Fraction Distributions of Lead,Cadmium, Copper,and Zinc in Metal‐Contaminated Soil before and after Extraction with Disodium Ethylenediaminetetraacetic Acid

Abstract: The fraction distributions of heavy metals have attracted more attention because of the relationship between the toxicity and their speciation. Heavy‐metal fraction distributions in soil contaminated with mine tailings (soil A) and in soil irrigated with mine wastewater (soil B), before and after treatment with disodium ethylenediaminetetraacetic acid (EDTA), were analyzed with Tessier's sequential extraction procedures. The total contents of lead (Pb), cadmium (Cd), copper (Cu), and zinc (Zn) exceeded the maximum permissible levels by 5.1, 33.3, 3.1, and 8.0 times in soil A and by 2.6, 12.0, 0.2, and 1.9 times in soil B, respectively. The results showed that both soils had high levels of heavy‐metal pollution. Although the fractions were found in different distribution before extraction, the residual fraction was found to be the predominant fraction of the four heavy metals. There was a small amount of exchangeable fraction of heavy metals in both contaminated soils. Furthermore, in this study, the extraction efficiencies of Pb, Cd, and Cu were higher than those of Zn. After extraction, the concentrations of exchangeable Pb, Cd, Cu, and Zn increased 84.7 mg·kg^?1, 0.3 mg·kg^?1, 4.1 mg·kg^?1, and 39.9 mg·kg^?1 in soil A and 48.7 mg·kg^?1, 0.6 mg·kg^?1, 2.7 mg·kg^?1, and 44.1 mg·kg^?1 in soil B, respectively. The concentrations of carbonate, iron and manganese oxides, organic matter, and residue of heavy metals decreased. This implies that EDTA increased metal mobility and bioavailability and may lead to groundwater contamination.     

重金属高污染农田土壤EDTA淋洗条件初探

通过室内振荡淋洗试验研究了乙二胺四乙酸二钠(EDTA)浓度、淋洗时间、液固比、淋洗次数对甘肃省白银市某高污染农田土壤中重金属去除效果的影响,并测定了EDTA淋洗前后土壤中重金属形态的变化。结果表明：淋洗剂浓度和液固比越高、淋洗时间越长、淋洗次数越多,对重金属的去除效果越好。在EDTA浓度为5 mmol/L、液固比为2.5、连续振荡淋洗3次、每次1 h时,对土壤中Cd、Cu、Pb、Zn 4种重金属的总去除率分别为 55.2%、21.9%、19.3% 和20.9%,其中Cd 淋洗效率最高。EDTA对土壤中交换态、碳酸盐结合态和铁锰氧化物结合态重金属的去除效果明显,但不能有效去除有机及硫化物态和残余态土壤重金属。     

Kinetics of Iron and Manganese Release from Contaminated Calcareous Soils

Knowledge of the release of heavy metals (HM) and their chemical speciation is necessary for characterizing HM behavior in soils. The kinetics and characteristics of iron (Fe) and manganese (Mn) release were studied in 10 contaminated calcareous soils using 0.01 M calcium chloride (CaCl₂), 0.01 M ethylenediamine tetraacetic acid (EDTA), and 0.01 M malic acid (malic acid) extractions. Iron and Mn in soil samples were fractionated before and after 2084 h kinetic release using a sequential extraction procedure. The proportion of Fe and Mn released by EDTA was greater than that with CaCl₂ and malic acid. A power model satisfactorily described Fe and Mn release from soils. In general, the mean release rate of Fe was greater than that of Mn, indicating a greater rate of Fe release from contaminated soils. It was shown that Fe and Mn distributions were similar in native soils and they were mainly found in Fe-Mn oxides and organic-matter (OM) fractions. There were changes in the proportional distribution of Fe and Mn in all soils during the 2084 h kinetic study with different extraction solutions. In general, the proportions of Fe and Mn associated with carbonate (CARB) and OM fractions tended to decrease, with corresponding increases in the Fe-Mn oxides for Mn and residual (RES) fractions for Fe during the kinetic study with all extraction solutions. The Fe and Mn solubility at the initial and final stages of release was controlled by siderite (FeCO₃), vivianite [(Fe)₃(PO₄)₂·8H₂O], MnCO₃(am), MnHPO₄, and rhodochrosite (MnCO₃) minerals in all extraction solutions. Based on a risk assessment and percentage of release of metals, there is a high potential for Mn release into the food chain from contaminated soils.     

Use of Single Extraction Methods to Predict Bioavailability of Heavy Metals in Polluted Soils to Rice

Human exposure to toxic heavy metals via dietary intake is of increasing concern. Heavy-metal pollution of a rice production system can pose a threat to human health. Thus, it was necessary to develop a suitable extraction procedure that would represent the content of metal available to rice plants (Oryza sativa L.). The aim of this study was to predict, on the basis of single extraction procedures of soil heavy metals, the accumulation of heavy metals (cadium, lead, copper, and zinc) in rice plants. Six extracting agents [Mehlich 1, Mehlich 3, EDTA (ethylenediaminetetraacetic acid), DTPA–TEA (diethylenetriaminepentaacetic acid–triethanolamine), ammonium acetate (NH₄OAc), and calcium chloride (CaCl₂)] were tested to evaluate the bioavailability of heavy metals from paddy soils contaminated with lead–zinc mine tailings to rice. The extraction capacity of the metals was found to be of the order EDTA > Mehlich 3 > Mehlich 1 > DTPA–TEA > NH₄OAc > CaCl₂. The correlation analysis between metals extracted with different extractants and concentrations of the metals in the grain and stalk of the plant showed positive correlations with all metals. The greatest values of correlation coefficients were determined between the NH₄OAc- and CaCl₂-soluble fractions of soil and contents in plants in all four metals studied. Therefore, NH₄OAc and CaCl₂ were the most suitable extractants for predicting bioavailability of heavy metals in the polluted soils to rice. The results suggested that uptake of heavy metals by rice was mostly from exchangeable and water-soluble fractions of the metals in the soils. Soil-extractable metals were more significantly correlated with metal accumulation in the stalk than in the grain. The pH had more significant influence on availability of heavy metals in the soils than total content of metals and other soil properties. The bioavailability of metals for rice plants would be high in acidic soils.     

Extraction kinetics of copper,zinc, iron,and manganese from contaminated sediment using Disodium Ethylenediaminetetraacetate

One technique for cleansing heavy metal contaminated soils is to wash the excavated soil with an extraction solution of a chelating agent. The rate of extraction is an important parameter when considering the length of time needed for soil clean-up and the amount and concentration of wash solution required. The extraction kinetics of copper, zinc, iron and manganese from a contaminated sediment of the Clark Fork River in western Montana, U.S.A., with Disodiun Ethylenediaminetetraacetate (Na₂EDTA) as the extraction agent, were investigated. The results showed the extraction process consisted of rapid extraction in the first minutes followed by much slower extraction for the remainder of the experiment. The rate of extraction, particularly in the rapid phase, demonstrated clear pH dependence: the lower the pH, the faster the extraction rate. In the EDTA concentration range of 0.01 M to 0.05 M, the effect of the EDTA concentration on the extraction rate was not important compared with that of the solution pH. Extraction kinetics for different size particles were similar, although in the first few minutes, EDTA extracted more metals from clay and silt than sand. The two reaction, diffusion, and two-constant kinetic models were compared to experimental results. The two reaction model did not fit any of the data well, and only iron extraction could be described with a simple diffusion model. In general the extraction rates can be well described by the two-constant model, C=A t ^B, up to 600 minutes and under different conditions such as solution pH, EDTA concentration, and different sediment particle size.     

Extractive Decontamination of Metal-Polluted Soils Using Oxalate

Oxalate (Ox) was investigated as an extractant for decontaminating two metal-polluted soils, one with elevated total zinc (ZnT = 2700 mg kg-1) from the Palmerton, Pennsylvania smelter site and the other from a grossly contaminated (PbT = 210 000 mg kg-1) automobile battery recycling facility in Indiana. Metal retention within the soils was substantially different as shown by sequential fractionation experiments. High Zn removal (>80%) was achieved with 1.0 M Ox when Zn existed predominantly in non-detrital metal fractions. However, Ox was an unsuitable Pb extractant due to the sparing solubility of PbOx(s). Despite the dramatically higher stability of ZnEDTA2- (log K = 16.5) compared to ZnOx° (log K = 3.4), Ox released more Zn than EDTA from the Palmerton soil because 40% of ZnT was associated with the oxide fraction. Extract analysis indicated that Ox, but nor EDTA, dissolved soil Fe oxides in the 24 hr extraction period. When contaminating metals are associated with soil oxides, Ox may be a superior extractant to powerful chelants like EDTA. It is essential to establish thoroughly metal solution chemistry and fixation behavior within the soil when extractive decontamination is proposed for site remediation.     

Laboratory Investigation of the Geochemical Behavior of Metals in Paddy Soils Contaminated with Mine Tailings

The geochemical behavior of metals, including Fe, Mn, Pb and Zn, in contaminated paddy soils was investigated during the cultivation of rice crops through laboratory microcosm experiments. From the two paddy fields contaminated by mine tailings, Siheung and Deokeum in Korea, paddy soils were collected and analyzed for their geochemical characteristics. The Siheung paddy soil showed higher levels of heavy metals, whereas the higher potential for the release of metals was anticipated due to the extremely acidic conditions at Deokeum. In microcosm experiments of flooded paddy soils over 18 weeks, Fe and Mn were released in subsurface pore waters by reductive dissolution, and Pb and Zn were dissolved in high amounts at the surface by oxidation of sulfides. Although amorphous Fe oxide-rich layers were formed at the surface of both paddy soils, the release of Pb and Zn were controlled at the surface by these layers only under slightly alkaline conditions at Siheung. Lead and Zn were associated with the reducible and carbonate fractions at the surface paddy soil of Siheung from the sequential extraction on core samples collected during the flooded period. In the acidic conditions at Deokeum, Pb and Zn were continuously released until the late stage of flooding. A great increase in the exchangeable fraction of metals was observed after the soils had drained. The bioavailability of metals for rice crops would be high under acidic conditions at Deokeum, despite the lower levels of heavy metal contamination.     

Phytoextraction of heavy metal contaminated soils with Thlaspi goesingense and Amaranthus hybridus: Rhizosphere manipulation using EDTA and ammonium sulfate

Selection of appropriate plant species and rhizosphere manipulation to enhance metal uptake are considered key factors in the development of phytoextraction technologies. A pot trial was conducted with two contaminated soils to investigate the effect of EDTA and ammonium sulfate on the accumulation of heavy metals into shoots of the low‐biomass hyperaccumlator Thlaspi goesingense Hálácsy (Brassicaceae) and the high‐biomass non‐hyperaccumulating plant Amaranthus hybridus (Amaranthaceae). Upon application of 1 g EDTA (kg soil)^—1 metal extractability with 1 M NH₄NO₃ increased substantially, whereas the application of (NH₄)₂SO₄ was less effective. The EDTA treatment increased the heavy metal concentrations in both plant species, however, the difference to the control was larger for A. hybridus. EDTA enhanced shoot concentrations in A. hybridus grown on soil Arnoldstein from 32.7 mg kg^—1 to 1140 mg kg^—1 for Pb and from 3.80 mg kg^—1 to 10.3 mg kg^—1 for Cd. Cd concentrations in shoots of T. goesingense were also increased by EDTA application, however, a slight decrease was observed for Pb. T. goesingense accumulated 2840 mg Pb kg^—1 without any treatment. This is the first report of Pb hyperacumulation by T. goesingense. A decrease of shoot Pb concentration was observed in T. goesingense upon treatment with ammonium sulfate. Although metal concentrations in the shoots were rather large and significantly increased upon application of EDTA, plant growth and heavy metal removal were still too small to obtain reasonable extraction rates in soils heavily polluted by metals. It should be also noted that metal lability largely increased in EDTA‐treated soils and this lability persisted for several weeks after the application of the chelating agent, which is likely to be associated with the risk of groundwater contamination.     

Heavy metal effects on soil populations and heavy metal tolerance of Rhizobium meliloti,nodulation, and growth of alfalfa

Effects of heavy metals on rhizobia and the symbiotic association with leguminous hosts are currently unclear. To investigate this problem, we examined Rhizobium meliloti (microsymbiont) and alfalfa (Medicago sativa) (macrosymbiont) collected from soils contaminated with varying concentrations of heavy metals (varying distances from a Zn smelter operating 90 yr.). Soil populations of R. meliloti were not correlated with metal concentrations in soil. The lowest rhizobial population was found in the soil with the highest extractable metal concentrations, but the highest populations were found in soil which was moderately contaminated. A greenhouse study in which alfalfa was grown in the same soils showed no significant trend for nodulation or nitrogenase activity of roots. Highest nodule number and nitrogenase activity were observed in those soils which had the lowest population of R. meliloti. When the heavy metal Minimum Inhibitory Concentration (MIC) of individual isolates was examined, no correlation was found between the MIC and soil metal concentration (total, or water or 0.01 M Ca(NO₃)₂ extractable).These results indicate that even in highly contaminated soils, metal activity was not high enough to exert an antagonistic influence on the soil rhizobial population or the symbiotic association between alfalfa and R. meliloti.     

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。     

化学萃取修复尾渣土壤的金属形态变化特征

The efficiency of EDTA, HNO3 and CaCl2 as extractants to remove Pb, Zn and Cu from tailing soils without varying soil pH was investigated with distributions of Pb, Zn and Cu being determined before and after extraction using the sequential extraction procedure of the optimized European Community Bureau of Reference （BCR）. Results indicated that EDTA and HNO3 were both effective extracting agents.The extractability of extractants for Pb and Zn was in the order EDTA 〉 HNO3 〉 CaCl2, while for Cu it was HNO3 〉 EDTA 〉 CaCl2. After EDTA extraction, the proportion of Pb, Zn and Cu in the four fractions varied greatly, which was related to the strong extraction and complexation ability. Before and after extraction with HNO3 and CaCl2, the percentages of Pb, Zn and Cu in the reducible, oxidizable and residual fractions changed little compared to the acid-extractable fraction. The lability of metal in the soil and the kinds of extractants were the factors controlling the effects of metal extraction.     

Removal of Heavy Metals from Calcareous Contaminated Soils by EDTA Leaching

The performance of EDTA for the treatment of calcareous soils contaminated with heavy metals from mining and smelting activities was evaluated in this study. Soil samples containing variable levels of contamination, from 500 to 35 000 mg kg^-1 Pb and 700 to 20 000 mg kg^-1 Zn, were subjected to EDTA treatment and the extraction of heavy metals was found to vary, ranging between 50 and 98% for Pb and 50 to 100% for Zn. Total residual concentrations were above the limits set by regulatory authorities; leachable metals, however, were efficiently removed and treated soils were all acceptable in terms of toxicity. The effect of EDTA concentration and pulp density was studied on a soil sample containing 12 000 mg kg^-1 Pb and 10 000 mg kg^-1 Zn. Heavy metals removal was improved at low pulp densities and when EDTA concentration was increased from 0.025 to 0.25 M. The tetrasodium salt Na₄-EDTA was found to be less effective for metals removal compared to the disodium salt Na₂-EDTA, though applied at higher concentrations. This experimental work has also demonstrated the great importance of soil matrix for the overall evaluation of the EDTA leaching as a cost effective remedial option. The simultaneous dissolution of calcite was found to consume approximately 90% of the available EDTA. It was thus concluded that for the treatment of calcareous soils the design criteria and cost estimations should be based on the calcite content of the soil.     

Cleaning heavy metal contaminated soil with soluble humic substances instead of synthetic polycarboxylic acids

Abstract

Soils contaminated with heavy metals constitute a serious and widespread ecological problem but to clean such soils requires strong chemicals such as polycarboxylates; frequently ethylenediaminetetraacetic acid and nitrilotriacetic acid are used. However, these compounds are synthetic and toxic and their replacement by natural products such as soluble humic substances as washing agents for cleaning heavy metal polluted soils would be environmentally very attractive. In fact, such a replacement seems possible at least on cadmium and copper contaminated soil inasmuch as humic substances, depending on the concentration, were found to extract up to 45% and 54% of total cadmium and copper from a highly contaminated calcareous soil. Even though higher amounts of the two metals were extracted by ethylenediaminetetraacetic acid and nitrilotriacetic acid, the humic substances undoubtedly extracted the most reactive fractions. However, the humic substances extracted only 4% of total lead and 17% of total nickel, whereas the percentages for the synthetic polycarboxylates were about 30% for nickel and lead. Ethylenediaminetetraacetic acid and nitrilotriacetic acid may therefore be replaced by humic substances as washing agents for cadmium, copper and maybe nickel contaminated soils, whereas they seem unsuited for cleaning lead contaminated soils, at least if the soils are as calcareous as the soil tested.     

Bioavailability,fractionation of pb and Zn in the rhizosphere of sunflower in chelators-amended contaminated soil

Assisted phytoremediation procedures have been widely employed as soil removal instrument of heavy metals from contaminated soils. Rhizosphere processes have a major impact on pb and Zn availability and its fractions in soils. The present study evaluates the effects of EDTA, citric acid (CA) and poultry manure extract (PME) on bioavailability and fractionation of pb, Zn in both the rhizosphere of sunflower (Helianthus annuus L.) and bulk soil. EDTA and CA were added to soils at the rates of 0, 0.5 and 1 mmol kg^?1 soil and PME at 0, 0.5 and 1 g kg^?1 soil as factorial in a completely randomized pattern with three replicates in greenhouse condition. Results showed that chelator application had a significant impact (p < 0.05) on pb, Zn extraction by different extractants and its fractions in soils. The order of concentrations of pb, Zn present in different fractions in soil treated by chelators was: oxides-bounded fraction > residual fraction > OM-bounded fraction > carbonate-bounded fraction > exchangeable fraction. Biochemical soil characteristics in the sunflower rhizosphere change resulting from its roots contributing to pb, Zn decline in mobile soil fractions, and change in soil pb, Zn fractions that are generally regarded as more stable.     

低分子有机酸去除土壤中重金属条件的研究

采用化学萃取实验,以湖南郴州柿竹园和湖南衡阳水口山矿区的重金属污染农田土壤为研究对象,采用柠檬酸、草酸、酒石酸作为低分子有机酸萃取剂,在一定的条件下对污染土壤中重金属进行萃取实验,确定各个单因素的适宜条件。结果表明,对于湖南郴州和衡阳两个污染地区土壤运用化学萃取技术萃取重金属来进行土壤修复是实际可行的;柠檬酸、酒石酸、草酸对各种土壤中的重金属都表现出了良好的萃取能力,是高效的土壤重金属萃取剂;单因素的适宜萃取条件为100mmol·L^-1有机酸溶液,固液比1∶5,恒定温度35℃,pH为3,反应时间24h,且萃取率随着电解质浓度的增大而提高;土壤中重金属存在形态与萃取效果有一定的相关性,稳定态（残渣态、硫化物和有机结合态、铁-锰氧化物结合态）金属含量高,表现为较低的萃取率;反之,萃取率高;柠檬酸、草酸、酒石酸3种萃取剂均能有效地降低衡阳污染土壤中的重金属浓度,3种萃取剂的萃取效率依次为酒石酸〉草酸〉柠檬酸。     

外源铜和镍在土壤中的化学形态及其老化研究

采用连续提取法测定了外源铜和镍进入田间土壤后的化学形态分布,比较研究了这2种重金属在3种不同类型土壤(红壤,水稻土和潮土)中随老化时间的形态转化和分布.结果表明,外源铜以残留态(40%～60%)和EDTA可提取态(40%)为主;随老化时间,EDTA可提取态、易还原锰结合态及铁铝氧化态向残留态转化;外源镍在酸性红壤中以可交换态(40%)和残留态(30%～50%)为主,在中性水稻土中以EDTA可提取态(30%)和残留态(30%～50%)为主,在碱性潮土中以铁铝氧化态(20%)和残留态(40%)为主.随老化时间,水溶态、可交换态、EDTA可提取态等向残留态转化.土壤pH较低时水溶态和可交换态含量较高,但是同时随老化时间的降低量也明显;pH较高时有利于易还原锰结合态和有机质结合态的转化.     

间作条件下螯合剂对龙葵和大叶井口边草吸收重金属的影响

用室内土培试验方法,在采自田间的Pb、Cd和As复合污染土壤中单作或间作龙葵和大叶井口边草条件下,筛选出修复Pb-Cd-As复合污染土壤较好的种植方式为间作。进一步在间作方式下,研究了外源添加不同浓度EDDS（乙二胺二琥珀酸）、NTA（氨三乙酸）和EDTA（乙二胺四乙酸）对植物吸收Pb、Cd和As的影响。结果表明,间作显著促进了龙葵地上部对Cd的吸收量和大叶井口边草地上部对As的吸收量,间作龙葵地上部吸收Cd和大叶井口边草地上部吸收As含量分别是单作龙葵和大叶井口边草的1.3倍和1.4倍,说明间作龙葵和大叶井口边草比单作更有利于修复Pb-Cd-As复合污染土壤。间作条件下,大叶井口边草对螯合剂的耐性比龙葵更强。3、6、12mmol.kg-1EDTA能极显著增加土壤中Pb、Cd有效态含量,从而促进龙葵地上部对Pb吸收和大叶井口边草地上部对Pb、Cd吸收。EDTA比NTA具有更强的提高土壤Pb、Cd有效态的能力,但对土壤As有效态促进作用与EDTA相比,NTA效果极显著,1.5、3mmol.kg-1NTA处理极显著提高土壤As有效态含量及促进龙葵和大叶井口边草地上部对As吸收。     

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.     

杭州市城市土壤重金属的潜在可淋洗性研究

研究了杭州市城市土壤 8个重金属元素 (Cd、Co、Cr、Cu、Ni、Pb、Zn、Mn)的含量、形态和潜在可淋洗性。结果表明 ,该城市土壤中Cd、Cr、Cu、Ni、Pb、Zn和Mn均有明显的积累 ,其中Cd、Co、Cr和Ni主要以稳定的残余态为主 ,而Cu、Pb、Zn和Mn则以可提取态为主 ,因此在强还原、强酸性或有利于有机质分解条件下Cu、Pb、Zn、Mn的释放潜力较高。用荷兰能源研究中心的淋洗方法 (pH4 0 )测试表明 ,该市城市土壤的重金属可淋洗性较低 ,在一般条件下该城市土壤重金属不会有较大的释放 ,这与该城市土壤中酸可提取态重金属比例较低并含有较高的有机质及粘粒含量有关     

Sorption and Fractionation of Copper in Soil at a Sewage Irrigation Farm in Australia

Abstract

Copper (Cu) is an important heavy metal to be considered in soil contamination, because high concentrations of copper in soil produce toxic effects and may accumulate in plant tissues. In Australia's oldest sewage irrigation farm, located in Werribee, Victoria, soil in the land filtration area is contaminated by Cu. However, Cu content in herbage tissues is in the normal range and has been trending downward since 1979. Therefore, studies on the sorption capacity and sequential extraction of Cu in soil at the Werribee Farm is of significance, not only for better understanding the mechanism of transport, chemical processes, and plant uptake of Cu, but also in providing information for the practical management of sewage farm soils. Methods of combining sorption isotherms with sequential extraction procedures were adopted, and the results showed that the soil in the land filtration area at Werribee Farm has a high sorption capacity for Cu, and distribution coefficients, K_f of Cu, were 629 L kg^?1 in surface soils (0–20 cm) and 335 L kg^?1 in subsurface soils (20–40 cm). The sequential extraction fractions demonstrate that exchangeable and carbonate fractions are very low, only comprising 3.49 to 5.49% of total copper. The other fractions are also discussed. This characteristic of Cu in soil is related to the low concentration of Cu in plant tissues.