contaminating metals did not affect the growth of vetiver grass, which was found to grow very well in this study. Results of this study indicate that rainbow pink can be considered to be a potential phytoextraction plant for removing Cd or Zn from metal-contaminated soils, and that vetiver grass can be regarded as a potential phytostabilization plant that can be grown in a site contaminated with multiple heavy metals.     

Accumulation of lead, zinc, copper and cadmium by 12 wetland plant species thriving in metal-contaminated sites in China

The concentrations of lead, zinc, copper and cadmium accumulated by 12 emergent-rooted wetland plant species including different populations of Leersia hexandra, Juncus effusus and Equisetum ramosisti were investigated in field conditions of China. The results showed that metal accumulation by wetland plants differed among species, populations and tissues. Populations grown in substrata with elevated metals contained significantly higher metals in plants. Metals accumulated by wetland plants were mostly distributed in root tissues, suggesting that an exclusion strategy for metal tolerance widely exists in them. That some species/populations could accumulate relatively high metal concentrations (far above the toxic concentration to plants) in their shoots indicates that internal detoxification metal tolerance mechanism(s) are also included. The factors affecting metal accumulation by wetland plants include metal concentrations, pH, and nutrient status in substrata. Mostly concentrations of Pb and Cu in both aboveground and underground tissues of the plants were significantly positively related to their total and/or DTPA-extractable fractions in substrata while negatively to soil N and P, respectively. The potential use of these wetland plants in phytoremediation is also discussed.     

Seasonal variations in the concentrations of cadmium, copper, lead and zinc in leaves of the horse chesnut (Aesculus hippocastanum L.)

The concentrations of cadmium, copper, lead and zinc have been measured in the leaves of a deciduous tree the horse chestnut (Aesculus hippocastanum L.) over the period of their lifetime (7 months). The average concentrations for the total sample based on ash weight are: (microg g(-1)) cadmium, 0.197; copper, 129; lead, 294; and zinc, 299. The temporal trends in the concentrations of the metals can be related to their dominant source. Copper and zinc concentrations are highest in the new leaves and decrease with time, suggesting the main source of the elements are uptake from the soil. The decrease occurs partly because of dilution by leaf material as it increases over the growing period. In the case of zinc, however, aerial deposits appear to be also a significant source. Lead concentrations, on the other hand, show an increase with time, which can be related to increasing deposits from aerosol lead arising from the combustion of petrol lead. The increase is enough to offset the dilution effect. For cadmium there is no significant trend, but the tendency is a decrease with time. It is not possible, however, to distinguish between soil uptake and aerial deposit as both are small compared with increase in leaf material.     

Effects of short-term pH fluctuations on cadmium, nickel, lead, and zinc availability to ryegrass in a sewage sludge-amended field

In this field experiment, sewage sludge was applied at 0, 5, 10, and 50tha(-1), and the availability of Cd, Ni, Pb, and Zn was assessed both by ryegrass uptake and by DTPA extractions. The aim was to investigate the role of important soil parameters, particularly pH, on heavy metal availability. It was found that metal uptake and extractability increased significantly in the 50tha(-1) treatment. In the 16th week of the experiment there was a significant, although temporary, increase in DTPA-extractable Cd, Ni, and Zn concentrations. Metal concentrations in ryegrass were also significantly elevated in week 20 compared to the subsequent cuttings. These fluctuations in both DTPA and ryegrass uptake occurred only at 50tha(-1) and were probably induced by a sudden pH decrease measured in the same treatment in week 16. This suggests that soils which have received high applications of sewage sludge may be prone to fluctuations in metal availability.     

Food chain transfer of cadmium and lead to cattle in a lead–zinc smelter in Guizhou, China

Cadmium (Cd) and Lead (Pb) are environmental pollutants. Environmental samples and bovine tissues were collected from the areas around a lead–zinc smelter in Guizhou, China for Cd, Pb, zinc (Zn) and copper (Cu) analysis. Cd in soil (10 mg/kg) and feed (6.6 mg/kg) from the polluted areas was 10 times higher than the Chinese Standards, resulting in higher Cd in bovine kidney (38 mg/kg) and liver (2.5 mg/kg). Pb in feed (132 mg/kg) from the polluted area was much higher than unpolluted areas, causing higher Pb levels in bovine tissues. Environmental Zn was elevated, but bovine tissue Zn was normal. Cu in bovine liver decreased with increased Cd and Pb. Metals in drinking water and in bovine muscle were within the Standard range. Thus, in the areas of this lead–zinc smelter, the environment has been contaminated with Cd and Pb, which has been transferred to cattle through the food chain.