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.     

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.     

Assessing the impact of nano- and micro-scale zerovalent iron particles on soil microbial activities: particle reactivity interferes with assay conditions and interpretation of genuine microbial effects

The effects of nano-scale and micro-scale zerovalent iron (nZVI and mZVI) particles on general (dehydrogenase and hydrolase) and specific (ammonia oxidation potential, AOP) activities mediated by the microbial community in an uncontaminated soil were examined. nZVI (diameter 12.5 nm; 10 mg g⁻¹ soil) apparently inhibited AOP and nZVI and mZVI apparently stimulated dehydrogenase activity but had minimal influence on hydrolase activity. Sterile experiments revealed that the apparent inhibition of AOP could not be interpreted as such due to the confounding action of the particles, whereas, the nZVI-enhanced dehydrogenase activity could represent the genuine response of a stimulated microbial population or an artifact of ZVI reactivity. Overall, there was no evidence for negative effects of nZVI or mZVI on the processes studied. When examining the impact of redox active particles such as ZVI on microbial oxidation-reduction reactions, potential confounding effects of the test particles on assay conditions should be considered.     

Effect of solution pH on aging dynamics and surface structural evolution of mZVI particles: H<Subscript>2</Subscript> production and spectroscopic/microscopic evidence

A microscale zero-valent iron (mZVI)-based in situ reactive zone is a promising technology for contaminated groundwater remediation. Estimation of mZVI aging behavior after its injection into the subsurface is essential for efficiency and longevity assessments. In this study, batch tests were conducted to investigate the effect of initial pH on mZVI aging dynamics, as well as the formation and evolution of aging products over 112 days. Results indicated that mZVI aging accelerated with decreasing initial pH. Corrosion rates of mZVI particles under pH 6.0 and 7.5 were approximately two orders of magnitude higher than those observed at pH 9.0. The morphological, structural, and compositional evolution of mZVI particles in three systems (pH = 6.0, 7.5, and 9.0) were investigated using scanning electron microscopy, X-ray diffraction, and X-ray photoelectron spectroscopy. In acidic and neutral solutions, a thick passivation layer with loosely and unevenly distributed aging precipitates was observed, and Fe₃O₄ was the final aging precipitate. Nevertheless, in alkaline solutions, minute aging precipitates were detected on the mZVI surface at 112 day. Characterization results suggested that mZVI was oxidized via the Fe⁰–Fe(OH)₂–Fe₃O₄ route. These findings shed new light on mZVI aging mechanisms, particularly its physicochemical characteristics and the structural evolution of mZVI in field-scale groundwater remediation applications.     

Zero-valent iron particles for PCB degradation and an evaluation of their effects on bacteria,plants, and soil organisms

Two types of nano-scale zero-valent iron (nZVI-B prepared by borohydride reduction and nZVI-T produced by thermal reduction of iron oxide nanoparticles in H₂) and a micro-scale ZVI (mZVI) were compared for PCB degradation efficiency in water and soil. In addition, the ecotoxicity of nZVI-B and nZVI-T particles in treated water and soil was evaluated on bacteria, plants, earthworms, and ostracods. All types of nZVI and mZVI were highly efficient in degradation of PCBs in water, but had little degradation effect on PCBs in soil. Although nZVI-B had a significant negative impact on the organisms tested, treatment with nZVI-T showed no negative effect, probably due to surface passivation through controlled oxidation of the nanoparticles.

     

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.     

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.     

Bimetallic iron-aluminum particles for dechlorination of carbon tetrachloride

Bimetallic iron-aluminum (Fe/Al) particles were synthesized and tested for their reactivity toward carbon tetrachloride using batch reactors and a flow-through column at near neutral pH. Preparation of bimetallic Fe/Al particles was conducted under acidic conditions under which iron was readily deposited onto the aluminum surface. The SEM image showed clusters of iron on the aluminum surface at the measured Fe:Al molar ratio of about 2:3. Results showed that the presence of zero-valent aluminum successfully prevented the formation of a passive layer at the iron surface and maintained the reactivity of iron. The dechlorination of carbon tetrachloride by bimetallic Fe/Al particles produced chloroform (9%), dichloromethane (17%) and methane (38%). Kinetic analysis suggests that bimetallic Fe/Al particles increased the reactivity toward carbon tetrachloride degradation by a factor of 10 compared to zero-valent iron and possessed a comparable reactivity with nano-sized Fe. The effectiveness of bimetallic Fe/Al particles was further confirmed by the continuous flow column study from which an ageing of bimetallic particles was also observed.     

Iron and organo-bentonite for the reduction and sorption of trichloroethylene

Hybrid barriers using dechlorination and immobilization were studied to remove trichloroethylene (TCE) in this study. Hybrid barriers of iron filings and organo (hexadecyltrimethylammonium, HDTMA)-bentonite were simulated in columns to assess the performance of the hybrid barriers. TCE reduction rate for the mixture of zero valent iron (ZVI) and HDTMA-bentonite was approximately seven times higher than that for ZVI, suggesting the reduction of TCE was accelerated when HDTMA-bentonite was mixed with ZVI. For the column of two separate layers of iron and HDTMA-bentonite, TCE reduction rate was nearly similar to that for ZVI alone, but the partition coefficient (Kd) was 4.5 times higher than that for ZVI only. TCE was immobilized in the first layer with HDTMA-bentonite due to sorption, and then dechlorinated in the second layer with iron filings due to reduction. The HDTMA-bentonite and minimally-desorbed HDTMA from the organo-bentonite are believed to contribute the increase in TCE concentration on iron surface so that more TCE could be available for reduction. Therefore, the incorporation of HDTMA-bentonite into ZVI not only can effectively retard the transport of chlorinated organic contaminants from landfill leachate or oil shock in subsurface environment, also can expedite the reduction rate of TCE.     

Microwave-induced nanoscale zero-valent iron degradation of perchloroethylene and pentachlorophenol

Microwave (MW) is applied to enhance perchloroethylene (PCE) or pentachlorophenol (PCP) removal using zero-valent iron (ZVI; Fe⁰) as the dielectric medium. ZVI has a much higher dielectric loss factor (39.5) than other media; it is capable of absorbing MW radiation rapidly to speed up the release of electrons, leading to rises of the ZVI particle surface temperature. If the MW power is continued, excessive electricity will accumulated inside ZVI particles, resulting in sparks. The results show that during the initial 5 sec (700 W), the linear aliphatic PCE has a faster decomposing rate than the ringed PCP (82.0% vs. 4.8%) because less energy is required for decomposing the linear-chlorine bond (90 kcal mol^?1) than ring-chlorine bonds (95 kcal mol^?1). Later, the removal rate for either PCE or PCP remains the same when the exposure time is between 5 and 60 sec. Without MW irradiation, linear PCE molecules have larger surface area to contact ZVI, and hence they have better removal efficiencies than PCP molecules. Using Fe⁰ as a microwave dielectric medium to treat PCE or PCP is a new and worthwhile treatment technology; it is environmentally friendly, and its use will eliminate the secondary pollution.

Implications Nanoscale iron particles are characterized by high surface-area-to-volume ratios, high specific surface area, and high surface reactivity. With a much higher dielectric loss factor, it is capable of absorbing MW radiation rapidly to speed up the release of electrons, leading to rise in temperature. The time needed to achieve a satisfactory treatment is also reduced, leading to significant saving of energy consumption to make this method cost-effective and also environmentally friendly for the industry to pursuit sustainable development.     

Calcite precipitation dominates the electrical signatures of zero valent iron columns under simulated field conditions

Calcium carbonate is a secondary mineral precipitate influencing zero valent iron (ZVI) barrier reactivity and hydraulic performance. We conducted column experiments to investigate electrical signatures resulting from concurrent CaCO₃ and iron oxides precipitation under simulated field geochemical conditions. We identified CaCO₃ as a major mineral phase throughout the columns, with magnetite present primarily close to the influent based on XRD analysis. Electrical measurements revealed decreases in conductivity and polarization of both columns, suggesting that electrically insulating CaCO₃ dominates the electrical response despite the presence of electrically conductive iron oxides. SEM/EDX imaging suggests that the electrical signal reflects the geometrical arrangement of the mineral phases. CaCO₃ forms insulating films on ZVI/magnetite surfaces, restricting charge transfer between the pore electrolyte and ZVI particles, as well as across interconnected ZVI particles. As surface reactivity also depends on the ability of the surface to engage in redox reactions via charge transfer, electrical measurements may provide a minimally invasive technology for monitoring reactivity loss due to CaCO₃ precipitation. Comparison between laboratory and field data shows consistent changes in electrical signatures due to iron corrosion and secondary mineral precipitation.     

Bio-beads with immobilized anaerobic bacteria,zero-valent iron,and active carbon for the removal of trichloroethane from groundwater

Chlorinated hydrocarbons are the most common organic pollutants in groundwater systems worldwide. In this study, we developed bio-beads with immobilized anaerobic bacteria, zero-valent iron (ZVI), and activated carbon (AC) powder and evaluated their efficacy in removing 1,1,1-trichloroethane (TCA) from groundwater. Bio-beads were produced by polyvinyl alcohol, alginate, and AC powder. We found that the concentration of AC powder used significantly affected the mechanical properties of immobilized bio-beads and that 1.0 % (w/v) was the optimal concentration. The bio-beads effectively degraded TCA (160 mg L^?1) in the anaerobic medium and could be reused up to six times. The TCA degradation rate of bio-beads was 1.5 and 2.3 times greater, respectively, than ZVI + AC treatment or microbes + AC treatment. Measuring FeS produced by microbial reactions indicated that TCA removal occurred via FeS-catalyzed dechlorination. Analysis of clonal libraries derived from bio-beads demonstrated that the dominant species in the community were Betaproteobacteria and Gammaproteobacteria, which may contribute to the long-term stability of ZVI reactivity during TCA dechlorination. This study shows that the combined use of immobilized anaerobic bacteria, ZVI, and AC in bio-beads is effective and practical for TCA dechlorination and suggests they may be applicable towards developing a groundwater treatment system for the removal of TCA.     

Enhanced reductive dechlorination of polychlorinated biphenyl-contaminated soil by in-vessel anaerobic composting with zero-valent iron

Anaerobic dechlorination is an effective degradation pathway for higher chlorinated polychlorinated biphenyls (PCBs). The enhanced reductive dechlorination of PCB-contaminated soil by anaerobic composting with zero-valent iron (ZVI) was studied, and preliminary reasons for the enhanced reductive dechlorination with ZVI were investigated. The results show that the addition of nanoscale ZVI can enhance dechlorination during in-vessel anaerobic composting. After 140 days, the average number of removed Cl per biphenyl with 10 mg g^?1 of added nanoscale ZVI was 0.63, enhancing the dechlorination by 34 % and improving the initial dechlorination speed. The ZVI enhances dechlorination by providing a suitable acid base environment, reducing volatile fatty acid inhibition and stimulating the microorganisms. The C/N ratios for treatments with the highest rate of ZVI addition were smaller than for the control, indicating that ZVI addition can promote compost maturity.     

Halide salts accelerate degradation of high explosives by zerovalent iron

Zerovalent iron (Fe(0), ZVI) has drawn great interest as an inexpensive and effective material to promote the degradation of environmental contaminants. A focus of ZVI research is to increase degradation kinetics and overcome passivation for long-term remediation. Halide ions promote corrosion, which can increase and sustain ZVI reactivity. Adding chloride or bromide salts with Fe(0) (1% w/v) greatly enhanced TNT, RDX, and HMX degradation rates in aqueous solution. Adding Cl or Br salts after 24h also restored ZVI reactivity, resulting in complete degradation within 8h. These observations may be attributed to removal of the passivating oxide layer and pitting corrosion of the iron. While the relative increase in degradation rate by Cl(-) and Br(-) was similar, TNT degraded faster than RDX and HMX. HMX was most difficult to remove using ZVI alone but ZVI remained effective after five HMX reseeding cycles when Br(-) was present in solution.     

Manganese and iron oxide immobilized activated carbons precursor to dead biomasses in the remediation of cadmium-contaminated waters

The aim of the present investigation was to exploit the high specific surface area of activated carbons in immobilizing the manganese and iron oxides as to obtain a suitable, efficient and cost effective and environment benign wastewater treatment process in the remediation of cadmium-contaminated waters. The manganese and iron oxides were impregnated in situ onto the surface and pores of the activated carbons precursors to the rice hulls and areca nut wastes. The solids were characterized with the help of Fourier transform infrared spectroscopy and X-ray diffraction analytical data, and the BET specific surface area as obtained. The surface morphology of these solids was discussed with the help of scanning electron microscopic images. The activated carbon samples along with the manganese and iron immobilized activated carbons were further employed in the batch and column reactor operations in the remediation of cadmium-contaminated waters. The batch data showed that an increase in sorptive pH from 2.0 to 10.0 and concentration from 1.0 to 20 mg/L favoured the uptake of cadmium by these solids. Moreover, the 1,000 times increase in background electrolyte concentrations NaNO₃ caused an insignificant decrease in cadmium uptake by these solids, which inferred that sorbing ions/species were sorbed specifically and forming ‘inner-sphere’ complexes onto the solid surface. The concentration dependence data were utilized to model various adsorption isotherms and indicated that Freundlich adsorption isotherm was reasonably fitted well. The kinetic data was fitted well to the pseudo-second-order rate equations; hence, the equilibrium sorption capacity was estimated. Furthermore, the dynamic experiments carried out by the column experiments and the breakthrough data were fitted well to the non-linear Thomas equations; accordingly, the loading capacity of the column was estimated. Iron or manganese immobilized activated carbons showed relatively higher loading capacity compared to its precursor activated carbons hence showing its possible implication in the remediation processes. Moreover, among these modified ACs, IIAC showed higher removal capacity than the MIAC solid.     

纳米级铁粉脱氯降解四氯化碳

四氯化碳的生产和使用,给人类带来了较大危害.为此,采用纳米铁粉这一新方法对其进行脱氯处理.试验以纳米级铁粉对四氯化碳的脱氯率为考察指标,选用L25(56)正交试验方案,考察了降解介质的初始pH值、纳米铁粉的质量、降解温度、摇床转速和脱氯时间5个影响因素.结果表明,pH值这一因素有极显著影响;在得出的纳米铁粉对四氯化碳脱氯的最佳工艺条件下,获得了99.5%的脱氯率,为有机氯化物脱氯开辟了一条新途径.     

Field-scale demonstration of induced biogeochemical reductive dechlorination at Dover Air Force Base, Dover, Delaware

Biogeochemical reductive dechlorination (BiRD) is a new remediation approach for chlorinated aliphatic hydrocarbons (CAHs). The approach stimulates common sulfate-reducing soil bacteria, facilitating the geochemical conversion of native iron minerals into iron sulfides. Iron sulfides have the ability to chemically reduce many common CAH compounds including PCE, TCE, DCE, similar to zero valent iron (Fe(0)). Results of a field test at Dover Air Force Base, Dover, Delaware, are given in this paper. BiRD was stimulated by direct injection of Epson salt (MgSO(4).7H(2)O) and sodium (L) lactate (NaC(3)H(5)O(3)) in five injection wells. Sediment was sampled before and 8 months after injection. Significant iron sulfide minerals developed in the sandy aquifer matrix. From ground water analyses, treatment began a few weeks after injection with up to 95% reduction in PCE, TCE, and cDCE in less than 1 year. More complete CAH treatment is likely at a larger scale than this demonstration.     

Chromate transport through columns packed with surfactant-modified zeolite/zero valent iron pellets

Chromate transport through columns packed with zeolite/zero valent iron (Z/ZVI) pellets, either untreated or treated with the cationic surfactant hexadecyltrimethylammonium (HDTMA), was studied at different flow rates. In the presence of sorbed HDTMA, the chromate retardation factor increased by a factor of five and the pseudo first-order rate constant for chromate reduction increased by 1.5-5 times. The increase in rate constant from the column studies was comparable to a six-fold increase in the rate constant determined in a batch study. At a fast flow rate, the apparent delay in chromate breakthrough from the HDTMA modified Z/ZVI columns was primarily caused by the increase in chromate reduction rate constant. In contrast, at a slower flow rate, the retardation in chromate transport from the HDTMA modified Z/ZVI columns mainly originated from chromate sorption onto the HDTMA modified Z/ZVI pellets. Due to dual porosity, the presence of immobile water was responsible for the earlier breakthrough of chromate in columns packed with zeolite and Z/ZVI pellets. The results from this study further confirm the role of HDTMA in enhancing sorption and reduction efficiency of contaminants in groundwater remediation.     

Remediation of 4-nonylphenol in aqueous solution by using free radicals generated by the oxidative reactions

Introduction

This study relates to use of zerovalent iron to generate hydroxyl free radicals and undergo subsequent oxidation to destroy 4-nonylphenol (NP) by mild process in aqueous solution and activation of oxygen gas (O₂) at room temperature. This technology is based on a novel oxidative mechanism mediated by zerovalent iron rather than commonly used reduction mechanism.

Materials and methods

A laboratory scale device consisting of a 250?ml pyrex serum vials fixed to a Vortex agitator was used. Different amounts of zerovalent iron powder (ZVI; 1, 10, and 30?g/l) at pH?4 and room temperature with bubbling of oxygen gas were investigated.

Results and conclusion

Experiments showed an observed degradation rate k _(obs) directly proportional to the amount of iron. 4-Nonylphenol degradation reactions demonstrated first-order kinetics with a half-life of about 10.5?±?0.5 and 3.5?±?0.2?min when experiments were conducted at [ZVI]?=?1 and 30?g/l respectively. Three analytical techniques were employed to monitor 4-nonylphenol degradation and mineralization: (1) spectrofluorimetry; (2) high-performance liquid chromatography; (3) total organic carbon meter (TOC meter). Results showed a complete disappearance of 4-nonylphenol after 20?min of contact with ZVI. The intermediate by-products of the reaction were not identified but the disappearance of NP was monitored by the three above-mentioned techniques.     

零价铁与厌氧微生物协同还原地下水中的硝基苯

通过间歇式实验,考察了零价铁与厌氧微生物协同还原地下水中硝基苯的效果。实验结果表明,由零价铁腐蚀为厌氧微生物提供H2电子供体还原硝基苯的效果明显优于零价铁和微生物单独作用,硝基苯去除率分别提高21.8%和57.0%。弱酸性条件有利于协同反应进行,当初始pH为5.0和6.0时,4 d后硝基苯去除率比初始pH为7.0时的提高74.4%和35.2%。增加零价铁投加量可提高协同还原的效果,零价铁最佳投加量为250 mg/L。零价铁腐蚀产生的Fe2+无法作为电子供体被微生物利用,但可作为无机营养元素促进协同过程。由于零价铁产H2速率受表面覆盖物影响不明显,在地下水修复过程中可保证协同效果并延长零价铁的使用寿命。