3种有机酸对伴矿景天修复效率及土壤微生物数量的影响

伴矿景天(Sedumplumbizincicola)是一种Cd和Zn的超积累植物,常用于Cd污染土壤的植物修复。有机酸能够提高土壤重金属的有效性,促进植物对重金属的积累,对重金属污染土壤的植物修复效率具有强化作用,并对土壤微生物数量有重要影响。以河潮土和红黄泥为供试土壤,探讨了乙二胺四乙酸(EDTA)、柠檬酸、草酸对伴矿景天修复效率和土壤微生物数量的影响。结果表明,有机酸能显著提高土壤有效态Cd含量,柠檬酸处理的效果最好,河潮土和红黄泥中有效态Cd含量较单种伴矿景天分别增加72.73%,12.99%(P<0.05);伴矿景天地上部Cd含量在河潮土和红黄泥中以EDTA处理最高,在河潮土和红黄泥中分别比单种伴矿景天增加99.24%和33.32%;与单种伴矿景天相比,添加有机酸处理河潮土和红黄泥中伴矿景天修复效率显著提高。添加有机酸比单种伴矿景天显著增加土壤中微生物数量,其中柠檬酸处理河潮土中细菌和真菌数量分别增加34.38%和68.42%(P<0.05),草酸处理红黄泥中放线菌数量增加150.00%。研究结果可为重金属污染土壤的植物强化修复提供理论支撑。     

不同pH值混合螯合剂对土壤重金属淋洗及植物提取的影响

为了得出混合螯合剂（MC）淋洗去除重金属的最佳pH值以及对后续植物提取重金属的影响,用Ca(OH)2将pH值为2.75的MC提高至pH值5、7和9,对重金属污染土壤进行了盆栽淋洗试验,而后种植东南景天（Sedum Alfredii）,测定淋出液及植物重金属含量。另外,通过浸提试验研究了含有不同阳离子的MC对重金属淋洗效果的影响。结果表明,pH值为5和7的MC显著提高了Cd、Pb和Cu的淋出率。与Na+、K+离子相比,Ca2+的存在能够提高MC对重金属的淋洗去除。pH值7和9的MC淋洗土壤后提高了东南景天的生物量,但是降低东南景天中Cd和Zn的浓度,导致其植物提取率低于无淋洗剂对照。在化学淋洗+植物提取联合技术中,Cd和Zn主要靠植物提取去除,植物提取率分别可达土壤Cd的30%～40%和土壤Zn的6.5%～6.9%;而Pb和Cu主要靠混合螯合剂淋洗去除,去除率分别为2.3%～2.6%和1.6%～2.0%。综合来说,如果需要同时去除Cd、Zn、Pb和Cu,降低土壤重金属有效态含量,用pH值9的MC淋洗土壤联合植物提取较为合适。     

有机物料及其用量对生菜生长与Pb含量的影响

为了降低叶菜中重金属Pb的含量,选择有机肥、猪粪、牛粪、鸡粪和花生麸5种有机物料为材料,分别以0.5%、1%、2%、4%4个水平的用量施入重金属污染土壤,通过种植3茬生菜（Lactuca sativa L.）的盆栽试验研究有机物料对重金属污染土壤上生菜生长及其Pb含量的影响。结果表明,与对照相比,有机物料利于生菜生长,有提高生菜生物量的趋势;大部分有机物料处理没有显著影响生菜地上部分的Pb含量;5种有机物料中,仅牛粪有提高生菜地上部Pb含量的趋势;生菜Pb含量平均值高低的顺序为牛粪〉鸡粪〉花生麸〉有机肥〉猪粪,但不同有机物料之间没有显著差异。与对照相比,大部分处理没有显著影响土壤的DTPA-Pb含量,初步揭示了供试有机物料没有显著影响生菜地上部Pb含量的原因。     

柠檬酸对鱼腥草吸收累积铅锌矿区土壤中重金属的影响

采用矿区实地田间试验,通过外源添加柠檬酸(1mmol/kg,3mmol/kg,6mmol/kg和9mmol/kg)处理,研究鱼腥草对重金属复合污染土壤Pb、Zn、Cd、Cr和Cu 5种重金属元素的吸收累积特性,并确定最佳的柠檬酸调控浓度。结果表明,柠檬酸添加浓度为1mmol/kg时能显著促进鱼腥草生物量的提高,比对照增产11.64%,其他处理浓度的柠檬酸对鱼腥草生物量有抑制作用,但不显著;柠檬酸处理能显著提高鱼腥草对Pb、Zn、Cd和Cr这4种重金属元素的吸收累积能力,对Pb和Zn吸收累积能力大于Cd和Cr,对Cu的吸收累积无明显促进作用。但当柠檬酸添加浓度为1mmol/kg时每667m2鱼腥草提取Pb、Zn、Cr和Cu的量分别比对照增加了35.16%,34.39%,59.00%和18.93%,对Cd无明显促进作用。鱼腥草在矿区重金属复合污染土壤上能正常生长,并对多种重金属胁迫具有一定的耐受能力和吸收累积能力,可用于矿区重金属复合污染土壤的植物修复。     

EDTA和柠檬酸对污染土壤中重金属的解吸动力学及其形态的影响

利用批处理振荡解吸平衡法研究了0.05 mol/L的乙二胺四乙酸钠(EDTA)和柠檬酸对污染土壤中Cd,Pb,Cu,Zn的解吸动力学特征,并采用优化的BIER(European Community Bureau of Reference)连续提取法分析了EDTA和柠檬酸处理前后土壤中重金属形态和生物有效性的变化.结果表明,污染土壤中重金属Cd,Pb,Cu,Zn的解吸率随着解吸时间的延长而不断增加,但解吸速率随解吸时间的延长而不断降低.EDTA对Pb,Cu的解吸能力显著大于柠檬酸,柠檬酸对Zn的解吸能力显著大于EDTA,柠檬酸和EDTA对Cd的解吸能力相差不大.EDTA和柠檬酸对4种重金属解吸能力的顺序分别为:Pb＞Cd＞Zn＞Cu和CA＞Zn＞Pb＞Cu.双常数方程是描述污染土壤中Cd,Pb,Cu,Zn解吸动力学过程的最佳方程.EDTA去除的重金属主要以酸提取态和可还原态存在,柠檬酸去除的重金属主要以酸提取态存在.EDTA和柠檬酸处理后.污染土壤中Cd,Pb,Cu,Zn的生物有效性降低.     

土壤有机质和螯合剂对龙葵富集重金属Cd的影响

采用盆栽实验研究外源添加土壤有机质和螯合剂对龙葵富集Cd含量、土壤中有效态Cd含量以及植株地上部生物量的影响。结果表明,不同有机质和螯合剂处理在相同Cd浓度下,地上、下部植株Cd含量和富集系数分别表现为有机质含量2%有机质含量4%有机质含量6%和EDTAEDDS对照,但植物地上部带走Cd量以6%有机质和EDTA处理为最高;土壤有效态Cd含量表现为2%4%6%,EDTAEDDS对照;地上部生物量以有机质6%和螯合剂对照处理为最高。随着Cd浓度的增大,相同有机质和螯合剂下,植物Cd含量、地上部带走Cd量和土壤有效态Cd含量均呈增大趋势,但富集系数逐渐降低,其中3种含量有机质土壤下地上部的Cd富集系数变化范围分别为0.43~84.44,0.42~78.74,0.41~76.06;不同螯合剂处理下地上部Cd富集系数的变化范围分别为0.46~90.83,0.57~113.70,0.54~113.28。当Cd添加浓度大于40mg/kg时,龙葵的生长开始受到抑制。     

施肥对铅镉污染土壤上芥菜铅镉含量及生理的影响

盆栽试验研究了不同化学肥料组合处理对铅镉污染土壤上芥菜(Brassica juncea)Pb、Cd含量及其生理特性的影响。结果表明, 与对照相比, 各肥料处理在显著提高芥菜生物量的基础上, 显著降低了芥菜地上部Cd含量(P<0.05), 其中碳酸氢铵+磷酸二氢铵+硫酸钾处理的效果最佳, 芥菜Cd含量仅为对照的41.0%; 施肥处理提高了芥菜地上部Pb含量, 但Pb没有健康风险; 施肥提高了叶菜的叶绿素含量, 但丙二醛、脯氨酸、细胞质膜透性与芥菜地上部Pb、Cd含量无显著相关性。重金属污染土壤施肥处理是一种值得推广的降低叶菜有害重金属含量的有效技术。     

螯合剂强化棉花对镉污染土壤修复的初步研究

采用土壤盆栽试验研究了4种有机螯合剂柠檬酸(CA)、乙二胺四乙酸(EDTA)、乙二醇双四乙酸(EGTA)和乙二胺二琥珀酸(EDDS)在不同添加量(0,2.5,5,7.5mmol/kg)时对棉花修复镉(Cd)污染土壤的影响。结果表明,添加螯合剂显著提高了土壤水溶态Cd的含量,添加EDTA、EGTA、EDDS 3种螯合剂,使水溶态Cd含量分别提高了46.5~92.2,52.0~101.1,16.7~84.1倍,其中EGTA增加的幅度最大。棉花生长受有机螯合剂种类和添加量的影响,EDDS和EDTA在高添加量(7.5mmol/kg)时对棉花产生较大的毒害作用,但在培养期内添加螯合剂对植株生物量无显著影响。使用螯合剂显著促进棉花植株Cd含量和地上部分的积累量,其中以EGTA处理效果最佳,地上部Cd含量为对照(CK)的4.01~5.20倍。从地上部Cd积累量和转运系数来看,4种螯合剂EGTA效果最好,CA效果最差。依据研究结果,棉花可作为土壤Cd污染修复植物使用,在植株收获前7d左右添加EGTA螯合剂可有效提高棉花对Cd污染土壤的修复效率。     

螯合剂对铅锌尾矿改良基质上蓖麻幼苗生长和铅锌积累的影响

采用盆栽试验,以铅锌尾矿与对照土壤按1∶1的质量比例混合为培养基质,研究了单独添加乙二胺四乙酸二钠盐(EDTA-Na2)和氨三乙酸(NTA)以及复合添加对蓖麻幼苗生长和重金属积累的影响。结果表明:添加螯合剂后蓖麻生物量和根系形态参数均显著下降。其中,根系形态参数中根尖数下降最明显,与对照相比差异极显著(p<0.01)。各螯合处理蓖麻叶绿素a、b和叶绿素a+b与对照相比均显著下降(p<0.05),且叶绿素b较叶绿素a下降幅度略大。蓖麻叶片中三种抗氧化酶活性均随螯合处理中EDTA添加量的增加先上升后下降。添加螯合剂使蓖麻各部位Pb、Zn含量明显增加,且Pb的增幅较Zn大。螯合剂添加显著提高蓖麻对Pb、Zn的积累能力,其中对Pb的积累能力大于Zn。添加螯合剂明显促进了Pb、Zn从根部向地上部的转移,转移系数在添加EDTA和NTA各3 mmol kg-1处理中达最大值。蓖麻对Pb和Zn有较强的耐性和积累能力,可用于铅锌尾矿废弃地植物修复的进一步研究。     

螯合剂在重金属污染土壤植物修复中的应用研究进展

重金属污染土壤的植物提取修复强化途径主要有2种,一是提高植物生物量,二是提高植物体内重金属含量。从螯合剂的作用机理,常用螯合剂种类,不同种类螯合剂对土壤中目标重金属的活化效果,以及螯合剂诱导下植物对目标重金属的吸收和积累效应,螯合剂使用对生态环境造成的负面影响等方面综述了重金属污染土壤螯合诱导强化植物提取修复技术的研究进展,同时对植物修复后的评价以及螯合诱导植物修复技术今后的发展方向进行了探讨。     

Effects of Chelating Compounds on Mobilization and Phytoextraction of Copper and Lead in Contaminated Soils

Six chelating compounds: ethylenediamine-tetraacetic acid (EDTA), ethylenediamine-N, N'-disuccinic acid (EDDS), tartaric acid, citric acid, glycine and histidine, were tested as potential agents to mobilize copper (Cu) and lead (Pb) from two soils polluted with the emissions from copper smelters. Copper was mobilized with the following efficiency: EDTA > citric and tartaric acids > histidine > EDDS and glycine, while Pb extractability followed the order: EDTA > EDDS >> tartaric and citric acid >> glycine and histidine. With respect to these results, EDTA and EDDS were chosen for a pot experiment on chelate-induced phytoextraction of Cu and Pb by maize (Zea mays). Chelates were applied at the rates of 0.2, 0.5, and 1.0 mmol kg^?1, and this experiment was carried out at two different watering regimes. Both EDTA and EDDS caused significant increase of Cu uptake from soils, but its concentrations in biomass were far below those required for efficient soil remediation. Lead uptake was only slightly affected by chelate application. Losses of Cu from soil by leaching were much higher than those caused by plant uptake.     

Phytoextraction of Pb and Cd from a contaminated agricultural soil using different EDTA application regimes: Laboratory versus field scale measures of efficiency

Enhanced phytoextraction of heavy metals using chelating agents and agricultural crops is widely discussed as a remediation technique for agricultural soils contaminated with low mobile heavy metals. In this study, phytoextraction efficiency of Zea mays after single and split applications of EDTA was tested on the laboratory and the field scale. EDTA effectively increased the mobility of target heavy metals (Pb and Cd) in the soil solution. Split applications provided generally lower water-soluble levels of Pb and Cd both in the pot and the field experiment. Therefore, the risk of groundwater contamination may be reduced after split applications. Higher Pb and Cd mobilisation after single applications increased plant stress, phytotoxicity and reduced plant dry above-ground biomass production compared to corresponding split doses. Single doses enhanced plant uptake of Pb and Cd and the phytoremediation efficiency compared to corresponding split doses. Results of plant dry above-ground biomass and heavy metal uptake obtained from the pot experiment could be to some extent verified in the field experiment. Plant uptake of Pb and Cd was lower and biomass production dropped after EDTA additions in the field experiment. Remediation factors in the field experiment were in general significantly lower than in the pot experiment mainly due to the much higher mass of soil per plant under field conditions. This highlights the limitations when going from the lab to the field scale. The low phytoremediation efficiency in the field and the mobilisation of high amounts of Pb and Cd down the soil profile may make the use of EDTA and Z. mays not suitable for the remediation of severely heavy metal contaminated soils in a reasonable time frame and may result in substantial groundwater pollution under used crop management.     

螯合剂对大叶井口边草Pb、Cd、As吸收性影响研究

用室内土培试验方法,研究在采自田间的Pb、Cd、As、Zn和Cu复合污染土壤上种植大叶井口边草条件下,外源分别添加0、1.5、3、6、12 mmol/kg乙二胺二琥珀酸（EDDS）、氨三乙酸（NTA）和乙二胺四乙酸（EDTA）对大叶井口边草吸收Pb、Cd和As的影响。结果表明,3种螯合剂处理对大叶井口边草生物量没有显著影响,说明大叶井口边草对3种螯合剂耐性较强;6、12 mmol/kg EDTA处理能极显著提高土壤Pb有效态浓度,进而促进大叶井口边草对Pb的吸收。大叶井口边草地上部Pb吸收量最高达（47.4 ± 1.7）mg/kg,是对照的3.66倍。6、12 mmol/kg EDTA处理能极显著地提高土壤中Cd的有效性,但未促进大叶井口边草地上部对Cd吸收。6 mmol/kg EDDS和3 mmol/kg NTA显著提高了土壤中As有效态浓度,进而提高大叶井口边草地上部对As的吸收,大叶井口边草地上部吸收As最高达（276 ± 10） mg/kg。6 mmol/kg EDTA和6 mmol/kg EDDS处理下大叶井口边草提取的Pb、As量最大,分别为（317 ± 53） μg/盆和（873 ± 41）μg/盆,说明6 mmol/kg EDDS处理下大叶井口边草对复合污染土壤中As的修复具有较大的潜力。     

Bean Plant Production of Dry Matter and Grain Related to Soil Citric Acid–Extractable Copper,Zinc, Cadmium,and Lead

Some knowledge concerning soil heavy‐metal content and its availability to plants is essential to evaluate the risk of potentially toxic elements in the alimentary chain. Assessment of heavy‐metal availability to plants was achieved by a simple extraction method. The goal of this work was to determine the contents of copper (Cu), zinc (Zn), cadmium (Cd), and lead (Pb), soluble in 2% citric acid solution (chelating agent), in dystrophic red latosol soil (RL_d) and humic red‐yellow latosol soil (RYL_h). We focused on relating the contents of Cu, Zn, Cd, and Pb to the production of dry matter and grains by bean plants cultivated in a glasshouse. Heavy‐metal contents extracted by citric acid increased with increasing dosage increments, mainly in RL_d; production of dry matter by bean plant was negatively affected by the studied metals. However, in some cases, grain production was increased.     

云南个旧市郊农作物重金属污染现状及健康风险

通过现场采样及室内分析,对云南个旧市郊鸡街镇的土壤和农作物重金属污染现状进行野外调查,并进行健康风险评价。结果表明,土壤Pb、Zn、Cu和Cd含量均超出《土壤环境质量标准》（GB15618—1995）二级标准,Pb、Cu和Cd的二乙三胺五乙酸（DTPA）提取态与总量呈极显著正相关（P〈0.01）,Zn则呈显著正相关（P〈0.05）。农作物中除萝卜、甘蓝、花椰菜和甘蔗Pb含量未超出对应的食品安全限量标准外,其余作物均超标,Pb超标率达80%,其中薄荷Pb含量最高,平均值为3.28mg.kg-（1鲜重）,超标9.93倍;朝天椒、土豆、大米和玉米Cd含量均超标,Cd超标率为20%,其中大米Cd含量最高,平均值为0.446mg.kg-1,超标1.23倍;Cu和Zn在所采的农作物中均未超标。薄荷对Pb和Cu、莴苣对Zn和Cd的富集系数高于其他农作物。豌豆尖、蚕豆、甘蓝、花椰菜、葱、朝天椒、甘蔗、韭菜、厚皮菜、白菜、萝卜、青花菜、土豆和金丝菜对Pb、Zn、Cu和Cd吸收能力较低,适合在污染区继续种植;薄荷、莴苣和青菜对4种重金属吸收能力较高,不适合在污染区继续种植。根据单因子评价方法,农作物受Pb轻度、中度、重度污染分别占50%、10%和20%,受Cd轻度、中度污染各占10%。对于不同种类农作物,不同重金属的综合污染指数为Pb〉Cd〉Zn〉Cu。居民经食用蔬菜途径日摄入Pb、Zn、Cu和Cd量分别为0.204、2.336、0.376mg.d-1和0.028mg.d-1,分别占暂定每日耐受摄入量（PTDI）的101.78%、7.08%、5.79%和39.29%。因此,经蔬菜途径摄入Pb对当地居民健康构成潜在威胁。     

Degradability of natural and synthetic chelating agents applied to a lead-contaminated soil

Purpose

Studying the rate of chelant degradation is important to select environmental friendly compounds to assist phytoextraction. The objective of the present study was to evaluate degradation rate of complexes formed between synthetic or organic chelants and Pb aiming to increase the efficiency of phytoextraction while reducing adverse effects resulting from the Pb leaching.

Materials and methods

The following six chelating agents were tested: citric acid P.A., commercial citric acid, glutamic acid P.A., monosodium glutamate, nitrilotriacetic acid (NTA), and ethylenediaminetetraacetic acid (EDTA), besides a control treatment (no addition of chelating agent); they were applied at a concentration of 10 mmol dm^?3 in pots containing 1 dm³ of Pb-contaminated soil.

Results and discussion

The results of this study showed that commercial citric acid adequately solubilized Pb to levels suitable for plant uptake and showed relatively rapid biodegradation in soil. Therefore, this commercial product may be a highly promising alternative for phytoextraction studies in the field. EDTA and NTA demonstrated high Pb solubilization ability but degraded comparatively slowly; therefore, they are not recommended for use in phytoextraction due to environmental risks regarding metal leaching.

Conclusions

The results of this study showed that commercial citric acid adequately solubilized Pb to levels suitable for plant uptake and showed relatively rapid biodegradation in soil, which is associated with a low risk of groundwater contamination. Therefore, this environmental friendly and low-cost product may be a highly promising alternative for inducing Pb phytoextraction.

     

Exogenously Applied Citric Acid Enhances Antioxidant Defense and Phytoextraction of Cadmium by Willows (<Emphasis Type="Italic">Salix</Emphasis> Spp.)

The effect of exogenously applied citric acid (CA) on phytoextraction and antioxidant defense was analyzed using willow species (Salix viminalis, S. alba, and S. matsudana) grown in soil contaminated with cadmium (Cd). Citric acid has been used as a chelating agent for the purpose of accelerating the solubility of Cd in soil and enhancing the phytoextraction of selected plants. Willows were exposed to 6 mg/kg of Cd, following the same with citric acid (20 mM/kg soil). Results revealed a positive effect of citric acid in mobilization of accumulated Cd from roots to shoots and leaves. The addition of citric acid alleviated Cd toxicity by helping plants to overcome oxidative stress, through CA’s chelating properties and the increased activity of antioxidant enzymes. Different protection strategies were evident through modification of activities of antioxidant enzymes such as catalase (CAT), ascorbate-peroxidase (APx), and guaiacol peroxidase (GPx) in young versus mature leaves in plants exposed to Cd. Furthermore, results revealed that addition of citric acid may be beneficial in the reduction of the negative effect of Cd stress on photosynthesis. The efficiency of coupling phytoextraction with the chelating agents represents a good strategy for decreasing damages caused by cadmium and has good potential in decontamination of a polluted environment.     

Heavy-Metal Phytoextraction Potential of Spinach and Mustard Grown in Contaminated Calcareous Soils

Laboratory batch and greenhouse pot experiments were conducted to determine the extraction efficiency of ethylenediaminetetraacetic acid (EDTA) for solubilizing lead (Pb) and cadmium (Cd) and to explore the natural and chemically induced Pb and Cd phytoextraction efficiencies of spinach and mustard after EDTA application. The EDTA was applied at 0, 1.25, 2.5, and 5.0 mM kg^?1 soil in three replicates. Addition of EDTA increased significantly the soluble fraction Pb and Cd over the control and maximum increases for Pb (1.42- and 1.96-fold) and Cd (1.45- and 1.38-fold) were observed with the addition of 5.0 mM EDTA kg^?1 in Gujranwala and Pacca soils, respectively. Similarly, addition of EDTA increased significantly the Pb and Cd concentrations in the plant shoots, soil solution, bioconcentration factor, and phytoextraction rate. Mustard exhibited better results than spinach when extracting Pb and Cd from both contaminated soils.     

生物炭对铜矿区污染土壤微生物活性及香根草富集铜、镉、铅的影响

矿区土壤易发生重金属污染,是土地资源利用和维护的一大难题。以铜矿区污染土壤为研究对象,按质量比添加0,1%,2%,4%,10% (w/w)的生物炭,进行香根草室内盆栽试验。研究添加生物炭对土壤pH和微生物活性、香根草富集与转运重金属的影响,探明重金属形态含量与生物炭、微生物活性的相关性,旨在为生物炭与香根草联合修复矿区重金属污染土壤提供理论参考。结果表明:生物炭的添加能提高土壤pH,显著提高土壤FDA水解酶、蔗糖酶和脲酶活性,显著促进土壤基础呼吸,但对土壤微生物量碳无显著影响;生物炭的添加使香根草生物量显著增大,降低土壤Cu和Pb的有效态占比,Cd的变化与此相反;添加生物炭促进香根草对Cd和Pb的富集,降低香根草对Cu的富集,减少Cu、Cd和Pb在香根草体内的转运,因此香根草可作为Cu、Cd和Pb的稳定化植物。土壤蔗糖酶活性与香根草叶片Cu、Cd和Pb含量、有效态和残渣态Cu含量呈显著正相关,土壤基础呼吸与叶片Cu、Cd和Pb含量、有效态Cu、Pb含量呈显著负相关,而与有效态Cd含量呈显著正相关。总之,生物炭可减弱矿区土壤重金属对香根草生长的毒害作用,并促进香根草对重金属的富集,两者结合可改善铜矿区污染土壤的理化性质和微生物活性,有利于重金属污染土壤修复,改善土壤质量。