表面活性剂增效电动技术修复多环芳烃污染土壤

研究了电动修复过程中修复时间和表面活性剂Triton X-100、鼠李糖脂对多环芳烃芘污染土壤的修复效果的影响。结果表明,在电动修复过程中,随着修复时间的增加,芘的去除率相应提高。通过向电解液中添加表面活性剂Triton X-100,芘的去除率从11.64%提高到了23.42%,当在电解液中添加浓度为40倍CMC的鼠李糖脂后去除率升高至36.29%,阳极附近土壤甚至达到了92.49%,这表明Triton X-100和鼠李糖脂均能促进土壤中芘的溶解和迁移,鼠李糖脂的促进作用高于Triton X-100。     

电动与渗透反应格栅联合修复镉污染地下水实验

通过实验方法研究了地下水中镉污染的电动力学修复效果，并分析其迁移变化特征。实验结果表明，电动修复中由于阴阳两极的氧化还原反应造成电极附近pH值产生明显变化，其中阳极附近的pH值由开始时的7.0逐渐变小到6.8，而阴极附近则相反，由开始时6.9逐渐增大到9.1，表明土壤的酸碱条件变化明显。Cd浓度变化反映在自然渗透条件下含水层中重金属污染物的迁移能力较弱，阳极附近地下水中Cd的去除率仅8.4%，而在电场作用下地下水中重金属的浓度发生明显变化，使得重金属污染物能在电极附近富集而被去除，当实验电场强度为0.5 V/cm时，Cd在阴极的累积使得阳极附近地下水中去除率为72.9%，说明电动修复重金属Cd污染地下水的效果明显好于自然渗透状态。     

铜污染土壤电动修复研究

应用实验方法研究了土壤重金属污染的电动力学修复方法,分析了土壤重金属污染物的迁移和变化特征。实验结果表明,在电场作用下土壤中重金属的浓度分布发生明显变化,使得大部分重金属能在电极附近富集而被去除。当实验的电场强度为0.5 V/cm时,在阳极附近土壤中铜的去除效率达到71.1%。阳极附近的pH值由开始时的6.8逐渐变小到4.4,而阴极附近则相反,由开始时的6.6逐渐增大到9.1,此外电动修复过程中电极附近的温度会发生相应的变化。     

铜污染土壤电动修复研究

应用实验方法研究了土壤重金属污染的电动力学修复方法，分析了土壤重金属污染物的迁移和变化特征。实验结果表明，在电场作用下土壤中重金属的浓度分布发生明显变化，使得大部分重金属能在电极附近富集而被去除。当实验的电场强度为0.5 V/cm时，在阳极附近土壤中铜的去除效率达到71.1%。阳极附近的pH值由开始时的6.8逐渐变小到4.4，而阴极附近则相反，由开始时的6.6逐渐增大到9.1，此外电动修复过程中电极附近的温度会发生相应的变化。     

电动增强技术修复镉污染土壤及其修复机理

选择小分子有机酸——酒石酸、草酸作为增强试剂,研究在不同浓度小分子有机酸作用下,电动修复土壤重金属镉Cd(Ⅱ)的迁移和去除机制。实验中以胡敏素为吸附剂并将其以包裹的形式添加在在电动装置中,以乙酸-乙酸钠为电解液,同时在两极室之间循环电解液以控制土壤p H值变化。结果表明,电动修复技术促进了重金属的去除。小分子有机酸的加入使弱酸提取态的重金属镉Cd(Ⅱ)的去除率大大提高,可达67.07%。不同浓度的小分子有机酸对电动修复的促进效果不同,随着浓度的持续增加,电动修复效果降低。     

鼠李糖脂对不同菌株降解柴油污染物的影响

通过一系列实验分析了鼠李糖脂对柴油污染物生物降解的影响。单菌株柴油降解实验结果表明,在添加生物表面活性剂鼠李糖脂后,各菌株细胞表面疏水性均发生不同程度的增加,并且对柴油的降解率均有所提高。在混合菌的柴油污染物降解实验中,发现当向土壤中添加了200 mg/L鼠李糖脂时,对柴油的降解才有较大的提高;而当添加100 mg/L的鼠李糖脂到水体中时,对柴油的降解就有较大的提高,而当鼠李糖脂浓度提高为200 mg/L时,柴油的降解率却没有进一步明显的提高。这说明鼠李糖脂对柴油降解的影响程度不仅与环境介质有关,还与添加的鼠李糖脂浓度有关。进一步分析表明,添加适当浓度的鼠李糖脂不仅可以提高对柴油的降解率,而且可加速其降解速度,缩短生物修复所需时间。     

鼠李糖脂对底泥三氯生脱附的影响因素

采用吸附/脱附平衡实验考察了温度对鼠李糖脂作用下三氯生(TCS)在底泥/水中分配的影响,以及鼠李糖脂浓度、泥水比、反应时间、TCS初始浓度对鼠李糖脂脱附底泥中TCS的影响;并通过Box-Behnken响应曲面法(RSM)确定了鼠李糖脂强化脱附底泥中TCS的影响因素排序、最佳脱附条件和调控策略。结果表明,在283~323 K的温度范围内,温度越高,TCS越容易向水相迁移;鼠李糖脂浓度越大、泥水比越低、时间越长、TCS初始浓度越低,越有利于鼠李糖脂脱附TCS。各影响因素作用排序为:泥水比鼠李糖脂浓度pH时间;最佳脱附条件:鼠李糖脂浓度2 996.96 mg·L~(-1)、泥水比10 g·L~(-1)、反应时间30 h及pH 7.9。此时,鼠李糖脂对底泥中TCS的最大脱附率可达90.70%。可为鼠李糖脂生物表面活性剂强化受TCS污染水体的原位修复的可行性提供判据。     

镉污染胶东棕壤的电动力学修复研究

在Cd污染的胶东棕壤土体两端加以1 V/cm的直流电压梯度进行电动力学修复.考察了电动力学修复过程中阴阳极电解液pH、电渗流量和电流密度的变化,并将处理后的土体分6段进行了分析,主要参数为pH、电导率、土壤中Cd的浓度及其形态分析.结果表明,经过445.0 h的电动力学修复,阳极附近3段土壤中Cd的去除率分别达到98.19%、97.01%和96.24%;阴极附近3段土壤中出现了Cd富集现象,且pH为5.88的土壤段Cd的富集率最高.     

比较两种表面活性剂淋洗去除土壤中的重金属

以停车场和湿地2种土壤为研究对象,分别使用表面活性剂鼠李糖脂和月桂基醚硫酸钠对土壤样品进行淋洗,考察2种表面活性剂对这2种土壤中重金属的去除能力差异及形态分布的影响,并分析淋洗后残留在土壤中表面活性剂的生物毒性。结果表明,2种表面活性剂均可在一定程度上去除2种土壤中的Cu、Cd、Pb和Zn。与湿地土壤相比,2种表面活性剂对停车场土壤中重金属的去除率均较高,且月桂基醚硫酸钠的去除能力优于鼠李糖脂。2种表面活性剂对可交换态重金属的去除效果最好,对残渣态重金属去除率较低。淋洗后2种土样中残留的鼠李糖脂及停车场土样中残留的月桂基醚硫酸钠的生物毒性低,湿地土壤中残留的月桂基醚硫酸钠具有一定生物毒性。     

鼠李糖脂对剩余污泥中铜和镍的去除

采用批次淋洗的方法研究了鼠李糖脂浓度、pH、淋洗时间、提取次数以及重金属形态对剩余污泥中Cu和Ni去除效果的影响。结果表明,随着鼠李糖脂浓度的增加,2种重金属的去除率增加,且鼠李糖脂在碱性条件下对Cu和Ni的去除效果较好,最高去除率可分别高达80.77%和46.74%;随着振荡时间和提取次数的增加,Cu和Ni的去除率随之增加,并明显高于去离子水的提取;对污泥重金属形态进行分析发现,鼠李糖脂能有效去除酸提取态的Cu和Ni。研究结论可为剩余污泥的资源化而产生重金属安全隐患问题提供解决的参考方案和奠定理论基础。     

EDTA强化电动力学修复重金属复合污染土壤

在自制的电动力学装置中,研究多种重金属复合污染土壤的电动力学修复,通过在阴极添加络合剂EDTA来提高修复效率。实验结果表明,EDTA的引入提高了修复过程中的电流值,且EDTA与重金属的络合提高了污染物向电极液的迁移效率,从而强化了电动力学修复效果。在设定的浓度(0、0.01、0.02、0.05和0.1 mol/L)中,0.1 mol/L的EDTA具有最佳的修复效率。在此实验条件下,污染土壤中的总铜、总铅和总镉的去除率分别为90.2%、68.1%和95.1%。电动力学修复后,对土壤重金属进行化学形态分析,发现电动力学修复显著改变了土壤重金属存在形态,修复后土壤中的铜、铅、镉主要以较稳定的有机态和残余态形式存在,显著降低了对周边生物和环境的毒害。     

水溶性羧甲基壳聚糖对Cd2+的解吸行为研究

为改善壳聚糖(CTS)的水溶性及对重金属的配位能力,合成水溶性好并能与重金属形成配位作用的水溶性羧甲基壳聚糖(WSCC),研究了WSCC对镉的增溶、解吸行为,考察了pH、离子强度、有机质含量和WSCC初始浓度对镉的解吸影响。结果表明:WSCC对碳酸镉的增溶效果显著,当其质量浓度为2g/L时溶液中Cd2+可达到275mg/L;WSCC对镉解吸能力随着土壤中有机质含量的增加而降低,pH的升高、离子强度的增加和WSCC初始浓度的增加有利于镉的解吸;WSCC对镉污染土壤的解吸更符合准二级动力学方程,该静态解吸研究可以为镉污染土壤的修复提供基础信息及依据。     

Biosurfactant technology for remediation of cadmium and lead contaminated soils

This research focuses on column experiments conducted to evaluate the potential of environmentally compatible rhamnolipid biosurfactant produced by Pseudomonas aeruginosa strain BS2 to remove heavy metals (Cd and Pb) from artificially contaminated soil. Results have shown that di-rhamnolipid removes not only the leachable or available fraction of Cd and Pb but also the bound metals as compared to tap water which removed the mobile fraction only. Washing of contaminated soil with tap water revealed that approximately 2.7% of Cd and 9.8% of Pb in contaminated soil was in freely available or weakly bound forms whereas washing with rhamnolipid removed 92% of Cd and 88% of Pb after 36 h of leaching. This indicated that di-rhamnolipid selectively favours mobilization of metals in the order of Cd>Pb. Biosurfactant specificity observed towards specific metal will help in preferential elution of specific contaminant using di-rhamnolipid. It was further observed that pH of the leachates collected from heavy metal contaminated soil column treated with di-rhamnolipid solution was low (6.60-6.78) as compared to that of leachates from heavy metal contaminated soil column treated with tap water (pH 6.90-7.25), which showed high dissolution of metal species from the contaminated soil and effective leaching of metals with treatment with biosurfactant. The microbial population of the contaminated soil was increased after removal of metals by biosurfactant indicating the decrease of toxicity of metals to soil microflora. This study shows that biosurfactant technology can be an effective and nondestructive method for bioremediation of cadmium and lead contaminated soil.     

Aseptic hydroponics to assess rhamnolipid-Cd and rhamnolipid-Zn bioavailability for sunflower (<Emphasis Type="Italic">Helianthus annuus</Emphasis>): a phytoextraction mechanism study

The availability of cadmium (Cd) and zinc (Zn) to sunflower (Helianthus annuus) was investigated in rhamnolipid- and ethylenediaminetetraacetic acid (EDTA)-buffered solutions in order to evaluate the influence of aqueous speciation of the metals on their uptake by the plant, in relation to predictions of uptake by the free ion activity model (FIAM). Free metal ion activity was estimated using the chemical equilibrium program MINTEQ or measured by Donnan dialysis. The uptake of Cd followed the FIAM for the EDTA-buffered solution at EDTA concentrations below 0.4 μM; for the rhamnolipid-buffered solution, the uptake of both metals in roots was not markedly affected by increasing rhamnolipid concentrations in solution. This suggests rhamnolipid enhanced metal accumulation in plant roots (per unit free metal in solution) possibly through formation and uptake of lipophilic complexes. The addition of normal Ca concentrations (low millimetre range) to the rhamnolipid uptake solutions reduced Cd accumulation in shoots by inhibiting Cd translocation, whereas it significantly increased Zn accumulation in shoots. This study confirms that although rhamnolipid could enhance accumulation of Cd in plants roots at low Ca supply, it is not suitable for Cd phytoextraction in contaminated soil environments where Ca concentrations in soil solution are orders of magnitude greater than those of Cd.     

Electrokinetic remediation of a Cu contaminated red soil by conditioning catholyte pH with different enhancing chemical reagents

The effect of enhancement reagents on the efficiency of electrokinetic remediation of Cu contaminated red soil is evaluated. The enhancement agents were a mix of organic acids, including lactic acid+NaOH, HAc-NaAc and HAc-NaAc+EDTA. The soil was prepared to an initial Cu concentration of 438 mgkg(-1) by incubating the soil with CuSO4 solution in a flooded condition for 1 month. Sequential extraction showed that Cu was partitioned in the soil as follows: 195 mgkg(-1) as water soluble and exchangeable, 71 mgkg(-1) as carbonate bound and 105 mgkg(-1) as Fe and Mn oxides. The results indicate that neutralizing the catholyte pH maintains a lower soil pH compared to that without electrokinetic treatment. The electric currents varied depending upon the conditioning solutions and increased with an increasing applied voltage potential. The electroosmotic flow rate changed significantly when different conditioning enhancing reagents were used. It was observed that lactic acid+NaOH treatments resulted in higher soil electric conductivities than HAc-NaAc and HAc-NaAc+EDTA treatments. Ultimately, enhancement by lactic acid+NaOH resulted in highest removal efficiency (81% Cu removal) from the red soil. The presence of EDTA did not enhance Cu removal efficiencies from the red soil, because EDTA complexed with Cu to form negatively charge complexes, which slowly migrated toward the anode chamber retarding Cu2+ transport towards the cathode.     

Promotion effect of graphene on phytoremediation of Cd-contaminated soil

Echinacea purpurea (L.) Moench was selected as a remediation plant in this study, and different concentrations of graphene oxide (GO) were added to Cd-contaminated soil. Through pot experiments, the effect of E. purpurea on Cd-contaminated soil was determined at 60 days, 120 days, and 150 days. A preliminary study on the remediation mechanism of GO was explored through changes in the forms of Cd in the rhizosphere soil, soil pH, and soil functional groups. Results showed that the optimal concentration of GO was 0.4 g/kg, and under the condition, the accumulation of Cd in the roots of E. purpurea was as high as 113.69 ± 23.86 mg/kg, and the maximum EF reached 5.87 ± 1.34. Compared with those of the control group, accumulated Cd concentration and EF in the roots increased by 60.34% and 2.32, respectively. Correlation analysis showed that the absorption and accumulation of Cd was negatively correlated with the exchangeable Cd content at 120 days, and the exchangeable Cd was negatively correlated with the relative content of functional groups in the soil with 0.4 g/kg GO (E2). The artificial application of GO to the soil can be used as an effective way to improve the effect of E. purpurea in the remediation of Cd soil pollution, and it has great application potential in the stabilization of plants and vegetations and restoration of high-concentration Cd-contaminated soil.

Graphical abstract

     

可渗透反应复合电极法对土壤重金属的电动去除

将零价铁(Fe0)、沸石等活性材料附着在电极上形成可渗透反应层并构成可渗透反应复合电极,采用不同的复合电极对Cd2+、Ni 2+、Pb2+和Cu2+等4种阳离子型重金属污染土壤进行了电动力学修复。研究了不同可渗透反应复合电极对土壤pH的控制效果以及对重金属的去除作用,分析了迁移到复合电极中的重金属形态变化。结果表明,复合电极中添加酸、碱性沸石并适时更换,可有效中和、截留阴阳极电解产生的OH-和H+,避免或减缓土壤酸碱迁移带的形成,防止重金属离子的过早沉淀及土壤过度酸化,极大提高了重金属的去除率。复合电极中Fe0可将迁移进来的重金属离子进行还原稳定,实现重金属污染物的捕获与固定,与迁移到沸石复合电极中的4种重金属不稳定态相比,"Fe0+沸石"复合电极中重金属不稳定态分别下降了61.4、60.5、61.4、57.1百分点。结果还显示,阴极采用"Fe0+沸石"复合电极并适时进行更换,施加1.5V/cm的直流电压修复10d后,土壤中Cd、Ni、Pb、Cu的总去除率分别为44.5%、41.5%、33.5%和36.7%,且进一步延长修复时间和持续更换电极可获得更为理想的修复效果。     

A two-stage process using electrokinetic remediation and electrochemical degradation for treating benzo[a]pyrene spiked kaolin

An innovative process that combines soil electrokinetic remediation and liquid electrochemical oxidation for the degradation of organic compounds present in a polluted soil was developed and evaluated by using benzo[a]pyrene spiked kaolin. In order to increase benzo[a]pyrene solubility during electrokinetic treatment, the addition of a co-solvent or surfactant, such as ethanol or Brij 35, as flushing solution was tested. The research carried out demonstrated the influence of the desorption agent employed on benzo[a]pyrene remediation from the kaolin matrix. Thus, if the flushing solution was ethanol at 40%, there was no presence of contaminant in either chamber. On the contrary, when a solution of surfactant Brij 35 was used, benzo[a]pyrene was transported towards the cathode chamber, where it was collected. Moreover, the extent of this recovery depends on the pH profile on the soil. When no pH control was used, around 17% of initial contaminant was detected in the cathode chamber; however, when pH control was applied, the recovery of benzo[a]pyrene could be higher than 76%, when the pH control in the anode chamber was set at 7.0.In order to obtain the total degradation of mobilised benzo[a]pyrene from the contaminated soil, the liquid collected by electrokinetic remediation was oxidised by electrochemical treatment. This oxidation was accomplished via an electrochemical cell with a working volume of 0.4 L, and graphite as electrode material. The benzo[a]pyrene was almost totally degraded in 1 d, reaching a degradation of about 73% in 16 h.