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。     

电动修复技术对土壤中镉迁移的影响

以镉含量为200 mg·kg~(-1)的模拟污染土壤为研究对象,使用电动修复技术对土壤中的镉进行去除。实验研究了不同修复电压下电流密度、电解液pH值、土壤中镉含量的变化,并重点研究了修复电压对土壤中镉迁移的影响规律。实验结果表明,通电电压越大,电场强度越强,镉的迁移量越大,电动修复效率越高,当修复电压为50 V时,阴极区域附近镉的迁移量与修复电压为5 V时相同位置镉的迁移量相比可以提高30%,实验结果为重金属污染土壤电动修复过程中镉的迁移量化研究提供了参考。     

分离式电解槽系统电动力学修复氟污染黏土

为解决氟污染土壤修复过程中不同形态的氟在电动力学作用下向土体中间迁移,导致修复后氟在电解槽中部累积所带来的去除率降低问题,采用自制的分离式电解槽系统,以去离子水作电解液,通过单因素实验,在0.5、1.0、1.5 V·cm~(-1)修复电压下,对电动力学修复氟污染黏土的效果进行了研究。结果表明:分离式电解槽系统可有效修复氟污染黏土,土壤氟的去除率随着修复电压的升高而增大,最高可达61.86%;修复后各部分土壤氟含量差异较小,土壤中剩余氟没有出现累积现象;能量消耗随着修复电压的升高快速增加,而能量效率不断减小。实际应用电动力学技术修复氟污染土壤时,在考虑土壤氟去除率的同时要兼顾能量效率,以保证修复方案在经济上可行。     

汞污染土壤的电动力学修复试验研究

利用电动力学修复汞污染土壤,并考察电动力学修复对土壤部分理化指标的影响。结果表明,常规的电动力学修复方法不能有效去除土壤中的汞污染物,需要一些强化措施,在阴极电解液中引入KI,KI的引入提高了修复过程中的电流,且KI会与汞化合物生成HgI2-4,提高了汞的迁移效率,从而改善了电动力学修复效果。同时,添加0.50mol/L的KI溶液的试验组具有最佳的修复效果,在此试验条件下,污染土壤中的汞总去除率为81.7%。电动力学修复后,土壤pH有明显改变,阳极区土壤酸化,阴极区土壤碱化;土壤有效氮在阳极区出现明显增加,在阴极区降低,而土壤有机质则没有明显变化。     

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。     

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。     

土壤电动修复中菲迁移的数值模拟

针对菲污染土壤修复建模的问题,通过对电动力学作用下菲污染土壤的迁移现象的室内模拟实验,确定了影响菲迁移的电渗流、电迁移、对流和弥散4个主要过程,建立了电动力学作用下菲在污染土壤中的迁移模型;运用COMSOL Multiphysics 5.3软件结合迁移模型的各项方程和选取的参数对菲的迁移过程进行了模拟计算。结果表明:当孔隙率分别为0.33、0.38、0.43和0.48时,菲的最大迁移率分别为31.89%、34.78%、37.97%和41.74%;当电压从0.5 V·cm~(-1)增加至2 V·cm~(-1)的过程中,电渗流通量增大,最大迁移率可达到44.35%;修复区域的浓度均呈"碗状"分布,模拟计算得到在中间靠近阳极区域的菲的浓度达到最小值2.14 mol·m~(-3),迁移率最大为38%。模拟计算的菲迁移分布结果与实验所得结果相吻合,证明该模型用于电动修复多环芳烃污染土壤的适用性。     

铜污染场地土壤的原位电动强化修复

电动修复技术是一种新型的污染土壤修复技术,相关的理论和实验室小试研究较多,但鲜见野外现场条件下的原位修复研究。本研究以某电镀厂铜污染区为修复对象,以可生物降解的络合剂乳酸和柠檬酸为阴极池增强试剂,考察在原位条件下电动修复技术对土壤中铜的去除效率,并评估修复过程的电能消耗。结果表明:在电压梯度7.5 V·m~(-1),阴极池乳酸和柠檬酸浓度为0.5 mol·L~(-1),处理24 d(乳酸处理)和17 d(柠檬酸处理)的条件下,乳酸处理较柠檬酸处理电流要高、且阴阳极池溶液和土壤的pH、电导率变化要小;乳酸处理后土壤铜含量明显下降(阳极和阴极附近土壤铜去除率分别为52.6%和35.7%),而柠檬酸处理条件下阳极和阴极附近铜的去除效率分别为27.2%和~(-1)7.5%,这可能与其较低的电流和较短的处理时间有关。与现有文献比较,乳酸处理总能耗(15.7 k Wh·m~(-3))处于较低水平,而Cu的去除率处于较高水平(35.7%~52.6%),优于文献报道的电动修复去除效率和电能消耗。     

氨水循环增强电动力学技术去除土壤中的氟

为了探讨氨水增强电动力学技术修复氟污染土壤的效果及对土壤p H值的影响,在自制的电动力学装置中,1V/cm电解电压下,以氨水作电解液,采用连续循环的方式进行研究。结果显示,氨水连续循环不仅增大了修复过程中的电流值,且使通过土壤的电流更加稳定,在提高土壤氟迁移效率的同时降低了能耗。在设定的浓度中(0、0.01、0.1和0.2mol/L),土壤氟的去除率随着氨水浓度的升高而增加,0.2 mol/L氨水具有最大电流值26.8 m A,土壤氟的去除率也达到57.9%,氨水循环增强时两极土壤p H值差异减小。采用氨水循环增强电动力学技术,可有效修复氟污染土壤,土壤中剩余氨还可以提高土壤肥力。     

电极-SBBR处理含铜有机污水

采用电极一SBBR系统去除Cu^2＋,考察了电流强度,IA竞争离子（阴离子SO4^2-、NO3^-、CL^-和阳离子Zn^2＋、Ph^2＋）、初始含Cu^2＋量及溶液pH值对除铜效除果的影响。结果表明,当电流强度为40mA时Cu^2＋去除率最高为98％。投加阴（SO4^2-、NO3^-、Cl^-）、阳（Zn^2＋、Pb^2＋）离子均会引起出水Cu^2＋浓度的增加,且Cl^-和Ph^2＋含量分别为45mg／L和30mg／L时对Cu^2＋去除的影响更为显著。进水Cu^2＋浓度为30mg／L时,Cu^2＋去除率最高为98．48％,当进水Cu^2＋≥70mg／L时,出水Cu^2＋浓度不能达标。酸性（pH4．0～4．5）与碱性（pH9．0～10．0）条件均不利于Cu^2＋的去除,且酸性条件的负面影响更显著．当pH为4．5～7．5时．Cu^2＋去除率最高为97．78％。     

Scaling up a treatment to simultaneously remove persistent organic pollutants and heavy metals from contaminated soils

Soil washing is a treatment process that can be used to remediate both organic and inorganic pollutants from contaminated soils, sludges, and sediments. A soil washing procedure was evaluated utilizing about 100 g samples of soil that had been field-contaminated with arsenic, chromium, copper, pentachlorophenol (PCP), polychlorinated dibenzo-p-dioxins (PCDDs) and polychlorinated dibenzofurans (PCDFs). The highest level of mobilization/detoxification was achieved in three soil washes with a mixture of 0.1M [S,S]-ethyelnediaminedisuccinate ([S,S]-EDDS) and 2% Brij 98 at pH 9 with 20 min of ultrasonication treatment at room temperature. This combination mobilized 70% of arsenic, 75% of chromium, 80% of copper, 90% of PCP, and 79% of PCDDs and PCDFs, so that the decontaminated soil met the maximum acceptable concentrations of the generic C-level criteria regulated by the Ministère du Développement Durable, de l’Environnement et des Parcs for the Province of Québec, Canada.The organic pollutants were back-extracted from the aqueous suspension with hexane. Heavy metals were virtually completely precipitated from the aqueous washing suspension with Mg⁰ particles at room temperature. The PCP was detoxified by catalytic hydrodechlorination with a stream of 5% (v/v) H₂-supercritical CO₂ that transported the organosoluble fraction through a reaction chamber containing 2% Pd/γ-Al₂O₃.In toto, this soil washing procedure demonstrates that persistent organic pollutants and selected heavy metals can be co-extracted efficiently from a field-contaminated soil with three successive washes with the same soil washing solution containing [S,S]-EDDS and a non-ionic surfactant (Brij 98) in admixture. An industrial-scale ex situ soil washing procedure with a combination of a non-ionic surfactant and a complexing reagent seems to be a plausible remediation technique for this former wooden utility pole storage facility.     

Solid/solution Cu fractionations/speciation of a Cu contaminated soil after pilot-scale electrokinetic remediation and their relationships with soil microbial and enzyme activities

The aim of this study was to investigate the detailed metal speciation/fractionations of a Cu contaminated soil before and after electrokinetic remediation as well as their relationships with the soil microbial and enzyme activities. Significant changes in the exchangeable and adsorbed-Cu fractionations occurred after electrokinetic treatment, while labile soil Cu in the solution had a tendency to decrease from the anode to the cathode, and the soil free Cu²⁺ ions were mainly accumulated in the sections close to the cathode. The results of regression analyses revealed that both the soil Cu speciation in solution phase and the Cu fractionations in solid phase could play important roles in the changes of the soil microbial and enzyme activities. Our findings suggest that the bioavailability of soil heavy metals and their ecotoxicological effects on the soil biota before and after electroremediation can be better understood in terms of their chemical speciation and fractionations.     

Nano-TiO2 enhances the toxicity of copper in natural water to Daphnia magna

The acute toxicity of engineered nanoparticles (NPs) in aquatic environments at high concentrations has been well-established. This study demonstrates that, at a concentration generally considered to be safe in the environment, nano-TiO₂ remarkably enhanced the toxicity of copper to Daphnia magna by increasing the copper bioaccumulation. Specifically, at 2 mg L⁻¹ nano-TiO₂, the (LC₅₀) of Cu²⁺ concentration observed to kill half the population, decreased from 111 μg L⁻¹ to 42 μg L⁻¹. Correspondingly, the level of metallothionein decreased from 135 μg g⁻¹ wet weight to 99 μg g⁻¹ wet weight at a Cu²⁺ level of 100 μg L⁻¹. The copper was found to be adsorbed onto the nano-TiO₂, and ingested and accumulated in the animals, thereby causing toxic injury. The nano-TiO₂ may compete for free copper ions with sulfhydryl groups, causing the inhibition of the detoxification by metallothioneins.     

Characterization of bacterial communities at heavy-metal-contaminated sites

The microbial community in soil samples from two long-term contaminated sites was characterized by using culture-dependent and culture-independent methods. The two sites investigated contained high amounts of heavy metals and were located in the upper Silesia Industrial Region in southern Poland. The evaluation of the aerobic soil microbial population clearly demonstrated the presence of considerable numbers of viable, culturable bacteria at both sites. A high fraction of the bacterial population was able to grow in the presence of high amounts of metals, i.e. up to 10 mM Zn²⁺, 3 mM Pb²⁺ or 1 mM Cu²⁺. Site 1 contained significantly (P < 0.05) lower bacterial numbers growing in the presence of 10 mM Zn²⁺ than site 2, while the opposite was observed for bacteria tolerating 1 mM Cu²⁺. This coincided with the contents of these two metals at the two sites. Ecophysiological (EP) indices for copiotrophs (r-strategists) and oligotrophs (K-strategists) pointed to high bacterial diversity at both sites. Fluorescence in situ hybridization (FISH) analysis indicated that Actinobacteria and Proteobacteria represent the physiologically active fraction of bacteria at the two sites. Shannon diversity (H′) indices for FISH-detected bacterial phylogenetic groups were not significantly different at the two sites.     

Copper and cadmium effects on growth and extracellular exudation of the marine toxic dinoflagellate Alexandrium catenella: 3D-fluorescence spectroscopy approach

In this study, metal contamination experiments were conducted to investigate the effects of copper and cadmium on the growth of the marine toxic dinoflagellate Alexandrium catenella and on the production of dissolved organic matter (Dissolved Organic Carbon: DOC; Fluorescent Dissolved Organic Matter: FDOM). This species was exposed to increasing concentrations of Cu²⁺ (9.93 × 10⁻¹⁰–1.00 × 10⁻⁷ M) or Cd²⁺ (1.30 × 10⁻⁸–4.38 × 10⁻⁷ M), to simulate polluted environments. The drastic effects were observed at pCu²⁺ = 7.96 (Cu²⁺: 1.08 × 10⁻⁸ M) and pCd²⁺ = 7.28 (Cd²⁺: 5.19 × 10⁻⁸ M), where cyst formation occurred. Lower levels of Cu²⁺ (pCu²⁺ > 9.00) and Cd²⁺ (pCd²⁺ > 7.28) had no effect on growth. However, when levels of Cu²⁺ and Cd²⁺ were beyond 10⁻⁷ M, the growth was totally inhibited. The DOC released per cell (DOC/Cell) was different depending on the exposure time and the metal contamination, with higher DOC/Cell values in response to Cu²⁺ and Cd²⁺, comparatively to the control. Samples were also analyzed by 3D-fluorescence spectroscopy, using the Parallel Factor Analysis (PARAFAC) algorithm to characterize the FDOM. The PARAFAC analytical treatment revealed four components (C1, C2, C3 and C4) that could be associated with two contributions: one, related to the biological activity; the other, linked to the decomposition of organic matter. The C1 component combined a tryptophan peak and a characteristic humic substances response, and the C2 component was considered as a tryptophan protein fluorophore. The C3 and C4 components were associated to marine organic matter production.     

Biodegradable chelate enhances the phytoextraction of copper by Oenothera picensis grown in copper-contaminated acid soils

Oenothera picensis plants (Fragrant Evening Primrose) grow in the acid soils contaminated by copper smelting in the coastal region of central Chile. We evaluated the effects of the biodegradable chelate MGDA (methylglycinediacetic acid) on copper extraction by O. picensis and on leaching of copper through the soil profile, using an ex situ experiment with soil columns of varying heights. MGDA was applied in four rates: 0 (control), 2, 6 and 10 mmol plant⁻¹. MGDA application significantly increased biomass production and foliar concentration, permitting an effective increase in copper extraction, from 0.09 mg plant⁻¹ in the control, to 1.3 mg plant⁻¹ in the 6 and 10 mmol plant⁻¹ treatments. With 10 mmol plant⁻¹ rate of MGDA, the copper concentration in the leachate from the 30 cm columns was 20 times higher than in the control. For the 60 cm columns, copper concentration was 2 times higher than the control. It can be concluded that at increased soil depths, copper leaching would be minimal and that MGDA applications at the studied rates would not pose a high risk for leaching into groundwater. It can thus be stated that applications of MGDA are an effective and environmentally safe way to improve copper extraction by O. picensis in these soils.     

Soil pollution assessment and identification of hyperaccumulating plants in chromated copper arsenate (CCA) contaminated sites, Korea

In recent decades, heavy metal contamination in soil adjacent to chromated copper arsenate (CCA) treated wood has received increasing attention. This study was conducted to determine the pollution level (PL) based on the concentrations of Cr, Cu and As in soils and to evaluate the remediative capacity of native plant species grown in the CCA contaminated site, Gangwon Province, Korea. The pollution index (PI), integrated pollution index (IPI), bioaccumulation factors (BAF_shoots and BAF_roots) and translocation factor (TF) were determined to ensure soil contamination and phytoremediation availability. The 19 soil samples from 10 locations possibly contaminated with Cr, Cu and As were collected. The concentrations of Cr, Cu and As in the soil samples ranged from 50.56-94.13 mg kg⁻¹, 27.78-120.83 mg kg⁻¹, and 0.13-9.43 mg kg⁻¹, respectively. Generally, the metal concentrations decreased as the distance between the CCA-treated wood structure and sampling point increased. For investigating phytoremediative capacity, the 19 native plant species were also collected in the same area with soil samples. Our results showed that only one plant species of Iris ensata, which presented the highest accumulations of Cr (1120 mg kg⁻¹) in its shoot, was identified as a hyperaccumulator. Moreover, the relatively higher values of BAF_shoot (3.23-22.10) were observed for Typha orientalis, Iris ensata and Scirpus radicans Schk, suggesting that these plant species might be applicable for selective metal extraction from the soils. For phytostabilization, the 15 plant species with BAF_root values > 1 and TF values < 1 were suitable; however, Typha orientalis was the best for Cr.     

Kinetics and equilibrium properties of the biosorption of Cu2+ by algae

The purpose of this study was to examine the kinetics and equilibrium properties of freshwater algae with Cu²⁺. This was a model system to explore using algae as biosensors for water quality. Methods included making luminescence measurements (fluorescence) and copper ion-selective electrode (CuISE) measurements vs. time to obtain kinetic data. Results were analyzed using a pseudo-first-order model to calculate the rate constants of Cu²⁺ uptake by algae: k _p(Cu?Calgae)?=?0.0025?±?0.0006?s^?1 by CuISE and k _p(Cu?Calgae)?=?0.0034?±?0.0011?s^?1 by luminescence. The binding constant of Cu?Calgae, K _Cu?Calgae, was 1.62?±?0.07?×?10⁷?M^?1. Fluorescence results analyzed using the Stern?CVolmer relationship indicate that algae have two types of binding sites of which only one appears to affect quenching. The fluorescence-based method was found to be able to detect the reaction of algae with Cu²⁺ quickly and at a detection limit of 0.1?mg?L^?1.