Adsorption and reduction from modified polypyrrole enhance electrokinetic remediation of hexavalent chromium-contaminated soil.

Toxic metal pollutant Cr(VI) in the environment will pose a severe threat to animal and human health. In this work, Fe3O4@PPy, Arg@PPy, and Arg/Fe3O4@PPy were prepared to enhance adsorption of Cr(VI) by doping Fe3O4 nanoparticles and amino radicals into the original PPy structure. Their characteristics were investigated by FTIR, SEM, EDS, BET analysis, and batch adsorption experiments. And they were used as permeable reaction barriers (PRB) to combine with electrokinetic remediation (EKR) to remediate Cr-contaminated soil. Adsorption experiment results showed that the maximum adsorption capacities of PPy, Fe3O4@PPy, Arg@PPy, and Arg/Fe3O4@PPy for Cr(VI) were 60.43 mg/g, 67.12 mg/g, 159.86 mg/g, and 141.50 mg/g, respectively. They all followed the kinetic pseudo-second-order model and the Langmuir isothermal model with a monolayer adsorption behavior. In the EKR/PRB system, the presence of Fe3O4@PPy, Arg@PPy, and Arg/Fe3O4@PPy obtained the higher Cr(VI) removal efficiency near the anode than that of the PPy, increasing by 74.60%, 26.04%, and 68.64%, respectively. A strong electrostatic attraction between anion contaminants and protonated modified PPy and a reduction from Cr(VI) to Cr(III) appeared in the EKR remediation process under acid conditions. This study opened up a prospect for applying modified PPy composites to treat toxic metal-contaminated soil.

Rapid Cr(VI) reduction structure in chromium contaminated soil: The UV-assisted electrokinetic circulation of background iron.

Substantially decreasing the severe hazards connected with the toxic Cr(VI), developing effective reduction remediation strategies may be crucial under favorable economic conditions for the contaminated soil containing Cr(VI) to protect human health. Several typical enhancers (phosphate, fulvic acid, citric acid) were used to test electrokinetic remediation (EKR) coupled with UV radiation-induced photochemical reduction for contaminated soil containing Cr(VI). The added citrate, while improving the Cr(VI) electromigration, worked as the ultimate sacrificial electron donors, with the dissolved soil background Fe(III) as electron shuttle, to Cr(VI) rapid reduction. The dissolved soil background Fe(III) convert into Fe(II) ions through the UV radiation-induced ligand-metal charge transfers reaction, which constituted a novel electrokinetic circulation reduction pathway for the elimination of surface-bound/dissolved Cr(VI) (difficult to electromigration) in the near-anodic soil layers. More than 80% dissolved and surface-bound Cr(VI) was eliminated from the soil. In particular, the dissolved and surface-bound Cr(VI) was enhanced by more than 62.37% removal in near-anodic soil layers compared to conventional citric acid-enhanced EKR and provided no extra cost other than UV radiation. This configuration may be a cost-effective and feasible remediation design in the future for the in-situ Cr(VI) reduction of contaminated sites.

Solidification of chromium-containing sludge with attapulgite combined alkali slag.

To solve the harm caused by hazardous chromium-containing sludge (CCS, chromium-containing sludge) waste to humans and the environment, this study used attapulgite to strengthen alkali slag to prepare cementitious materials to solidify/stabilize CCS. Single-factor and orthogonal experiments were used to optimize the preparation parameters of alkali slag cementitious materials. The compressive strength, heavy metal leaching toxicity, and microscopic characterization of a CCS solidified body were tested to investigate the solidification effect and mechanism of CCS formation. The best attapulgite content was 4%; the solidified body after the treatment of chromium-containing sludge had a good performance of heavy metal leaching and mechanical properties. The addition of attapulgite enhanced the compressive strength. Compared with the original CCS, the leaching concentration of heavy metals in the solidified body was significantly reduced. Among them, the solidified efficiency of chromium is stable above 90%. The changes in the results of XRD and FTIR for each component were studied. It indicated that the solidified body may solidify/stabilize heavy metals through physical encapsulation of the amorphous form and chemical immobilization. This research recognized the use of waste to treat waste, realized the combined effect of solidification/adsorption, and indicated the possibility of application of attapulgite and its solidified products in construction.

The Utilization of Alkali-Activated Lead-Zinc Smelting Slag for Chromite Ore Processing Residue Solidification/Stabilization.

Lead-zinc smelting slag (LZSS) is regarded as a hazardous waste containing heavy metals that poses a significant threat to the environment. LZSS is rich in aluminosilicate, which has the potential to prepare alkali-activated materials and solidify hazardous waste, realizing hazardous waste cotreatment. In this study, the experiment included two parts; i.e., the preparation of alkali-activated LZSS (pure smelting slag) and chromite ore processing residue (COPR) solidification/stabilization. Single-factor and orthogonal experiments were carried out that aimed to explore the effects of various parameters (alkali solid content, water glass modulus, liquid-solid ratio, and initial curing temperature) for alkali-activated LZSS. Additionally, compressive strength and leaching toxicity were the indexes used to evaluate the performance of the solidified bodies containing COPR. As a result, the highest compressive strength of alkali-activated LZSS reached 84.49 MPa, and when 40% COPR was added, the strength decreased to 1.42 MPa. However, the leaching concentrations of Zn and Cr from all the solidified bodies were far below the critical limits (US EPA Method 1311 and China GB5085.3-2007). Heavy-metal ions in LZSS and COPR were immobilized successfully by chemical and physical means, which was detected by analyses including environmental scanning electron microscopy with energy-dispersive spectrometry, Fourier transform infrared spectrometry, and X-ray diffraction.

Preparation of Glass-Ceramics via Cosintering and Solidification of Hazardous Waste Incineration Residue and Chromium-Containing Sludge.

Residues from the incineration of hazardous wastes are classified as hazardous byproducts because they contain heavy metals. Chromium-containing sludge (CCS) is industrial sludge produced during the electroplating process and includes heavy metals, such as Cr, Pb, and Cu. These heavy metals can infiltrate natural ecosystems and cause significant environmental damage. To limit the toxicity of leached products, hazardous waste incineration residues (HWIRs) can be repurposed as raw materials for producing glass-ceramics. In this study, we designed an orthogonal experiment to optimize the heat treatment process, yielding glass-ceramics with excellent properties and realizing heavy metal solidification. The toxic characteristic leaching procedure was used to determine the leaching toxicity of the cosintered solidified heavy metals, revealing that their solidification efficiencies exceed 90%. Moreover, X-ray diffraction analysis indicates that certain heavy metals participate in the formation of heavy-metal-containing crystal lattices (FeCr2O4 and PbFe12O19), thereby reducing their leaching concentration. These results show that cosintering HWIR and CCS is an effective approach for heavy metal solidification and provides valuable insights into its utilization for producing building materials.

Application of UV radiation for in-situ Cr(VI) reduction from contaminated soil with electrokinetic remediation.

Restoring hexavalent chromium (Cr(VI)) to trivalent chromium (Cr(III)) from contaminated soil is a cost-effective alternative for attenuating Cr(VI) toxicity to the ecosystem. A new electrokinetic remediation (EKR) system with UV light was explored to overcome an energy barrier to catalyze Cr(VI) reduction from the surface soil near the anodic reservoir. Natural organic matters and minerals from the contaminated soil acted as electron donors and catalysts for Cr(VI) photo-reduction and no additional chemical reagent. There was almost no residual Cr(VI) in anolyte after UV/EKR compared with the conventional EKR. The reduction improved the efficiency of EKR in the soil near the anodic reservoir by dropped the Cr(VI) negative mass flux caused by electroosmosis advection and concentration diffusion. The pathways of Cr(VI) photo-reduction are possibly dominated by ligand-to-metal charge transfer, i.e., photocatalytic cyclic reduction by Fe(III)/Fe(II) complexes on the surface of the minerals and in soil pore fluid and the photo-induced decomposition of chromate ester. It is concluded that UV/EKR is a clean, efficient, and low-cost method for remediation of Cr(VI)-contaminated soil.

Efficient electrokinetic remediation of heavy metals from MSWI fly ash using approaching anode integrated with permeable reactive barrier.

During electrokinetic remediation (EKR) of heavy metals (HMs) (Pb, Zn, Cu, and Cd) from municipal solid waste incineration (MSWI) fly ash enhanced by a permeable reactive barrier (PRB), the nearer to the anode, the higher the concentration of H+ ions and the greater the remediation effect. Therefore, a potentially new method of PRB-enhanced EKR using an approaching anode (A-EKR + PRB) was studied to help H+ ions to quickly migrate to the sample near the cathode. Consequently, the HM leaching and total concentrations were reduced, while an energy reduction of nearly 40% was achieved. The results showed that the best remediation ability was obtained when MSWI fly ash was treated for 16 days at a voltage gradient of 2.5 V/cm, the approaching anode was moved after 4 days, and the PRB contained 10 g of activated carbon. After remediation, the environmental risk analysis showed that A-EKR + PRB reduced all the fractions of HMs, especially the acid extractable and oxidizable fractions, which might have been due to the enhancement of acid dissolution and oxidation by the approaching anode. In addition, the environmental risks of the remaining HMs were reduced, and the results indicated that A-EKR + PRB is an advisable choice for remediation of MSWI fly ash.

Detoxification and immobilization of chromite ore processing residue using the alkali-activated cementitious materials mixed with ascorbic acid.

The existence of leachable Cr(Ⅵ) in chromite ore processing residue (COPR) makes it hazardous waste. Therefore, resourceful utilization of COPR is necessary to protect the ecosystem and living biota from hazardous effect of Cr(Ⅵ) caused by its leaching. In this study, detoxification and immobilization of COPR was carried out through introduction of ascorbic acid (AA) in alkali-activated cementitious materials. Several dosages of AA were treated with water extractable/soluble Cr(Ⅵ) to achieve the optimum dosage which could be further utilized in solidification process. While, the compressive strength was developed through utilizing different modulus of water glass, liquid to solid ratios and curing temperatures. The results showed that 0.3% of AA was enough to reduce the Cr(Ⅵ) into Cr(Ⅲ), and highest compressive strength of 120 MPa was achieved after using the modulus of 1.6, liquid to solid ratio of 0.24 and curing temperature of 30 °C. The solidified samples having AA had not exceeded the toxicity limit up to 60% addition of COPR, and samples without addition of AA were effective for solidification of 20% COPR. Regarding mechanism, the compressive strength, leaching behavior and microscopic analysis i.e. X-ray diffraction (XRD), Fourier transform infrared spectrometry (FTIR) and scanning electron microscope with energy dispersive spectrometry (SEM-EDS) showed that immobilization of chromium was carried out through physical and chemical means.

Solidification of electroplating sludge with alkali-activated fly ash to prepare a non-burnt brick and its risk assessment.

Electroplating sludge (ES), a byproduct of the electroplating industry, is considered as hazardous waste because of the presence of several kinds of toxic heavy metals (HMs, i.e., Cr, Ni, Cu and Zn). The improper treatment of ES has resulted in the contamination of the environment and is ultimately harmful to the living biota. Solidification/stabilization is regarded as a promising technique to deal with hazardous wastes with the use of a geopolymer, an excellent material, in this technique. In this research, ES was solidified using fly ash (FA) and ordinary Portland cement together so that non-burnt bricks (NBBs) could be prepared. The risk assessment of these bricks was carried out in a homemade experimental device by simulating rainfall. The results showed that the compressive strength of NBBs was up to 15 MPa; hence, it could be used for construction purposes. The hazard quotient (HQ) of HMs (including Zn, Ni and Cu) was much less than the limit value, while both the HQ and cancer risk of Cr were over the corresponding limit values.

Synergism of citric acid and zero-valent iron on Cr(VI) removal from real contaminated soil by electrokinetic remediation.

This study focused on enhanced electrokinetic remediation of Cr(VI) in real contaminated soil. The citric acid (CA) as the electrolyte and Fe(II) released from zero-valent iron (ZVI) under anoxic conditions functioned as the main reducer. They were used for overcoming the high insoluble Cr(VI) fraction in real contaminated soil and high Cr(VI) residue in acidic soil near the anode simultaneously. The synergism of CA and ZVI is that CA helps the release of Cr(VI) to react with the generated Fe(II) and alleviates the hindrance of Fe and Cr co-precipitates in electromigration of Cr; meanwhile, the end product Fe(III) from ZVI catalyzed the Cr(VI) reduction by CA. The removal of Cr(III) and Cr(VI) was significantly improved in real contaminated soil. The optimum result (82.86%) was obtained at a voltage gradient of 2.5 V/cm after 12-day remediation with a 10 g ZVI dose when the catholyte and anolyte were 0.2 mol/L and 0.1 mol/L CA, respectively. This configuration has a significant improvement in overcoming the current obstacles for Cr(VI) electrokinetic remediation from real contaminated soil and prospects for large-scale practical applications.

Solidification/stabilization of municipal solid waste incineration fly ash using uncalcined coal gangue-based alkali-activated cementitious materials.

The proper disposal of municipal solid waste incineration fly ash (MSWI FA) is necessary due to the presence of hazardous metals (Cu2+, Zn2+, Pb2+ and Cd2+). The solidification/stabilization through alkali-activated cementitious materials (having aluminosilicates) is regarded as one of the best methods for its disposal. In this paper, an uncalcined coal gangue-based alkali-activated cementitious material was used to solidify the MSWI FA. The compressive strength of these cementitious materials was evaluated through different contents of alkali activators, SiO2/Na2O molar ratios, liquid/solid ratios and curing temperatures by utilizing a single-factor experiment. The specimens with the highest compressive strength (31.37 MPa) were used for solidification of MSWI FA. The results indicated that compressive strength decreased with the addition of MSWI FA which caused the higher leaching of heavy metals. The solidification efficiencies of Cu2+, Zn2+, Pb2+ and Cd2+ were more than 95%. In addition, leaching concentrations had not surpassed the critical limit up to 20% addition of MSWI FA in solidified samples and representing the potential application of these samples for construction and landfill purposes. Heavy metals in MSWI FA were solidified through physical encapsulation and chemical bonding which was verified by speciation analysis, X-ray diffraction, Fourier transform infrared spectrometry and scanning electron microscopy with energy dispersive spectrometry analyses.

Effect of chemical additives on electrokinetic remediation of Cr-contaminated soil coupled with a permeable reactive barrier.

Chromium (Cr) contamination in soil, especially Cr(VI), is a serious threat to the environment and human health. The electrokinetic remediation (EKR) is a promising technology to remediate the Cr(VI). Therefore, in this study, EKR coupled with a permeable reactive barrier (PRB) was used to treat the Cr(VI)-contaminated soil. The CTMAB-Z, a modified zeolite (prepared with cetyltrimethyl ammonium bromide) alone and a mixture of CTMAB-Z and Fe(0) were used as PRB-1 and PRB-2 reactive media, respectively. The effect of chemical enhancers/additives, i.e. DL-tartaric acid and Tween 80 on EKR of Cr(VI) was also analysed in the contrasting experiments. While the effects of repair time, voltage gradient and DL-tartaric acid concentration on Cr(VI) remediation were investigated by using the multifactor orthogonal experiment which was based on contrasting experiments. The contrasting experiment results showed that the highest Cr(VI) removal rate (66.27%) and leaching efficiency (71.29%) were observed in the experimental group which had DL-tartaric acid and PRB-2. Furthermore, the multifactor orthogonal experiment results had depicted that the highest Cr(VI) removal rate (80.92%) and leaching efficiency (85.25%) were achieved after treating the samples at a voltage gradient of 2.5 V cm-1 for 8 days in the presence of 0.15 M concentration of DL-tartaric acid. This study demonstrated that Cr(VI) remediation through EKR process could be significantly enhanced by the use of PRB and additives.

The Solidification of Lead-Zinc Smelting Slag through Bentonite Supported Alkali-Activated Slag Cementitious Material.

The proper disposal of Lead-Zinc Smelting Slag (LZSS) having toxic metals is a great challenge for a sustainable environment. In the present study, this challenge was overcome by its solidification/stabilization through alkali-activated cementitious material i.e., Blast Furnace Slag (BFS). The different parameters (water glass modulus, liquid-solid ratio and curing temperature) regarding strength development were optimized through single factor and orthogonal experiments. The LZSS was solidified in samples that had the highest compressive strength (after factor optimization) synthesized with (AASB) and without (AAS) bentonite as an adsorbent material. The results indicated that the highest compressive strength (AAS = 92.89MPa and AASB = 94.57MPa) was observed in samples which were prepared by using a water glass modulus of 1.4, liquid-solid ratio of 0.26 and a curing temperature of 25 °C. The leaching concentrations of Pb and Zn in both methods (sulfuric and nitric acid, and TCLP) had not exceeded the toxicity limits up to 70% addition of LZSS due to a higher compressive strength (>60 MPa) of AAS and AASB samples. While, leaching concentrations in AASB samples were lower than AAS. Conclusively, it was found that the solidification effect depends upon the composition of binder material, type of leaching extractant, nature and concentration of heavy metals in waste. The XRD, FTIR and SEM analyses confirmed that the solidification mechanism was carried out by both physical encapsulation and chemical fixation (dissolved into a crystal structure). Additionally, bentonite as an auxiliary additive significantly improved the solidification/stabilization of LZSS in AASB by enhancing the chemical adsorption capacity of heavy metals.

Electrokinetic remediation of heavy metals from municipal solid waste incineration fly ash pretreated by nitric acid.

Municipal solid waste incineration (MSWI) fly ash has a high concentration of heavy metals (HMs) which are hazardous to the environment. Moreover, it has high pH and buffering capacity which hinders the removal of HMs. Another constraining factor is the considerable fraction of HMs which exist in oxidizable and reducible states. The acid pretreatment of MSWI fly ash is a key solution to this problem. Therefore, the current experiment is carried out to evaluate the effect of acid pretreatment of MSWI fly ash and reaction/proposed time on the removal efficiency of HMs through an electrokinetic experiment. The leaching experiment results show that acid pretreatment has increased the desorption/release of heavy metal ions (Pb2+, Cd2+, Cu2+ and Zn2+). It enhances the migration of HM ions in electrolytic cells which get precipitated at the cathode, thereby increasing the removal efficiency of HMs in the electrokinetic experiment. Moreover, it is found that prolonged proposed time (12 d) has significant effect on the removal efficiency of HMs. Finally, it is concluded that acid pretreatment and prolonged proposed time have enhanced the removal electrokinetic remediation of HMs which is carried out via three processes, i.e. desorption (enhanced by acidification), migration and precipitation.

Application of iron-loaded activated carbon electrodes for electrokinetic remediation of chromium-contaminated soil in a three-dimensional electrode system.

Hexavalent chromium from industrial residues is highly mobile in soil and can lead to the contamination of groundwater through runoff and leaching after rainfall. This paper focuses on the three-dimensional (3D) electrokinetic remediation (EKR) of chromium-contaminated soil from an industrial site. Activated carbon particles coupled with Fe ions (AC-Fe) were used as the third electrode. The optimum dose ratio of the electrode particles and remediation time were selected on the basis of single-factor experiments. X-ray photoelectron spectroscopy (XPS) analysis was carried out to explore the reduction of Cr(VI) on the surface of the electrode particles (AC-Fe). The results showed that AC-Fe had a positive effect on Cr(VI) reduction with a removal rate of 80.2%, which was achieved after 10 d by using a 5% dose of electrode particles. Finally, it was concluded that the removal mechanism combined the processes of electromigration, electrosorption/adsorption and reduction of Cr(VI) in the 3D EKR system.

Waste solidification/stabilization of lead-zinc slag by utilizing fly ash based geopolymers.

Solidification/stabilization (S/S) is recognized as an effective technology for solid waste treatment. In S/S, the application of geopolymers synthesized by industrial waste (rich in active silicon and aluminum) to immobilize hazardous waste is a research focus. In this article, a fly ash based geopolymer was used to immobilize lead-zinc slag containing Pb, Ni, Zn and Mn. A fly ash based geopolymer with good mechanical strength was obtained through single factor experiments and the compressive strength of the geopolymer reached 29.72 MPa. The effects of immobilizing lead-zinc slag in the fly ash based geopolymer were discussed by means of compressive strength, leaching test and speciation analysis. The solidification/stabilization mechanism was further investigated using XRD, FTIR and SEM. The mechanical properties of the fly ash based geopolymer were negatively affected by addition of lead-zinc slag, and compressive strength decreased to 8.67 MPa when 60% lead-zinc slag was added. The geopolymer has the ability to reduce toxicity of lead-zinc slag by immobilizing heavy metals (Pb, Ni, Zn and Mn), but the ability was not unlimited. The migration of heavy metals to residual form indicates that heavy metals may either be bonded into the geopolymer matrix via the T-O bond (T = Si, Al) or captured in framework cavities to maintain the charge balance. The NASH (Na2O-Al2O3-SiO2-H2O) gel structure observed by XRD, FTIR and SEM can physically encapsulate the contaminants during geopolymerization. It is finally concluded that heavy metals were immobilized in the fly ash based geopolymer through a combination of chemical bonding and physical encapsulation.

Biomineralization of a calcifying ureolytic bacterium Microbacterium sp. GM-1

Background: Biomineralization is a significant process performed by living organisms in which minerals are produced through the hardening of biological tissues. Herein, we focus on calcium carbonate precipitation, as part of biomineralization, to be used in applications for environmental protection, material technology, and other fields. A strain GM-1, Microbacterium sp. GM-1, isolated from active sludge, was investigated for its ability to produce urease and induce calcium carbonate precipitation in a metabolic process. Results: It was discovered that Microbacterium sp. GM-1 resisted high concentrations of urea up to 60 g/L. In order to optimize the calcification process of Microbacterium sp. GM-1, the concentrations of Ni2+ and urea, pH value, and culture time were analyzed through orthogonal tests. The favored calcite precipitation culture conditions were as follows: the concentration of Ni2+ and urea were 50 µM and 60 g/L, respectively, pH of 10, and culture time of 96 h. Using X-ray diffraction analysis, the calcium carbonate polymorphs produced by Microbacterium sp. GM-1 were proven to be mainly calcite. Conclusions: The results of this research provide evidence that Microbacterium sp. GM-1 can biologically induce calcification and suggest that strain GM-1 may play a potential role in the synthesis of new biominerals and in bioremediation or biorecovery.

The application of homemade Neosinocalamus affinis AC in electrokinetic removal technology on heavy metal removal from the MSWI fly ash.

This present paper was focused on the manufacture of activated carbon (AC) and its application in the electrokinetic remediation (EKR) technology on removal of the heavy metals (HMs) from the municipal solid waste incineration fly ash. AC was produced from Neosinocalamus affinis (NF) by chemical activation with H3PO4 in N2 atmosphere, the effects of activation temperatures, soaking time and impregnation ratios on the adsorption capacity of AC on HMs were examined through equilibrium adsorption experiments. The AC produced under the condition of 450 °C of activation temperature, 10 h of soaking time and 1.5 of impregnation ration was applied in the EKR experiment. The addition of AC in the S3-region of the electrolyzer could effectively improve the removal efficiencies of HMs. The technical parameters of voltage gradient, processing time and proportion were further optimized in the coupled experiments, the maximum removal of Cu, Zn, Cd, and Pb was 84.93%, 69.61%, 79.57%, and 78.55% respectively obtained under the optimal operating conditions of 2 V/cm of voltage gradient, 8 d of processing time and 20% of proportion.