微米Cu／Fe对污染土壤洗脱液中有机氯农药的降解

以表面活性剂TritonX-100（TX-100）为洗脱剂,某有机氯农药（organochlorinepesticides,OCPs）污染场地土壤为对象,七氯、氯丹和灭蚁灵为目标污染物,研究微米Cu／Fe双金属对污染土壤洗脱液中OCPs的降解效果。考察了洗脱液中OCPs初始浓度、洗脱液pH值、微米零价铁加入量和cu负载量对Cu／Fe去除OCPs效果的影响。结果表明,微米Cu／Fe可以有效的去除土壤洗脱液中目标污染物。当微米零价铁加入量为1．0g（25g／L）,cu负载量为1．0％,洗脱液pH值为6．89时,Cu／Fe对2号土壤洗脱液中七氯、γ-氯丹、α-氯丹和灭蚁灵的去除效果最好,去除率分别为100．0％、99．3％、80．8％和71．1％。洗脱液中OCPs初始浓度越低,微米零价铁加入量越大,Cu／Fe对OCPs去除率越高;偏酸性条件有利于Cu／Fe对γ-氯丹和灭蚁灵的去除,而α-氯丹在中性条件下去除效果最好;1号土壤和2号土壤洗脱液的最佳铜负载量分别为2．O％和1．0％。     

Evaluation of the effect of small organic acids on phytoextraction of Cu and Pb from soil with tobacco Nicotiana tabacum

Phytoremediation, the use of plants to extract contaminants from soils and groundwater, is a promising approach for cleaning up soils contaminated with heavy metals. However its use is limited by the time required for plant growth, the nutrient supply and, moreover, by the limited metal uptake capacity. Synthetic chelators have shown positive effects in enhancing heavy metal extraction, but they have also revealed several negative side-effects. The objective of this study was to investigate the use of three natural low molecular weight organic acids (NLMWOA) (citric, oxalic, and tartaric acid) as an alternative to synthetic chelators. Slurry-, column-, toxicity- and phytoextraction experiments were performed. For the phytoextraction experiment the three NLMWOA were applied to a copper- and a lead-contaminated soil respectively. A significant increase in copper uptake was visible only in the citric acid treatment (67 mg kg-1) in comparison to the EDTA treatment (42 mg kg-1). The NLMWOA application showed no enhanced effect concerning the lead phytoextraction. A possible explanation for this lack of significance could be the rate of the degradation of NLMWOA. This rate might well be too high for these heavy metals with low mobility and bioavailability such as lead. The amounts of NLMWOA applied to the soil were very high (62.5 mmol kg-1 of soil) and the effect was too little. In this respect EDTA, which was applied in very small amounts (0.125 mmol kg-1) was more efficient. Thus making NLMWOA unsuitable to enhance phytoextraction of heavy metals from soil.     

污染土壤的淋洗法修复研究进展

污染土壤淋洗技术是修复污染土壤的一种新方法 ,是对污染土壤生物修复的一种补充 ,使污染土壤修复的系统化成为可能。淋洗法主要使用淋洗剂清洗土壤 ,使土壤中污染物随淋洗剂流出 ,然后对淋洗剂及土壤进行后续处理 ,从而达到修复污染土壤的目的。因为淋洗剂的种类和淋洗方式的不同 ,土壤淋洗法可分为许多种类。土壤淋洗法主要受土壤条件、污染物类型、淋洗剂的种类和运行方式等因素影响。综合考虑多方面因素 ,就有潜力设计出经济高效的土壤淋洗系统。土壤淋洗法有很多优点 ,尽管也存在一些问题 ,但其技术上的优势也是其他方法难以取代的 ,所以有良好的应用前景。     

Metal (Cu, Cd and Zn) removal and stabilization during multiple soil washing by saponin

The influence of multiple saponin washing on copper, cadmium and zinc removal and stability in three types of soils (loamy sand, loam, silty clay) was investigated. Distribution of metals and their mobility measured as the ratio of exchangeable form to the sum of all fractions in soils was differential. After single washing the highest efficiency of metal removal was obtained in loamy sand (82-90%) and loam (67-88%), whereas the lowest in silty clay (39-62%). In loamy sand and loam metals had higher mobility factors (44-61% Cu, 60-76% Cd, and 68-84% Zn) compared to silty clay (9% Cu, 28% Cd and 36% Zn). Triplicate washing led to increase both efficiency of metal removal and percentage content of their stable forms.In consequence, fractional patterns for metals before and after treatment changed visibly as a result of their redistribution. Based on the redistribution index, the most stable metal (mainly in residual and organic fractions) after triplicate washing was Cu in loamy sand and loam. For silty clay contaminated with Cd, effective metal removal and its stabilization required a higher number of washings.     

砷污染农田的植物提取修复技术研究进展

由于粗放的矿物采冶方式,矿区大量的砷扩散到周边农田中,会导致农田土壤砷污染问题。部分地区的砷背景值高,部分地区在农业生产活动中使用含砷化肥、农药等,均会加剧农田砷污染问题。植物提取修复是一种利用超富集植物将土壤污染物吸收并转移到植物地上部,待植物成熟收割以整体移除污染物的方法。与其他砷污染农田土壤的修复技术相比,植物提取修复技术具有无二次污染的特点。该技术辅以合理的农艺措施,可使土壤砷污染减量,并实现边生产边修复的目标,应用潜力广泛。分析了砷污染土壤植物提取修复技术的原理与现状;重点探讨了近年来强化砷植物提取修复的方法,包括修复植物的种质创新、超富集植物与根际微生物联合作用和农艺措施优化等几个方面;最后展望了农田土壤砷污染修复技术的未来研究方向,以期为该技术的进一步发展提供参考。     

Decontamination of electronic waste-polluted soil by ultrasound-assisted soil washing

Laboratorial scale experiments were performed to evaluate the efficacy of a washing process using the combination of methyl-β-cyclodextrin (MCD) and tea saponin (TS) for simultaneous desorption of hydrophobic organic contaminants (HOCs) and heavy metals from an electronic waste (e-waste) site. Ultrasonically aided mixing of the field contaminated soil with a combination of MCD and TS solutions simultaneously mobilizes most of polybrominated diphenyl ethers (PBDEs), polychlorinated biphenyls (PCBs), polycyclic aromatic hydrocarbons (PAHs), and the analyte metal (Pb, Cu, and Ni) burdens. It is found that 15 g/L MCD and 10 g/L TS is an efficient reagent combination reconciling extraction performance and reagent costs. Under these conditions, the removal efficiencies of HOCs and heavy metals are 93.5 and 91.2 %, respectively, after 2 cycles of 60-min ultrasound-assisted washing cycles. By contrast, 86.3 % of HOCs and 88.4 % of metals are removed from the soil in the absence of ultrasound after 3 cycles of 120-min washing. The ultrasound-assisted soil washing could generate high removal efficiency and decrease the operating time significantly. Finally, the feasibility of regenerating and reusing the spent washing solution in extracting pollutants from the soil is also demonstrated. By application of this integrated technology, it is possible to recycle the washing solution for a purpose to reduce the consumption of surfactant solutions. Collectively, it has provided an effective and economic treatment of e-waste-polluted soil.

     

木质素盐在原油污染土壤清洗中的应用

木质素磺酸盐价格低廉,容易获得,若将其作为洗油剂中的牺牲剂,可较大幅度地降低洗油成本.以华北油田原油、华北平原典型表层土壤为模拟原料,配制了石油污染土壤,探讨木质素磺酸铵和木质素磺酸钠的洗油性能,以及木质素磺酸盐与壬基酚聚氧乙烯醚、曲拉通和平平加的复配效果.实验以碳酸钠和硅酸钠为助剂,经反复实验筛选,确定了4组最佳洗油剂配方:(Ⅰ)6(曲拉通):6(平平加):8(木素钠):40(硅酸钠):40(碳酸钠);(Ⅱ)6(曲拉通):6(壬酚聚醚):8(木素钠):35(硅酸钠):45(碳酸钠);(Ⅲ)9(曲拉通):3(壬酚聚醚):8(木素钠):50(硅酸钠):30(碳酸钠);(Ⅳ)6(曲拉通):6(壬酚聚醚):3(木素铵):5(木素钠):35(硅酸钠):45(碳酸钠).以此配方为基础,利用正交实验设计对搅拌温度、时间、固液比和加药浓度等工艺条件进行了优化.结果表明:当搅拌温度75℃、搅拌时间50 min、固液比1:15、加药总浓度为0.3g/L时,洗油率可达92.25%.清洗后污油无明显乳化现象,且浮于液面,只须简单刮油即可回收.     

木质素盐在原油污染土壤清洗中的应用

木质素磺酸盐价格低廉,容易获得,若将其作为洗油剂中的牺牲剂,可较大幅度地降低洗油成本.以华北油田原油、华北平原典型表层土壤为模拟原料,配制了石油污染土壤,探讨木质素磺酸铵和木质素磺酸钠的洗油性能,以及木质素磺酸盐与壬基酚聚氧乙烯醚、曲拉通和平平加的复配效果.实验以碳酸钠和硅酸钠为助剂,经反复实验筛选,确定了4组最佳洗油剂配方：（Ⅰ）6（曲拉通）：6（平平加）：8（木素钠）：40（硅酸钠）：40（碳酸钠）;（Ⅱ）6（曲拉通）：6（壬酚聚醚）：8（木素钠）：35（硅酸钠）：45（碳酸钠）;（Ⅲ）9（曲拉通）：3（壬酚聚醚）：8（木素钠）：50（硅酸钠）：30（碳酸钠）;（Ⅳ）6（曲拉通）：6（壬酚聚醚）：3（木素铵）：5（木素钠）：35（硅酸钠）：45（碳酸钠）.以此配方为基础,利用正交实验设计对搅拌温度、时间、固液比和加药浓度等工艺条件进行了优化.结果表明：当搅拌温度75℃、搅拌时间50 min、固液比1：15、加药总浓度为0.3g/L时,洗油率可达92.25%.清洗后污油无明显乳化现象,且浮于液面,只须简单刮油即可回收.     

Enhanced phytoextraction of Cu, Pb, Zn and Cd with EDTA and EDDS

Chemically enhanced phytoextraction has been proposed as an effective approach to removing heavy metals from contaminated soil through the use of high biomass plants. Using pot experiments, the effects of the application of EDTA, EDDS and citric acid on the uptake of Cu, Pb, Zn and Cd by corn (Zea mays L. cv. Nongda 108) and bean (Phaseolus vulgaris L. white bean) plants were studied. The results showed that EDDS was more effective than EDTA at increasing the concentration of Cu in corn and beans. The application of 5 mmol kg-1 soil EDDS to soil significantly increased concentrations of Cu in shoots, with maximum levels of 2060 and 5130 mg kg-1 DW in corn and beans, respectively, which were 45- and 135-fold higher than that in the corresponding control plants to which chelate had not been applied. Concentrations of Zn in shoots were also higher in the plants treated with EDDS than in those treated with EDTA. For Pb and Cd, EDDS was less effective than EDTA. The maximum Cu phytoextraction was found with the EDDS treatment. The application of EDTA and EDDS also significantly increased the shoot-to-root ratios of the concentrations of Cu, Pb, Zn and Cd in both plant species. The results of metal extraction with chelates showed that EDDS was more efficient at solubilizing Cu and Zn than EDTA, and that EDTA was better at solubilizing Pb and Cd than EDDS.     

重金属污染土壤中提高植物提取修复功效的探讨

随着对重金属超积累植物研究的加深 ,用植物提取修复技术来改良重金属污染的土壤已逐步进入实用阶段。本文所探讨的提高此技术功效的方法基于两个方面 :提高土壤溶液中重金属的浓度 ,促进植物对重金属的吸收 ;根据已了解的超积累的生理机制可能采取的一些措施     

表面活性剂清洗处理重度石油污染土壤

为了优化表面活性剂清洗处理重度石油污染土壤的方法和具体洗脱条件参数,采集山东省东营市胜利油田污染土壤,研究了阴离子-非离子混合表面活性剂对该土壤中石油类污染物的去除效果。应用化学热洗原理,主要考查了表面活性剂配比、投加量、清洗温度及清洗助剂对去除效果的影响。实验得到的清洗处理最佳条件为：使用LAS与TX-100质量比为8∶2的组合表面活性剂,总表面活性剂浓度为3 g/L,助剂硅酸钠浓度为5 g/L,75℃条件下搅拌1 h。清洗后土壤含油量从20%下降到4.6%,去除率达到76.9%。废水回用实验表明,清洗处理的废水对土壤中石油烃类物质仍有一定的去除效果。废水回用比从30%到100%时,对土壤中石油烃的去除率都可达到55%以上。对废水进行二次回用时仍能去除18.8%的污染物。     

环境友好型淋洗剂对重金属污染土壤的修复效果

以广西某废弃铅锌冶炼企业重金属复合污染土壤为对象,采用土柱淋洗的方法,分别将自制的茶皂素、柠檬酸和EDTA 3种淋洗剂进行复合淋洗,并对复合淋洗的最佳配比、淋洗剂添加方式和淋洗时间进行研究,得到对环境友好且淋洗效果好的复合淋洗剂。最后,对淋洗前后土壤中Cu、Pb和Zn的赋存形态进行研究,探讨淋洗机理。研究结果表明,茶皂素和柠檬酸复合时对重金属Cu、Pb、Zn的去除率分别达到了77.00%、52.09%和58.66%,综合考虑淋洗效率以及经济环保等因素,选择将茶皂素和柠檬酸复合进行淋洗。复合淋洗实验结果表明,柠檬酸和茶皂素体积比为3：1复合方式淋洗30 h,淋洗效果最佳,对重金属Cu、Pb和Zn的去除率分别达到82.77%、65.49%和78.12%。茶皂素和柠檬酸复合淋洗能有效的去除土壤中酸可提取态和有机结合态的重金属,氧化物结合态的Pb和Zn也有较大程度的降低,同时还发现,茶皂素和柠檬酸共同作用对残余态的Pb去除效果也较好,可达到50%以上。从茶籽饼中提取茶皂素与天然有机酸柠檬酸复合淋洗,用于修复污染面积小、污染浓度高且污染比较集中的重金属污染土壤,效果好且对环境友好。     

老化石油污染土壤的清洗处理

以华北油田老化长达1年以上的石油污染土壤为研究对象,采用自行选配的清洗剂对该污染土壤进行了一次清洗和二次清洗处理.实验结果表明,一次清洗后,污染土壤样品的含油率从26.34%～29.90%降到6.34%～7.84%,洗油率达80.06%～81.06%;经二次清洗处理后,污染土壤样品的含油率从26.34%～29.90%降到4.05%～4.85%,洗油率达88.06%～88.19%.在一次清洗和二次清洗的基础上,通过模拟实验确定了洗油污水回用的最佳回用率为80%,最佳加药质量浓度为0.4 g/L,该条件下污水的最终产生量也较少.按照该参数对华北油田的石油污染土壤进行了清洗实验,洗油率达79.20%～80.51%.     

The influence of humic acids on the phytoextraction of cadmium from soil

Cadmium poses a major environmental and human health threat because of its constant release through anthropogenic activities. A need, therefore, exists for cost-effective remediation procedures. Phytoremediation, the use of plants to extract contaminants from soils and groundwater, has revealed great potential. However, it is limited by the fact that plants need time, nutrient supply and, moreover, have a limited metal uptake capacity. Synthetic chelators have shown positive effects in enhancing heavy metal extraction through phytoremediation, but they have also revealed a vast number of negative side-effects. The objective of this research was to investigate the use of humic acids as an alternative to synthetic chelators. Humic acids were applied to a cadmium-contaminated soil at various dosages, and the uptake of cadmium into Nicotiana tabacum SR-1 was determined in relation to the amounts of total and bioavailable cadmium in the soil. It was found that the theoretical bioavailability of cadmium, as determined by diethylenetriaminepentaacetic acid (DTPA) extraction, did not change, but its plant uptake was enhanced significantly, in some cases up to 65%. Humic acids added at a rate of 2 g kg(-1) soil increased the cadmium concentration in the shoots from 30.9 to 39.9 mg kg(-1). A possible reason for this enhancement is the decrease in pH, resulting in higher cadmium availability. Another possibility taken into account is that plants may take up cadmium complexes with humic acid fragments, which result from microbiological degradation or, self-dissociation.     

The study of operating variables in soil washing with EDTA

This study discusses the operating variables for removal of metals from soils using EDTA, including the type of EDTA, reaction time, solution pH, dose, temperature, agitation, ultrasound and number of extractions. For As, Cd, Cu, Pb and Zn, the removal efficiency order was: H₄-EDTA > Na₂EDTA > (NH₄)₂EDTA. At low EDTA concentrations the removal increased progressively with increasing dose while above 0.4 mmol/g only small increases in extraction efficiency were observed. EDTA induced a two-step process including a rapid desorption within the first hour, and a gradual release in the following hours. The extraction efficiency of metals decreased with increasing pH in the range of 2-10. Consecutive extractions using low concentrations were more effective than a single extraction with concentrated EDTA if the same dose of EDTA was used.     

Acid washing and stabilization of an artificial arsenic-contaminated soil.

An acid-washing process was studied on a laboratory scale to extract the bulk of arsenic(V) from a highly contaminated Kuroboku soil (Andosol) so as to minimize the risk of arsenic to human health and the environment. The sorption and desorption behavior of arsenic in the soil suggested the possibility of arsenic leaching under acidic conditions. Artificially contaminated Kuroboku soil (2830 mg As/kg soil) was washed with different concentrations of hydrogen fluoride, phosphoric acid, sulfuric acid, hydrogen chloride, nitric acid, perchloric acid, hydrogen bromide, acetic acid, hydrogen peroxide, 3:1 hydrogen chloride-nitric acid, or 2:1 nitric acid-perchloric acid. Phosphoric acid proved to be most promising as an extractant, attaining 99.9% arsenic extraction at 9.4% acid concentration in 6 h. Sulfuric acid also attained high percentage extraction. The arsenic extraction by these acids reached equilibrium within 2 h. Elovich-type equation best described most of the kinetic data for dissolution of soil components as well as for extraction of arsenic. Dissolution of the soil components could be minimized by ceasing acid washing in 2 h. The acid-washed soil was further stabilized by the addition of lanthanum, cerium, and iron(III) salts or their oxides or hydroxides which form insoluble complex with arsenic. Both salts and oxides of lanthanum and cerium were effective in immobilizing arsenic in the soil attaining less than 0.01 mg/l As in the leaching test.     

EDTA在铅污染土壤治理中的优化处理方法

为了探究EDTA在土壤重金属污染治理中的优化处理方法,采用湿筛和水中重力沉降的方法,从人工Pb污染土壤（原土）中分离提取砂土、粉土和粘土,分析讨论了EDTA对土壤中Pb的去除效果,并从EDTA清洗前后土壤中Pb的BCR形态分布出发,分析了EDTA对不同粒径土壤中各形态Pb的去除效果。研究发现,实验用土壤中砂土、粉土和粘土含量分别为11.2%、75.6%和13.2%,EDTA浓度越高,土壤中Pb去除效果越好,且砂土中Pb最易被去除（~100%）,粉土与原土其次（88.66%~96.50%）,粘土最难被去除（64.78%~79.60%）,但随着EDTA浓度增加,粒径对去除Pb的影响减弱。在土壤修复实践中,可通过利用不同浓度EDTA处理不同粒径土壤的方法达到优化效果。BCR形态分布说明外源性Pb进入土壤后主要以弱酸提取态和可还原态存在,EDTA清洗主要去除弱酸提取态和可还原态,粘土中的各形态去除率均最小。     

Enhanced phytoextraction of an agricultural Cr- and Pb-contaminated soil by bioaugmentation with siderophore-producing bacteria

Bioaugmentation-assisted phytoextraction may enhance the phytoextraction efficiency thanks to larger metal mobilization by microbial metabolites. Green fluorescent protein-tagged cells of Pseudomonas aeruginosa, Pseudomonas fluorescens or Ralstonia metallidurans, able to produce siderophores, were inoculated in an agricultural soil containing Cr (488 mg kg(-1)) and Pb (382 mg kg(-1)) and maize was cultivated. Bacteria were inoculated as free or immobilized cells in Ca-alginate beads, with skim milk in the aim at improving both the bacterial survival and the in situ siderophore production. Skim milk addition increased inoculated Pseudomonads concentration in soil. Soil inoculation with free cells of R. metallidurans supplied with skim milk increased Cr accumulation in maize shoots by a factor of 5.2 and inoculation with immobilized P. aeruginosa cells supplied with skim milk increased Cr and Pb uptake by maize shoots by a factor of 5.4 and 3.8, respectively. However total metal taken up by the whole plant decreases almost always with bioaugmentation. Translocation factor also increased with P. aeruginosa or R. metallidurans by a factor of 6 up to 7. Inoculated bacteria concentration in soil was correlated with metals in the exchangeable fraction. Cr and Pb concentrations in the exchangeable fraction were correlated with metal contents in shoots or roots. Our results suggest that bioaugmentation-assisted phytoextraction is a relevant method in the aim at increasing the phytoextraction rate which usually limits the use of phytoremediation technologies.     

重金属污染土壤旋流洗脱设备的设计及性能评估

针对高浓度重金属污染土壤,尤其是污染负荷较高的黏土土壤,传统的物化方法难以实现其高效的洗脱。利用旋流场中土壤颗粒高速自转/公转,实现土壤颗粒污染物的强化快速脱附。土壤旋流洗脱实验分为旋流器的分离性能和单一/复合污染物的脱附性能2部分。在土壤-水体系下,旋流器的最优操作条件为：进口流量0.7 m3·h-1,分流比0.12,固液比为1:20。对于Pb污染物,底流脱附效率均能达到近85%,溢流也能够达到70%。对于Cu污染物,底流和溢流脱附均能达到90%左右。对于Cr(VI)污染物,底流脱附最高能达到60%左右,但溢流洗脱效率极低。复合污染能够在单次通过后脱除Pb、Cu、Cr(VI)等多种重金属污染,且洗脱效果与单一污染洗脱时基本一致。对实际的场地修复具有指导意义。     

Evaluation of biosurfactants for crude oil contaminated soil washing

An evaluation of the ability of aqueous biosurfactant solutions (aescin, lecithin, rhamnolipid, saponin and tannin) for possible applications in washing crude oil contaminated soil was carried out. The biosurfactants behaviour in soil-water, water-oil and oil-soil systems (such as foaming, solubilization, sorption to soil, emulsification, surface and interfacial tension) was measured and compared with a well-known chemical surfactant (sodium dodecyl sulphate, SDS) at varying concentrations. Results showed that the biosurfactants were able to remove significant amount of crude oil from the contaminated soil at different solution concentrations for instance rhamnolipid and SDS removed up to 80% oil and lecithin about 42%. The performance of water alone in crude oil removal was equally as good as those of the other biosurfactants. Oil removal was due to mobilization, caused by the reduction of surface and interfacial tensions. Solubilization and emulsification effects in oil removal were negligible due to the low crude oil solubilization of 0.11%. Therefore, these studies suggest that knowledge of surfactants' behaviour across different systems is paramount before their use in the practical application of oil removal.