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。     

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。     

Remediation of cadmium-contaminated paddy soils by washing with chemicals: effect of soil washing on cadmium uptake by soybean

We conducted a pot experiment to evaluate the effect of soil washing with CaCl(2) on Cd absorption by two soybean cultivars. The results were as follows: (1) Soybean growth was not significantly different in washed and unwashed soils, but the seed Cd concentration for both cultivars decreased significantly, up to 25%, in the washed soils compared with the unwashed soils. (2) In the washed soils, the Cd concentration in the soil solution indicated an obviously lower value from sowing to the flowering stage; however, the change in Cd speciation was not evident in the CaCl(2)-washed soil solution. Consequently, the effect of soil washing using CaCl(2) on Cd-contaminated paddy soils can be expected to continue after a CaCl(2)-washed paddy field is converted to an upland field.     

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。     

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。     

硫代硫酸盐浸提法修复汞污染土壤及含汞浸出液的光分解回收处理

汞污染土壤对环境的危害巨大,已成为国内外主要关注的环境问题之一。以某PVC化工厂附近的含汞土壤样品为研究对象,开展了硫代硫酸盐浸提脱汞的研究,对浸提前后的含汞土壤开展了Förstner七步顺序提取实验,考察分析了含汞土壤及浸提后土壤中汞的存在形态,并对含汞的硫代硫酸盐浸出液开展了紫外光分解、沉淀脱除汞的研究。结果表明：该土壤样品中含汞总量高达2 400 mg·kg⁻¹;其中41.3%的Hg以水溶态、交换态、盐酸溶态和硝酸溶态形式存在,属于易释放汞;以有机质结合态和硫化态形式存在的Hg分别占33.9%和24.2%,属于稳定形态的汞。以硫代硫酸钠为浸出剂,可以有效地浸出含汞土壤中的易释放形态汞;采用0.01 mol·L⁻¹的硫代硫酸钠溶液,在室温下浸出约6 h,可将含汞土壤中95%以上的易释放汞浸提出来,浸提后土壤中残余的汞基本上仍以有机质结合态和硫化态形式存在。对含汞11.6 mg·L⁻¹的硫代硫酸盐浸出液,经254 nm的紫外线照射5 min,即可将99.1%以上的汞-硫代硫酸盐络合物分解转变为稳定的硫化汞沉淀,从而将汞从浸出液中分离回收。本研究表明,硫代硫酸盐浸提处理及采用紫外光分解分离回收汞可从含汞土壤中分离除去易释放形态汞。     

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%.     

有色金属冶炼厂镉污染土壤淋洗除镉

以云南省某废弃有色金属冶炼厂镉污染土壤为研究对象,分别采用单一淋洗和复合淋洗方法探究盐酸、FeCl3、鼠李糖脂淋洗剂及淋洗条件对土壤中镉去除效果的影响。结果表明,在盐酸(1 mol·L-1)+鼠李糖脂(2%)配比为2∶1,液固比为8∶1,淋洗时间为24 h的条件下,土壤中镉的去除率可达86.78%,可将镉污染强度为1 180 mg·kg-1的土壤修复至满足《土壤环境质量建设用地土壤污染风险管控标准》(GB 36600-2018)第二类用地管制值(Cd-1)的要求。该方法可有效去除土壤中活性态镉,使土壤生物毒性明显降低。     

吐温80对柴油污染老化土壤的洗脱特征及影响

研究了柴油污染土壤的老化特性及吐温80（Tween 80）修复柴油污染老化土壤的效率和对总油中含有不同基团物质的洗脱特性,进行了一系列不同浓度的Tween 80洗脱柴油污染老化土壤实验,并使用红外分光光度法对洗脱后的土壤和残留液中的总油及各基团浓度进行测定。结果表明,经过1年时间的老化,约53%的柴油从土壤中挥发,土壤中残留的总油中约40.55%为稳定吸附态。随着洗脱液中Tween 80浓度的提高,老化土壤中总油量不断减少,但当Tween 80浓度超过3 000 mg·L-1时土壤中总油含量的减少速率和Tween 80的增溶效率的增加速率显著降低,因此3 000 mg·L-1浓度的Tween 80作为洗脱液性价比最高,其对吸附态总油的洗脱率为20.30%,对老化土中总油的洗脱率为67.68%。Tween 80溶液洗脱石油污染老化土时,对含烷烃（CH3）基团和含烯烃（CH2）基团的物质洗脱效率较高,而对于含芳烃（CH）基团的物质洗脱效率相对较低。     

Remediation of toxic metal contaminated soil by washing with biodegradable aminopolycarboxylate chelants

Ex situ soil washing with synthetic extractants such as, aminopolycarboxylate chelants (APCs) is a viable treatment alternative for metal-contaminated site remediation. EDTA and its homologs are widely used among the APCs in the ex situ soil washing processes. These APCs are merely biodegradable and highly persistent in the aquatic environments leading to the post-use toxic effects. Therefore, an increasing interest is focused on the development and use of the eco-friendly APCs having better biodegradability and less environmental toxicity. The paper deals with the results from the lab-scale washing treatments of a real sample of metal-contaminated soil for the removal of the ecotoxic metal ions (Cd, Cu, Ni, Pb, and Zn) using five biodegradable APCs, namely [S,S]-ethylenediaminedisuccinic acid, imminodisuccinic acid, methylglycinediacetic acid, DL-2-(2-carboxymethyl) nitrilotriacetic acid (GLDA), and 3-hydroxy-2,2′-iminodisuccinic acid. The performance of those biodegradable APCs was evaluated for their interaction with the soil mineral constituents in terms of the solution pH and metal-chelant stability constants, and compared with that of EDTA. Speciation calculations were performed to identify the optimal conditions for the washing process in terms of the metal-chelant interactions as well as to understand the selectivity in the separation ability of the biodegradable chelants towards the metal ions. A linear relationship between the metal extraction capacity of the individual chelants towards each of the metal ions from the soil matrix and metal-chelant conditional stability constants for a solution pH greater than 6 was observed. Additional considerations were derived from the behavior of the major potentially interfering cations (Al, Ca, Fe, Mg, and Mn), and it was hypothesized that use of an excess of chelant may minimize the possible competition effects during the single-step washing treatments. Sequential extraction procedure was used to determine the metal distribution in the soil before and after the extractive decontamination using biodegradable APCs, and the capability of the APCs in removing the metal ions even from the theoretically immobilized fraction of the contaminated soil was observed. GLDA appeared to possess the greatest potential to decontaminate the soil through ex situ washing treatment compared to the other biodegradable chelants used in the study.     

Decontamination of soil containing POPs by the combined action of solid Fenton-like reagents and microwaves

The effect on halogenated aromatics of solid, non-toxic oxidants such as sodium percarbonate and the urea/hydrogen peroxide complex (Fenton-like reagents) was investigated. A microwaves-assisted, solvent-free method for soil decontamination is presented. It marks a considerable advance in the search of more efficient, environment-friendly procedures for the degradative oxidation of persistent organic pollutants. Residual pollutants in treated soil samples were determined by GC/MS analysis after solvent extraction or direct thermal desorption. Results showed that 4-chloronaphthol, 2,4-dichlorophenoxyacetic acid and p-nonylphenol had been degraded completely, 2,4-dibromophenol to a large extent.     

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.     

不同化学淋洗剂对复合重金属污染土壤的修复机理

化学淋洗技术是一种常用的重金属污染土壤修复技术,化学淋洗剂的选择尤为重要。以乙二胺四乙酸二钠（EDTA）、柠檬酸（CA）和三氯化铁（FeCl3）为化学淋洗剂,采用振荡淋洗法研究淋洗时间与淋洗剂浓度对Cu、Zn、Pb和Cd去除效果的影响,分析重金属污染土壤淋洗前后重金属形态与基本理化性质的变化。结果表明：3种化学淋洗剂对重金属的快速反应阶段基本在60 min内,在240 min达到淋洗平衡,对Pb和Cd的淋洗主要是非均相扩散过程;EDTA、柠檬酸和FeCl3对重金属的去除能力依次为Pb>Cd>Cu>Zn,Cd>Zn>Cu>Pb与Pb≈Cd>Cu>Zn,EDTA的淋洗效率最高,Cd的解吸能力最强;EDTA和FeCl3可有效去除弱酸可溶态与可还原态重金属,柠檬酸能有效去除弱酸可溶态重金属,修复后的土壤仍有环境风险;3种淋洗剂修复后的土壤中总有机碳与粒径分布无明显变化,FeCl3会酸化土壤。综合考虑,EDTA、柠檬酸和FeCl3均为淋洗效果好的环境友好型化学淋洗剂,该研究成果可用于现场淋洗去除土壤中重金属的小试。     

超声强化EDDS/EGTA淋洗修复重金属污染土壤

采用响应面法中的Box-Behnken实验设计,研究了超声强化N,N'-乙二胺二琥珀酸(EDDS)和乙二醇双(2-氨基乙基醚)四乙酸(EGTA)复合淋洗对土壤中Cu、Zn、Pb 和Cd 等4种重金属的去除效果,拟合了各重金属去除率、潜在生态风险指数削减率与EDDS投加量、EGTA投加量、超声功率和初始pH等淋洗条件之间的关系,模拟值与观测值相关性高,模拟精度较高。EGTA在较广pH范围对高生理毒性的Cd具有较强的洗脱效果,酸性条件下可有效洗脱Zn;Cu去除率在酸性条件下随着EDDS投加量的增加而显著提高,Pb去除率则在碱性条件随着EDDS投加量的增加而显著提高。基于模型优化结果的验证实验显示,当EDDS/重金属摩尔质量比为0.81、EGTA/重金属摩尔质量比为3.92、超声功率为569.85 W、pH为3.95时,潜在生态风险指数削减率最大,达到86.05%,Cu、Zn、Pb和Cd去除率分别为72.48%、62.40%、59.25%和87.45%,与模型拟合结果偏差较小,表明模型具有较好的拟合和预测能力。     

Scavenging of BHCs and DDTs from soil by thermal desorption and solvent washing

Intensive remediation of abandoned former organochlorine pesticides (OCPs) manufacturing areas is necessary because the central and surrounding soils contaminated by OCPs are harmful to crop production and food safety. Organochlorine and its residues are persistent in environments and difficult to remove from contaminated soils due to their low solubility and higher sorption to the soils. We performed a comprehensive study on the remediation of OCPs-contaminated soils using thermal desorption technique and solvent washing approaches. The tested soil was thermally treated at 225, 325, 400, and 500 °C for 10, 20, 30, 45, 60, and 90 min, respectively. In addition, we tested soil washing with several organic solvents including n-alcohols and surfactants. The optimal ratio of soil/solvent was tested, and the recycling of used ethanol was investigated. Finally, activities of polyphenol oxidase (PPO), urease (URE), alkaline phosphatase, acid phosphatase (ACP), and invertase (INV) were assayed in the treated soils. The tested soil was thermally treated at 500 °C for 30 min, and the concentration of contaminants in soil was decreased from 3,115.77 to 0.33 mg kg^?1. The thermal desorption in soil was governed by the first-order kinetics model. For the chemical washing experiment, ethanol showed a higher efficiency than any other solvent. Using a 1:20 ratio of soil/solvent, the maximum removal of OCPs was achieved within 15 min. Under this condition, approximately 87 % of OCPs was removed from the soils. More than 90 % of ethanol in the spent wash fluid could be recovered. Activities of some enzymes in soils were increased after ethanol treatment. But ALP, ACP, and INV activities were decreased and PPO and URE showed slightly higher activities following remediation by thermal treatment. Both heating temperature and time were the key factors for thermal desorption of OCPs. The n-alcohol solvent showed higher removal of OCPs from soils than surfactants. The highly efficient removal of OCPs from soil was achieved using ethanol. More than 90 % of ethanol could be recovered and be reused following distillation. This study provides a cost-effective and highly efficient way to remediate the OCPs-contaminated soils.     

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.     

热水洗辅助微生物修复高含油落地油泥

为解决油田落地油泥含油率高但不能直接进行生物无害化处置的问题,探索一种热水洗辅助微生物修复工艺。利用热水洗实验考察了清洗配方和水温对降低含油率的影响;从落地油泥中分离出石油烃降解菌,以用于含油残砂的微生物降解过程,同时探究填料和烃降解微生物对残砂中石油烃降解效果的影响。结果表明,鼠李糖脂清洗剂在总用量为0.5%、水洗时间30 min和50 ℃条件下,可将油泥含油率由107.1 mg·g⁻¹降至为39.3 mg·g⁻¹;水洗后残砂中的土著菌群数量出现了明显下降。分离获得了2株烃降解菌,并优选出具有增加油泥溶氧和保水的沼渣。将烃降解微生物和优选沼渣加入残砂后,石油烃生物降解效率得到显著提升,200 d后含油率降为4.62 mg·g⁻¹。在此过程中,微生物优先降解分子量小的饱和烃和芳香烃组分,对胶质和沥青质等组分降解程度偏低。该研究结果可为油田高含油落地油泥的环保处置提供参考。     

EPA SITE demonstration of the BioTrol soil washing process.

A pilot-scale soil washing process, patented by BioTrol, Inc., was demonstrated on soil contaminated by wood treating waste, primarily pentachlorophenol (PCP) and creosote-derived polynuclear aromatic hydrocarbons (PAHs). Although soil washing was the main object of this demonstration, the treatment train that was evaluated included two other BioTrol technologies for treatment of waste streams from the soil washer. The three technologies were: The BioTrol Soil Washer (BSW)--a volume reduction process, which uses water to separate contaminated soil fractions from the bulk of the soil. The BioTrol Aqueous Treatment System (BATS)--a biological water treatment process. The Slurry Bioreactor (SBR)--a BioTrol biological slurry treatment process conducted in an EIMCO BIOLIFT reactor. The sandy soil at the site, consisting of less than 10 percent of fines, was well suited for treatment by soil washing. The soil washer was evaluated in two tests on soil samples containing 130 ppm and 680 ppm of PCP, respectively. The BSW successfully separated the feed soil (dry weight basis) into 83 percent of washed soil, 10 percent of woody residues, and 7 percent of fines. The washed soil retained about 10 percent of the feed soil contamination while 90 percent of the feed soil contamination was contained within the woody residues, fines, and process water. The soil washer achieved up to 89 percent removal of PCP and 88 percent of total PAHs, based on the difference between their levels in the as-is (wet) feed soil and the washed soil.(ABSTRACT TRUNCATED AT 250 WORDS)     

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.