云南滇池沉积物中重金属的形态分布特征

Fractionation of heavy metals in sediments can help in understanding potential hazards of heavy metals. The present study analyzed total concentrations and fractions of selected heavy metals （Cd, Cr, Cu, Pb, and Zn） in surface sediments from Dianchi Lake, Yunnan Province, China, as well as factors that may affect distributions of the various heavy metal fractions. Total concentrations of the heavy metals decreased in the order Zn 〉 Cu 〉 Pb 〉 Cr 〉 Cd. These heavy metals, except Cr, were much higher than their background levels, indicating that Dianchi Lake was polluted by Cd, Zn, Pb, and Cu. Cadmium occurred mainly as the non-residual fraction （sum of the HOAc-soluble, reducible, and oxidizable fractions） （97.6%）, and Zn （55.7%） was also predominantly found in the non-residual fraction. In contrast, most of the Cr （88.5%）, Pb （81.8%）, and Cu （59.2%） occurred in the residual fraction. Correlation analysis showed that total heavy metal concentrations, organic matter and reducible Fe were the main factors affecting the distributions of the various heavy metal fractions. In the Walhai section of Dianchi Lake （comprising 97% of the lake area）, the concentrations of Cd, Zn, Pb, and Cu in the non-residual fraction were significantly lower （P ≤ 0.01 or 0.05） than those of the Caohal section （3% of the lake area）. This indicated that potential heavy metal hazards in the Caohai section were greater than the Waihai section.     

长江口崇明岛土地利用方式对滨海土壤中重金属和砷的分布和形态特征的影响

The reclamation of tidal flats has been one of the important approaches to replenish the arable lands in the coastal areas; pollution status of reclaimed soils has received wide attention recently, especially for the study of heavy metals due to the relative high pollutant concentrations in wetlands. To understand the impact of land use change on heavy metal and arsenic(As) geochemistry by the reclamation of wetlands for agriculture, surface soils and soil profiles were collected from the agricultural land reclaimed in the 1990 s and the intertidal flat wetland at Dongtan on Chongming Island in the Yangtze River Estuary, China. The soil samples were analyzed for total concentrations and chemical speciation of chromium(Cr), zinc(Zn), copper(Cu), lead(Pb), nickel(Ni), cadmium(Cd) and As using inductively coupled plasma mass spectrometry(ICP-MS). Results showed that soil properties(salinity, total organic carbon and grain-size distribution) and the concentrations of heavy metals and As in the soils differed under the different land use types. The conversion of wetland to forest had caused obvious losses of all the measured heavy metals. In paddy field and dryland with frequent cultivation, the concentrations of Cr, Zn, Cu, Ni and As were higher when compared to forest land which was disturbed rarely by human activities. Speciation analysis showed that Cr, Zn, Cu, Ni and As were predominated by the immobile residual fraction, while Pb and Cd showed relatively higher mobility. In general, metal(except Ni) and As mobility decreased in the following order: wetland dryland ≥ paddy field forest land, which suggested that the reclaimed soils had lower metal and As mobility than the intertidal flat wetland. The results of this study contribute to a better understanding of the effects of land use on heavy metals and As in the reclaimed soils of the study area and other similar coastal areas.     

陇海铁路郑州—圃田段铁路旁土壤重金属污染

The pollution status and horizontal distribution of heavy metals (Ni, Pb, Cr, Zn, Cu, and Cd) in the soil on railroad side along the Zhengzhou-Putian section of Longxi-Haizhou Railroad were studied by collecting soil samples along a sampling section perpendicular to the railroad at the distances of 0, 10, 20, 30, 50, 100, 200, 300, and 500 m from the railroad edge. The concentrations of heavy metals in the sampling soils were higher than those of the control site. The concentrations of Pb, Zn, and Cd were found to be the highest in the soils at the railroad edge, and then decreased with increasing distance from the railroad. The highest concentrations of Ni, Cr, and Cu in soils were located at about 10-30 m from the railroad. Compared with the single factor pollution index (SFPI) of heavy metals calculated for the control site, the average SFPI from the sampling sites decreased in the order of Cr > Cd > Pb > Zn > Ni > Cu. There were notable negative correlations between the integral pollution index (IPI) of soil heavy metals at all sampling sites and the distances from the railroad. According to three IPIs calculated from the background values of heavy metals in och-aquic Cambisols, the heavy metal concentrations in the control soil, and the 2nd levels for soil heavy metals in GB15618-1995, the study area could be divided, based on the distances from the railroad, into four pollution zones: heavy pollution zone (0-10 m), medium pollution zone (10-50 m), slight pollution zone (50-100 m), and warning zone (100-500 m), respectively.     

施用碱稳定固体的酸性土壤的Cu和Zn的形态分布

Fractionation of metals in a granite-derived acid sandy loam soil amended with alkaline-stabilised sewagesIudge biosolids was conducted in order to assess metal bioavailability and environmental mobility soil solution was extracted by a centrifugation and filtration technique. Metal speciation in the soil solution wasdetermined by a cation exchange resin method. Acetic acid and EDTA extracting solutions were used forextraction of metals in soil solid surfaces. Metal distribution in different fractions of soil solid phase was determined using a three-step sequential extraction scheme. The results show that the metals in the soilsolution existed in different fractions with variable lability and metals in the soil solid phase were also presentin various chemical forms with potentially different bioavail ability and environmental mobility Alkaline-stabilised biosolids could elevate solubility of Cu and proportion of Cu in organically complexed fractionsboth in soil liquid and solid phases, and may therefore increase Cu mobility. In contrast, the biosolids lowered the concentrations of water-soluble Zn (labile fraction) and exchangeable Zn and may hence decrease bioavailability and mobility of Zn. However, Fe and Mn oxides bound and organic matter bound fractions are likely to be Zn pools in the sludge-amended soil. These consequences possibly result from the liming effect and metal speciation of the sludge product and the difference in the chemistry between the metals in soil.     

对矿区和冶炼区土壤重金属污染进行化学和矿物学特征分析

The binding of metallic contaminants （Pb, Cd, and Zn） and As on soil constituents was studied on four highly contaxninated alluvial soil profiles from the mining/smelting district of Pribram （Czech Republic） using a combination of mineralogical and chemical methods. Sequential extraction analysis （SEA） was supplemented by mineralogical investigation of both bulk samples and heavy mineral fractions using X-ray diffraction analysis （XRD） and scanning electron microscopy with an energy dispersive X-ray spectrometer （SEM/EDS）. The mineralogy of Fe and Mn oxides was studied by voltammetry of microparticles （VMP） and diffuse reflectance spectrometry （DRS）. Zinc and Pb were predominantly bound in the reducible fraction attributed to Fe oxides and Mn oxides （mainly birnessite, Na4Mn14O27.9H2O）, which were detected in soils by XRD and SEM/EDS. In contrast, Cd was the most mobile contaminant and was predominantly present in the exchangeable fraction. Arsenic was bound to the residual and reducible fractions （corresponding to Fe oxides or to unidentified Fe-Pb arsenates）. SEM/EDS observations indicate the predominant affinity of Pb for Mn oxides, and to a lesser extent, for Fe oxides. Thus, a more suitable SEA procedure should be used for these mining-affected soils to distinguish between the contaminant fraction bound to Mn oxides and Fe oxides.     

杭州市城市土壤中重金属、磷和其它元素的特征

Health implications of inhaling and/or ingesting dust particles with high concentrations of heavy metals from urban soils are a subject of intense concern. Understanding the geochemistry of these metals is key to their effective management. Total concentrations of heavy metals, phosphorus (P) and 8 other elements from topsoil samples collected at 82 locations in Hangzhou City were measured to: a) assess their distribution in urban environments; and b) understand their differentiation as related to land use. Metal mobility was also studied using a three-step sequential chemical fractionation procedure. About 8.5%, 1.2%, 3.6%, 11.0% and 30.3% of the soil samples had Cd, Cr, Cu, Pb, and Zn concentrations, respectively, above their allowable limits for public and private green areas and residential use. However, in commercial and industrial areas, most samples had metal concentrations below their allowable limits. Statistical analyses revealed that the 16 measured elements in urban soils could be divided into four groups based on natural or anthropic sources using a hierarchical cluster analysis. Additionally, Cu, Pb, and P showed similar spatial distributions with significant pollution in commercial zones, suggesting vehicle traffic or commercial activities as dominant pollutant sources. Also, Cd, Co, Cr, Ni, Zn, Mn and Fe had the highest concentrations in industrial locations, signifying that industrial activities were the main sources of these seven metals. Moreover, the data highlighted land-use as a major influence on heavy metal concentrations and forms found in topsoils with large proportions of soil Cd, Co, Cr, and Ni found in residual fractions and soil Cu, Pb and Zn mainly as extractable fractions.     

pH Effect on kinetics of Heavy Metal Sorption in Soils

The pH effect on the sorption kinetics of heavy metals in soils was studied using a constant flow leaching method.The soil samples were red soil collected from Yingtan,Jiangxi,and yellow-brown soil from Nanjing,Jiansu,The heavy metals tested were zinc and cadmium.Assuming that the experimental data diffed to the following kinetic rate equation:1/c.dx/dt=kx∞-kx,the rate constant k of sorption could be determined from the slope of the straight line by plotting of 1/c,dx/dt vs.x.The results showed that the pH effect on the rate constants of heavy mental sorption in soils was very significant.The values of k decreased with increasing pH.The sorptions were more sensitive to pH in red soil than in yellow-brown soil.     

4种湿地植物根系泌氧由根诱导的pH,Eh和Fe(II)变化和根际土壤中铅和锌的组分研究

A rhizobox experiment was conducted to compare iron (Fe) oxidation and changes of pH, redox potential (Eh) and fractions of zinc (Zn) and lead (Pb) in rhizosphere and non-rhizosphere soils of four emergent-rooted wetland plants (Echinodorus macrophyllus, Eleocharis geniculata, Hydrocotyle vulgaris and Veronica serpyllifolia) with different radial oxygen loss (ROL) from roots. The results indicated that all these wetland plants decreased pH and concentration of Fe(Ⅱ) but increased the Eh in the rhizosphere soils. Pb and Zn were transformed from unstable fractions to more stable fractions in the rhizosphere soils, so decreasing their potential metal mobility factors (MF). Among the four plants, E. macrophyllus, with the highest ROL and root biomass, possessed the greatest ability in formation of Fe plaque and in the reduction of heavy metal MFs in the rhizosphere soil. Wetland plants, with higher ROLs and root biomass, may thus be effective in decreasing potential long-term heavy metal bioavailabilities.     

重金属迁移与土壤性质的关系

Cu, Zn, Pb and Hg runoff from yellow limestone soil and purple soils and the relationships between the mobility of the heavy metals and the soil characteristics were studied in laboratory using a rainfall simulator. The results showed that the concentrations of soluble Zn in surface runoff were significantly negatively correlated with the contents of < 0.002 mm particles and CEC of the soils, indicating that Zn was mostly adsorbed by clays in the soils. The contents of Cu and Hg in surface runoff were positively related to their contents in the soils. The amounts of Cu, Zn, Pb and Hg removed by surface runoff were influenced by the amounts of soil and water losses and their contents in the soils, and were closely related to the contents of soil particles 1~0.02 mm in size.     

长期使用含铜杀真菌剂对苹果园土壤中自由态铜离子、固相铜形态分级以及微生物活性的影响

Soil samples were collected from apple orchards 5,15,20,30,and 45 years old,and one adjacent forest soil was used as reference to investigate the free Cu2+ion activity in soil solution and the soil Cu fractionation in the solid phase following long-term application of copper fungicide,Bordeaux mixture,in apple orchards and to investigate the relationships among soil free Cu2+ions,Cu fractionation and soil microbial parameters.The total Cu concentration in the orchard soils varied from 21.8 to 141 mg kg-1,increasing with the orchard age,and the value for the reference soil was 12.5 mg kg-1.The free Cu2+ion concentrations in the soil solutions extracted by 0.01 mol L-1 KNO3 ranged from 3.13×10-8(reference)to 4.08×10-6 mol L-1(45 years-old orchard).The concentration of Cu complexed in the fulvic fraction increased with orchard age from 5.16 to 52.5 mg kg-1.This was also the case for other soil Cu fractions except the residual one.The residual soil Cu remained practically constant,ranging from 4.28 to 5.66 mg kg-1,suggesting that anthropogenic soil Cu mainly existed in the more labile active fractions.Regression analyses revealed that both the free Cu2+ions in the soil solution and the humic acid-complexed Cu fraction in the solid phase were strongly related with soil microbial parameters.     

Modulation of Uptake and Translocation of Iron and Copper from Root to Shoot in Common Bean by Siderophore-Producing Microorganisms

Microbes have developed high-affinity uptake mechanisms to assimilate iron (Fe) and other metals such as aluminum (Al), gallium (Ga), chromium (Cr), and copper (Cu). Siderophores, which are metal chelating compounds, and membrane receptor proteins are involved in these specialized mechanisms. A few siderophore-producing microorganisms associated with plant roots also influence the uptake of some metals. In this study, the potential microbial-assisted Cu and Fe uptake by Phaseolus vulgaris (common bean) plants was evaluated. Seedlings of cultivated common bean varieties Bayo-INIFAP (B) and Negro-150 (N) and wild types yellowish (WY) and black (WB) were developed in the presence of a Cu and Fe solution and associated with the siderophore-producing microorganisms R. leguminosarumbv. Phaseoli (strains 19, 44, and 46); Pseudomonas fluorescens(strain Avm), and Azospirillum brasilense (strain 154). Seedlings of cultivated variety N and black wild type WB inoculated with the strain CPMex.44 accumulated 71% and 30% more Fe than the un-inoculated plants, respectively; however, the wild black bean accumulated the highest absolute amount of Fe (221.56 mg/kg of dry matter) as compared with the cultivated black variety N (126.16 mg/kg of dry matter) (P < 0.05). In the wild type WY seedlings, the highest Fe accumulation was observed when the seeds were inoculated with the Pseudomonas strain Avm (206 mg/kg of dry matter) (P < 0.05). The interaction of Pseudomonas strain Avm with seedlings of the cultivated B variety and the wild type WB promoted the highest accumulation of Cu (51 and 54 mg/kg of dry matter, respectively), 7 and 14 mg more than in the respective non-inoculated seedlings. No promotion of Fe accumulation was observed in the seedlings of the cultivated B variety and in roots; instead, less Fe was accumulated. The wild type WY did not show any improvement in Cu accumulation. In this study, Rhizobiumstrains promoted Fe but not Cu uptake in P. vulgaris seedlings while Pseudomonas strains promoted the uptake of both Cu and Fe.     

Changes in Cd,Cu, Ni,Pb and Zn Fractionation and Liberation Due to Mussel Shell Amendment on a Mine Soil

Mining activities are related to relevant environmental pollution issues that should be controlled. We used sequential extractions to fractionate Cd, Cu, Ni, Pb and Zn retained on unamended or mussel shell‐amended mine soil samples, all of them treated with a mixture of the five heavy metals (total metal concentration of 1·57 mmol L⁻¹), after 1, 7 and 30 days of incubation. In addition, we used the stirred flow chamber technique to study the release of each of the five heavy metals from these different unamended and shell‐amended soil samples. The results indicate that the shell amendment caused a decrease in the most soluble fraction, while increasing the most recalcitrant (least mobile) fraction. With equivalent implications, the stirred flow chamber experiments showed that mussel shell amendment was associated to a decrease in heavy metal release and increased retention. The highest mussel shell dose and incubation time caused the most relevant changes in pH values and thus in metal retention, also indicating the importance of pH modifications in the mechanism of retention acting in the amended samples. In view of these results, the use of mussel shell amendment can be encouraged to increase heavy metal retention in acid mine soils, in order to minimise risks of environmental pollution. Copyright © 2016 John Wiley & Sons, Ltd.     

Creation of Technosols to Decrease Metal Availability in Pyritic Tailings with Addition of Biochar and Marble Waste

Creation of Technosols with the use of different materials is a sustainable strategy to reclaim mine tailings and reduce metal mobility. For this purpose, a short‐term incubation experiment was designed with biochars derived from pig manure, crop residues and municipal solid waste added to tailings alone or in combination with marble waste. We aimed to assess the efficiency of the different amendments to decrease Cd, Pb and Zn availability in the Technosols and the fractions where metals were retained. Results showed that all amendments reduced metal mobility, directly related to increases in pH. Those materials with higher content of carbonates were more effective to immobilize metals (~99%). Municipal solid waste was highly effective to decrease metal mobility owing to the higher carbonate content, but addition of marble waste was needed to enhance metal immobilization with pig manure and crop residue. Decreases in Cd mobility were related to retention by the carbonate, Mn/Fe oxides and oxidizable (organic compounds) fractions. Decreases in Pb mobility were related to retention in the Mn/Fe oxides and residual fractions, while decreases in Zn mobility were related to retention in Mn/Fe oxides and oxidizable fractions. Association of Zn and Pb with the oxidizable fraction was also related to the recalcitrance of the organic compounds and so dependent on biochar type. Scanning electron microscopy coupled with energy dispersive X‐ray showed that biochar showed great affinity to interact with iron oxides, calcium sulfates and phyllosilicates. Copyright © 2017 John Wiley & Sons, Ltd.     

Transfer of Heavy Metals from Soils to Vegetables and Associated Human Health Risks at Selected Sites in Pakistan

Contamination of the food chain with heavy metals is considered as one of the major environmental pathways of human exposure to metals leading to potential health risks. This study aimed to investigate the concentrations of heavy metals such as copper (Cu), zinc (Zn), chromium (Cr), nickel (Ni), and manganese (Mn) in agricultural soils and food crops (fruit, leaf, and root vegetables), and their associated health risks to the local population in selected southern districts of Khyber Pakhtunkhwa Province, Pakistan. The concentrations of the selected metals in soil varied over a wide range, in the following decreasing order: Mn > Zn > Cr > Ni > Cu. The bioaccumulation of metals in vegetables was within the permissible risk limits, except for Cr which showed higher contamination in all the tested food crops. The trend of metal transfer factors for different vegetables was in the order of Cu > Ni > Cr > Mn > Zn, while the calculated daily intake of metals (DIM) in adults and children through consumption of food crops was in the decreasing order of Mn > Zn > Ni > Cr > Cu. The health risk index (HRI) values for the heavy metals for both adults and children were less than 1. Therefore, no significant health risk is anticipated for the local consumers through ingestion of these food crops.     

尾矿库尾砂及周边农田土壤重金属形态分布及其生物有效性

采用BCR（community bureau of reference）连续提取法对大宝山矿山槽对坑尾矿库尾砂和周边农田土壤重金属Cd、Pb、Cu和Zn的形态分布及其生物有效性进行了分析。结果表明,尾砂中Cd、Pb、Cu和Zn残渣态占绝对优势,占其总量的百分数均在85%以上。农田土壤中Cd、Cu和Zn都以残渣态为主,分别占其总量的60%、60%和90%以上,Pb以残渣态和可还原态为主,占其总量的93.44%。农田土壤重金属有效性较尾砂大,尾砂和农田土壤重金属生物有效性均以Pb为最高。     

Chelate-Assisted Phytoextraction of Cadmium and Lead using Mustard and Fenugreek

A screen-house experiment was conducted to study cadmium (Cd) and lead (Pb) phytoextraction using mustard and fenugreek as test crops. Cadmium was applied at a rate of 20 mg kg^?1 soil for both crops, and Pb was applied at 160 and 80 mg kg^?1 soil for mustard and fenugreek, respectively. The disodium salt of ethylenediamine tetraacetic acid (EDTA) was applied at 0, 0.5, 1.0, and 1.5 g kg^?1 soil. Dry-matter yield (DMY) of both crops decreased with increasing rates of EDTA application. Application of 1.5 g EDTA kg^?1 soil caused 23% and 70% declines in DMY of mustard and fenugreek shoots, respectively, in the soils receiving 20 mg Cd kg^?1 soil. Similarly, in soil with 160 mg Pb kg^?1 soil, application of 1.5 g EDTA kg^?1 resulted in 25.4% decrease in DMY of mustard shoot, whereas this decrease was 55.4% in fenugreek grown on a soil that had received 80 mg Pb kg^?1 soil. The EDTA application increased the plant Cd and Pb concentrations as well as shoot/root ratios of these metals in both the crops. Application of 1.5 g kg^?1 EDTA resulted in a 1.50-fold increase in Cd accumulation and a 3-fold increase in Pb accumulation by mustard compared to the control treatment. EDTA application caused mobilization of Cd and Pb from carbonate, manganese oxide, and amorphous iron oxide fractions, which was evident from decrease in these fractions in the presence of EDTA as compared to the control treatment (no EDTA).     

重金属汞、镉和铬对明亮发光杆菌的生物毒性

以明亮发光杆菌（Photobacterium phosphoreum）T3变种作为毒性测试物种,测定了重金属Hg2＋、Cd2＋和Cr6＋的单一毒性;采用二次二因子回归通用旋转组合实验设计,研究了Hg2＋＋Cd2＋、Hg2＋＋Cr6＋和Cd2＋＋Cr6＋3种二元重金属混合物的联合毒性作用和主因子作用,建立了3个相应的数学模型。结果表明,与单一重金属Hg2＋、Cd2＋与Cr6＋相比,它们的二元混合物对明亮发光杆菌生物毒性的效应和强度完全不同;单一重金属Hg2＋、Cd2＋与Cr6＋对明亮发光杆菌的毒性有显著的正效应,毒性从大至小依次为Hg2＋、Cd2＋、Cr6＋,对明亮发光杆菌的EC50分别为0.044、6.05mg·L-1和30.65mg·L-1;3种二元重金属混合物对发光细菌的联合毒性作用也不同,总体上,Hg2＋与Cd2＋、Cd2＋与Cr6＋为加和作用,而Hg2＋与Cr6＋以拮抗作用为主。     

上海市浦东新区土壤及蔬菜重金属现状调查及评价

对上海市浦东新区非污灌区的4个蔬菜园艺场和张江镇2个污灌区的土壤及其对应生长的蔬菜中的7种重金属进行检测。结果表明4个蔬菜园艺场符合无公害食品生产的园艺场环境要求,而张江镇污灌区的土壤Cd污染严重,其次是Cu、Zn和Hg污染,其上生长的蔬菜中Cr和Cd100%超标,属轻度污染。张江镇污灌区土壤和蔬菜的污染主要是由于上世纪70年代应用黄浦江疏浚底泥吹泥和污水灌溉等因素,致使土壤及农产品中重金属遭受污染。     

污泥农用对土壤和作物重金属累积及作物产量的影响

以3 a定位试验为基础,比较3种不同处理的污泥肥料（消化污泥、污泥堆肥及污泥复混肥）农田施用下土壤养分、土壤和作物籽粒中Mn、Cu、Zn、Pb、Cd 5种重金属的积累以及作物产量的变化情况,以阐明污泥农用对土壤及作物的影响。研究表明,3种污泥肥料提高了土壤中氮素和有机质的含量;与空白和普通化肥处理相比,3种污泥肥料增加了土壤中Mn和Cu的含量,而对土壤交换态重金属含量没有显著影响;3种污泥处理均增加了小麦籽粒中Zn的含量;相对普通化肥处理,3种污泥肥料处理对小麦和玉米产量均无显著影响。合理施用污泥肥料可以有效地提高作物产量;污泥肥料施用对土壤重金属有一定累积效应,但短期施用对土壤比较安全。     

Uptake and translocation of cadmium and nutrients by Aeluropus littoralis

To our knowledge there has been no research on Aeluropus littoralis as a halophyte plant, when grown in soil contaminated with cadmium (Cd). Hence, the ability of A. littoralis to take up Cd and some nutrients was investigated in a pot experiment. Five levels of soil Cd concentration were tested (15, 30, 60, 120 and 240 mg Cd kg^?1 soil). Plants were harvested at three different times and analyzed for Cd, N, P, K, Mg, Mn, Cu, Fe and Zn concentrations. Plant biomass decreased as a result of excess Cd. Cadmium concentration in plant shoots increased with increasing Cd supply, significantly affecting the plant nutrient content. An excess Cd supply increased macronutrient and decreased micronutrient concentrations in the plant. Although, the research process will become more complicated, this new approach may help to investigate the tolerance of A. littoralis to Cd stress for use in phytoremediation.