Relative toxicity of cadmium,lead, and zinc on barley

Abstract

The relative toxicity of cadmium (Cd), lead (Pb), and zinc (Zn) on the growth performance of barley (Hordeum vulgare L.) was measured. Lead and Zn resulted in an increase in dry matter production at the lower additions. All the Cd and the higher Pb and Zn additions resulted in significant decreases in growth over the controls, the roots showing a greater decrease in dry matter accumulation than did shoots. Roots accumulated higher amounts of Cd, Pb, and Zn in direct proportion to that soil‐applied. A significant inverse relationship between relative yield and tissue element concentration was observed. Toxicity occurred in the following order: Cd > Pb > Zn. Threshold concentration, critical tissue concentrations, and loading rates to produce a 10% yield reduction were also calculated. Our study indicates the possibility of estimating barley yield based on plant tissue Cd, Pb, and Zn concentrations.     

Speciation of cadmium,copper, lead,and zinc in contaminated soils

Abstract

To investigate the activity of free cadmium (Cd²⁺), copper (Cu²⁺), lead (Pb²⁺), and zinc (Zn²⁺) ions and analyze their dependence on pH and other soil properties, ten contaminated soils were sampled and analyzed for total contents of Cd, Cu, Pb, and Zn (Cd_T, Cu_T, Pb_T, and Zn_T, respectively), 0.43 MHNO₃‐extractable Cd, Cu, Pb, and Zn (Cd_N, Cu_N, Pb_N, and Zn_N, respectively), pH, dissolved organic matter (DOC), cation exchange capacity (CEC), ammonium oxalate extractable aluminum (Al) and iron (Fe), and dissolved calcium [Ca²⁺]. The activity of free Pb²⁺, Cd²⁺, Cu²⁺, and Zn²⁺ ions in soil solutions was determined using Donnan equilibrium/graphite furnace atomic absorption (DE/GFAA). The solubility of Cd in soils varied from 0.16 to 0.94 μg L^‐1, Cu from 3.43 to 7.42 μg L^‐1, Pb from 1.23 to 5.8 μg L^‐1, and Zn from 24.5 to 34.3 μg L^‐. In saturation soil extracts, the activity of free Cd²⁺ ions constituted 42 to 82% of the dissolved fraction, for Cu²⁺the range was 0.1 to 7.8%, for Pb²⁺ 0.1 to 5.1% and for Zn²⁺2 to 72%. The principal species of Cd, Cu, Pb, and Zn in the soil solution is free metal ions and hydrolyzed ions. Soil pH displayed a pronounced effect on the activity of free Cd²⁺, Cu^2t, Pb²⁺, and Zn²⁺ ions.     

Leaching of zinc,lead and cadmium in columns of calcareous soils

Leaching of zinc, lead and cadmium was studied in columns packed with soil differing in pH, clay, organic matter and calcium carbonate contents. Distribution of 1 N HCI extractable heavy metals in different layers of the columns as a function of the amount of water leached was the criteria for measuring leachability of the three metals. Leachates contained only traces of the metals. Movement of surface applied metals could be observed only upto 30mm depth. Cadmium, which was observed to be the most mobile element, was leached to a depth of 30–40mm in a pH 7.5, light textured soil with 0.9 % calcium carbonate. Presence of superphosphate at the soil surface reduced the extent of leaching to an appreciable extent.     

接种微生物对土壤中Cd、Pb、Zn生物有效性的影响

针对提高植物修复土壤重金属污染的效果,以印度芥菜作为重金属富集植物,通过盆栽试验研究了巨大芽胞杆菌和胶质芽胞杆菌的混合微生物制剂(A处理)和黑曲霉发酵液(B处理)对植物修复Cd、Pb、Zn污染土壤的作用效果。结果表明:巨大芽胞杆菌和胶质芽胞杆菌的混合微生物制剂,不仅可以促进富集植物的生长,使其印度芥菜的生物量提高24.73%,并且可促进土壤Cd、Pb、Zn的活化,使土壤Cd、Pb、Zn有效态含量分别提高15.02%、7.65%和2.23%,增强富集植物对土壤的Cd、Pb、Zn富集吸收,使印度芥菜对土壤Cd、Pb、Zn的提取量分别提高52%、121%和23%,显著提高其植物修复效果。从对植物生理生化指标的影响来看,A处理对植株的伤害程度要低于B处理,它是一种有助于植物修复Cd、Pb、Zn污染土壤的微生物制剂,在植物修复领域有较高的利用价值。然而,黑曲霉混合发酵液不适于促进植物修复应用。     

Effect of excess lead,cadmium, copper,and zinc on water relations in sunflower

The effect of excess concentrations of lead (Pb), cadmium (Cd), copper (Cu), and zinc (Zn) on water relations in young sunflower (Helianthus annuus L.) plants was studied in water culture under greenhouse conditions. The accumulation of the heavy metals was more intensive in the root than in the shoot. The rates of heavy metal accumulation in root were arranged in the following decreasing order: Cu, Cd, Zn, and Pb. Their transport into the above‐ground parts followed the order: Zn, Cu, Pb, and Cd. Transpiration and relative water content were significantly decreased by excess concentrations of the heavy metals. The number of stomata per unit leaf area was increased while the size of the stomata was decreased. The concentration of free proline significantly increased in the leaves of intact plants as well as in leaf discs incubated in the presence of heavy metals. The concentration of soluble proteins decreased as well, particularly when plants were exposed to high concentrations of the heavy metals. It was concluded that excess concentrations of the heavy metals significantly affected plant water status, causing water deficit and subsequent changes in the plants. The most intensive effect on the plants was exerted by Cd, less intensive by Cu and Zn and the least intensive by Pb.     

Suitability of four woody plant species for the phytostabilization of a zinc smelting slag site after 5 years of assisted revegetation

Purpose

Zinc smelting activity generates large volumes of highly toxic waste slags and poses a potential extreme environmental risk for the surrounding areas. The establishment of a vegetation cap for the phytostabilization of abandoned mine tailing heaps using plants is usually considered a beneficial approach. This study aimed to evaluate the suitability of phytostabilization of zinc smelting slag using four woody plants combined with organic amendments, to investigate the distribution of heavy metals in the slag–plant system, and to better understand how the direct revegetation of a zinc smelting slag site can influence the mobility and geochemical fraction of heavy metals.

Materials and methods

Slags were collected from the areas planted with vegetation (Arundo donax, Broussonetia papyrifera, Robinia pseudoacacia, and Cryptomeria fortunei) and a bare area in a zinc smelting waste slag site using an indigenous method. Physicochemical properties were determined with the usual procedures. The geochemical fraction and bioavailability of heavy metals was determined using the three-step modified European Community Bureau of Reference (BCR) sequential extraction and diethylene triamine pentaacetic acid (DTPA) sequential extraction schemes. Heavy metal concentrations (Cu, Pb, Zn, and Cd) in the slag and plant samples were also measured.

Results and discussion

Vegetation planted directly in the zinc smelting waste slag significantly enhanced the nutrient accumulation and reduced the bioavailability of heavy metals (Cu, Zn, and Cd) with the exception of A. donax for Zn and Cd. The presence of four woody plants increased the bioavailability of Pb. Sequential extraction revealed that revegetation reduced the acid-soluble extractable fraction and increased the fraction of heavy metals associated with the Fe/Mn oxy(hydr)oxides or organic matter. This is attributed to the establishment of plant-enhanced weathering of minerals in the waste slag that resulted in the formation of an amount of dissolved metals, and the amount of dissolved metals was partly redistributed into the soluble extractable fraction of the zinc smelting waste slag. The final concentration of metals (Cu, Pb, Zn, and Cd) in the soluble extractable fraction is dependent on the dynamics of metals induced by root activity in the rhizosphere. Much lower levels of heavy metals with lower translocation factors accumulated in the four woody plants than in the associated slags.

Conclusions

We conclude that the studied four woody plants showed a beneficial vegetation cover and phytostabilization potential within 5 years of revegetation. These woody plants have the potential for high heavy metal tolerance and low heavy metal accumulation. Therefore, these woody plants could be used for revegetation and phytostabilization of zinc smelting slag sites under field conditions.

     

镉、铅、锌对红壤微生物生物量的影响

Nitrogen(N)losses from ammonium bicarbonate or urea applied to wheat and then followed immediately by irrigation were investigated.Ammonia volatilization was determined by a micrometeorological method (ammonia sampler),total N loss was estimated by the ^15N mass balance method ,and denitrification loss was measured by the diference method(calculated from the difference between the total N loss and ammonia loss) and a direct method (measuring the emission of (N2 N2O)-^15N).Total ammonia losses from ammonium bicarbonate and urea in 33 days were 8.7% and 0.9% of the applied nitrogen ,respectively.The corresponding total N losses were 21.6% and 29.5%,Apparent denitrification losses(by the difference method) were rather high,being 12.9% from ammonium bicarbonate and 28.6% from urea .However,no emission of (N2 N2O)-^15N was detected using the direct method.     

Flame absorption spectroscopic determination of cadmium, copper, iron, lead, and zinc in mussels

A rapid method is proposed for determination of Cd, Cu, Fe, Pb, and Zn in mussel samples. The elements are extracted with concentrated nitric acid in borosilicate glass tubes at 90 degrees C for 1 h, and determined by flame atomic absorption spectroscopy. Detection limits for a 300 mg sample corresponded to 0.3 microgram Cd/g, 0.7 microgram Cu/g, 33 microgram Fe/g, 0.7 microgram Pb/g, and 6 micrograms Zn/g. The coefficient of variation for 20 independent analyses was 7% for Cd, 7% for Cu, 6% for Fe, 14% for Pb, and 8% for Zn. Recoveries were 107 +/- 3% for Cd, 90 +/- 3% for Cu, 94 +/- 1% for Fe, 90 +/- 5% for Pb, and 96 +/- 3% for Zn. The accuracy of the method was determined by analyzing NBS Oyster Tissues.     

Distribution of different fractions of cadmium,zinc, lead,and copper in unpolluted and polluted soils

McLaren and Crawford's method for fractionating soil Cu was modified, and used to fractionate soil Cd, Zn, Pb, and Cu in 38 soil samples from 11 soil profiles from industrially polluted and nearby unpolluted areas. Pollutant metals, especially Cd and Zn, were more soluble than the native soil metals. On average, approximately 45% of Cd was present in the CaCl₂ soluble (CA) fraction, whereas corresponding values for the other metals were below 10%. The percentages of each metal in the CA fraction followed the order Cd > Zn > Pb > Cu. The same order was observed for the acetic acid soluble (AAC) fraction. Approximately 30% of total Pb and Cu were present in the pyrophosphate soluble (PYR) fraction, and only 10% of total Cd and Zn. Approximately 20% of total Zn or Pb and 10% of Cd or Cu were present in the free oxide (OX) fraction. Only 20% of Cd and between 40–50% of the other 3 metals were present in the residual (RES) fraction. The results show that Cd is more labile than the other 3 metals.     

添加物对镉、锌、铅污染土壤上小白菜的生长和养分吸收的影响

A pot experiment was carried out to study the effects of two amendments, lime and calcium magnesium phosphate, on the growth and Cd,Pd,Zn,Cu,Mn,Fe,N,P and K uptake of pakchoi (Brassica chinensis) in a Cd,Pb and Zn polluted acid soil in the southern part of China. The growth of pakchoi was apparently improved by lime and calcium magnesium phosphate application, the uptake of Cd,Pb,Cu and Zn by pakchoi was significantly depressed and the symptom caused by heavy metals pollution was eliminated. Meanwhile, the absorption of N,K and Mn was also inhibited by these amendments. Soil pH was the main factor controlling the uptake of the heavy metals by pakchoi. This suggests that lime and calcium magnesium phosphate could be used as effective amendments for eliminating the toxicity of heavy metals to the vegetable and inhibiting their absorption by the crop.     

Extraction of copper,lead, zinc or cadmium ions sorbed on calcium carbonate

The amount of sorbed metal ion released from CaC0₃ by 16 different extractants was found to vary with the chemical nature of the solution and the metal ion involved. In general, acid solutions dissolved a high proportion of both substrate and Cu, Ph, Cd coatings; complexing agents dissolved the same coatings but left most of the calcite; and competing cations (e.g. NH₄ ⁺, Ca²⁺) displaced primarily chemisorbed Cd and Cu. In Zn studies, little metal ion was retrieved by any extractant due to the limited solubility of the coatings formed at pH < 7.7. The diverse behavior observed in the sorption studies has been interpreted in terms of solubility and absorption equilibria. The pH of the CaC0₃ suspensions was high enough to precipitate all added Pb as hydroxy species, and excess Cu tended to precipitate at pH > 6.4 if one increased the soluble carbonate level (e.g. by adding acid). Unlike Cd and Cu, Zn was not chemisorbed; it formed sparingly soluble compounds such as ZnC0₃.2Zn(OH)₂, with excess coming out as Zn(OH)₂ at pH > 7.7. The significance of the results in respect to the mobility of metal ions in calcareous soils, and the evaluation of available levels, has been considered.     

Sorption of lead,copper, zinc,and cadmium by soils: effect of nitriloacetic acid on metal retention

Abstract

Laboratory experiments were carried out to evaluate lead (Pb), copper (Cu), zinc (Zn), and cadmium (Cd) sorption‐desorption by three soils of contrasting characteristics. Talamanca (silt loam, montmorillonite, Calcic Haploxeralfs), Mazowe (clay, kaolinite, Rhodic Kandiustalf), and Realejos (sandy silt loam, allophane, Typic Hapludands). A second objective was to study the effect of nitriloacetic acid (NTA) on the sorption process. The Talamanca soil, which had a native pH of 6.4 and presented the highest effective cation exchange capacity (ECEC), sorbed more of each of the metal tested than did the other two soils. When the other two soils were compared metal sorption was also related to pH and ECEC. The very low sorption capacity showed by Realejos may be attributed to the low net surface negative charge density of this soil, arising from its allophanic nature. A common feature of the three soils was the relative strong sorption of both Pb and Cu relative to Cd and Zn with Pb showing the highest sorption levels. The selectivity sequences of metals retention were Pb>Cu>Zn>Cd for Talamanca soil, Pb>Cu>Zn≈Cd for Mazowe, and Pb>Cu>Cd>Zn for Realejos. Metal desorption values were low. The order of metal desorption (Cd≈Zn>Cu>Pb) was the same for the three soils studied. Quantitative differences observed in the extractability of the sorbed metals between the soils (Realejos>Mazowe>Talamanca) indicated that soil properties which enhanced metal sorption contributed at the same time to slow down the backward reaction. The addition of NTA to the soil suspension significantly depressed metal sorption by the three soils investigated. Compared with the free ligand system Pb, Cu, Zn, and Cd sorption in the presence of NTA decreased roughly 50%.     

Effect of pH on chemical forms and plant availability of cadmium,zinc, and lead in polluted soils

The effect of pH on chemical forms and plant availability of heavy metals in three polluted soils was investigated. The soils were adjusted to pH values of 7.0, 6.0, and 4.5, then sequentially extracted so that Cd, Zn, and Pb could be partitioned into five operationally defined chemical fractions: exchangeable, carbonate, Fe-Mn oxide, organic, and residual. Kidney beans were grown in the soils to investigate plant availability of the metals in relation to changes of their levels in chemical forms resulting from alteration of soil pH. Alteration of pH resulted in changes of chemical forms of the metals in the soils, and at lower pH the changes were more significant. When soil pH values were decreased from 7.0 to 4.55, levels of Cd, Zn, and Pb in exchangeable form increased, decreased in carbonates and decreased slightly in Fe-Mn oxide forms. Their levels in organic and residual forms were unchanged. Although concentration of metals in plants increased with reduction in soil pH values, dry matter yields were also restricted, so that the amount of metal uptake were almost similar. The uptake rate of the metals in the exchangeable + carbonate forms was the same for the three elements in all the cases.     

The accumulation of lead,zinc, cadmium and fluoride in the wood mouse (Apodemus sylvaticus L.)

The concentrations of Pb, Zn, Cd, and fluoride were determined in liver, kidney and femur tissues 30 days after wood mice were provided with water containing soluble salts of these elements in their drinking water. There were eight treatment groups: Pb, Zn, Cd, and fluoride only; Zn and Cd (ZnCd); fluoride and Pb (FPb); fluoride, Pb, Zn, and Cd (FPbZnCd); and a control. Lead concentrations were highest in bone but were also significantly higher in the kidney but not liver when compared to the control. The highest kidney Pb levels were in the FPbZnCd treatment but they were not significantly higher than the Pb only group. Zinc concentrations were highest in kidney and not femur as is usually the case in field caught animals. Cadmium was also highest in the kidney in the high Cd treatments, however, the ZnCd treatment group had significantly lower kidney Cd levels than the Cd only group demonstrating the antagonistic effect of high Zn on Cd accumulation. This effect was reversed when high fluoride and Pb were also present (in the FPbZnCd group) and the kidney Cd reached its highest level. Fluoride showed the typically high levels in bone with only the combined treatment (FPbZnCd) showing a significant increase in kidney fluoride. These results are discussed in terms of the accumulation in wild small mammals caught in polluted sites particularly grasslands established on fluorspar wastes.     

Total content and extractable fraction of cadmium,cobalt, copper,nickel, lead,and zinc in calcareous orchard soils

Abstract

The levels and availability of six heavy metals cadmium (Cd), cobalt (Co), copper (Cu), nickel (Ni), lead (Pb), and zinc (Zn) in calcareous orchard soils were measured in an investigation of a method for the determination of total content and extractable fraction of these metals by atomic absorption spectrometry. The digestion step was performed comparatively using two different types of heating. Cadmium, Cu, Ni, Pb, and Zn were determined by flame atomic absorption spectrometry (F‐AAS) and Cd was determined by electrothermal or graphite furnace atomic absorption spectrometry (GF‐AAS) using the method of standard addition. The detection limits, precision values, and accuracy (recovery assays) show the reliability of the method. The conditions for the determination of the extractable fraction of the metals were also optimized. Extraction time for Cd and Zn was studied, and the application of two hours of shaking was selected. The tested method was applied to real samples corresponding to highly calcareous orchard soils characteristic of the Mediterranean area. Only Zn, Cu and Pb showed high levels in their extractable forms, whereas Cd and Co had highest levels in their total contents. An important bio‐availability was observed in all the studied metals, but mainly for Cd and Pb.     

Redistribution of cadmium,copper, lead,nickel, and zinc among soil fractions in a contaminated calcareous soil after application of nitrogen fertilizers

This study was conducted to evaluate the redistribution of the heavy metals Cd, Cu, Pb, Ni, and Zn among different soil fractions by N fertilizers. In a lab experiment, soil columns were leached with distilled water, KNO₃, NaNO₃, NH₄NO₃, or Ca(NO₃)₂ · 4H₂O. After leaching, soil samples were sequentially extracted for exchangeable (EXCH), carbonate (CARB), organic‐matter (OM), Mn oxide (MNO), Fe oxide (FEO), and residual (RES) fractions. Distilled water significantly increased the concentrations of Cd and Ni in EXCH fraction, while concentration of Cu and Zn did not change significantly. Application of KNO₃, NaNO₃, NH₄NO₃, or Ca(NO₃)₂ · 4H₂O significantly increased the concentrations of Cd and Zn in EXCH fraction, while concentration of Pb and Ni was decreased. Application of all fertilizers caused an increase of Cu in the OM fraction. Moreover, leaching with these solutions significantly increased Cd [except in Ca(NO₃)₂ · 4H₂O], Cu, and Zn concentrations in the CARB fraction, while Pb and Ni concentrations were decreased. With application of all leaching solutions, Zn in the EXCH, CARB, FEO, and MNO fractions was significantly increased, while Zn in the OM fraction did not change. The mobility index indicated that Ca(NO₃)₂ · 4H₂O increased the mobility of Cd, Cu, and Zn in the soil, whereas NaNO₃ decreased the mobility of Pb and Ni in the soil. The mobility index of Pb decreased by all leaching solutions. Thus, these results suggest that applying N fertilizers may change heavy‐metal fractions in contaminated calcareous soil and possibly enhance metal mobility and that N‐fertilization management therefore may need modification.     

土壤酶活性评价镉锌铅复合污染的可行性研究

模拟试验研究表明在Cd、Zn、Pb复合污染处理土壤中,过氧化氢酶、脲酶活性与碱性磷酸酶或转化酶活性可构成综合评价体系,反映土壤Cd、Zn、Pb污染含量以及土壤Cd-Zn、Zn-Pb复合污染效应,用其评价土壤Cd、Zn、Pb复合污染具有一定可行性。     

Retention of copper, cadmium and zinc in soil and its textural fractions influenced by long-term field management

The present study investigated the impact of long‐term soil management on the metal retention capacity of soil. We examined the sorption behaviour of Cu, Cd and Zn in soils and in the various particle‐size fractions of these soils, which had been amended with farmyard manure, mineral fertilizers or were fallow for 38 years in a long‐term field experiment. The soils investigated contained different amounts and origins of organic matter and differed in soil pH, but the mineral phase showed less response to the different soil managements. Batch adsorption and desorption experiments as well as a sequential fractionation schema, which defines seven geochemical fractions, were used to investigate the retention properties of soil. Sequential extraction was conducted with original as well as with metal‐spiked soils. Results showed that amounts of Cu, Cd and Zn retained differed by a factor of more than 3 among the treatments in the long‐term field experiment, when a massive concentration of metal was added to soil. An increased sorption on smaller particle size fractions occurred (clay ≫ silt > fine sand ≥ coarse sand) due to the larger surface area as well as the greater carbon content in the smaller fractions. Soil sorption behaviour in another long‐term field experiment was estimated based on the present particle‐sorption data. Differences in the sorption behaviour were related to differences in soil mineralogy and amounts of Fe‐ and Mn‐oxides. Fractionation of the original and the metal‐spiked soil underlined the contribution of organic matter to sorption capacity (sequence: Cu ≫ Cd > Zn). Different organic matter contents and a different soil pH considerably changed the amounts of metals in the defined geochemical fractions. Freshly added Cu, Cd and Zn ions were found mainly in more mobile fractions. In contrast, metals in non‐spiked soils appeared in less‐mobile fractions reflecting their long‐term sorption behaviour.     

Derivative potentiometric stripping analysis (dPSA) used for the determination of cadmium,copper, lead,and zinc in Sicilian olive oils

Derivative potentiometric stripping analysis (dPSA) was utilized to evaluate the Cd(II), Cu(II), Pb(II), and Zn(II) content in olive oil samples produced in Sicily in the crop year 2000-2001. The repeatability of the method was attested at 86.36% for cadmium, at 94.94% for copper, at 99.00% for lead, and at 98.92% for zinc. Recovery tests were carried out, both on cleanup procedures and on extraction steps, on olive oil spiked at different levels; obtained recoveries were 84.52 +/- 9.86 for cadmium, 97.34 +/- 2.72 for copper, 100.68 +/- 0.67 for lead and 83.35 +/- 1.72 for zinc. Theoretic detection limits were 1.2 ng g(-1) for Cd, 3.6 ng g(-1) for Cu, 5.9 ng g(-1) for Pb, and 14.3 ng g(-1) for Zn. Found concentrations range were 15.94-58.51 ng g(-1) for Cu, 32.64-156.48 ng g(-1) for Pb, and 157.00-385.22 ng g(-1) for Zn. Copper, lead, and zinc were found in all samples. The main advantage of this determination consists of a not too aggressive metals extraction procedure using hydrochloric acid, which avoids losses of elements typical of sample calcinations methods.     

Transfer functions for solid-solution partitioning of cadmium, copper, nickel, lead and zinc in soils: derivation of relationships for free metal ion activities and validation with independent data

Models to predict the solid-solution partitioning of trace metals are important tools in risk assessment, providing information on the biological availability of metals and their leaching. Empirically based models, or transfer functions, published to date differ with respect to the mathematical model used, the optimization method, the methods used to determine metal concentrations in the solid and solution phases and the soil properties accounted for. Here we review these methodological aspects before deriving our own transfer functions that relate free metal ion activities to reactive metal contents in the solid phase. One single function was able to predict free-metal ion activities estimated by a variety of soil solution extraction methods. Evaluation of the mathematical formulation showed that transfer functions derived to optimize the Freundlich adsorption constant ( K _f ), in contrast to functions derived to optimize either the solid or solution concentration, were most suitable for predicting concentrations in solution from solid phase concentrations and vice versa . The model was shown to be generally applicable on the basis of a large number of independent data, for which predicted free metal activities were within one order of magnitude of the observations. The model only over-estimated free-metal ion activities at alkaline pH (>7). The use of the reactive metal content measured by 0.43 m HNO₃ rather than the total metal content resulted in a close correlation with measured data, particularly for nickel and zinc.