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。     

冻融-化学淋洗法协同修复重金属Cd和Pb污染黏性土

针对质地黏重、低渗透性黏性土的淋洗效率低下,该文提出冻融协同化学淋洗的修复方案,并以某冶炼厂受Cd、Pb污染场地黏性土为研究对象,选用乙二胺四乙酸二钠(ethylene diaminetetraacetic acid disodium salt,EDTA)为淋洗剂,进行了冻融-淋洗土柱的实证试验。结果表明,土体的反复冻融(冻胀-吸水、融沉-排水)破坏土体颗粒原有结构,有助于淋洗液与污染物充分接触,淋洗效果明显,经7次冻融后,Cd、Pb去除率分别达到77.24%、37.78%。采用改进的BCR(European Communities Bureau of Reference)连续提取法分析了土柱中Cd、Pb的赋存特征,经7次冻融后,土壤中弱酸提取态、可还原态、残渣态结合的Cd质量分数较淋洗前分别降低了41.46%、63.02%、26.33%,而土壤中可还原态和残渣态结合的Pb质量分数分别降低了32.32%、67.36%。冻融协同化学淋洗修复技术的淋洗剂用量远小于传统淋洗法,为今后利用寒区冻融交替现象,大规模对季冻区重金属污染土壤的异位修复提供了新的思路。     

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。     

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。     

酶与茶皂素组合液对重金属Cd和Pb复合污染土壤的生态修复作用

[目的]评价α-淀粉酶与茶皂素对污染土壤中的Cd,Pb洗脱效果,为重金属污染土壤的修复提供更准确的科学依据。[方法]以重金属Cd,Pb污染的耕作层土壤为研究对象,利用α-淀粉酶和茶皂素复合淋洗对Cd,Pb污染土壤进行生态修复,并测定土壤淋洗前后Cd,Pb形态的变化。[结果]在反应时间12h,pH 4.0,反应温度30℃,茶皂素溶液和酶溶液配比4∶1条件下,Cd,Pb去除率分别为88.87%,43.97%。通过对修复前后重金属的形态分析,发现酸提取态、可还原物态的重金属较容易去除,淋洗后土壤中Cd和Pb均达到土壤环境质量Ⅱ级标准。[结论]α-淀粉酶和茶皂素组合对土壤中Cd,Pb有明显的去除效果,起到协同、增强作用。表明α-淀粉酶和茶皂素组合在生态修复重金属污染的土壤方面具有一定的应用前景。     

花生油与羟丙基β环糊精对有机氯农药污染场地土壤异位增效淋洗修复研究

针对长三角典型区域内某废弃有机氯农药(OCPs)污染场地土壤,选择花生油和羟丙基β环糊精(HPCD)作为环境友好的淋洗剂,并嵌合超声强化、升温辅助等增效洗脱技术,研究了其对OCPs污染场地土壤的洗脱修复效果。结果发现,在100 ml/L 花生油和50 g/L HPCD、50?C水浴和35 kHz超声 30 min、连续淋洗5次条件下,土壤中DDTs、氯丹(Chlordanes)、灭蚁灵(Mirex)和总量OCPs的最大去除率分别为99.6% ± 2.2%、94.0% ± 1.3%、91.3% ± 2.0% 和96.0% ± 2.5%。同时采用Tenax TA树脂连续提取法,监测每次连续淋洗后土壤中各组分OCPs解吸特性,发现随着淋洗次数的增加,土壤中OCPs的400-h Tenax 可提取量逐渐减少,OCPs的快速解吸组分(Fr)和慢速解吸组分(Fsl)比例较原始土壤中的相应比例显著下降(P<0.01),OCPs的快速解吸速率常数(kr)、慢速解吸速率常数(ksl)和超慢速解吸速率常数(kvl)也较原始土壤中相应解吸速率常数显著降低(P<0.01)。综合考虑修复效率和土壤修复后潜在环境风险,3次淋洗可以认为较为合理。本研究为OCPs污染场地土壤的异位增效淋洗技术研发和淋洗终点判断提供了一种有效手段。     

正丙醇与羟丙基-β-环糊精复配对高浓度DDT污染土壤的增效洗脱修复研究

以武汉某高浓度滴滴涕(DDT)污染场地土壤为研究对象,采用正丙醇和羟丙基-β-环糊精(HPCD)为洗脱剂进行相关的洗脱试验,并嵌合升温措施,研究了其对DDT污染场地土壤的洗脱修复效果。试验结果表明,20%正丙醇和50 g L-1HPCD复配、50℃水浴连续洗脱5次,可以使土壤中DDT总量的平均去除率达到96.41%。研究为DDT污染场地土壤的异位增效洗脱技术研发提供了一种有效手段。     

化工厂遗留地铬污染土壤化学淋洗修复研究

选取了济南市某铬渣堆放场地表土壤为实验目标,采用振荡淋洗法研究了水、EDTA、柠檬酸、盐酸、Ca Cl2、Na OH和磷酸等淋洗剂对铬污染场地铬污染物的淋洗效果,并从中筛选出最佳淋洗剂,探讨了淋洗剂浓度、土液质量比、振荡淋洗时间、淋洗液p H等对淋洗条件的影响。结果显示,选取的土壤样品均超过国家土壤标准,钛白生产车间土样污染程度最轻,北部厂区污染最重,最高铬污染物含量达到7 149 mg kg-1;土壤活性指数I显示,万吨铬盐生产车间土壤的活性指数最高达到0.291 8,铬盐生产车间活性指数最低;水、盐酸、柠檬酸、Ca Cl2、Na OH、磷酸等对总铬的去除率比较低,EDTA的淋洗效果最佳;EDTA的最佳淋洗浓度为0.1 mol L-1;最适土液质量比为1∶10;最适振荡淋洗时间为1 h;最适淋洗液p H为5;所有淋洗试验最高去除率为p H 10时,北部厂区样品在0.1 mol L-1EDTA淋洗液,土液质量比为1∶10,振荡淋洗时间1 h取得,总铬的去除率可达到22%,Cr6+去除率可达到98.5%。     

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。     

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。     

纳米磺化石墨烯用于异位洗脱污染土壤多环芳烃工艺的优化

Ex-situ soil washing technology offers advantages such as speed and efficiency of remediation and range of application and has been developed to conform with legal requirements and best management practices in USA and some European countries. In this study,nano-sulfonated graphene(SGE) was used as a washing agent to evaluate different processing(washing) parameters for the ectopic leaching removal of polycyclic aromatic hydrocarbons(PAHs) from a coking plant soil. X-ray photoelectron spectroscopy(XPS) and fourier transform infrared spectroscopy(FTIR) were used to analyze the characteristics of the SGE tested. The results showed that SGE had a strong adsorption capacity for PAHs through the role of π-π, H-π, and anion-π interactions. The washing parameters, an SGE concentration of 2 000 mg L~(-1), a liquid/soil(L/S) ratio of 10:1, and 4 cycles of successive washing, were set to arrive to the optimum condition for achieving more than 80% of PAH removal. Under the optimum condition, the PAH removal rate decreased with increasing ring numbers. After one washing cycle at SGE concentration of 2 000 mg L~(-1) and L/S ratio of 10:1, the PAH removal rate of the SGE tested was much higher than that of Tween 80(TW80) or methyl-β-cyclodextrin(MCD)(P 0.01). Therefore, SGE is a promising material for the nanoremediation of PAH-contaminated soils.     

淋洗法修复铬渣污染场地实验研究

铬渣污染场地已经列为我国土壤污染重点治理对象,急需修复铬渣污染土壤的关键技术。本文通过室内模拟实验,采用振荡淋洗的方法研究了水、EDTA、EDDS、柠檬酸、草酸、盐酸、磷酸、环糊精和十二烷基苯磺酸钠等淋洗剂对铬渣污染场地Cr的淋洗效果,探讨了淋洗剂浓度、淋洗时间、土水比、淋洗次数等对淋洗效果的影响,并研究了不同淋洗剂复合对Cr的淋洗效果以及不同浓度柠檬酸淋洗前后重金属形态的变化。结果表明：水、EDTA、EDDS、环糊精和十二烷基苯磺酸钠对Cr的去除率较低,柠檬酸在浓度为0.5mol·L-1、土水比1：20、反应时间为24h、淋洗次数为2次的条件下可以达到最佳淋洗效果,Cr的去除率可达到82.8%;SDBS、EDTA与柠檬酸单独组合顺序或者混合淋洗,都没有增加柠檬酸对Cr的去除率。重金属形态分析表明,柠檬酸淋洗有效地改变了Cr的形态从而达到较高的修复效果。当柠檬酸浓度小于0.25mol·L-1时,对铬的去除主要以C（rⅥ）为主;当柠檬酸浓度大于0.25mol·L-1时,对铬的去除主要以C（rⅢ）为主。本文的研究结果为异位淋洗修复铬渣污染土壤提供理论依据。     

Remediation of lead-, arsenic-, and cesium-contaminated soil using consecutive washing enhanced with electro-kinetic field

Purpose

Extensive deposition of Pb, As, and Cs in soils may damage ecosystems and human’s health. Soil washing is the most conventional remediation method, and its efficiency depends on metal solubility in soil. This study aims to optimize operating variables of electro-kinetic field (EKF)-enhanced soil washing procedures.

Materials and methods

Soil samples from a Mississippi River Delta rice field were homogeneously spiked with Pb, As, and Cs, and contaminated soil was aged for 3 months. The remediation involved a first stage electro-kinetic process, followed by a soil washing procedure. Soil pH changes under EKF were studied. Effects of citric acid and reversed EKF were investigated for alleviating possible alkaline precipitation. In the washing procedure, soil washing time and cycles with different extractants were examined. The overall EKF-enhanced soil washing efficiencies were discussed as well.

Results and discussion

The implement of EKF offered an acidic soil environment around the anode areas for solubilizing metal(loid)s. Combined with EKF, citric acid was more conductive to desorb metal(loid)s. In addition, the reversed EKF effectively alleviated metal(loid) precipitation caused by alkalization in the first stage cathode areas. The EKF significantly enhanced metal(loid) extractions in the anode area of soils using Na₂EDTA, CaCl₂, and citric acid at pH of 2. The most preferable removal of Pb (80–98 %), As (48–63 %), and Cs (10–13 %) was achieved with three extractants. CaCl₂ and citric acid were proved to be suitable alternatives to Na₂EDTA for Pb extraction. A washing process of 2 h extraction with double washing cycles was optimized.

Conclusions

Soil washing time and cycles were major factors governing the metal(loid) removal from soil. Washing process of 2 h extraction with double cycles was optimized for further extraction based on higher washing efficiency. The EKF effectively improved washing efficiency while some electrical parameters need further studies for cost performance consideration.

     

稻壳基生物炭对生菜Cd吸收及土壤养分的影响

探讨稻壳基生物炭对Cd污染土壤上叶菜吸收Cd和土壤Cd形态的影响作用,明确稻壳基生物炭对土壤Cd污染的调控效应,可为合理利用稻壳基生物炭降低叶菜Cd含量提供参考。采用盆栽试验,研究了稻壳基生物炭在不同用量水平下对2茬生菜地上部Cd含量、土壤养分含量及Cd赋存形态的影响。结果表明,在5~25 g-kg-1用量范围内,稻壳基生物炭显著降低了2茬生菜地上部和根系Cd含量,且在最大用量25 g-kg-1时效果最好,地上部Cd含量分别比未施稻壳基生物炭的对照处理降低了19.6%和45.8%,根系Cd含量分别降低了36.8%和28.0%。在25 g-kg-1用量水平下,稻壳基生物炭对土壤p H、有效磷、速效钾及有机质含量提升效果明显,但显著降低了土壤碱解氮含量。施加稻壳基生物炭对土壤有效态Cd含量及Cd化学形态也有不同影响。随着稻壳基生物炭用量的增加,土壤NH4OAc提取态Cd含量和弱酸提取态Cd含量显著降低,在用量为25 g-kg-1时,分别比对照降低17.9%和10.4%,可还原态Cd含量无显著变化,可氧化态Cd含量呈减低趋势,残渣态Cd含量增加17.6%。因此推测,提升土壤p H、降低土壤有效态Cd含量、增加残渣态Cd含量可能是稻壳基生物炭降低生菜体内Cd含量的主要原因。稻壳基生物炭可以作为土壤改良剂,抑制Cd污染土壤上叶菜对Cd的吸收,改善土壤养分状况。     

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。     

Persistence of CaCl2 washing effect for amelioration of a Cd-contaminated paddy field soil

Abstract

Soil washing is one of the methods used to remediate soil contaminated with heavy metals, and when the contaminated elements have been effectively removed the washed soil can be used for agriculture. Soil washing was conducted using 0.5 mol L^?1 CaCl₂ solution at pH 4 as an extracting agent to remediate a paddy field soil contaminated with Cd. Dolomite powder was applied to neutralize the soil to the original pH 6.2. After CaCl₂ washing, the content of Cd extractable in 0.1 mol L^?1 HCl decreased from 2.4 to 0.8 mg kg^?1. Subsequently, a pot experiment was carried out to evaluate the effect of soil washing on Cd concentration in polished rice (Cd_pr) for three successive years. Using the washed soil, Cd_pr was ≤ 0.2 mg kg^?1 with and without a treatment that simulates midseason drainage, whereas it was > 0.5 mg kg^?1 in the unwashed soil with the midseason drainage treatment. The reasons for low Cd_pr growth in the washed soil were the low content of exchangeable Cd in the soil and the resultant high soil pH (> 7). To evaluate the effect of soil pH on Cd_pr in the fourth year, we adjusted soil pH to 5 with H₂SO₄ before transplanting rice seedlings. The Cd_pr in the washed soil with the midseason drainage treatment increased to 0.47 mg kg^?1, whereas it was less than 0.2 mg kg^?1 under continuous flooding. Thus, high pH or whole season flooding are important to keep Cd_pr at ≤ 0.2 mg kg^?1 even after soil washing. With the application of dolomite and other ordinary fertilizers, soil properties were little affected by the present soil washing procedure because the difference in rice yield between the washed and unwashed plots was not significant within each year.     

磁性黏土颗粒对污染土壤中镉去除作用的初步研究

农田土壤中镉（Cd）污染备受关注，亟需开发出可以在土壤中快速去除Cd的修复材料与方法。磁性黏土矿物吸附材料因具有重金属吸附容量高和便于回收再利用等特点已成为当前土壤修复净化方面的研究热点。本研究使用了一种毫米级磁性黏土颗粒吸附材料测试其对土壤Cd的去除性能，材料记为巯基改性凹凸棒@沸石（MSAZ）。通过对不同类型人工模拟Cd污染土实验表明，材料最佳施用量为MSAZ:土壤质量比1:5，此时在人工模拟污染红壤中0.43 mol/L HNO3提取态Cd的单次材料施用去除率高达95%，在人工模拟的棕壤和黑土也可达75%-80%。通过对实际的Cd高背景旱地土壤和Cd污染水稻土的去除实验表明，MSAZ对这两种土壤中0.43 mol/L HNO3提取态Cd的首次施用去除率均约40%；经过五次重复利用后，MSZA对污染水稻土中0.43 mol/L HNO3提取态Cd的累积去除率可达98%，并且该材料依然保持着85%的吸附能力，回收率仍高于80%。本研究的磁性黏土颗粒具有较强的土壤Cd去除性能和应用潜力，可为农田土壤Cd污染的原位修复提供材料及技术支持。     

Washing agents from sewage sludge: efficiency of Cd removal from highly contaminated soils and effect on soil organic balance

Purpose

To compare Cd removal from different soils with three washing agents recovered from sewage sludge (dissolved organic matter (DOM), soluble humic-like substances (HLS), soluble humic substances (SHS)). Also, to investigate how washing with these agents changes soil organic-matter composition (OM).

Materials and methods

Sandy clay loam (S1) and clay (S2) highly contaminated with Cd (300 mg kg^?1) were washed with DOM, HLS, or SHS solutions at various pHs, and with various washing times and washing modes (single or double). Cd distribution and OM composition were determined (including content of humic substances (HS), fulvic fraction (FF), labile humic acids (L-HA), and stable humic acids (S-HA)).

Results and discussion

Cd removal proceeded with pseudo-second-order kinetics. Equilibrium was reached in 30 min (S1) and 60 min (S2). DOM, HLS, and SHS removed 75–82% of Cd from S1, and 80–87% from S2. The most mobile fraction of Cd was removed after one wash. S2 retained more OM, including HS, than S1. Although washing did not change the HA/FF ratio in most variants, washing with DOM and HLS increased the percentage of L-HA in both soils. Washing with SHS increased S-HA content in both soils, but the percent content of S-HA was similar to that in the unwashed soil.

Conclusions

DOM, HLS, and SHS derived from sewage sludge can effectively remediate clay and sandy clay soils highly contaminated with Cd. Washing with an SHS solution can increase the content of the most stable carbon forms (HA), which is beneficial for carbon sequestration in remediated soils.