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.     

Effect of solid-phase speciation on metal mobility and phytoavailability in sludge-amended soil

Sequential extraction was utilized for partitioning Cd, Cr, Ni, and Zn, in soil and sludge samples into five operationally-defined fractions: exchangeable, bound to carbonates, bound to Fe-Mn oxides, bound to organic matter and residual. The highest amounts of Cd, Ni, and Zn, expressed as per cent of the total, were found in the Fe-Mn oxide fraction of the sewage sludge. Chromium was significantly associated with the organic fraction of the sludge. The residue was the most abundant fraction for all metals studied in the untreated soil, and for Cd and Ni in the sludge-treated soil. The concentration of exchangeable Cd and Cr was relatively low in the untreated soil and did not change much after sludge application, whereas the concentrations of exchangeable Zn increased about 50 times and the concentrations of exchangeable Ni doubled in the sludge-treated soil. The lysimetric experiment revealed an increase in Zn and Ni uptake by ryegrass and in the percentage of metals leached from the soil profile after massive sludge application. In contrast only negligible changes were observed for Cd and Cr. The assumption that mobility and biological availability are related to metal speciation was confirmed by the agreement between the distribution pattern of Cd, Cr, Ni and Zn in the soils, the uptake of the metals by plants and their capacity for leaching out from the soils.     

Characterization of soil heavy metal pools in paddy fields in Taiwan: chemical extraction and solid-solution partitioning

Background, aim, and scope  Ongoing industrialization has resulted in an accumulation of metals like Cd, Cu, Cr, Ni, Zn, and Pb in paddy fields across Southeast Asia. Risks of metals in soils depend on soil properties and the availability of metals in soil. At present, however, limited information is available on how to measure or predict the directly available fraction of metals in paddy soils. Here, the distribution of Cd, Cu, Cr, Ni, Zn, and Pb in 19 paddy fields among the total, reactive, and directly available pools was measured using recently developed concepts for aerated soils. Solid-solution partitioning models have been derived to predict the directly available metal pool. Such models are proven to be useful for risk assessment and to derive soil quality standards for aerated soils. Material and methods  Soil samples (0–25 cm) were taken from 19 paddy fields from five different communities in Taiwan in 2005 and 2006. Each field was subdivided into 60 to 108 plots resulting in a database of approximately 3,200 individual soil samples. Total (Aqua Regia (AR)), reactive (0.43 M HNO₃, 0.1 M HCl, and 0.05 M EDTA), and directly available metal pools (0.01 M CaCl₂) were determined. Solid-solution partitioning models were derived by multiple linear regressions using an extended Freundlich equation using the reactive metal pool, pH, and the cation exchange capacity (CEC). The influence of Zn on metal partitioning and differences between both sampling events (May/November) were evaluated. Results  Total metals contents range from background levels to levels in excess of current soil quality standards for arable land. Between 3% (Cr) and 30% (Cd) of all samples exceed present soil quality standards based on extraction with AR. Total metal levels decreased with an increasing distance from the irrigation water inlet. The reactive metal pool relative to the total metal content is increased in the order Cr << Ni = Zn < Pb < Cu < Cd and ranged from less than 10% for Cr to more than 70% for Cd. Despite frequent redox cycles, Cd, Pb, and Cu appear to remain rather reactive. The methods to determine the reactive metal pool in soils yield comparable results, although the 0.43 M HNO₃ extraction is slightly stronger than HCl and EDTA. The close correlation between these methods suggests that they release similar fractions from soils, probably those reversibly sorbed to soil organic matter (SOM) and clay. The average directly available pool ranged from less than 1% for Cu, Pb, and Cr to 10% for Ni, Zn, and Cd when compared to the reactive metal pool. For Cd, Ni, Zn, and to a lesser extent for Cu and Pb, solid-solution partitioning models were able to explain up to 93% (Cd) of the observed variation in the directly available metal pool. CaCl₂ extractable Zn increased the directly available pool for Ni, Cd, and Cu but not that of Pb and Cr. In the polluted soils, the directly available pool was higher in November compared to that in May. Differences in temperature, rainfall, and changes in soil properties such as pH are likely to contribute to the differences observed within the year. The solid-solution partitioning model failed to explain the variation in the directly available Cr pool, probably because Cr is present in precipitates rather than being adsorbed onto SOM and clay. Despite obvious differences in parent material, source of pollution, climate, and land use, solid-solution partitioning of Cd in paddy fields studied here was similar to that in soils from Belgium and the Netherlands. Discussion  To assess risks of metals in soils, both analytical procedures as well as models are needed. The three methods tested here to determine the reactive metal pool are highly correlated and either of these can be used. The directly available pool was predicted most accurately by the 0.43 M HNO₃ method. The similarity of metal partitioning in paddy soils compared to well-drained soils suggests that changing redox conditions in paddy fields have a limited effect on the geochemical behavior of metals like Cd, Ni, and Zn. Small but significant differences in the directly available metal pool during the year suggest that redox cycles as well as differences in rainfall and temperature affect the size of the directly available metal pool. The large observed spatial heterogeneity of contaminant levels requires ample attention in the setup of soil monitoring programs. Conclusions  The directly available pool (0.01 M CaCl₂) of Cd, Zn, and Ni in paddy fields can be described well by an extended Freundlich model. For Cu and Pb, more information on dissolved organic carbon is needed to obtain a more accurate estimate of the directly available pool. Recommendations and perspectives  Soil testing protocols and models used in risk assessment consider the availability of pollutants rather than the total metal content. Results from extensive testing indicate that approaches developed for nontropical regions can be applied in paddy fields as well for metals like Cd, Ni, and Zn. This study shows that the chemical behavior under drained conditions in paddy fields is comparable to that observed in soils across the European Union, which allows regions with large scale soil pollution including Taiwan to apply such concepts to derive meaningful experimental protocols and models to assess risks of metals in soils.     

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。     

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。     

新乡市寺庄顶污灌区土壤中重金属的形态分布及生物有效性研究

对长期电池废水灌溉的新乡市寺庄顶污灌区和对照区土壤重金属进行取样分析,结果表明,对照区土壤中Cd,Ni,Zn,Cu和Cr含量都能达标,污灌区土壤中Cr含量能达标,Cd,Ni,Zn和Cu的含量超标,其平均含量分别为65.31,1 196.64,2 799.25,145.78 mg/kg,是国家土壤环境质量二级标准的108.85,19.94,9.33和1.46倍。形态分析结果表明,污灌区污染最严重的Cd主要以铁-锰氧化物结合态存在,所占比例平均为56.84%;Ni主要以铁-锰氧化物结合态和残余态存在,所占比例平均为37.44%和39.55%;Zn主要以残余态存在,所占比例平均为78.24%;Cu主要以有机结合态存在,所占比例平均为57.70%;Cr主要以有机结合态和残余态存在,所占比例平均为45.55%和34.18%。与对照相比,污灌降低了Cd,Ni,Zn,Cu和Cr残余态所占比例,提高了重金属迁移能力和生物有效性。在4种超标重金属中Cd可交换态所占比例最高,平均为24.54%,由于其生物有效性最高,Cd迁移能力和植物毒性最值得关注。     

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.     

Comparison of routine soil tests and EPA method 3050 as extractants for heavy metals in Delaware soils

Abstract

Agricultural use of sewage sludges can be limited by heavy metal accumulations in soils and crops. Information on background levels of total heavy metals in soils and changes in soil metal content due to sludge application are; therefore, critical aspects of long‐term sludge monitoring programs. As soil testing laboratories routinely, and rapidly, determine, in a wide variety of agricultural soils, the levels of some heavy metals and soil properties related to plant availability of these metals (e.g. Cu, Fe, Mn, Zn, pH, organic matter, texture), these labs could participate actively in the development and monitoring of environmentally sound sludge application programs. Consequently, the objective of this study was to compare three soil tests (Mehlich 1, Mehlich 3, and DTP A) and an USEPA approved method for measuring heavy metals in soils (EPA Method 3050), as extractants for Cd, Cu, Ni, Pb and Zn in representative agricultural soils of Delaware and in soils from five sites involved in a state‐monitored sludge application program.

Soil tests extracted less than 30% of total (EPA 3050) metals from most soils, with average percentages of total metal extracted (across all soils and metals) of 15%, 32%, and 11% for the Mehlich 1, Mehlich 3, and DTPA, respectively. Statistically significant correlations between total and soil test extractable metal content were obtained with all extractants for Cu, Pb, and Zn, but not Cd and Ni. The Mehlich 1 soil test was best correlated with total Cu and Zn (r=0.78***, 0.60***, respectively), while the chelate‐based extractants (DTPA and Mehlich 3) were better correlated with total Pb (r=0.85***, 0.63***). Multiple regression equations for the prediction of total Cu, Ni, Pb, and Zn, from soil test extractable metal in combination with easily measured soil properties (pH, organic matter by loss on ignition, soil volume weight) had R² values ranging from 0.41*** to 0.85***, suggesting that it may be possible to monitor, with reasonable success, heavy metal accumulations in soils using the results of a routine soil test.     

Distribution and Availability of Heavy Metals in Raw and Acidulated Phosphate Rock–Amended Soils

Abstract

The effectiveness of the application of raw (PR‐1), and partially acidulated phosphate rock (PR), at 25% (PR‐25) and at 50% (PR‐50), was investigated to reduce extractability and plant uptake of Pb, Cd, Cu, Ni, and Zn in three calciorthids soils.Furthermore, the effects of soil treatments on metal extractability were evaluated by sequential extraction. Similarly, such effects were assessed on the phytoavailability of metals of maize (Zea mays L.) through a pot experiment. Water‐soluble and exchangeable metal fractions (the bioavailable fractions) were influenced distinctively by PR treatments and soil properties. In addition, decrease of soluble and exchangeable metal fractions was compensated by an increase in metal extracted from other fractions. Most bioavailable soil metals correlated significantly with their associated level in plant tissue. Finally, plant metal uptake decreased with PR treatments, suggesting that PR application was likely to be effective in controlling metal immobilization in these soils.     

The effect of EDTA on the extractability of Zinc (Zn), Cadmium (Cd) and Nickel (Ni) in Vertisol and Alluvial soils

Ethylendiamintetraacetic acid (EDTA) is persistent in the environment. The presence of EDTA in soil may alter the mobility and transport of Zn, Cd and Ni in soils because of the formation of water soluble chelates, thus increasing the potential for metal pollution of natural waters. Mobility of metals is related to their extractability. To investigate metal extractability affected by EDTA, Zn, Cd and Ni were added to Vertisol and Alluvial soil at rates of 50, 2 and 5 mg kg^-1, respectively. Both natural and metal amended soils were treated with Na₂EDTA at rates of 0; 0.2 and 0.5 mg kg^-1. After five months of incubation soil samples were extracted with 0.1 N HCl, 0.005 M DTPA + 0.01 M CaCl₂ + 0.1 M TEA (0.005 M Diethylenetriaminepentaacetic acid + 0.01 M Calcium cloride + 0.1 M Triethanolamine) and 1 M Mg(NO₃)₂, the latter of which extracts the exchangeable from of metald (Zn, Cd and Ni).

According to experiment results, Zn, Cd and Ni in all extraction increased with increasing rates of EDTA in the natural and metal amended soils.     

Extractability and plant uptake of heavy metals in alum shale soils

Abstract

Fifty soil samples (0–20 cm) with corresponding numbers of grain, potatoes, cabbage, and cauliflower crops were collected from soils developed on alum shale materials in Southeastern Norway to investigate the availability of [cadmium (Cd), copper (Cu), zinc (Zn), lead (Pb), nickel (Ni), and manganese (Mn)] in the soil and the uptake of the metals by these crops. Both total (aqua regia soluble) and extractable [ammonium nitrate (NH₄NO₃) and DTPA] concentrations of metals in the soils were studied. The total concentration of all the heavy metals in the soils were higher compared to other soils found in this region. Forty‐four percent of the soil samples had higher Cd concentration than the limit for application of sewage sludge, whereas the corresponding values for Ni, Cu, and Zn were 60%, 38%, and 16%, respectively. About 70% the soil samples had a too high concentration of one or more of the heavy metals in relation to the limit for application of sewage sludge. Cadmium was the most soluble of the heavy metals, implying that it is more bioavailable than the other non‐essential metals, Pb and Ni. The total (aqua regia soluble) concentrations of Cd, Cu, Zn, and Ni and the concentrations of DTPA‐extractable Cd and Ni were significantly higher in the loam soils than in the sandy loam soils. The amount of NH₄NCyextractable metals did not differ between the texture classes. The concentrations of DTPA‐extractable metals were positively and significantly correlated with the total concentrations of the same metals. Ammonium nitrate‐extractable metals, on the other hand, were not related to their total concentrations, but they were negatively and significantly correlated to soil pH. The average concentration of Cd (0.1 mg kg^‐1 d.w.) in the plants was relatively high compared to the concentration previously found in plants grown on the other soils. The concentrations of the other heavy metals Cu, Zn, Mn, Ni, and Pb in the plants were considered to be within the normal range, except for some samples with relatively high concentrations of Ni and Mn (0–11.1 and 3.5 to 167 mg kg‘¹ d.w., respectively). The concentrations of Cd, Cu, Zn, Ni, and Mn in grain were positively correlated to the concentrations of these respective metals in the soil extracted by NH₄NO₃. The plant concentrations were negatively correlated to pH. The DTPA‐extractable levels were not correlated with plant concentration and hence DTPA would not be a good extractant for determining plant availability in these soils.     

Simultaneous Sorption of Cd,Cu, Ni,Zn, Pb,and Cr on Soils Treated with Sewage Sludge Supernatant

Disposal of sewage sludge creates the potential for heavy metal accumulation in theenvironment. This study assessed nine soils currently used as Dedicated Land Disposal units(DLDs) for treatment and disposal of municipal sewage sludge in the vicinity of Sacramento,California. Adsorption characteristics of these soils for Cd, Cu, Ni, Zn, Pb, and Cr were studiedby simultaneously mixing these elements in the range of 0-50 µmol L-1 with sludgesupernatant and reacting with the soil using a soil:supernatant ratio of 1:30, pH = 4.5 or 6.5, andconstant ionic strength (0.01 M Na-acetate). The concentration of metals in the supernatant wasdetermined after a 24 hr equilibration period. Adsorption isotherms showed that metal sorptionwas linearly related to its concentration in the supernatant solution. The distribution coefficientKd (Kd = concentration on solid phase/concentration in solution phase) was computed as theslope of the sorption isotherm. The distribution coefficients were significantly correlated to soilorganic matter content for Ni, Cu, Cd, and Pb at pH 4.5 and for Ni, Cu, Zn, and Cd at pH 6.5.There was also a correlation between Kd and soil specific surface area but no relationship to othersoil properties such as CEC, clay content, and noncrystalline Fe and Al materials. Therefore, soilorganic carbon and surface area appear to be the most important soil properties influencing metaladsorption through formation of organo-metal complexes. The Kd values for all elements werehigher at pH 6.5 than at 4.5. Selectivity between metals resulted in the following metal affinitiesbased on their Kd values: Pb>Cu>Zn>Ni>Cd≈Cr at pH 4.5 andPb>Cu≈Zn>Cd>Ni>Cr at pH 6.5.     

新乡市大棚菜田土壤重金属积累特征及污染评价

采用微波消解-ICP-AES技术,测定不同种植年限大棚菜田土壤样品中As、Pb、Zn、Cd、Cr、Mn、Ni、Cu等重金属的含量,研究不同种植年限与大棚菜田土壤重金属累积的相关性以及大棚菜田土壤重金属累积特征,并利用地积累指数法进行污染评价。结果表明:大棚菜田土壤重金属Zn、Pb、Ni、Mn和Cu的含量与种植年限具有极显著相关性;大棚菜田土壤中重金属Cd和Cr的含量与种植年限不相关。重金属元素间相关性分析表明,Zn与Pb、Cd、Ni、Mn、Cr、Cu,Pb与Cd、Ni、Mn、Cr、Cu,Cd与Ni、Mn、Cr,Ni与Mn、Cr、Cu,Mn与Cr、Cu具有污染同源性,Cu与Cd、Cr不具有污染同源性。地积累指数法污染评价结果显示Cd的污染等级达到了6级,已构成了极严重污染;Zn和Cu的污染等级达到2级,已构成了中度污染;Pb、Mn的污染等级达到1级,已经构成了轻~中度污染;As、Ni、Cr均未构成污染。     

泉州走马埭典型土壤重金属的赋存形态分析

采用改进的Tessier连续萃取方法研究了泉州走马埭国家农田示范保护区典型土壤中重金属(Cr、Ni、Cu、Zn、Cd、Pb)的化学形态分布,通过土壤重金属的赋存形态分析比较了6种重金属的生物可利用性。研究结果表明,土壤中不同重金属元素化学形态分布具有不同的特点:Cr和Ni主要以残渣态存在,其余形态所占的比例很小;Cu以残渣态含量最高,碳酸盐结合态含量最低;Zn以残渣态为主,可交换态含量最低;Cd以可交换态和碳酸盐结合态为主,水溶态含量最低;Pb以残渣态和铁锰氧化物结合态为主,水溶态含量最低。土壤中除Cd外,Zn、Cu、Cr、Pb、Ni在正常自然条件下相对比较稳定。     

包头市铜厂周边土壤中重金属垂直分布特征与形态分析

为了解包头市铜厂周边地区土壤剖面中重金属污染状况,采用火焰原子吸收分光光度法和Tessier连续提取法,对土壤中6种重金属（Cu,Zn,Mn,Ni,Pb和Cd）的垂直分布特征、形态及潜在生物可利用性进行了分析。结果表明:研究区土壤剖面各层土壤中6种重金属含量均超过内蒙古土壤背景值,Cu,Pb和Cd为主要污染物。随采样深度的增加,Cu,Zn,Pb和Mn的含量呈现下降趋势,且由相关性系数可知重金属Cu,Zn和Pb可能有相同人为或自然污染源;土壤剖面中6种重金属均主要以残渣态存在,含量均在50%以上,对生物危害较小;潜在生物可利用性分析结果为:Cu（32.61%） > Mn（31.85%） > Ni（24.90%） > Zn（16.60%） > Cd（15.23%） > Pb（14.87%）,Cu和Mn的潜在生物可利用性较大,其次为Ni,Zn,Cd和Pb潜在生物可利用性较小。     

新乡市环宇大道工业区周边土壤重金属的污染特征和评价

通过实地采样及室内化学分析的方法,研究了新乡市环宇大道工业区周边土壤Pb、Cd、Ni、Zn、Cu和Cr 6种重金属污染特征和风险评价,并应用Tessier五步连续萃取的方法对土壤中超标的Cd,Ni和Zn进行形态分析。结果表明:(1)土壤中Pb、Cd、Ni、Zn、Cu和Cr的平均含量分别是63.08 mg kg-1、176.85 mg kg-1、307.2 mg kg-1、485.6 mg kg-1,38.7 mg kg-1和47.9 mg kg-1,Pb、Cu、Cr平均含量达标,Cd、Ni、Zn平均含量均超标,分别是国家土壤环境质量二级标准的176.85、5.12、1.62倍。(2)Ni和Zn主要以铁锰氧化物结合态和残渣态存在,Cd主要以铁锰氧化物结合态存在,其次为碳酸盐结合态,3种重金属的迁移能力依次为:Cd>Zn>Ni。(3)每种重金属都存在不同程度的潜在生态风险,Cd的潜在生态风险最大并构成了很强的危害。     

龙游硫铁矿区农田土壤重金属污染的空间 变异及在水稻中的积累

为了解浙江龙游硫铁矿区农田重金属污染状况,采集矿区265件农田土壤样品,分析8种重金属Cu、As、Hg、Zn、Cd、Ni、Pb、Cr元素全量,利用地统计学软件GS+9.0对研究区土壤各元素指标进行半变异函数拟合,并利用普通克里格法进行插值并绘制空间分布图。采集30件水稻籽粒样品,分析重金属在研究区中水稻籽粒的累积特征,并进行了健康风险评价。结果表明:矿区土壤中8种重金属元素的变异系数从0.72到1.76,离散程度较高。8种重金属的土壤空间半变异函数Cu、As、Hg元素符合指数模型,Zn、Cd、Ni、Pb符合球状模型,Cr符合高斯模型。元素Cu、Pb、Zn、Cr、Ni的块金值与基台值的比值C0/C0+C都小于0.25,说明空间变化主要受地质背景等因素影响;元素Cd、Hg和As的块金值与基台值的比值C0/C0+C在0.25~0.75之间,说明除了地质背景因素,人为活动等随机因素也有影响。矿区水稻籽粒中重金属Ni和Cd的变异系数最高,分别为0.95和0.87,说明Ni和Cd元素可能存在异常积累。矿区水稻籽粒对重金属的富集能力由大到小依次为Cd、Zn、Cu、Ni、As、Hg、Cr、Pb。健康风险评价结果表明矿区农田水稻籽粒中元素As、Cd的风险商大于1,存在潜在健康风险;而其他6种重金属Cu、Hg、Zn、Ni、Pb和Cr基本属于安全范围。     

Zinc speciation and isotopic exchangeability in soils polluted with heavy metals

Correct characterization of heavy metal availability is a prerequisite for the management of polluted soils. Our objective was to describe zinc (Zn) availability in polluted soils by measuring the isotopic exchangeability of Zn in soil/solution ( E value) and in soil/plant systems ( L value), by assessing the transfer of Zn and ⁶⁵Zn in the fractions of a six-step selective sequential extraction (SSE) in incubated soils and by identifying Zn forms in soils by means of extended X-ray absorption fine structure (EXAFS) spectroscopy. We distinguished three pools of exchangeable Zn: the pool of Zn exchangeable within 1 minute, which is observed in all soils, Zn exchangeable in the medium term, and the slowly and not exchangeable Zn. The amount of Zn present in the first two pools was similar to the L value measured with Thlaspi caerulescens . The first three steps of the SSE solubilized the first pool and a fraction of the second pool. Most of the second pool and a fraction of the third pool were extracted in the fourth step of the SSE, while the rest of the third pool was extracted in the final steps of the SSE. The EXAFS study conducted on two soils showed that more than half of the Zn was present in species weakly bound to organic compounds and/or outer sphere inorganic and organic complexes. Other species included strongly sorbed Zn species and Zn species in crystalline minerals. The EXAFS study of selected SSE residues showed that the specificity and the efficiency of the extractions depended on the properties of the soil studied.     

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.     

Forms of Cu,Ni, and Zn in soils of sudbury,ontario and the metal concentrations in plants

Forms of Cu, Ni, and Zn in the contaminated soils of the Sudbury mining/smelting district were studied to assess metal mobility and plant availability. Soil, tufted grass (Deschampsia caespitosa (L.) Beauv.), tickle grass (Agrostis scabra Willd.), dwarf birch (Betula pumila L. var. glandulifera Regel) and white birch (Betula paprifera Marsh.) leaf and twig samples were taken from 20 locations around three Cu-Ni smelters. The sampling sites were collected to cover a wide range of soil pH and soil Cu and Ni concentrations. The water-soluble, exchangeable, sodium acetate-soluble, and total concentrations of the metals in the soils were analyzed. The soils were contaminated with Cu and Ni up to 2000 µg g^?1. Zinc concentrations were also elevated in some samples above the normal soil level of 100 µg g^?1. The mobility of Cu and Zn, expressed as the proportion of metals in Fl and F2 forms, increased with soil pH decrease. A strong positive correlation was found between the soil exchangeable (F2) Ni and the soil pH. Concentrations of Cu and Ni in birch twigs showed a good linear relationship with exchangeable forms of the metals in soils. A highly significant correlation was also found between total Ni in soils and the metal content of the twigs. No significant correlation was found between Zn concentrations in the soils and plants. Birch twigs are a good indicator (better than leaves) of Cu and Ni contamination of the Sudbury soils. The mobile forms of Cu and Ni and low pH seem to be the main factors that will control the success of revegetation. Strong variability of the soil metal mobility requires any reclamation effort be site-specific.