利用化学和生物指标评价不同来源土壤铜的生物有效性

Bioavailability is a key parameter in assessing contaminant transfer to biota. However, the input patterns and soil use types may impact the metal bioavailability. Several soil parameters were measured including chemical properties, such as pH, organic C, and Cu solution/solid speciation, and biological properties, such as soil microbial biomass C （SMBC）, seed germination, and root elongation, to evaluate the bioavailability of Cu contaminated soils from three different sources, i.e., non-ferrous metal mining, Cu-based fungicides, and Cu-smelting. The results revealed that free Cu2＋ ion in soil solution and the ratios of Cu fractions to total Cu content in the solid phase could not be used to predict total Cu content in soils. The indexes of seed germination and root elongation appeared not to be good biomonitors of Cu contamination in soils, which were more sensitive to soil pH and soil organic carbon （SOC）. Relationships between SMBC and soil Cu forms or the ratio of SMBC/SOC and soil Cu forms showed that free Cu2＋ ion and humie acid-complexed Cu could significantly inhibit soil microbial activities. Our findings suggested that both metal chemical forms and biological bioassays should be considered as a complementary technique rather than an alternative to evaluate the metal bioavailability from different pollution sources.     

受土壤类型和金属负荷量影响的重金属形态分布

Two series of soil subsamples, by spiking copper(Cu),lead(Pb),zinc(Zn)and cadmium(Cd)in an orthogonal design,were prepared using red soil and brown soil,respectively.The results indicated that heavy metal fractions in these soil subsamples depended not only on soil types,but also on metal loading quantity as well as on interactions among metals in soil.Lead and Cu in red soil appeared mostly in weakly specifically adsorbed(WSA),Fe and Mn oxides bound(OX),and residual(RES)fractions.Zine cxisted in all fractions except organic bound one,and Cd was major in water soluble plus exchangeable(SE)one.Different from the results of red soil,Pb and Cu was present in brown soil in all fractions except organic one,but over 75% of Zn and 90% of Cd existed only in SE fraction.Meanwhile,SE fraction for any metal in red soil was lower than that in brown soil and WSA and OX fractions were higher.It is in agreernent with low cation exchange capacity and large amounts of metal oxides included in red soil.Metal fractions in soil,especially for water soluble plus exchangeable one ,were obviously influenced by other coexisting metals.The SE fraction of heavy metals increased with increasing loading amounts of metals in red soil but not obviously in brown soil,which suggest that metal availability be easily affected by their total amounts spiked in red soil.In addition,more metals in red soil were extracted with 0.20 mol L^-1 NH4Cl（pH5.40）than that with 1.0 mol L^-1 Mg(NO3)2(pH7.0),but the reverse happened in brown soil,implicating significantly different mechanisms of metal desorption from red soil and brown soil.     

外生菌根诱导油松根际土壤重金属形态变化

To understand the role of ectomycorrhizas in improving the tolerance of its host to excessive heavy metals in soil, this study was conducted to exam the patterns of four fractions （the exchangeable, the carbonate-bound, the Fe-Mn oxide- bound and the organically bound） of both Cu and Cd in the rhizosphere of Chinese pine （Pinus tabulaeformis） seedlings grown in excessive Cu and Cd environment. The results showed that the speciation of Cu and Cd in the rhizosphere was significantly influenced by inoculation of ectomycorrhizal fungus Boletus edulis. Compared to the rhizosphere, the content of exchangeable Cu slightly decreased in the mycorrhizosphere of the seedlings grown in 166 and 400 mg kg^-1 Cu contaminated soil, whereas the exchangeable Cd in the mycorrhizosphere decreased remarkably to only 33% and to 60% that of the rhizosphere at 0.75 and 1.50 mg kg^-1 Cd levels, respectively. These indicate the potential capacity of mycorrhizas to alleviate the damage of heavy metals to the host plants by reducing the bioavailability of heavy metals in soil. Distribution of the 4 tested fractions of Cu and Cd at different contamination levels showed that there was a strong tendency of changing from loosely associated fractions to strongly associated fractions in the mycorrhizosphere. The most stable Cd fraction, organically bound Cd, was significantly larger in the mycorrhizosphere than in the rhizosphere at different Cd contamination levels. This phenomenon was also observed for Cu but the difference was not statistically significant.     

华北矿区残留态铜、铅在土壤剖面中的分布与迁移

Residual heavy metals are commonly considered to be immobile in soils, leading to an underestimation of their environmental risk. This study investigated the distribution and transport of residual heavy metals along soil profiles, using the Xiaoqinling gold mining region in North China as a case study. Soil samples were collected at three depths from three locations near the tailing heap. The speciation of copper (Cu) and lead (Pb) (exchangeable, carbonate-bound, Fe-Mn oxide-bound, organic matter-bound, and residual fractions) was determined using a sequential extraction procedure. The residual fraction’s morphology was observed using scanning electron microscopy (SEM). Results showed that metal fraction distributions along the soil profiles were influenced by each fraction’s mobility. Residual fraction with high chemical stability cannot be transformed from or into other fractions. This led to the conclusion that the high concentration of residual metals in soils mainly resulted from residual fraction transport.The SEM analysis showed that fine particles (submicrons) were mainly attached to large particles and were likely released and transported by water flow. The more sorptive fractions (non-residual fractions) were mainly retained in the top soil, and the more mobile fractions (residual fraction) were mainly leached to the deep soil. Cu and Pb concentrations in the residual fraction decreased slightly and those in the non-residual fractions decreased significantly with soil depth. These suggest a relatively higher residual metal mobility along the soil pro?les. Therefore, residual metals can be transported in soils and their environmental risk can not be ignored in assessing soil contamination.     

氧化节杆菌生物降解苯并芘

A pot experiment was conducted with multi-metal (Pb, Cd, Cu, and Zn) contaminated acidic soil to investigate changes in available metal burden resulting from the application of industrial wastes (fly ash and steel slag). The efficiency of amendments-induced metal stabilization was evaluated by diffusive gradients in thin films (DGT), sequential extraction, and plant uptake. The stability of remediation was assessed by an acidification test and by chemical equilibrium modeling. Addition of fly ash (20 g kg-1 ) and steel slag (3 g kg-1 ) resulted in similar increase in soil pH. Both amendments significantly decreased the concentrations of metals measured with DGT (C DGT) and the metal uptake by Oryza sativa L. Significant correlations were found between C DGT and the concentration of a combination of metal fractions (exchangeable, bound to carbonates, and bound to Fe/Mn oxides), unraveling the labile species that participate in the flux of metal resupply. The capability of metal resupply, as reflected by the R (ratio of C DGT to pore water metal concentration) values, significantly decreased in the amended soils. The C DGT correlated well with the plant uptake, suggesting that DGT is a good indicator for bioavailability. Acidification raised the extractable metal concentration in amended soil but the concentration did not return to the pre-amendment level. Equilibrium modeling indicated that the soil amendments induced the precipitation of several Fe, Al and Ca minerals, which may play a positive role in metal stabilization. Chemical stabilization with alkaline amendments could be an effective and stable soil remediation strategy for attenuating metal bioavailability and reducing plant metal uptake.     

污泥加石灰后作为肥料用于玉米生长中施肥研究

The use of sewage sludge on agricultural land provides an alternative for its disposal. Therefore, the aim of the present study was to evaluate the feasibility of using industrial sewage sludge produced in Pakistan, as an agricultural fertilizer. The agricultural soil amended with 250 g kg^-1 sewage sludge with or without lime treatment was used for the growth of the common local grain crop, maize （Zea maize）. The mobility of the trace and toxic metals in the sludge samples was assessed by applying a modified BCR sequential extraction procedure. The single extraction procedure was comprised of the application of a mild extractant （CaCl2） and water, for the estimation of the proportion of easily soluble metal fractions. To check the precision of the analytical results, the concentrations of trace and toxic metals in every step of the sequential extraction procedure were summed up and compared with total metal concentrations. The plant-available metal contents, as indicated by the deionized water and 0.01 mol L^-1 CaCl2 solution extraction fractions and the exchangeable fraction of the sequential extraction, decreased significantly （P 〈 0.05） with lime application because of the reduced metal availability at a higher pH, except in the cases of Cd and Cu, whose mobility was slightly increased. Sludge amendment enhanced the dry weight yield of maize and the increase was more obvious for the soil with lime treatment. Liming the sewage sludge reduced the trace and toxic metal contents in the grain tissues, except Cu and Cd, which were below the permissible limits of these metals. The present experiment demonstrates that liming was an important factor in facilitating the growth of maize in sludge-amended soil.     

苏南地区土壤重金属向蔬菜的迁移研究

Vegetable fields in peri-urban areas receive large amounts of extraneous heavy metals because of rapid urbanization and industrialization in China. The concentrations of Cu, Zn, and Pb in 30 soil samples and 32 vegetable samples, collected from 30 different sites in southern Jiangsu Province of China, were measured and their transfer from soil to vegetable was determined. The results showed that the soil samples had wide ranges of pH (4.25-7.85) and electrical conductivity (EC) (0.24-3.42 dS m^-1). Among the soil samples, there were four soil samples containing higher Cu and two soil samples containing higher Zn concentrations than those specified in the Chinese Soil Environmental Quality Standard II. However, no vegetable sample was found to contain a high level of Cu or Zn. In contrast, one vegetable sample contained 0.243 mg Pb kg^-1 FW, which was above the Chinese Food Hygiene Standard, whereas the corresponding soil Pb concentration was lower than the Chinese Soil Environmental Quality Standard II. The transfer coefficients of Cu of all vegetable samples exceeded the suggested coefficient range, implying that extraneous Cu had high mobility and bioavailability to vegetables. There was no significant correlation between extractable soil heavy metal concentrations with four kinds of extractants and soil pH, EC, heavy metal concentrations in vegetables and soils, except that soil pH correlated well with the extractable soil Cu, Zn, and Pb concentrations with 1.0 mol L^-1 NH₄NO₃. Moreover, diethylenetriamine pentaacetic acid (DTPA) extraction method was a more effcient method of extracting heavy metals from the soils independent of soil pH and EC than other three methods used.     

中国东部太湖地区酸性水稻土团聚体上铜的专性和非专性吸附动力学研究

The Taihu Lake region in East China has become prone to soil acidification, which changes heavy metals such as copper(Cu) in soil into water-soluble species and increases the mobility and contamination risks of heavy metals in the biological environment. In this study, the kinetics of Cu2+sorption by the bulk soil and the aggregate size fractions of an acidic paddy soil collected from the Taihu Lake region, the effects of temperature on Cu2+sorption, and the p H changes of the solution were investigated by static sorption and magnetic stirring. The aggregate size fractions were prepared by low-energy ultrasonic dispersing and freeze-drying. The total sorption amounts of the bulk soil and the aggregate size fractions for Cu2+followed a descending order of clay > coarse sand > bulk soil > silt> sand, corresponding to those of organic matter content, free iron oxide content, free aluminum oxide content, and cation exchange capacity. The kinetic sorption curves of Cu2+by the bulk soil and the aggregates, which were divided into two stages(rapid and slow sequentially), were well fitted by the first-order equation, the diffusion equation, and the Elovich equation, showing significant correlations(P < 0.05). Specific and non-specific sorption dominated in the fast and slow stages, respectively, and the former was predominant throughout the sorption process. The specific sorption accelerated and the non-specific sorption decelerated with rising temperature. The p H of the solution decreased significantly during the specific sorption and remained unchanged or increased slightly during the non-specific sorption. When the specific sorption terminated, the p H of the solution was minimized nearly simultaneously.The sorption progress of Cu2+by the bulk soil significantly preceded that by the aggregates. Therefore, heavy metal contamination may be another factor reducing soil p H and metal sorption forms should be taken into consideration in studies of mitigating soil heavy metal pollution or determining environmental capacity of heavy metal in soil.     

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.     

三峡库区坡地表层风化特征研究

Extractability and mobility of Cu and Zn and their relationships with 1） accumulation of Cu and Zn and 2） soil pH were studied in three sandy soils （Wabasso, Ankona, and Winder） from commercial citrus groves in Florida, USA. The soils, with a broad range of Cu and Zn concentrations, were fractionated by a modified procedure of Amacher, while Cu and Zn mobility were evaluated using column leaching. The extractability of Cu and Zn increased with decreasing soil pH. Also with increasing total soil Cu and Zn for extractable Cu in the Wabasso sand a threshold level, where the metal extraction rate increased, was noted at 100 mg kg^-1, whereas for extractable Zn in the Wabasso sand the threshold level was found at 60 mg kg^-1 and in the Ankona sand at 120 mg kg^-1. These results suggested that the release potential of Cu and Zn was greater in the Wabasso sand than in the Ankona sand. The column leaching experiment showed that at total soil Cu or Zn concentrations 〈 100 mg kg^-1 all leachates had low Cu and Zn concentrations. However at total concentrations 〉 200 mg kg^-1 for Cu and 〉 150 mg kg^-1 for Zn with decreasing soil pH, the concentrations of both Cu and Zn in the leachates increased exponentially. Also in these sandy soils soluble Cu and Zn mainly originated from the exchangeable fractions, and pH was a key factor controlling Cu and Zn extractability and mobility.     

Assessment of the interactions of metals and nitrilotriacetic acid in soil/sludge mixtures

The solution phase forms of Cu, Mn, Ni, and Zn in digested sewage sludge and a soil/sludge mixture were investigated. Gel filtration chromatographic analysis indicated that Cu and possibly Ni were maintained in solution by association with a soluble, high molecular weight organic fraction; Mn solubility was due to the presence of unbound inorganic species and soluble Zn was distributed equally between the two forms. Speciation of the metals in the solution phase of the soil/sludge mixture generally reflected that of the sludge. However, the total amount of soluble Mn in the soil/sludge mixture was approximately 25 times greater than in the sludge and was attributed to heavy metal induced release of indigenous soil Mn. Increases in the quantities of soluble Ni and Zn in both the sludge and the soil/sludge mixture following equilibration with 40 mg L^?1 NTA were due to conversion of solid phase forms to soluble metal-NTA complexes. The preferential complexation of NTA with Cu already present in soluble organic forms resulted in a change in speciation without a corresponding increase in solubility. The importance of changes in speciation with regard to potential metal mobility and bioavailability within sludge-amended soil is discussed.     

Metal‐Associated Forms and Speciation in Biosolid‐Amended Oxisols

Abstract

The objective of this study was to determine the effects of pH and ionic strength on the distribution and speciation of zinc (Zn), copper (Cu), and cadmium (Cd) in surface soil samples from two Brazilian Oxisols amended with biosolids. Soils and biosolids were equilibrated in an experimental dual‐chamber diffusion apparatus that permits the soils and biosolids to react through a solution phase via diffusion across a membrane. After equilibrium was reached, soil and biosolids samples were sequentially fractionated to identify various solid forms of Zn, Cu, and Cd. Metal concentrations in the solution phase were determined and mass balance calculated. Equilibrating pH had no major effect on Cu solubility from biosolids and, at pH range from 4 to 7, most Cu remained in the biosolids. Soluble Zn and Cd concentration increased with decreasing pH because of the increased solubility of the biosolids. Copper and Zn were primarily associated with the residual fraction and Fe oxides in one soil, but were primarily associated with chemically unstable fractions, or adsorbed to the surface of oxides, in the other soil. In both soils, Cd was primarily associated with readily bioavailable fractions. The effect of pH on the metal distribution was more evident than the ionic strength effect. Free ions were the predominant metal species in solution, especially at lower pH values.     

Speciation of Metals in Sewage Sludge and Sludge-amended Soils

This study is aimed at ascertaining the chemical partitioning ofCu, Zn, Pb, Ni, Cr and Cd in sewage sludge and agricultural soils repeatedly amended with sludge. The operationally determined speciation was investigated by using selective five steps sequential extraction method for partitioning these metals into different chemicalforms, likely to be released in solution under various environmental conditions. It provides qualitative evidence regarding the form of the association of metals and indirectly of their bioavailability. It can help to explain the process by which metals are eliminated from sewagesludge and also indicate the impact of the use of sludge on agriculturalsoils, as amendments. Data obtained by extraction procedure showed different metal distribution trend among the fractions in sewage sludgeand sludge-amended soils. Comparison of distribution pattern of metals in sludge and sludge-applied soils shows that there is possible redistribution of metals among the different phases. The sum of the metal content in the fractions compared well with the total metal content in sewage sludge, the ratios averaging 1.02, 1.04, 1.07, 0.94, 1.06, and 1.12 for Cu, Zn, Pb, Ni, Cr, and Cd, respectively. The metal recovery efficiency in sludge-amended soils was found to be: 108±6%, 102±5%, 115±8%, 111±4%, 104±7%and 124±28% for Cu, Zn, Pb, Ni, Cr and Cd, respectively.     

施污土壤与污泥中Cu、Pb、Cd、Zn的形态分布

污泥中的重金属元素是限制其大规模农田利用的重要因素。施污土壤和污泥中重金属的形态研究可以用来评价土壤中重金属的生物有效性以及它们在土壤中的移动性。用修正BCR三步连续提取法进行分步提取研究了污水污泥和施污后的西红柿地土壤中Cu、Pb、Cd、Zn的形态分布状况。施用污泥堆肥10t hm-2后的土壤中Cu、Pb、Cd、Zn的全量与各种形态含量无明显增加,Cu、Pb、Zn含量远低于国家土壤环境质量标准。土壤中Cu的各种形态分布关系是:残渣态>可还原态=可氧化态>可交换态和弱酸溶解态,Cu在土壤中的存在是以最稳定的残渣态为主。堆肥污泥与干化污泥相比,残渣态Cu的比例明显增加。土壤中Pb的各种形态分布关系是以残渣态和可还原态为主,但可氧化态的分布比例最小。土壤中Cd的可交换态、可还原态和残渣态各占据相等的含量,但可氧化态Cd的含量几乎为零。Zn在土壤中的各种形态分布关系是:可交换态和弱酸溶解态>可氧化态>可还原态>残渣态,Zn在土壤中的存在是以最易迁移的可交换态和弱酸溶解态为主。这些金属元素在土壤中的相对稳定性顺序为:Cu>Pb>Cd>Zn。Zn在土壤中的移动性要远高于Cu。     

水稻子实对不同形态重金属的累积差异及其影响因素分析

在分析成都平原核心区土壤重金属(Cd、Cr、Pb、Cu、Zn)全量、各形态含量及相应点位种植的水稻子实重金属含量的基础上,通过统计分析、空间插值及线性回归方程的模拟,研究了土壤Cd、Cr、Pb、Cu、Zn全量的空间分布状况、各形态重金属含量统计特征,以及水稻子实对重金属各形态的累积差异及其影响因素。结果表明,成都平原水稻土重金属污染较轻,除Cd外,均低于国家土壤环境质量二级标准。土壤中重金属的可交换态含量均较低,Cd主要以铁锰氧化态存在,Cr、Cu、Zn、Pb主要以残渣态存在。水稻子实对5种重金属的累积效应顺序为:Cd>Zn>Cu>Pb>Cr。与水稻重金属累积关系密切的重金属活性形态(可交换态、碳酸盐结合态、铁锰氧化物结合态和有机物结合态)主要有:Cd的碳酸盐结合态、Cr的可交换态、Pb的有机物结合态和Cu的碳酸盐结合态含量;Zn各活性形态对水稻子实含量的影响不明显。土壤理化性质对不同活性形态重金属元素的影响效应各不相同。活性态Cd主要受有机质、pH和容重的影响;活性态Cr与pH、有机质、CEC和容重密切相关;活性态Pb与有机质、容重、中细粉粒、砂粒等均有密切的关系;Cu的活性主要受粘粒、有机质含量的影响;Zn的有效性主要受pH、有机质、砂粒、容重的影响。总的看来,对土壤Cd、Cr、Pb、Cu、Zn各活性形态含量影响效应较强的是有机质、pH、容重,而与土壤吸附性能密切相关的颗粒组成、CEC的影响不甚明显。     

Laboratory Study on the Mobility of Major Species in Fly Ash–Brine Co-disposal Systems: Up-flow Percolation Test

Soil pollution is a universal environmental issue, and the clean-up of contaminated soils can be costly and time consuming. Traditional methods often do not provide an effective solution when it comes to fine-grained and highly impermeable soils and/or immobile contaminants. Electro-remediation, however, is a promising technique. The aim of this study was to relate electrokinetic removal of heavy metals from a contaminated, aged sediment sludge to the metal speciation in the sludge. Metal speciation was determined by a Tessier-based sequential extraction method. Two electro-remediation experiments were conducted in the laboratory in order to investigate removal of metals. The studies were done in a cell designed for a predictive laboratory test of feasibility of electro-remediation of soil. Maximum removal percentages during the experiment using a constant current of 1 mA/cm² over ～180 h with a corresponding potential gradient of 0.5 V/cm were larger than 15 % for Cd (21 %), Cu (15 %), and Zn (23 %); Ni and Pb showed removal less than 10 %; Cr demonstrated no removal. Removal of non-contaminant metals Mn and Ca exceeded that of heavy metals. The removal rates were compared to metal speciation in the non-treated sludge, measured by the sequential extraction. It was observed that the electrokinetic removal did not directly relate to the metal distribution over the fractions within the sludge. The aging of metals and other geochemical characteristics of the contaminated sludge affected the removal of heavy metals. Therefore, sequential extraction alone does not provide a predictive tool for the effectiveness of electro-remediation. Additional geochemical information is needed.     

Feasibility of a counter-current extraction procedure for the removal of heavy metals from contaminated soils

Effective remediation and sanitation technologies for soils contaminated with heavy metals are limited. We investigated the feasibility of a counter-current metal extraction procedure for the removal of selected heavy metals (Cd, Cu, Ph, and Zn) from two contaminated soils. The process involved a decarbonation (removal of carbonates), acid solubilisation, washing, and liming step. Results from batch equilibration experiments simulating the counter-current process showed more than 85% of the Cd present to be removed. Removal efficiencies for Cu and Pb were limited to approximately 15%, this mainly due to resorption of these elements during the decarbonation step. As most Zn was found to be present in a more difficult acid-extractable solid phase, its extractability accounted for only 25%. While reaction (pH) conditions of both decarbonation and solubilisation determined removal efficiencies, washing the extracted soil with deionized water only slightly increased the amount of metals removed. Metal distribution among solid phases — exchangeable, carbonate, reducible, organically bound, and residual — was affected by the different treatments. The amount of metals contained in the exchangeable and residual fractions determined their extractability. Except for Cu, the reducible and organically bound fractions were less important. After solubilisation 13 to 70% of the metals were present in an exchangeable solid phase. This implicates that washing the solubilized soil with a salt may increase the extractability of metals, especially for Zn and Pb. Based on our results the process is critically evaluated and possibilities for optimization formulated.     

剩余污泥厌氧消化过程重金属形态转化及生物有效性分析

为研究污泥厌氧消化过程中物理化学性质的变化对典型重金属形态转化的影响,对其农用的可行性及生物有效性进行评估,对取自某城市污水处理厂的剩余污泥进行了序批式厌氧消化实验,在试验过程中测定了污泥理化学性质,采用Tessier分步提取法提取了污泥样品中的典型重金属,并采用电感耦合等离子发射光谱仪（ICP-OES）测定各形态重金属含量及总量。结果表明,厌氧消化过程中重金属的形态发生了显著变化,由不稳定态向比较稳定的残渣态和有机结合态转变,某些重金属形态与污泥理化性质如pH、碱度、VS/TS及氨氮显著相关。厌氧消化可以有效地降低污泥中重金属的潜在迁移能力和生物有效性,经厌氧消化后污泥可以更好地进行土地利用。     

北京市五环内绿地土壤4种重金属的形态特征及其生物有效性

[目的]了解北京市五环内绿地表层(0—20cm)土壤重金属(Cu,Cd,Pb和Zn)的形态特征及其生物有效性,为北京市绿地土壤重金属污染防治提供比较可靠的参考依据。[方法]在建成时间为2~400a的绿化区内共采集表层土壤样品151个,运用改进BCR提取法分析样品中重金属的赋存形态,而后通过风险评价编码法(RAC)和次生相与原生相分布比值法(RSP)对重金属生物有效性进行评估。[结果]样品中重金属Cu,Cd,Pb和Zn的含量分别为31.42,0.29,29.89,76.78 mg/kg,Cu,Zn在中部和东北部含量较高,Pb在中部地区含量较高,Cd在西北部、东北部和南部存在少量高值区。Cu,Cd,Pb和Zn形态分布的总体规律均为:残渣态可氧化态弱酸溶态可还原态,稳定态含量均远高于有效态,有效态含量比例表明重金属生物有效性大小顺序为:CdZnCuPb风险评价编码法(RAC)表明,Cd和Zn环境风险程度为低风险,Cu和Pb无环境风险。次生相与原生相分布比值法(RSP)显示,Cu,Cd,Pb和Zn元素RSP值分别为0.06,0.49,0.18,0.13,土壤整体上未受到重金属污染,但是有少部分地区存在被污染现象。[结论]北京市五环内绿地土壤总体上不存在重金属Cu,Cd,Pb和Zn污染,环境风险较低,但应对重金属赋存形态保持关注。     

Effect of biosolid application to Mollisol Chilean soils on the bioavailability of heavy metals (Cu,Cr, Ni,and Zn) as assessed by bioassays with sunflower (Helianthus annuus) and DGT measurements

Purpose

This study assessed the effect of biosolid application on the bioavailable fraction of some trace elements (Cu, Cr, Ni, and Zn) using a bioassay with sunflower (Helianthus annuus) and a chemical assay, diffusion gradient in thin films (DGT).

Materials and methods

Five surface soil samples (0–20 cm) were collected from an agricultural zone in Central Chile where biosolids are likely to be applied. Municipal biosolids were mixed with the soil at concentrations of 0, 30, 90, and 200 Mg ha^?1. The experiment to determine the bioavailability of metals in the soil using the bioassay was performed using sunflower. The DGT technique and Community Bureau of Reference (BCR) sequential extraction were used to determine the bioavailable fractions of the metals.

Results and discussion

The application of biosolids increased the phytoavailability of Zn, Ni, and Cr in most of the soils, as indicated by the increasing concentrations in sunflower plants as the biosolid application rate increased. In two of the soils, Codigua and Pelvín, this increase peaked at an application rate of 90 Mg ha^?1. Decreases in the bioavailable fractions of Zn, Ni, and Cr were observed with higher biosolid application rates. The bioavailability of metals was estimated through multiple linear regression models between the metals in the sunflower plants and the different chemical fractions of metals in the soils treated with different biosolid rates, which displayed a positive contribution of the labile (water soluble, carbonate, and exchangeable), oxide, and organic metal forms in the soil, particularly with respect to Ni and Zn at application rates of 30 and 90 Mg ha^?1. The bioavailable fraction of metals was determined in soils using the DGT technique. The effective concentration (C _E) results were compared with those in sunflower plants. The DGT technique could effectively predict the bioavailable fractions of Cr, Ni, and Zn in the Taqueral soil but only that of Zn in the Polpaico soil.

Conclusions

The application of biosolids significantly increased the labile fraction of most of the metals in the studied soils, particularly at the highest biosolid application rate. C _E increased as the concentration of biosolids increased for most of the metals. The effectiveness of the DGT technique for predicting the bioavailability of metals was dependent on the soil type and the metal. However, the C _E for soil Cu was not related to plant Cu for all soils studied.