PBTCA稳定零价纳米铁的制备及其去除水中Cr(Ⅵ)

以2-膦酸丁烷-1,2,4三羧酸(PBTCA)为稳定剂,通过FeCl3.6H2O与NaBH4反应,利用液相还原法制备稳定纳米级零价铁颗粒(P-NZVI),并用透射电子显微镜(TEM)、扫描电子显微镜(SEM)及X射线衍射(XRD)进行表征,颗粒平均粒径为73 nm。考察了Cr(Ⅵ)溶液初始浓度、pH、NZVI投加量、温度等条件对Cr(Ⅵ)去除效果的影响,并与同等条件下不加稳定剂制备的纳米铁(N-NZVI)进行对比。结果表明:Cr(Ⅵ)的去除率随温度和纳米铁投加量增加而升高,随pH和Cr(Ⅵ)溶液初始浓度升高而降低。在相同实验条件下,P-NZVI对Cr(Ⅵ)的去除效果明显优于N-NZVI,表明改性后纳米铁在地表水原位修复领域具有较好的应用前景。     

Remediation of soil contaminated with pyrene using ground nanoscale zero-valent iron

The sites contaminated with recalcitrant polycyclic aromatic hydrocarbons (PAHs) are serious environmental problems ubiquitously. Some PAHs have proven to be carcinogenic and hazardous. Therefore, the innovative PAH in situ remediation technologies have to be developed instantaneously. Recently, the nanoscale zero-valent iron (ZVI) particles have been successfully applied for dechlorination of organic pollutants in water, yet little research has investigated for the soil remediation so far. The objective in this work was to take advantage of nanoscale ZVI particles to remove PAHs in soil. The experimental factors such as reaction time, particle diameter and iron dosage and surface area were considered and optimized. From the results, both microscale and nanoscale ZVI were capable to remove the target compound. The higher removal efficiencies of nanoscale ZVI particles were obtained because the specific surface areas were about several dozens larger than that of commercially microscale ZVI particles. The optimal parameters were observed as 0.2 g iron/2 mL water in 60 min and 150 rpm by nanoscale ZVI. Additionally, the results proved that nanoscale ZVI particles are a promising technology for soil remediation and are encouraged in the near future environmental applications. Additionally, the empirical equation developed for pyrene removal efficiency provided the good explanation of reaction behavior. Ultimately, the calculated values by this equation were in a good agreement with the experimental data.     

Reducing As availability in calcareous soils using nanoscale zero valent iron

Environmental Science and Pollution Research - Different methods, including the use of nanoscale zero-valent iron (NZVI), have been used to treat arsenic (As)-contaminated environments, with much...     

Enhanced degradation of bisphenol S by persulfate activated with sulfide-modified nanoscale zero-valent iron

Environmental Science and Pollution Research - Sulfide-modified nanoscale zero-valent iron (S-nZVI) has been considered an efficient material to remove heavy metals and organic contaminants. The...     

Dechlorination comparison of mono-substituted PCBs with Mg/Pd in different solvent systems

It is widely recognized that polychlorinated biphenyls (PCBs) are a dangerous environmental pollutant. Even though the use and production of PCBs have been restricted, heavy industrial use has made them a wide-spread environmental issue today. Dehalogenation using zero-valent metals has been a promising avenue of research for the remediation of chlorinated compounds and other contaminants that are present in the environment. However, zero-valent metals by themselves have shown little capability of dechlorinating polychlorinated biphenyls (PCBs). Mechanically alloying the metal with a catalyst, such as palladium, creates a bimetallic system capable of dechlorinating PCBs very rapidly to biphenyl. This study primarily aims to evaluate the effects of solvent specificity on the kinetics of mono-substituted PCBs, in an attempt to determine the mechanism of degradation. Rate constants and final byproducts were determined for the contaminant systems in both water and methanol, and significant differences in the relative rates of reaction were observed between the two solvents.     

Heterogeneous Fenton oxidation of Direct Black G in dye effluent using functional kaolin-supported nanoscale zero iron

This study investigated kaolin-supported nanoscale zero-valent iron (nZVI/K) as a heterogeneous Fenton-like catalyst for the adsorption and oxidation of an azo dye, Direct Black G (DBG). New findings suggest that kaolin as a support material not only reduced the aggregation of nanoscale zero-valent iron (nZVI) but also improved the adsorption of DBG. It consequently improved Fenton oxidation by increasing the local concentration of DBG in the vicinity of nZVI. This was confirmed by scanning electron microscopy and X-ray diffraction for the surface morphology of nZVI/K before and after the Fenton-like reaction. Furthermore, nZVI/K proved to be a catalyst for the heterogeneous Fenton-like oxidation of the DBG process in the neutral pH range. More than 87.22 % of DBG was degraded, and 54.60 % of total organic carbon was removed in the optimal conditions: 0.6 g/L dosage of nZVI/K, 33 mM H₂O₂, 100 mg/L initial DBG concentration, temperature of 303 K and pH of 7.06. Finally, it was demonstrated that nZVI/K removed DBG from dye wastewater through the processes of adsorption and oxidation.     

Transformation and biodegradation of 1,2,3-trichloropropane (TCP)

PURPOSE: 1,2,3-Trichloropropane (TCP) is a persistent groundwater pollutant and a suspected human carcinogen. It is also is an industrial chemical waste that has been formed in large amounts during epichlorohydrin manufacture. In view of the spread of TCP via groundwater and its toxicity, there is a need for cheap and efficient technologies for the cleanup of TCP-contaminated sites. In situ or on-site bioremediation of TCP is an option if biodegradation can be achieved and stimulated. This paper presents an overview of methods for the remediation of TCP-contaminated water with an emphasis on the possibilities of biodegradation. CONCLUSIONS: Although TCP is a xenobiotic chlorinated compound of high chemical stability, a number of abiotic and biotic conversions have been demonstrated, including abiotic oxidative conversion in the presence of a strong oxidant and reductive conversion by zero-valent zinc. Biotransformations that have been observed include reductive dechlorination, monooxygenase-mediated cometabolism, and enzymatic hydrolysis. No natural organisms are known that can use TCP as a carbon source for growth under aerobic conditions, but anaerobically TCP may serve as electron acceptor. The application of biodegradation is hindered by low degradation rates and incomplete mineralization. Protein engineering and genetic modification can be used to obtain microorganisms with enhanced TCP degradation potential.     

Enhanced removal of mercury and lead by a novel and efficient surface-functionalized imogolite with nanoscale zero-valent iron material

Environmental Science and Pollution Research - A novel hybrid nanomaterial, nanoscale zero-valent iron (nZVI)-grafted imogolite nanotubes (Imo), was synthesized via a fast and straightforward...     

Microbial reduction of nitrate in the presence of nanoscale zero-valent iron

Microbial reduction of nitrate in the presence of nanoscale zero-valent iron (NZVI) was evaluated to assess the feasibility of employing NZVI in the biological nitrate treatment. Nitrate was completely reduced within 3 d in a nanoscale Fe(0)-cell reactor, while only 50% of the nitrate was abiotically reduced over 7 d at 25 °C. The removal rate of nitrate in the integrated NZVI-cell system was unaffected by the presence of high amounts of sulfate. Efficient removal of nitrate by Fe(II)-supported anaerobic culture in 14 d indicated that Fe(II), which is produced during anaerobic iron corrosion in the Fe(0)-cell system, might act as an electron donor for nitrate. Unlike abiotic reduction, microbial reduction of nitrate was not significantly affected by low temperature conditions. This study demonstrated the potential applicability of employing NZVI iron as a source of electrons for biological nitrate reduction. Use of NZVI for microbial nitrate reduction can obviate the disadvantages associated with traditional biological denitrification, that relies on the use of organic substrates or explosive hydrogen gas, and maintain the advantages offered by nano-particle technology such as higher surface reactivity and functionality in suspensions.     

Remediation of Soil Contaminated with Pyrene Using Ground Nanoscale Zero-Valent Iron

Abstract

The sites contaminated with recalcitrant polycyclic aromatic hydrocarbons (PAHs) are serious environmental problems ubiquitously. Some PAHs have proven to be carcinogenic and hazardous. Therefore, the innovative PAH in situ remediation technologies have to be developed instantaneously. Recently, the nanoscale zero-va-lent iron (ZVI) particles have been successfully applied for dechlorination of organic pollutants in water, yet little research has investigated for the soil remediation so far. The objective in this work was to take advantage of nanoscale ZVI particles to remove PAHs in soil. The experimental factors such as reaction time, particle diameter and iron dosage and surface area were considered and optimized. From the results, both microscale and nanoscale ZVI were capable to remove the target compound. The higher removal efficiencies of nanoscale ZVI particles were obtained because the specific surface areas were about several dozens larger than that of commercially microscale ZVI particles. The optimal parameters were observed as 0.2 g iron/2 mL water in 60 min and 150 rpm by nanoscale ZVI. Additionally, the results proved that nanoscale ZVI particles are a promising technology for soil remediation and are encouraged in the near future environmental applications. Additionally, the empirical equation developed for pyrene removal efficiency provided the good explanation of reaction behavior. Ultimately, the calculated values by this equation were in a good agreement with the experimental data.     

In situ fixation of metals in soils using bauxite residue: chemical assessment

Contamination of soils with heavy metals and metalloids is a widespread problem all over the world. Low cost, non-invasive, in situ technologies are required for remediation processes. We investigated the efficiency of a bauxite residue (red mud) to fix heavy metals in two soils, one contaminated by industrial activities (French soil), and one by sewage sludge applications (UK soil). This Fe-oxide rich material was compared with lime, or beringite, a modified aluminosilicate that has been used for in situ fixation processes. Four different crop species were successively grown in pots. Metal concentrations in the soil pore waters were analyzed during the growing cycles. At the end of the experiment fluxes of heavy metals were measured using a diffusive gradient in thin film technique (DGT). Furthermore, a sequential extraction procedure (SEP) and an acidification test were performed to investigate the mechanisms of metal fixation by different soil amendments. In both soils, the concentrations of metals in the soil pore water and metal fluxes were greatly decreased by the amendments. An application of 2% red mud performed as well as beringite applied at 5%. Increasing soil pH was a common mechanism of action for all the amendments. However, the red mud amendment shifted metals from the exchangeable to the Fe-oxide fraction, and decreased acid extractability of metals. The results suggest that specific chemisorption, and possibly metal diffusion into oxide particles could also be the mechanisms responsible for the fixation of metals by red mud.     

Using nanoscale zero-valent iron for the remediation of polycyclic aromatic hydrocarbons contaminated soil

The sites contaminated with recalcitrant organic compounds, such as polycyclic aromatic hydrocarbons (PAHs) with multiple benzene rings, are colossal and ubiquitous environmental problems. They are relatively nonbiodegradable and mutagenic, and 16 of them are listed in the U.S. Environment Protection Agency priority pollutants. Thus, the efficient and emerging remediation technologies for removal of PAHs in contaminated sites have to be uncovered urgently. In this decade, the zero-valent iron (ZVI) particles have been used successfully in the laboratory, pilot, and field, such as degradation of chlorinated hydrocarbons and remediation of the other pollutants. Nevertheless, as far as we know, little research has investigated for soil remediation; this study used nanoscale ZVI particles to remove pyrene in the soil. The experimental variables were determined, including reaction time, iron particle size, and dosage. From the results, both the micro- and nanoscales of ZVI were capable of removing the target compound in soil, but the higher removal efficiencies were by nanoscale ZVI because of the massive specific surface area. The optimal operating conditions to attain the best removal efficiency of pyrene were obtained while adding nanoscale ZVI 0.1 g/g soil within 60 min and 150 rpm of mixing. Thus, nanoscale ZVI has proved to be a promising remedy for PAH-contaminated soil in this study, as well as an optimistically predictable application for additional pilot and field studies.     

Amendment of hydroxyapatite in reduction of tetrachloroethylene by zero-valent zinc: its rate enhancing effect and removal of Zn(II)

The effects of hydroxyapatite (HAP) on dechlorination of tetrachloroethylene (PCE) by zero-valent zinc (ZVZ) were examined in batch systems. PCE was primarily transformed to trichloroethylene by ZVZ, with 1,2-trans-dichloroethylene representing a minor product. Dechlorination of PCE was accelerated by the presence of HAP, and the pseudo-first order rate constants increased with increasing amount of HAP. Zn(II), mostly generated from oxidative dissolution of ZVZ by PCE, was effectively removed from the solution by HAP. Ion substitution, coprecipitation, and adsorption are proposed as the possible mechanisms for Zn(II) removal. These reactions appeared to occur simultaneously and the contribution of each reaction to overall removal of Zn(II) was primarily dependent on HAP loading at constant ZVZ loading. The results indicate that the use of HAP in combination with conventional zero-valent metals is promising in that it can achieve both degradation of organic contaminants and stabilization of inorganic contaminants.     

Removal of trace Cr(VI) from aqueous solution by porous activated carbon balls supported by nanoscale zero-valent iron composites

Environmental Science and Pollution Research - In this study, porous activated carbon balls supported by nanoscale zero-valent iron composites (Fe@PACB-700) were used for the first time for the...     

Comparison of biotic and abiotic treatment approaches for co-mingled perchlorate, nitrate, and nitramine explosives in groundwater

Biological and abiotic approaches for treating co-mingled perchlorate, nitrate, and nitramine explosives in groundwater were compared in microcosm and column studies. In microcosms, microscale zero-valent iron (mZVI), nanoscale zero-valent iron (nZVI), and nickel catalyzed the reduction of RDX and HMX from initial concentrations of 9 and 1 mg/L, respectively, to below detection (0.02 mg/L), within 2 h. The mZVI and nZVI also degraded nitrate (3 mg/L) to below 0.4 mg/L, but none of the metal catalysts were observed to appreciably reduce perchlorate ( approximately 5 mg/L) in microcosms. Perchlorate losses were observed after approximately 2 months in columns of aquifer solids treated with mZVI, but this decline appears to be the result of biodegradation rather than abiotic reduction. An emulsified vegetable oil substrate was observed to effectively promote the biological reduction of nitrate, RDX and perchlorate in microcosms, and all four target contaminants in the flow-through columns. Nitrate and perchlorate were biodegraded most rapidly, followed by RDX and then HMX, although the rates of biological reduction for the nitramine explosives were appreciably slower than observed for mZVI or nickel. A model was developed to compare contaminant degradation mechanisms and rates between the biotic and abiotic treatments.     

Using Nanoscale Zero-Valent Iron for the Remediation of Polycyclic Aromatic Hydrocarbons Contaminated Soil

Abstract

The sites contaminated with recalcitrant organic compounds, such as polycyclic aromatic hydrocarbons (PAHs) with multiple benzene rings, are colossal and ubiquitous environmental problems. They are relatively nonbiodegradable and mutagenic, and 16 of them are listed in the U.S. Environment Protection Agency priority pollutants. Thus, the efficient and emerging remediation technologies for removal of PAHs in contaminated sites have to be uncovered urgently. In this decade, the zero-valent iron (ZVI) particles have been used successfully in the laboratory, pilot, and field, such as degradation of chlorinated hydrocarbons and remediation of the other pollutants. Nevertheless, as far as we know, little research has investigated for soil remediation; this study used nanoscale ZVI particles to remove pyrene in the soil. The experimental variables were determined, including reaction time, iron particle size, and dosage. From the results, both the micro- and nanoscales of ZVI were capable of removing the target compound in soil, but the higher removal efficiencies were by nanoscale ZVI because of the massive specific surface area. The optimal operating conditions to attain the best removal efficiency of pyrene were obtained while adding nanoscale ZVI 0.1 g/g soil within 60 min and 150 rpm of mixing. Thus, nanoscale ZVI has proved to be a promising remedy for PAH-contaminated soil in this study, as well as an optimistically predictable application for additional pilot and field studies.     

纳米铁-微生物耦合体系去除硝酸盐的影响因素研究

采用液相还原法制备出纳米铁粒子,并与自养反硝化细菌耦合,以解决单独使用生物反硝化和纳米铁还原法的不足。本实验在纳米铁-微生物耦合体系可以有效还原硝酸盐的基础上,研究了pH、温度和DO等环境因素对该耦合体系脱氮速率和产物的影响,以期通过优化参数达到最好的脱氮效果。结果表明,该体系在中性条件下能够快速将硝酸盐还原,随pH升高,氨氮比例无显著变化,均在40%左右,但还原速率有所下降;随温度的升高,氨氮比例有所上升,而反应速率明显升高,但该体系在5℃时仍能将硝酸盐完全去除;耦合体系中的DO过高或过低都会导致产物中氨氮比例的增加,0.4 mg/L左右为较适宜DO水平,但对硝酸盐还原速率的影响不大,当DO为0.8 mg/L时,硝酸盐仍可以在8 d内完全去除。因此,该耦合脱氮体系对pH、温度和DO的适应能力较强,有利于实际地下水的原位修复。     

Nanoscale zero-valent iron (nZVI): aspects of the core-shell structure and reactions with inorganic species in water

Aspects of the core-shell model of nanoscale zero-valent iron (nZVI) and their environmental implications were examined in this work. The structure and elemental distribution of nZVI were characterized by X-ray energy-dispersive spectroscopy (XEDS) with nanometer-scale spatial resolution in an aberration-corrected scanning transmission electron microscope (STEM). The analysis provides unequivocal evidence of a layered structure of nZVI consisting of a metallic iron core encapsulated by a thin amorphous oxide shell. Three aqueous environmental contaminants, namely Hg(II), Zn(II) and hydrogen sulfide, were studied to probe the reactive properties and the surface chemistry of nZVI. High-resolution X-ray photoelectron spectroscopy (HR-XPS) analysis of the reacted particles indicated that Hg(II) was sequestrated via chemical reduction to elemental mercury. On the other hand, Zn(II) removal was achieved via sorption to the iron oxide shell followed by zinc hydroxide precipitation. Hydrogen sulfide was immobilized on the nZVI surface as disulfide (S(2)(2-)) and monosulfide (S(2-)) species. Their relative abundance in the final products suggests that the retention of hydrogen sulfide occurs via reactions with the oxide shell to form iron sulfide (FeS) and subsequent conversion to iron disulfide (FeS(2)). The results presented herein highlight the multiple reactive pathways permissible with nZVI owing to its two functional constituents. The core-shell structure imparts nZVI with manifold functional properties previously unexamined and grants the material with potentially new applications.     

Laboratory evaluation of zero-valent iron to treat water impacted by acid mine drainage

This study examines the applicability and limitations of granular zero-valent iron for the treatment of water impacted by mine wastes. Rates of acid-neutralization and of metal (Cu, Cd, Ni, Zn, Hg, Al, and Mn) and metalloid (As) uptake were determined in batch systems using simulated mine drainage (initial pH 2.3-4.5; total dissolved solids 14000-16000 mgl(-1)). Metal removal from solution and acid-neutralization occurred simultaneously and were most rapid during the initial 24 h of reaction. Reaction half-lives ranged from 1.50+/-0.09 h for Al to 8.15+/-0.36 h for Zn. Geochemical model results indicate that metal removal is most effective in solutions that are highly undersaturated with respect to pure-metal hydroxides suggesting that adsorption is the initial and most rapid metal uptake mechanism. Continued adsorption onto or co-precipitation with iron corrosion products are secondary metal uptake processes. Sulfate green rust was identified as the primary iron corrosion product, which is shown to be the result of elevated [SO(4)(2-)]/[HCO(3)(-)] ratios in solution. Reversibility studies indicate that zero-valent iron will retain metals after shifts in redox states are imposed, but that remobilization of metals may occur after the acid-neutralization capacity of the material is exhausted.     

Heavy metals detection in river water with cantilever nanobiosensor

Abstract

Heavy metals can be highly toxic depending on the dose and the chemical form. In this context, sensing devices such as nanobiosensors have been presented as a promising tool to monitor contaminants at micro and nanoscale. In this work, cantilever nanobiosensors with phosphatase alkaline were developed and applied to detect heavy metals (Pb, Ni, Cd, Zn, Co, and Al) in river water. The nanobiosensor surface was functionalized by the self-assembled monolayers (SAM) technique using 16-mercaptohexadecanoic acid, N-(3-dimethylaminopropyl)-N′-ethylcarbodiimide (EDC) and N- hydroxysuccinimide (NHS), and phosphatase alkaline enzyme. The sensing layer deposited on the cantilever surface presented a uniform morphology, at nanoscale, with 80?nm of thickness. The nanobiosensor showed a detection limit in the ppb range and high sensitivity, with a stability of fifteen days. The developed cantilever nanobiosensor is a simple tool, suitable for the direct detection of contaminants in river water.