Pilot-scale electrokinetic treatment of a Cu contaminated red soil

A pilot-scale experiment for electrokinetic treatment of 700 kg of copper contaminated red soil was conducted using a constant voltage of 80 V. Dynamic removal percentages of Cu from the soil and energy consumption during the treatment were evaluated together with changes of soil pH, electrical conductivity and soil microbial functional diversity before and after the electrokinetic treatment. The results indicate that 76% of Cu was successfully removed from the soil after 140 d of treatment when lactic acid was used as enhancing reagent for adjusting the catholyte pH and dissolving soil Cu by complexation, and the pilot-scale electrokinetic experiment consumed electric energy of 224 kW h t-1 soil. The post-treatment soil pH values decreased about 0.1-1.6 units compared with the initial value (pH 4.8), and soil electrical conductivities in most of soil sections also significantly decreased. Soil microbial functional diversity varied after the electrokinetic treatment, particularly the increase of substrate richness index, which is possibly due to the stimulation of lactic acid that was introduced into the soil column during the experiment.     

Removal of hexavalent chromium of contaminated soil by coupling electrokinetic remediation and permeable reactive biobarriers

Purpose

In this study, a novel and ecological alternative have been developed to treat soils contaminated with hexavalent chromium coupling two well-known systems: electrokinetic remediation and permeable reactive biobarriers. The electric field promotes the electromigration of the hexavalent chromium oxyanions towards the anode. The biobarriers were placed before the anode electrode, in order to promote the reduction and retention of the chromium migrating in its direction. Thus, this technology provided a global treatment to soil removal without subsequent treatments of the contaminated effluents.

Methods

The electrokinetic system was coupled with two different permeable reactive biobarriers composed by Arthrobacter viscosus bacteria, supported either in activated carbon or zeolite. An electric field of 10?V was applied and two different treatment times of 9 and 18?days were tested.

Results

Removal values of 60% and 79% were obtained when electrokinetic treatment was coupled with zeolite and activated carbon biobarriers, respectively, for a test period of 18?day. The reduction of hexavalent chromium to trivalent chromium was around 45% for both systems.

Conclusions

In this work, two types of biobarriers were efficiently coupled to electrokinetic treatment to decontaminate soil with Cr(VI). Furthermore, the viability of the new coupling technology developed (electrokinetic?+?biobarriers) to treat low-permeability polluted soils was demonstrated.     

An experiment in the electrokinetic removal of copper from soil contaminated by the brass industry

The feasibility of electrokinetic remediation of copper-contaminated soil was evaluated following eight days of electroreclamation. The results indicate that electrokinetic reclamation of Cu is totally ineffective in soil composed primarily of clay minerals and organic matter. The strong absorption of copper by this kind of soil, in our view mainly a result of retention by the clay component, makes it resistant to mobilization by the electrogenerated acidic front as well as by citrates (the competitors of natural chelating agents, i.e., humates). Such conditions, while adverse for the electroremediation process, may cause this kind of soil to act as a natural barrier to the leaching of copper ions.     

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。     

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。     

Impact of electrokinetic remediation on microbial communities within PCP contaminated soil

Electrokinetic techniques have been used to stimulate the removal of organic pollutants within soil, by directing contaminant migration to where remediation may be more easily achieved. The effect of this and other physical remediation techniques on the health of soil microbial communities has been poorly studied and indeed, largely ignored. This study reports the impact on soil microbial communities during the application of an electric field within ex situ laboratory soil microcosms contaminated with pentachlorophenol (PCP; 100mg kg(-1) oven dry soil). Electrokinetics reduced counts of culturable bacteria and fungi, soil microbial respiration and carbon substrate utilisation, especially close to the acidic anode where PCP accumulated (36d), perhaps exacerbated by the greater toxicity of PCP at lower soil pH. There is little doubt that a better awareness of the interactions between soil electrokinetic processes and microbial communities is key to improving the efficacy and sustainability of this remediation strategy.     

铅污染土壤电动修复增强技术的研究

利用电动修复技术对铅污染土壤的修复进行了实验室研究,研究了修复时间和络合剂EDTA对电动修复效果的影响,分析了土壤重金属的迁移和变化特征。结果表明,在电场力作用下随着修复时间的增长污染物的去除率相应提高,去除率由修复时间5 d时的13%增加到15 d时的20%。以EDTA作为阴极控制液,EDTA可与硝酸铅反应形成溶解态的络合物,提高铅离子的移动性,从而提高修复效果。随着EDTA浓度由0.1 mol/L到0.2 mol/L,Pb的去除率由44.4%提高到61.5%,说明添加络合剂可以提高修复效果。另外,电动修复效果与铅的形态分布有密切关系,交换态和碳酸盐结合态有利于重金属铅的去除。     

Removal of pyrene from contaminated sediments by mangrove microcosms

The potential of mangrove wetland systems to remove pyrene from surface- or bottom-contaminated sediments was investigated by microcosm studies. The performance of two mangrove plant species, Kandelia candel and Bruguiera gymnorrhiza in pyrene removal was also compared. During the six-months experimental period, the growth of both species in the surface-contaminated microcosms was not significantly different from that in the bottom-contaminated ones, and was comparable to the control (without any pyrene contamination). At the end of six-months treatment, pyrene concentrations in contaminated sediments declined from an initial 3 microg g(-1) to less than 0.4 microg g(-1), indicating that pyrene was successfully removed by mangrove microcosms. Around 96.4% and 92.8% pyrene in microcosms planted with K. candel were removed from the surface- and bottom-contaminated sediments, respectively. The removal percentages were slightly lower in microcosms planted with B. gymnorrhiza. Significant accumulation of pyrene in roots was only found in microcosms having bottom-contaminated sediments, and pyrene concentrations were 3.05 microg g(-1) and 4.50 microg g(-1) in roots of K. candel and B. gymnorrhiza, respectively. These values were much higher than that in control microcosms (without pyrene contamination, root pyrene concentrations were 0.27 microg g(-1) for K. candel and 0.34 microg g(-1) for B. gymnorrhiza) and in microcosms with contaminated sediments placed at the surface layer. Nevertheless, the overall contribution of root accumulation and plant uptake to the removal of pyrene from contaminated sediments was insignificant.     

Removal of arsenic from contaminated groundwater by solar-driven membrane distillation

Experimental investigations were carried out on removal of arsenic from contaminated groundwater by employing a new flat-sheet cross flow membrane module fitted with a hydrophobic polyvinylidenefluoride (PVDF) microfiltration membrane. The new design of the solar-driven membrane module in direct contact membrane distillation (DCMD) configuration successfully produced almost 100 per cent arsenic-free water from contaminated groundwater in a largely fouling-free operation while permitting high fluxes under reduced temperature polarization. For a feed flow rate of 0.120 m³/h, the 0.13 μm PVDF membrane yielded a high flux of 74 kg/(m² h) at a feed water temperature of 40 °C and, 95 kg/m² h at a feed water temperature of 60 °C. The encouraging results show that the design could be effectively exploited in the vast arsenic-affected rural areas of South-East Asian countries blessed with abundant sunlight particularly during the critical dry season.     

Field application of electrokinetic remediation for multi-metal contaminated paddy soil using two-dimensional electrode configuration

In this study, we evaluated the feasibility of in situ electrokinetic remediation for arsenic (As)-, copper (Cu)-, and lead (Pb)-contaminated soil, in a pilot-scale field application with two-dimensional electrode configurations. Square and hexagonal configurations with different electrode spacing, 1 m and 2?m, were investigated under a constant 100 V. A square configuration with electrode spacing of 2 m removed 61.5 % of As, 11.4 % of Cu, and 0.9 % of Pb, respectively, and a hexagonal configuration with the same spacing showed a higher removal efficiency in top (59 % of As, 0–0.5 m) and middle (53 % of As, 0.5–1.0 m) layers, but much lower removal efficiency in the bottom layer (1–1.5 m), which was thought to be due to groundwater flow through periodic rise and fall of tides. Fractionation analysis showed that As bound to Fe–Mn oxyhydroxide was the main form of As removed by the electrokinetic process. The two-dimensional configuration wasted less electrical energy by Joule heating, and required fewer electrode installations, compared to the one-dimensional electrode configuration.     

Removal of ammonia from contaminated air by trickle bed air biofilters

A trickle bed air biofilter (TBAB) was evaluated for the oxidation of NH3 from an airstream. Six-millimeter Celite pellets (R-635) were used for the biological attachment medium. The efficiency of the biofilter in oxidizing NH3 was evaluated using NH3 loading rates as high as 48 mol NH3/m3 hr and empty-bed residence times (EBRTs) as low as 1 min. Excess biomass was controlled through periodic backwashing of the biofilter with water at a rate sufficient to fluidize the medium. The main goal was to demonstrate that high removal efficiencies could be sustained over long periods of operation. Ammonia oxidation efficiencies in excess of 99% were consistently achieved when the pH of the liquid nutrient feed was maintained at 8.5. Quick recovery of the biofilter after backwashing was observed after only 20 min. Evaluation of biofilter performance with depth revealed that NH3 did not persist in the gas phase beyond 0.3 m into the depth of the medium (26% of total medium depth).     

Photo-Fenton treatment of TNT contaminated soil extract solutions obtained by soil flushing with cyclodextrin

The technical feasibility and performances of coupling flushing abilities of cyclodextrin solutions for 2,4,6-trinitrotoluene (TNT) removal from contaminated soil and the ability of Photo-Fenton treatment for final disposal of soil extract solutions containing high TNT loads have been investigated at laboratory scale. Methylated-beta-cyclodextrin (MCD) has shown better ability than hydroxypropyl-beta-cyclodextrin (HPCD) to complex TNT. The MCD solution increased the aqueous concentration of TNT in soil extract effluents as much as 2.1 times the concentrations obtained during the water flush of the soil. TNT in soil extract solution has been treated by Photo-Fenton. Our results indicate that MCD has a beneficial effect on the degradation rates of TNT. This relative improvement of TNT degradation rate (1.3 time) in presence of high amounts of hydroxyl radical scavengers can be ascribed to the formation of a ternary complex (TNT-cyclodextrin-iron) which can direct hydroxyl radical reaction toward TNT. Complete mineralization of soil extraction solutions was not achieved and TNT degradation pathway has been elucidated in order to ensure that no potential toxic intermediate is left at the end of the treatment time. After successive TNT hydroxylations, oxidative opening of the TNT aromatic ring quickly occurred, leading to the accumulation of short chain carboxylic acids such as oxalic acid and formic acid.     

污染土壤的微波辐照技术研究进展

简要介绍了土壤污染的状况,总结了国外学者对重金属和有机物两大类污染土壤所进行的微波修复工作,探讨了修复机理及影响因素,最后展望了微波修复污染土壤的研究重点.     

Application of bioassays to evaluate a copper contaminated soil before and after a pilot-scale electrokinetic remediation

Remediation programmes are considered to be complete when human risk-based criteria are met. However, these targets are often unsatisfied with the ecological parameters that may be important with regard to future soil use. Five soil subsamples, collecting along a pilot-scale soil column after electrokinetic treatment, were studied, from which about 42.0%-93.3% soil Cu had been successfully removed. A series of biological assays including soil microbial biomass carbon, basal soil respiration, soil urease activity, earthworm assays, and seed assays were used to evaluate their ecological risks. The results showed that the bioassay data from the treatment variants did not supposedly reflecting the decreased soil Cu concentrations after the electrokinetic treatment, but were highly correlated with some soil physicochemical characteristics. It suggests that bioassays are necessary to assess the ecotoxicity of soil after electrokinetic treatment.     

Phytoextraction of metals from a multiply contaminated soil by Indian mustard

The effects of nitrilotriacetate (NTA) and citric acid applications on metal extractability from a multiply metal-contaminated soil, as well as on their uptake and accumulation by Indian mustard (Brassica juncea) were investigated. Desorption of metals from the soil increased with chelate concentration, NTA being more effective than citric acid in solubilising the metals. Plants were grown in a sandy soil collected from a contaminated field site and polluted by Cd, Cr, Cu, Pb and Zn. After 43 days of plant growth, pots were amended with NTA or citric acid at 5 mmol kg-1 soil. Control pots were not treated with any chelate. Harvest of plants was performed 1 week after chelate addition. Soil water-, NH4NO3- and DTPA-extractable Cd, Cu, Pb and Zn fractions were enhanced only in the presence of NTA. In comparison to unamended plants, Indian mustard shoot dry weights suffered significant reductions following NTA application. NTA treatment increased shoot metal concentrations by a factor of 2-3, whereas citric acid did not induce any difference compared to the control. Chromium was detected in the above-ground tissues only after NTA amendment. Due to differences in dry matter yield, a significant enhancement of metal uptake was observed in NTA-treated plants for Cu and Zn.     

Removal of Pb and MDF from contaminated soils by EDTA- and SDS-enhanced washing

Heavy metal- and organic-contaminated sites are ubiquitous, but few studies have been conducted to address such an issue. EDTA- and SDS-enhanced washing was studied for remediation of Pb- and/or marine diesel fuel (MDF)-contaminated soils. The feasibility of recovery and reuse of EDTA and SDS, as well as the physicochemical interactions among the chemical agents, contaminants and soils were extensively investigated using batch experiments. The optimal washing sequence was then determined. The experimental results showed that EDTA could be recovered and reused for four cycles without significant loss of its chelating capacity, while the extraction capability of SDS was noticeably reduced after each reuse cycle. The free phase of marine diesel fuel (MDF) in soils physically isolated the sorbed Pb on soils and thus reducing its extraction by EDTA. The presence of SDS alone or together with low concentration of EDTA was found to enhance Pb removal probably via electrostatic interaction and dissolution of soil organic matter. However, it hindered Pb extraction by high concentration of EDTA, because of the potential formation of complexes between some strongly-bound Pb and SDS, that are more resistant to desorption. Therefore, EDTA washing followed by SDS achieved the highest Pb removal efficiency. On the other hand, MDF removal by SDS was significantly hindered by coexisting Pb in soils, probably because the formation of Pb-dodecyl sulfate (DS) complex would decrease the effective amount of SDS available for forming micelles in solution and enhance MDF sorption. EDTA alone or together with SDS could enhance MDF removal, but the residual MDF after EDTA-washing became more resistant to SDS removal. Consequently, SDS washing followed by EDTA is considered as the optimal washing sequence for MDF removal.     

Roles of oxidant,activator, and surfactant on enhanced electrokinetic remediation of PAHs historically contaminated soil

Electrokinetic (EK) remediation technology can enhance the migration of reagents to soil and is especially suitable for in situ remediation of low permeability contaminated soil. Due to the long aging time and strong hydrophobicity of polycyclic aromatic hydrocarbons (PAHs) from historically polluted soil, some enhanced reagents (oxidant, activator, and surfactant) were used to increase the mobility of PAHs, and remove and degrade PAHs in soil. However, under the electrical field, there are few reports on the roles and combined effect of oxidant, activator, and surfactant for remediation of PAHs historically contaminated soil. In the present study, sodium persulfate (PS, oxidant, 100 g L^?1) or/and Tween 80 (TW80, surfactant, 50 g L^?1) were added to the anolyte, and citric acid chelated iron(II) (CA-Fe(II), activator, 0.10 mol L^?1) was added to catholyte to explore the roles and contribution of enhanced reagents and combined effect on PAHs removal in soil. A constant voltage of 20 V was applied and the total experiment duration was 10 days. The results showed that the removal rate of PAHs in each treatment was PS + CA-Fe(II) (21.3%) > PS + TW80 + CA-Fe(II) (19.9%) > PS (17.4%) > PS + TW80 (11.4%) > TW80 (8.1%) > CK (7.5%). The combination of PS and CA-Fe(II) had the highest removal efficiency of PAHs, and CA-Fe(II) in the catholyte could be transported toward anode via electromigration. The addition of TW80 reduced the electroosmotic flow and inhibited the transport of PS from anolyte to the soil, which decreased the removal of PAHs (from 17.4 to 11.4% with PS, from 21.3 to 19.9% with PS+CA-Fe(II)). The calculation of contribution rates showed that PS was the strongest enhancer (3.3~9.9%), followed by CA-Fe(II) (3.9~8.5%) (with PS), and the contribution of TW80 was small and even negative (?1.4~0.6%). The above results indicated that the combined application of oxidant and activator was conducive to the removal of PAHs, while the addition of surfactant reduced the EOF and the migration of oxidant and further reduced the PAHs removal efficiency. The present study will help to further understand the role of enhanced reagents (especially surfactant) during enhanced EK remediation of PAHs historically contaminated soil.

     

Combined chemical and biological treatment of oil contaminated soil

Combined chemical (Fenton-like and ozonation) and biological treatment for the remediation of shale oil and transformer oil contaminated soil has been under study. Chemical treatment of shale oil and transformer oil adsorbed in peat resulted in lower contaminants' removal and required higher addition of chemicals than chemical treatment of contaminants in sand matrix. The acidic pH (3.0) conditions favoured Fenton-like oxidation of oil in soil. Nevertheless, it was concluded that remediation of contaminated soil using in situ Fenton-like treatment will be more feasible at natural soil pH. Both investigated chemical processes (Fenton-like and ozonation) allowed improving the subsequent biodegradability of oil. Moderate doses of chemical oxidants (hydrogen peroxide, ozone) should be applied in combination of chemical treatment (both, Fenton-like or ozonation) and biotreatment. For remediation of transformer oil and shale oil contaminated soil Fenton-like pre-treatment followed by biodegradation was found to be the most efficient.     

Ozone treatment of soil contaminated with aniline and trifluralin

Column studies were conducted to determine the ability of ozone to degrade aniline and trifluralin in soil. Ozone rapidly degraded aniline from soil under moist soil conditions, 5% (wt). Removal of 77-98% of [UL-14C]-aniline was observed from soil columns (15 ml, i.d. = 2.5 cm), exposed to 0.6% O(3) (wt) at 200 ml/min after 4 min. Initial ozonation products included nitrosobenzene and nitrobenzene, while further oxidation led to CO(2). Ring-labeled-[UL-14C]-trifluralin removal rates were slower, requiring 30 min to achieve removals of 70-97%. Oxidation and cleavage of the N-propyl groups of trifluralin was observed, affording 2,6-dinitro-4-(trifluoromethyl)-aniline, 2,6-dinitro-N-propyl-4-(trifluoromethyl)-benzamine, and 2,6-dinitro-N-propyl-N-acetonyl-4-(trifluoromethyl)-benzamine. Base solutions revealed that trifluralin was similarly oxidized to CO(2), where 72-83% of the activity recovered comprised 14CO(2). Use of ozone-rich water improved contaminant removal in trifluralin-amended soil columns, but did not improve removal in aniline, pentachloroaniline, hexachlorobenzene amended soil columns, suggesting that ozonated water may improve contaminant removal for reactive contaminants of low solubility.