石灰水对混合试剂洗脱土壤重金属淋洗效果的影响

为了探索石灰水对混合试剂(MC)洗脱后土壤中重金属的淋洗效果,对重金属污染土壤进行了盆栽淋洗试验研究。结果表明:石灰水淋洗MC洗脱土壤,淋出液中Cd、Zn、Pb和Cu浓度均显著高于去离子水淋洗MC洗脱土壤,这主要由于石灰水提高土壤pH,释放土壤所吸附的络合态重金属,这种现象在酸性污染土壤中表现更明显。对于酸性污染土壤,可采用MC+石灰水+去离子水依次进行淋洗处理,其Cd和Zn去除率与MC+去离子水+去离子水依次淋洗处理相比提高22.6%和28.8%;对于中性重金属污染土壤,两处理间重金属去除率差异不显著。石灰水淋洗可提高土壤重金属去除率,并提高土壤pH,改善MC洗脱对土壤的酸化,有利于淋洗后土壤的农业利用。     

茶皂素对潮土重金属污染的淋洗修复作用

为了探讨茶皂素淋洗修复土壤重金属污染的可行性,该文采用振荡提取和土柱淋洗的方法,研究了茶皂素对污染土壤中重金属的去除作用。结果表明,茶皂素溶液的浓度和土壤的pH值对重金属去除率有明显影响。土柱淋洗试验中,采用质量分数7%茶皂素溶液作淋洗液,pH 5.0±0.1、土液质量体积比1：4为最佳淋洗修复条件,此时,Pb、Cd、Zn、Cu的去除率分别为6.74%、42.38%、13.07%、8.75%,去除率的大小顺序为Cd＞Zn＞Cu＞Pb。茶皂素淋洗能有效去除酸溶态和可还原态的重金属,从而大大降低了重金属的环境风险,同时说明茶皂素用于土壤重金属污染淋洗修复有较大潜力。     

酒石酸与表面活性剂联合作用对土壤重金属污染修复行为的影响

为寻找新型无污染的淋洗剂,采用复配法将酒石酸与提取的茶皂素进行复配,制得酒石酸-茶皂素复配溶液,比较了酒石酸和酒石酸-茶皂素复配溶液的表面性能与重金属去除能力。结果表明,(1)酒石酸—茶皂素复配溶液CCMC值为0.05%,HLB值为24.29,优于酒石酸的CCMC值(0.10%)和HLB值(23.08);(2)通过对不同淋洗剂浓度、振荡时间、pH、离子强度、水土比对重金属Pb2+、Cd2+去除率的影响,得出去除Pb2+、Cd2+的最佳工艺为:振荡时间12h,质量分数7%,pH 5.0,Ca(NO3)2浓度0.01mol/L,水土比20∶1,在此条件下,2种螯合剂对重金属Pb2+、Cd2+去除率均达最高值,且酒石酸复配溶液对重金属Pb2+、Cd2+去除率高于酒石酸单一处理。     

农田土壤重金属淋洗剂筛选与效应分析

为分析不同淋洗剂在不同淋洗条件下对重金属淋洗效果的影响,采用振荡淋洗法对比研究4种淋洗剂(柠檬酸(CA)、酒石酸(TA)、乙二胺四乙酸二钠盐(EDTA)和氨三乙酸三钠盐(NTA))不同浓度、淋洗时间、pH和固液比对重金属复合污染农田土壤中Pb、Cd、Cu和Zn的淋洗效果及单因素最佳淋洗条件下土壤淋洗前后重金属不同形态含量的变化。结果表明,CA和TA的最佳淋洗浓度为0.3mol/L,EDTA和NTA为0.05mol/L;CA和NTA的最佳淋洗时间为480min,EDTA和TA为720min;4种淋洗剂的最佳淋洗pH均为3,最佳固液比均为1∶20。单因素最佳淋洗条件下,EDTA对土壤重金属去除效果最佳,对Pb、Cd、Zn和Cu的去除率分别为67.4%,61.0%,13.8%和76.0%;NTA效果次之,去除率分别为41.6%,42.4%,9.9%和54.3%。土壤重金属去除率随淋洗剂pH的降低而升高,随固液比的增加而增加,随淋洗剂CA与TA浓度增大而增大。淋洗剂对土壤重金属的解吸动力学曲线符合准二级动力学模型,解吸过程为化学解吸,且解吸反应速率受土壤重金属含量与淋洗剂浓度控制。土壤重金属在淋洗剂作用下的解吸速率为Cd>Pb≈Zn≈Cu。EDTA和NTA淋洗显著降低土壤中Pb、Cd、Zn和Cu铁锰氧化态和有机结合态的含量,CA和TA显著降低Pb、Cd、Zn和Cu铁锰氧化态的含量。淋洗剂对重金属的去除效率为EDTA>NTA>CA>TA。     

新型TSADA的合成及其土壤重金属污染修复行为

为提高茶皂素(TS)修复土壤重金属离子的能力,经水提-沉淀法从茶籽饼提取茶皂素,以其为原料设计合成新型绿色茶皂素基螯合剂(茶皂素-1-酰胺二乙烯三胺,TSADA),用FT - IR研究TSADA的结构,并对其表面性能进行研究.结果表明,其临界胶束浓度低于茶皂素,而亲水亲油平衡值、起泡力及稳泡性均优于茶皂素.同时考察了振荡时间、螯合剂浓度、pH值及离子强度对螯合剂去除污染土壤重金属率的影响,发现,TSADA去除重金属率随振荡时间、浓度的增加而升高,随pH值和离子强度的增加而降低.螯合剂去除Pb2+、Cd2+离子的最佳工艺为:振荡时间为12h,质量分数为7％,pH值为5.0,Ca(NO3)2浓度为10 mmol/L.此条件下2种螯合剂对土壤中Pb2+、Cd2+离子去除率均达最大,TSADA对Pb2+和Cd2+离子去除率均优于茶皂素;TSADA对Pb2+和Cd2+离子的最大去除率分别为67.3％和99.9％.     

谷氨酸N,N-二乙酸及液体肥联合强化对东南景天修复重金属污染土壤的影响

化学强化可提高超富集植物对土壤重金属的提取效果。采用盆栽试验,研究了可生物降解螯合剂谷氨酸N,N-二乙酸(GLDA)、液体肥的不同用量及复配使用对超富集植物东南景天吸收土壤重金属Cd、Zn的影响,并探讨了其渗滤液对环境的风险。结果表明:单一使用GLDA或者液体肥均能提高东南景天对土壤Cd、Zn的提取效率,其中1.25 mmol/kg GLDA处理的Cd、Zn提取量分别是空白处理的1.36,1.46倍,0.5 g/kg液体肥处理的Cd、Zn提取量分别是空白处理的1.40,1.43倍,这2种低用量单独使用的处理对Cd提取效率最高,达到41%～42%,且对应的渗滤液重金属含量均比空白处理要低,其环境风险较小。GLDA与较高用量(2 g/kg土)液体肥复配时,其东南景天对土壤Cd、Zn的提取量与空白处理相比有所下降。结果表明,GLDA和液体肥在强化植物修复方面有明显潜力,而且以低剂量单独使用强化效果较佳,值得进一步的田间试验核实。     

混合试剂在不同电解质条件下对土壤重金属淋洗效果的影响

为了得出不同电解质(CaCl2和KCl)对混合试剂(EDTA和柠檬酸)去除土壤重金属的影响,对重金属污染土壤进行盆栽淋洗实验.结果表明,含电解质CaC12的混合试剂有利于去除酸性污染土壤中重金属;而含KC1的混合试剂有利于去除中性污染土壤中重金属.含电解质CaC12和KC1混合试剂[EDTA-+-CA+ 1/2(CaC12+KCl)]对土壤重金属的淋洗效果不明显;但电解质用量的增加(如EDTA+ CA+ CaCl2+KCl)提高了酸性土壤中Cd、Zn、Pb和Cu的去除率,提高幅度分别达22％,16％,18％和9％.Cd和Zn污染的酸性土壤,可用CA+ CaCl2+KCl混合试剂淋洗;但Pb和Cu的去除还要靠EDTA.中性重金属污染土壤可采用EDTA+ CaCl2+ KCl混合试剂淋洗.     

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     

工业废弃地多金属污染土壤组合淋洗修复技术研究

采用批量淋洗实验方法,对比了采用人工螯合剂乙二胺四乙酸二钠盐(EDTA-Na2)和天然有机酸草酸(oxalic acid,OX)对工业废弃地污染土壤中重金属的去除效果,并采用不同浓度草酸和EDTA组合的两步淋洗法研究多金属污染土壤的最佳淋洗方式。结果表明,EDTA淋洗剂对土壤中Zn、Pb、Cu、Ni去除效果较好,而对Cr去除效果较差,实验条件下,EDTA对金属的去除率并未随着浓度增加而增加;相反,草酸对Cr去除效果较好,且去除率随着淋洗剂浓度的增加而增加,而对Zn、Cu、Ni的去除效果随着淋洗剂浓度增加而降低,对Pb的去除率非常低;采用先以0.20 mol L-1草酸提取2 h,再以0.01 mol L-1EDTA提取2 h的两步淋洗法可以达到对多金属同时去除,且对Zn、Cu、Cr、Ni的去除率明显高于单用草酸和EDTA,总去除率分别为Zn 75.21%、Pb 21.30%、Cu 59.81%、Cr 60.72%和Ni 62.10%,更为有意义的是两步淋洗法对非残渣态金属去除效果分别高达Zn 91.93%、Pb 57.75%、Cu 75.33%、Cr 73.94%、Ni 77.99%。利用不同化学淋洗剂对金属去除能力的差异进行组合的多步淋洗法是一种较为高效的去除工业废弃地污染土壤中重金属的化学淋洗修复方法。     

新型茶皂素硫酸钠合成及其修复土壤重金属污染研究

经水提-沉淀法从茶籽饼提取茶皂素,以其为原料设计合成了新型绿色茶皂素基螯合剂(茶皂素硫酸钠)。对其表面性能进行研究发现,其表面张力低于茶皂素,而HLB值、起泡力及稳泡性均优于茶皂素。同时考察了振荡时间、螯合剂浓度、pH及离子强度对螯合剂去除重金属率的影响。结果表明,重金属去除率随振荡时间和浓度增加而升高,随pH、离子强度增加而降低。得出去除Pb2+、Cd2+离子的最佳工艺:振荡时间为12h,质量分数为7%,pH为5.0,Ca(NO3)2浓度为0.01mol/L,此条件下螯合剂对土壤中Pb2+、Cd2+离子去除率最大,茶皂素硫酸钠对Cd2+离子的去除率大于Pb2+离子,且茶皂素硫酸钠对此2种离子的去除率均优于茶皂素,尤其对Pb2+离子去除率改善效果显著。     

Mixed chelators of EDTA,GLDA, and citric acid as washing agent effectively remove Cd,Zn, Pb,and Cu from soils

Purpose

Soil washing with chelators is a viable treatment alternative for remediating multi-contaminated soils. The aim of this study was to investigate the removal efficiencies of Cd, Zn, Pb, and Cu in alkaline and acid multi-metal-contaminated soils by washing with the mixed chelators (MC).

Materials and methods

The batch experiments were carried out to evaluate the removal efficiencies of heavy metals in contaminated soils by the MC with different molar ratios of EDTA, GLDA, and citric acid, and evaluated the washing factors, including contact time, pH, MC concentration, and single and multiple washings at the same MC dose, on the removal efficiencies.

Results and discussion

Results showed that the removal efficiencies for Cd, Zn, Pb, and Cu by the MC (the molar ratio of EDTA, GLDA, and citric acid was 1:1:3) were as much as those of the only EDTA washing from both soil at the same application dose of total chelators; moreover, the application dose of EDTA decreased by 80%. For the alkaline-contaminated soil, the removal efficiencies of Cd, Zn, Pb, and Cu decreased with the increasing of the solution pH, which was opposite to acid-contaminated soil. This was attributed to that the metal-ligand complex could be obviously re-adsorbed on the soil surface sites, particularly in low pH values. The removal efficiencies of Cd, Zn, Pb, and Cu depended on MC concentration. A higher MC concentration led to a more effective removal of Cd, Zn, Pb, and Cu in alkaline-contaminated soil; however, their changes were slightly increased in acid-contaminated soil. At the same dose of MC, single washing with higher MC concentration might be favorable to remove heavy metals, moreover, with much less wastewater generation.

Conclusions

The MC (the molar ratio of EDTA, GLDA, and citric acid was 1:1:3) may be a useful, environmentally friendly, and cost-effective chelators to remediate heavily multi-metal-contaminated soil.

     

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。     

土壤重金属生物淋滤修复过程中廉价碳源的筛选研究

在室内模拟实验条件下,重点研究了一步和二步生物淋滤过程中黑曲霉利用各种廉价碳源替代蔗糖产酸修复重金属污染土壤的效果。结果发现,杨树叶、桃树叶、土豆皮去除重金属效果较好。其中杨树叶对冶炼厂土壤中重金属去除率分别为Cu63．5％、Cd100％、Pb16．8％和Zn27％;桃树叶去除效果分别为Cu61．8％、Cd100％、Pb14．6％和Zn28．5％;土豆皮去除效果分别为Cu61％、Cd100％、Pb10．6％和Zn34％。廉价碳源的使用可降低污染土壤生物淋滤修复成本。     

茶皂素对污染土壤中重金属的修复作用

采用振荡离心的方法研究了生物表面活性剂茶皂素在不同浓度、pH值和离子强度下对污染土壤中重金属去除效果的影响;并采用BCR法研究了茶皂素处理前后土样中各形态的重金属含量变化。试验结果表明:随着茶皂素浓度的增加,重金属的去除率随之增加,在茶皂素浓度为7%时,对供试土样中重金属的去除率达到最大值,去除率分别为Cd 96.36%,Zn 71.73%,Pb 43.71%,Cu 20.56%;随着土壤环境pH值的增加,重金属的去除率随之减少,适宜的pH范围在5.0左右;离子强度对Pb,Cu的去除效率影响不大,Zn,Cd的去除率随着离子强度的增加而减少。比较茶皂素处理前后土样中重金属各形态含量的变化,发现酸溶态的重金属更易被茶皂素去除,其次为可还原态、可氧化态和残渣态的重金属很难被去除。     

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.     

Removal of trace and major metals by soil washing with Na<Subscript>2</Subscript>EDTA and oxalate

Background, aim, and scope  

Various metals such as cationic metals (Cu, Pb, Zn) and anionic metals (As, Cr) often coexist in real soils, and normal soil washing techniques for the removal of cationic metals with a single-washing reagent make it rather difficult to simultaneously remove all of them. Oxalate could effectively remove anionic As and EDTA could effectively remove the cationic metals, so it was possible to remove all coexisting cationic and anionic metals by washing with the combination of Na₂EDTA and oxalate. The objective of this study was to (1) discuss the possibility of removing five metals, As, Cd, Cu, Pb, and Zn, effectively from the soil by washing with Na₂EDTA-combined oxalate; (2) optimized through the consecutive washing.     

Interaction of Cd-hyperaccumulator Solanum nigrum L. and functional endophyte Pseudomonas sp. Lk9 on soil heavy metals uptake

Bioaugmentation is a promising method for assisting phytoextraction of heavy metals from contaminated soil, and the development of bioaugmentation-assisted phytoextraction requires the understanding of the mechanism involved in the interaction between plants and inocula. In this study, a pot study was conducted to evaluate the effect of bacterial endophyte Pseudomonas sp. Lk9 which can produce biosurfactants, siderophores and organic acids on the growth and metal uptake of Cd-hyperaccumulator Solanum nigrum L. growing in multi-metal-contaminated soil. The results revealed that Lk9 inoculation could improve soil Fe and P mineral nutrition supplies, enhance soil heavy metal availability, and affect host-mediated low-molecular-weight organic acids secretion, thereby significantly increasing S. nigrum shoot dry biomass by 14% and the total of Cd by 46.6%, Zn by 16.4% and Cu by 16.0% accumulated in aerial parts, compared to those of non-inoculated control. The assessment of phytoextraction showed that Lk9 inoculation elevated the bioaccumulation factor of Cd (28.9%) and phytoextraction rates of all metals (17.4%, 48.6% and 104.6% for Cd, Zn and Cu, respectively), while the translocation factors had negligible difference between Lk9 inoculation (3.30, 0.50 and 0.40 for Cd, Zn and Cu, respectively) and non-inoculated control (2.95, 0.53 and 0.42 for Cd, Zn and Cu, respectively). It was also found that the symbiotic association between S. nigrum and Lk9 significantly increased the soil microbial biomass C by 39.2% and acid phosphatase activity by 28.6% compared to those in S. nigrum without Lk9. This study would provide a new insight into the bioaugmentation-assisted phytoextraction of heavy metal-contaminated soils.     

Phytoextraction of Metal-Contaminated Soil by Sedum alfredii H: Effects of Chelator and Co-planting

Phytoextraction is a promising technology that uses hyperaccumulating plants to remove inorganic contaminants, primarily heavy metals, from soils and waters. A field experiment was conducted to evaluate impacts of a mixture of chelators (MC) upon the growth and phytoextraction of heavy metals by the hyperaccumulator Sedum alfredii Hance in a co-planting system in a paddy soil that was historically irrigated with Pb and Zn contaminated mining wastewaters. The co-planting system used in this study was comprised of a Zn- and Cd-hyperaccumulator (S. alfredii) and a low-accumulating crop (Zea mays). Results showed that yields of S. alfredii were significantly increased with the addition of the MC and by co-planting with Z. mays. Our study further revealed that concentrations of Zn, Pb, and Cd in the corn grains of Z. mays conform to the Chinese hygiene standards for animal feeds and in the other parts of Z. mays conform to the Chinese organic fertilizer standards. The uptake of Zn, Cd, and Pb by S. alfredii was significantly increased with the addition of MC. The uptake of Zn by S. alfredii was also significantly enhanced by co-planting with Z. mays, but the interaction between MC and co-planting was not significant, meaning the effects of the two types of treatments should be additive. When the MC was applied to the co-planting system in the soil contaminated with Zn, Cd, and Pb, the highest phytoextraction rates were observed. This study suggested that the use of the hyperaccumulator S. alfredii and the low-accumulating crop Z. mays in the co-planting system with the addition of the MC was a more promising approach than the use of a single hyperaccumulator with the assistance of EDTA (ethylenediaminetetraacetic acid). This approach not only enhances the phytoextraction rates of the heavy metals but also simultaneously allows agricultural practices with safe feed products in the metal-contaminated soils.