Forms of Cd,Cu, Pb,and Zn in soil and their uptake by cereal crops when applied jointly as carbonates

The cereal crops (barley -Hordeum vulgare L., maize -Zea mays L., wheat -Triticum vulgare L.) were grown in a greenhouse using a sandy soil type treated with various doses of cadmium carbonate (salt), copper carbonate (malachite), lead carbonate (cerussite), and zinc carbonate (smithsonite), added jointly. The following levels of these metals were used: Cd ? 5, 10, 50μg g^?1 soil; Cu and Pb - 50,100, 500 μg g^?1 soil; Zn-150, 300, 1500 μg g-1 soil. Sequential extraction was adopted to partition the metals into five operationally-defined fractions: exchangeable, carbonate, Fe-Mn oxides, organic, and residual. The residual was the most abundant fraction in the untreated (control) soil for all the metals studied (50 to 60% of the total metal content). The concentrations of exchangeable Cd, Cu, Pb, and Zn were relatively low in untreated soil but increased (over the three year period) in treated soils for Cd, Zn, and Cu, whereas only small changes were observed for Ph. This experiment showed a significant increase in Cd, Zn, and Cu in tissue of plants grown on the treated soil, but a non-significant change in plant tissue with respect to Pb concentration.     

南京城郊蔬菜基地土壤有效态铅、锌、铜和镉的空间分异及其驱动因子研究

利用地统计学和地理信息系统相结合的方法,从小尺度区域角度上研究了南京城郊土壤中铅(Pb)、锌(Zn)、铜(Cu)和镉(Cd)4 种重金属有效态含量的空间分布特征及其主要的影响因子。结果表明:(1) 研究区土壤中有效 Zn 变异程度相对较大,有效 Pb 的变异程度相对较小,而有效 Cu 和 Cd 为中等程度变异。(2) 研究区有效 Pb、Zn 含量空间分布具有中等程度的空间自相关性,而 Cu、Cd 空间分布具有强烈的空间自相关性;有效 Zn、Cd 的空间自相关尺度相对较大,而有效 Cu、Pb 相对较小。(3) 研究区土壤中有效 Pb 的空间分布主要受交通影响,交通量越大的道路附近土壤中有效 Pb 含量越高;有效 Zn 主要受城市生活废水的影响,城市生活污水灌溉和城市地表径流是土壤中有效 Zn 积累的主要原因;有效 Cu 主要与蔬菜种植过程中有机肥(主要是牛粪)施用关系密切,有机肥施用量越大,土壤中有效 Cu 含量越高;有效 Cd 受地形影响较大,地形低洼处土壤中有效 Cd 含量相对较高。     

Differential Sorption Behavior of Cadmium,Lead, Zinc,and Copper in Some Tropical Soils and Their Environmental Implications

This study evaluated cadmium (Cd), lead (Pb), zinc (Zn), and copper (Cu) sorption characteristics of three tropical soils. Data obtained conformed to Freundlich sorption model and the S-shaped isotherm curve. Sorption efficiency of Zn and Pb were highest in alkaline soil while slightly acid soil had the highest Cd and Cu sorption efficiency for monometal sorption. In competitive sorption, metals were more sorbed in slightly acid soil while the least efficiency was recorded in acid soil. Distribution coefficient; K_d (average across soil types) in monometal sorption followed the order: Pb > Zn > Cd > Cu. For competitive sorption, the order was Zn > Pb > Cu > Cd. When in competition, Cd was preferentially sorbed in slightly acid and alkaline soils and Zn for acid soil. Conclusively, lead is more in equilibrium solution when in competition with Cd, Zn and Cu making it potential agent of soil and groundwater pollution.     

Cadmium,Lead, Copper,Zinc, and Nickel in Lettuce and Dry Beans as Related to Mehlich-3 Extraction in Three Brazilian Latossols

Lettuce (Lactuca sativa L.) and dry beans (Phaseolus vulgaris L.) were grown in three Brazilian Red-Yellow Latossols (Oxisols) in greenhouse conditions with cadmium (Cd), lead (Pb), copper (Cu), zinc (Zn), and nickel (Ni) applied to soils in treatments arranged as a randomized complete block design. Plant metals were analyzed in lettuce shoots and dry beans roots, stems, leaves, and seeds. After plant growth, soil samples from the pots were extracted with Mehlich-3 (M-3) for metal availability evaluation. The release of Ni in the M-3 extraction was dependent on the soil exchangeable aluminum (Al^{3 +}). Mehlich-3 was efficient for determination of availability of Cd, Pb, Cu, Zn, and Ni for dry beans and availability of Cd and Ni for lettuce. The dry bean leaves Cd, Pb, Cu, Zn, and Ni were highly correlated with their recovering from soils with M-3. The same was observed for Cd and Ni in lettuce shoots and the M-3 recovered metals from soils.     

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.     

Forms of trace metals from inorganic sources in soils and amounts found in spring barley

Barley (Hordeum vulgare L.) was grown on a sandy soil given different doses of cadmium carbonate (salt), copper carbonate (malachite), lead carbonate (cerussite), and zinc carbonate (smithsonite) in a pot experiment conducted in a greenhouse. The element compounds were added to the soil in amounts equivalent to the following levels of the metals: Cd 5, 10, 50 μq ^?1; Cu and Pb 50, 100, 500 μg g^?1; Zn 150, 300, 1500 μg g^?1. Sequential extraction was used for partition these metals into five operationally-defined fractions: exchangeable, bound to carbonates, bound to Fe-Mn oxides, bound to organic matter and residual. The residue was the most abundant fraction in the untreated soil for all the metals studied (43 to 61% of the total contents). The concentration of exchangeable Cd (0.2 μg g^?1), Cu (0.01 μg g^?1), Pb (0.1 μg g^?1), and Zn (1.4 μg g^?1) were relatively low in the untreated soil but increased markedly in the treated soils for Cd (up to 31 μg g^?1) and Zn (up to 83 μg g^?1), whereas only small changes were observed for Cu and Pb. The pot experiment showed a significant increase in the Cd and Zn contents of barley grown on the treated soils, but only small changes in Cu and Pb concentrations.     

Distribution of Heavy Metals in Some Tree Leaves along the Main Road in an Agricultural Area

Four types of tree leaves were investigated (olive, fig, oak, and carob). The tree leaf samples, washed and unwashed, were analyzed for lead (Pb), cadmium (Cd), copper (Cu), and zinc (Zn) by atomic absorption spectrophotometry. Variable levels were found in these plants. In addition, all heavy‐metal concentrations of the samples were significantly higher than their counterparts of the control, indicating heavy‐metal pollution was taking place. Very high correlations were found between heavy metals in the same plant, between different plants, and between plants and soil, indicating common sources of heavy metals, possibly soil and soil pollution sources such as traffic. The accuracy of the analytical method used for heavy metals was checked by analysis of standard reference materials, rye grass (CRM 281) and spinach leaf (SRM 1570a). The percentages of recovery of both reference materials for Cd, Cu, Pb, and Zn were better than 93%.     

Determination of cadmium, copper, and lead in sodium chloride food salts by flame atomic absorption spectroscopy

A method for determination of Cd, Cu, and Pb in sodium chloride food salt samples has been developed. It consists of extraction in 4-methyl-2-pentanone of the complexes formed with ammonium pyrrolidine dithiocarbamate and further analysis of the extracts by flame atomic absorption spectroscopy. Detection limits in ng/g salt were 0.2 for Cd, 0.7 for Cu, and 10.0 for Pb. The coefficients of variation of 12 independent analyses were 13% for Cd (at a level of 0.4 ppb), 18% for Cu (1.6 ppb), and 5% for Pb (40 ppb). The recoveries were 100 +/- 0% for Cd, 115 +/- 14% for Cu, and 100 +/- 13% for Pb.     

膨润土对重金属离子的竞争性吸附研究

通过间歇震荡平衡法研究了膨润土对4种重金属离子Cd2+、Zn2+、Cu2+、Pb2+的竞争性吸附特性及其机制。研究结果表明:与单一离子体系比较,膨润土在竞争体系中对Cd2+、Zn2+、Cu2+、Pb2+4种重金属离子的吸附量均呈下降趋势。竞争体系下,其它重金属离子的存在显著抑制了膨润土对Cd2+的吸附,降幅为19.20%~37.50%,而对Pb2+的吸附能力几乎没有影响,降幅仅为0.41%~2.83%。膨润土对4种重金属离子的富集系数,其大小顺序依次为Pb2+>Cu2+>Zn2+>Cd2+。该选择性吸附顺序与重金属离子的一级水解常数密切相关。     

Comparison of Heavy Metal Adsorptions by Thai Kaolin and Ballclay

The adsorption characteristics of heavy metals: cadmium(II), chromium(III), copper(II), nickel(II), lead(II), and zinc(II) ions by kaolin (kaolinite) and ballclay (illite) from Thailand were studied. This research was focussed on the pH, adsorption isotherms of single-metal solutions at 30–60 °C by batch experiments, and on ion selectivityin mixed and binary combination solutions. It was found that, except Ni, metal adsorption increased with increased pH of the solutions and their adsorption followed both Langmuir and Freundlich isotherms. Adsorption of metals in the mixture solutions by kaolin was: Cr > Zn > Cu ≈ Cd ≈ Ni > Pb, and for ballclay was: Cr > Zn > Cu > Cd ≈ Pb > Ni. The adsorption of metals was endothermic, with the exception of Cd, Pb and Zn for kaolin, Cu and Zn for ballclay. Kaolin and ballclay exhibited relatively hard Lewis base adsorption site. The presence of other metals may reduce or promote the adsorption of heavy metals. The presence of Cr³⁺ induced the greatest reduction of metal adsorptiononto kaolin, as did the presence of Cu²⁺ for ballclay.     

Interactive Effects of Copper, Cadmium and Lead on Zinc Accumulation in the Gastropod Mollusc Littorina Saxatilis

The effects of copper, cadmium and lead on the bioaccumulation of zinc were studied in populations of the gastropod mollusc Littorina saxatilis from sites in the Isle of Man subjected to varying degrees of mine-related metal contamination. Exposures to 2 mg/L Zn alone and in combinations with 0.01 mg/L, 0.1 mg/L and 1 mg/L of the respective metals were conducted at ～10 ^°C in semi-static assays. Copper had a significant antagonistic effect on Zn accumulation at 1 mg/L Cu, but was not antagonistic at 0.01 and 0.1 mg/L Cu. Prior exposure to metals in the field did not appear to affect the interactive effect of copper as all populations showed similar patterns. Combinations of Zn with Cd or Pb at the above concentrations did not show any significant effects on Zn accumulation. On the other hand, Zn had an antagonistic effect on Cd and Pb accumulation but showed inconsistent effects on Cu accumulation. Interactions of Cu and Zn in particular may have repercussions for interpretation of biomonitoring data in L. saxatilis.     

天然沸石对重金属离子的竞争性吸附研究

通过室内分析的方法研究了天然沸石对4种重金属离子Cd2 、Zn2 、Cu2 、Pb2 的竞争性吸附特性。研究结果表明,与单一离子体系比较,沸石在竞争体系中对Cd2 、Zn2 、Cu2 、Pb2 4种重金属离子的吸附量均呈下降的趋势。竞争体系下,其它重金属离子的存在显著地抑制了沸石对Cd2 的吸附,而对Pb2 的吸附几乎没有影响。天然沸石对4种重金属离子的富集系数,其大小顺序依次为Pb2 >Cu2 >Zn2 >Cd2 。该选择性吸附顺序可能与重金属离子的水合能、离子半径、有效水合离子半径等因素密切相关。     

Heavy Metal Concentrations in Gray Calcareous Soils of Baiyin Region,Gansu Province,P.R. China

Concentrations of cadmium (Cd), copper(Cu), lead (Pb), zinc (Zn), manganese (Mn) and nickel(Ni) were measured in cultivated gray calcareous soilscollected in the two basins of Baiyin urban area. Thevalues revealed fluctuating and enriched Cd, Pb, Cuand Zn concentrations in the cultivated soils,suggesting recent inputs from anthropogenic sources.There also existed differences between these twodrainage areas, indicating the characteristics ofpollution sources differed. Concentrations of Cd, Pband to a lesser extent Cu and Zn were higher in thisregion as compared with the micrometal backgroundvalues in gray calcareous soil, which may beattributed to the proximity of these soil sites tocontaminated streams, or to the utilization offarmyard manure or fertilizers. Comparison of obtainedmetal concentration levels with other areas in theworld revealed elevated values for Cd and Pb, showinga considerable amount of pollution in the area.Continuous monitoring and further studies of the areaare recommended to ascertain long-term effect that mayhave not yet been reached and to prevent pollution offarmland from worsening.     

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.     

Simultaneous determination of Cd(II), Cu(II), Pb(II), and Zn(II) in citrus essential oils by derivative potentiometric stripping analysis

Citrus essential oils are widely used in the food, cosmetics, and pharmaceutical industries, so the determination of heavy metals content is of great importance to guarantee their quality. The present work deals with the quantification of Cd(II), Cu(II), Pb(II), and Zn(II) in different varieties of citrus essential oils, using derivative potentiometric stripping analysis. Two different metals extraction procedures, involving concentrated hydrochloric acid treatment and acid-alcoholic dissolution, are tested on lemon, mandarin, sweet orange, and bergamot essential oils, and they give very similar results. Cd(II), Cu(II), Pb(II), and Zn(II) recovery tests spanned from 95 to 100.50%, providing evidence that metals quantification remained unaffected by the cleanup steps of the two procedures. The repeatability of the hydrochloric acid extraction method, applied on different varieties of essential oils, is >95.00% for Cd(II), Cu(II), Pb(II), and Zn(II), whereas the repeatability of the acid-alcoholic dissolution method is >93.00% for Cu and Cd only in lemon oil. Detection limits obtained for the four analytes, using both procedures, ranged from 0.10 to 0.98 ng g(-)(1) in lemon, mandarin, sweet orange, and bergamot essential oils.     

Metal Uptake in Plants and Health Risk Assessments in Metal‐Contaminated Smelter Soils

Metal pollution is an important concern because of its potential to affect human health. Metals such as lead and cadmium can enter soil via the food chain and exceed normal limits, producing harmful effects. In this study, six common garden and residential plant species were grown in soils from Spelter, WV, USA, contaminated with a variety of metals including lead (Pb), zinc (Zn), cadmium (Cd), and copper (Cu). Plant species included radish, carrot, chicory, spinach, lettuce, and clover. Metal concentrations in plant tissues were compared with metal concentration in soil by a multi‐step chemical extraction. The largest accumulation of Pb (126 mg kg⁻¹) and Zn (1493 mg kg⁻¹) was seen in radish roots, with Cd (40 mg kg⁻¹) having the largest accumulation in carrot roots. Comparisons of plant availability with soil chemical extractions indicated that the combined soluble and exchangeable fractions could estimate available Zn and Cd for all six plant species. For Pb and Cu, however, the comparisons indicate that these two elements were not readily available in Spelter soils. A health risk assessment was carried out for residents at Spelter on the basis of edible tissue concentrations and publicly available consumption data. Uptake of Cd by carrot roots was about five times more than the regulatory limits for men, eight times more for women, and 12 times more for children. On the basis of the results, carrot and lettuce grown in these soils have the potential to cause toxicological problems in men, women, and young children resulting from Cd and Zn accumulation. Copyright © 2013 John Wiley & Sons, Ltd.     

重金属Cd、Zn、Cu和Pb复合污染对土壤生物活性的影响

通过野外土样采集及室内培养试验(25℃),研究了云南东川铜矿区土壤酶和微生物特征,以及模拟重金属Cd、Zn、Cu、Pb复合污染对土壤微生物和酶活性的影响。结果表明,矿区土壤(距矿口0~800 m)重金属污染严重,Pb、Cd、Zn、Cu全量和有效含量是对照土壤(距矿口10 000 m)的3.7~141.0倍和2.2~773.2倍;距矿口越近,土壤有机质、有效氮、有效磷和速效钾含量及土壤pH亦越低,土壤酶活性和土壤微生物数量、微生物生物量碳和氮受到的抑制程度也显著增强。与对照土壤相比,距矿口0~800 m的土壤蔗糖酶、脲酶、酸性磷酸酶、过氧化氢酶和脱氢酶活性分别降低25.5%~47.3%、22.6%~74.2%、30.9%~83.1%、16.7%~69.1%和34.6%~92.3%;细菌、放线菌和真菌数量分别较对照下降30.5%~80.1%、8.1%~49.9%和3.3%~8.3%。土壤酶中的酸性磷酸酶和过氧化氢酶,土壤微生物中的细菌对重金属污染较为敏感。恒温(25℃)培养试验中,低量的Cd、Zn、Cu、Pb复合污染刺激了土壤酶活性和细菌、真菌、放线菌、微生物生物量碳和氮的数量,但高量的Cu、Zn、Pb、Cd复合污染使土壤酶活性、细菌、真菌、放线菌、微生物生物量碳和氮均显著下降。重金属Cd、Zn、Cu、Pb之间存在着一定的协同或拮抗作用,Cd、Zn、Cu和Pb之间在微生物生物量碳和氮上表现出明显的协同效应,Pb与Cd、Zn、Cu对细菌数量的复合效应机制为拮抗效应,Cd、Zn、Cu和Pb对真菌数量和放线菌数量的复合效应机制表现为协同效应和拮抗效应并存。     

在法国前铅和锌冶炼厂附近的城市土壤重金属的污染、分离和利用

smelters in Northern France were studied by analysing the chemical forms of these metals and evaluating their phytoavailability. These metals were determined using flame or electrothermal absorption atomic spectrometry （FAAS or ETAAS）, depending on their concentration levels. After optimisation of the ETAAS method, characteristic mass of In in water and aqua regia were 9.9 and 18 pg, respectively, showing the high sensitivity of the analytical Soil contamination by metals from anthropogenic activities （e.g., mining and smelting） is a major concern for the environment and human health. Environmental availability of cadmium （Cd）, lead （Pb）, zinc （Zn）, copper （Cu）, and indium （In） in 27 urban soils located around two former Pb and Zn smelters in Northern France were studied by analysing the chemical forms of these metals and evaluating their phytoavailability. These metals were determined using flame or electrothermal absorption atomic spectrometry （FAAS or ETAAS）, depending on their concentration levels. After optimisation of the ETAAS method, characteristic mass of In in water and aqua regia were 9.9 and 18 pg, respectively, showing the high sensitivity of the analytical procedure. Metal partitioning was conducted using a four-step sequential extraction procedure. The results showed that Cd and Zn were mainly in the acid-extractable and reducible forms in the urban soils studied. In contrast, Pb and In were largely in the reducible fraction. However, in some samples, the amount of In extracted in the residual or exchangeable fraction was higher than that in the reducible fraction. Copper was mainly found in the reducible and residual fractions. A pot experiment was conducted in a glasshouse with seven soils （six contaminated and one uncontaminated） and two plant species, ryegrass and lettuce. The results showed transfer of metals from the contaminated soils to the shoots of ryegrass and the edible part of lettuce. The metal bioconcentration factor was in the order of Cd Cu > In > Zn Pb for lettuce leaves, whereas for ryegrass shoots, three orders were found, Cd > Zn > Cu In > Pb, Cd ≥ In > Zn > Cu Pb, and Zn > Cd > Cu > In > Pb, depending on the physico-chemical properties of the soils, such as pH, cation exchange capacity, carbonates, and organic matter. It was established that the metal toxicity was related to the contamination levels and the physico-chemical properties, including pH, organic matter, and in a lesser extent, Ca, Mg, and phosphorus contents, of the soils. However, it was shown that lettuce could grow on soils having high Cd and CaCO₃ contents. Cadmium was one of the most available metals while Pb was always the least available in the soils studied.     

典型设施栽培土壤重金属含量变化及其风险评价

采用野外调查采样和室内分析相结合的方法,对典型设施栽培地山东寿光的部分土壤重金属含量进行测定,并根据温室蔬菜产地环境质量评价标准,选取单项污染指数法和尼梅罗综合指数法对土壤的重金属污染状况进行了环境质量评价。结果表明,重金属Cu、C r、Pb在设施栽培土壤耕层(0—20 cm)的含量达最大值,显著高于露地土壤;而设施栽培土壤中Zn和Cd的含量分别在20—40 cm和40—60 cm的土层达到最大值,其中Zn含量在0—20 cm和60—80 cm的土层显著高于露地土壤,Cd含量在0—20 cm,40—60 cm,60—80 cm和80—100 cm的土层显著高于露地土壤。从不同使用年限设施栽培土壤中重金属含量变化看出,重金属在设施栽培24~年的土壤中含量最高。对研究区设施栽培土壤重金属含量进行风险评估及分级发现,山东寿光设施土壤耕层主要受到重金属Cd的污染。     

Phytoavailability of Some Micronutrients (Zn and Cu), Heavy Metals (Pb,Cd), and Yield of Rice Affected by Sewage Sludge Perennial Application

A study was conducted as a split-plot arrangement based on a randomized complete block design with three replications to test sewage sludge (SS) influence on yield and phytoavailability of lead (Pb), cadmium (Cd), zinc (Zn), and copper (Cu) by rice. The results indicated that fertilizer (main factor) and application periods (subfactor) affected studied traits. Three years of application of 40 ton ha^?1 SS + 50% chemical fertilizer (CF) gave the greatest paddy yield. The greatest Cu uptake by grain (10.38 ppm) occurred with 3 years application of 20 ton ha^?1 SS. With application of 40 ton ha^?1 SS + 50% CF, the greatest contents of Cd in root and Pb in shoots were recorded. The greatest accumulations of Cd in shoot and Zn in grain (30.56 and 25.81 ppm, respectively) were determined with the 20 ton ha^?1 SS treatment, as well. The greatest concentrations of Pb and Cd in grain (102.2 and 14.78 ppm, respectively) and Pb in root (552.2 ppm) were obtained with 3 years of application of 40 ton ha^?1 SS + 50% CF.