Degradation of nitrobenzene-containing wastewater by sequential nanoscale zero valent iron-persulfate process

As nitrobenzene(NB)is structurally stable and difficult to degrade due to the presence of an electron withdrawing group(nitro group).The sequential nanoscale zero valent iron-persulfate(NZVI-Na_(2)S_(2)O_(8))process was proposed in this study for the degradation NB-containing wastewater.The results showed that the NB degradation efficiency and the total organic carbon removal efficiency in the sequential NZVINa_(2)S_(2)O_(8)process were 100%and 49.25%,respectively,at a NB concentration of 200 mg L^(-1),a NZVI concentration of 0.75 g L^(-1),a Na_(2)S_(2)O_(8)concentration of 26.8 mmol L^(-1),an initial pH of 5,and a reaction time of 30 min,which were higher than those(88.53%and 35.24%,respectively)obtained in the NZVI/Na_(2)S_(2)O_(8)process.Sulfate radicals(SO_(4)·-)and hydroxyl radicals(·OH)generated in the reaction were identified directly by electron paramagnetic resonance spectroscopy and indirectly by radical capture experiments,and it was shown that both SO_(4)^(·-)and·OH played a major role in the sequential NZVI-Na_(2)S_(2)O_(8)process.The possible pathways involved in the reduction of NB to aniline(AN)and the further oxidative degradation of AN were determined by gas chromatography-mass spectrometry.

Sorption Kinetic of Arsenate as Water Contaminant on Zero Valent Iron

This study investigates the sorption of arsenate from water using zero-valent iron ZVI as sorbent. Batch experiments were carried out to study the sorption kinetics of arsenate under different concentrations of arsenate varies from 0.5 to 200 mg/l. A kinetic model was considered to describe the arsenates sorption on ZVI material. The kinetics of the arsenate sorption processes were described by the Langmuir kinetic model. The sorption capacity increases with high initial concentration which obtained the maximum sorption 2.1 mg/g at 200 mg/l of arsenate initial concentration. The results show that the rapid initial sorption rates of arsenate were occurred at the beginning of experiments running time, followed by a slower removal that gradually approaches an equilibrium condition. The data from laboratory batch experiments were used to verify the simulation results of the kinetic model resulting in good agreement between measured and modeled results. The results indicate that ZVI could be employed as sorbent materials to enhance the sorption processes and increase the removal rate of arsenate from water.

Remediation of Malathion Contaminated Soil Using Zero Valent Iron Nano-Particles

In this study, iron nano-particles were used to remediate malathion contaminated soil in the concentration range of 1 - 10 μg?g–1. The zero valent iron nano-particles were prepared by reducing ferric chloride solution with sodium boro- hydride for remediation of the soil. The optimized quantity of iron nano particles was found to be 0.1 g?kg–1 of soil con- taminated with 10 μg?g–1 of malathion. Malathion was determined in the soil after leaching to water at pH 8.2 and fol- lowed by its oxidation with slight excess of N-bromosuccinimide (NBS). The unconsumed NBS was estimated by measuring the decrease in the color intensity of rhodamine B. Degradation product formed during the oxidation of ma-lathion by zero valent iron was monitored by the Attenuated Total Reflectance Fourier Transform Infrared Spectros- copy (ATR-FTIR). The results clearly showed that quantitative oxidation of malathion was achieved within eight min- utes after the addition of zero valent iron nano particles.

Evaluating Effectiveness and Permanence of Selenium Treatment in a Solid Matrix via Aqueous-Mediated Zero Valent Iron Reaction

Increasingly, as regulatory limits become more stringent, selenium has become a parameter of concern. Selenium is a naturally occurring element that is largely mobilized by anthropogenic activity such as mining for fuel and subsequent combustion, metal ore refining and processing, and agricultural irrigation. Of concern is removing selenium liquid matrices and immobilizing it from leachable solid matrices. Chemical reduction and stabilization using zero valent iron (ZVI) is applicable to both concerns. The solid matrix case study is applicable to ash ponds solids or industrial bag house dust solids. This paper presents data for treatment and stabilization of selenium within a solid matrix using ZVI. The methodology uses an aqueous mediate reaction to promote a stable solid matrix of non-leachable selenium. The paper describes matrix challenges and key variables that effected successful treatment. Testing with simulated and real bag house dust solids were used to establish data to support the permeance of the reaction. The data show that ZVI converts ionic selenium to a zero valent state in the solid matrix. It was also recognized that a fraction of ionic selenium may fail to react with the ZVI, but the results show that despite the presence of the unreacted ionic selenium, the toxicity characteristic leachate procedure (TCLP) results following treatment do not exceed the 1 mg/L hazardous waste criteria.

Dechlorination of chlorophenols by zero valent iron impregnated silica

Laboratory studies were conducted to find out the efficacy of uniquely prepared zero valent iron impregnated silica in transforming xenobiotic chlorophenols namely 4-chlorophenol, 2,4-dichlorophenol and 2,4,6-trichlorophenol. Continuous mode column experiments were performed to investigate the transformation of chlorophenols by varying pH, column height, flow rate and initial chlorophenol concentration. Reusability study of the zero valent iron impregnated silica was studied as well as the morphological changes and the chemical composition of the catalyst medium were also investigated. Dechlorination kinetic studies were conducted and the order of dechlorination of chlorophenols was found to be 2,4,6-trichlorophenol 〉 2,4-dichlorophenol 〉 4-chlorophenol. The optimum pH, column height and flow rate were found to be 7, 20 cm and 0.75 L/hr respectively for all chlorophenols in the reaction duration of 4 hr. Intermediates formed during dechlorination study were identified by gas chromatography-mass spectroscopy analysis. This method was applied to real pulp and paper wastewater and was found satisfactory.

Steady performance of a zero valent iron packed anaerobic reactor for azo dye wastewater treatment under variable influent quality

Zero valent iron （ZVI） is expected to help create an enhanced anaerobic environment that might improve the performance of anaerobic treatment. Based on this idea, a novel ZVI packed upflow anaerobic sludge blanket （ZVI-UASB） reactor was developed to treat azo dye wastewater with variable influent quality. The results showed that the reactor was less influenced by increases of Reactive Brilliant Red X-3B concentration from 50 to 1000 mg/L and chemical oxygen demand （COD） from 1000 to 7000 mg/L in the feed than a reference UASB reactor without the ZVI. The ZVI decreased oxidation-reduction potential in the reactor by about 80 mV. Iron ion dissolution from the ZVI could buffer acidity in the reactor, the amount of which was related to the COD concentration. Fluorescence in situ hybridization test showed the abundance of methanogens in the sludge of the ZVI-UASB reactor was significantly greater than that of the reference one. Denaturing gradient gel electrophoresis showed that the ZVI increased the diversity of microbial strains responsible for high efficiency.

Reductive immobilization and long-term remobilization of radioactive pertechnetate using bio-macromolecules stabilized zero valent iron nanoparticles

Reductive immobilization of radioactive pertechnetate(99TcO4^-) in simulated groundwater was studied by prepared carboxymethyl cellulose(CMC) and starch stabilized zero valent iron nanoparticles(nZVI),and long-term remobilization of reduced Tc was also evaluated under anoxic and oxic conditions.The stabilized nZVI can effectively reduce soluble 99Tc(Ⅶ) to insoluble 99 Tc(Ⅳ),and they can be easily delivered into a contaminated groundwater zone and facilitate in situ remediation.In this study,CMCstabilized nZVI showed higher reactivity than that using starch as the stabilizer.Batch experiments indicated that more than 99% of 99 Tc(Ⅶ)(CO=12 mg/mL) was reduced and removed from groundwater by CMC-stabilized nZVI with a CMC content of 0.2%(w/w) at a broad pH of 5-8.X-ray diffraction(XRD)and X-ray photoelectron spectroscopy(XPS) analyses further confirmed that 99Tc(Ⅶ)O4^-transformed into 99Tc(Ⅳ)O2(s).The presence of bicarbonate exhibited insignificant effect on Tc immobilization,while humic acid(HA) inhibited reaction mainly due to retardation on electron transfer and formation of Tc(IV)-HA complexes.More interesting,the immobilized Tc(Ⅳ) remained insoluble even after 120 d under anoxic condition,while only^21 % was remobilized when exposed to air.Therefore,biomacromolecules stabilized nZVI nanoparticles could be a viable alternative for in situ remediation of radioactive contamination in groundwater.

Advanced treatment of biologically pretreated coking wastewater by intensified zero-valent iron process(IZVI) combined with anaerobic filter and biological aerated filter(AF/BAF)

Experiments were conducted to investigate the behavior of the sequential system of intensified zero-valent iron process(IZVI) and anaerobic filter and biological aerated filter(AF/BAF) reactors for advanced treatment of biologically pretreated coking wastewater. Particular attention was paid to the performance of the integrated system for the removal of chemical oxygen demand(COD), ammonia nitrogen(NH3-N) and total nitrogen(TN). The average removal efficiencies of COD, NH3-N and TN were 76.28%, 96.76% and 59.97%, with the average effluent mass concentrations of 56, 0.53 and 18.83 mg/L, respectively, reaching the first grade of the national discharge standard. Moreover, the results of gas chromatography/mass spectrum(GC/MS) and gel permeation chromatography(GPC) analysis demonstrated that the refractory organic compounds with high relative molecular mass were partly removed in IZVI process by the function of oxidation-reduction, flocculation and adsorption which could also enhance the biodegradability of the system effluent. The removal efficiencies of NH3-N and TN were achieved mainly in the subsequent AF/BAF reactors by nitrification and denitrification. Overall, the results obtained show that the application of IZVI in combination with AF/BAF is a promising technology for advanced treatment of biologically pretreated coking wastewater.

Combined zero valent iron and hydrogen peroxide conditioning significantly enhances the dewaterability of anaerobic digestate

The importance of enhancing sludge dewaterability is increasing due to the considerable impact of excess sludge volume on disposal costs and on overall sludge management. This study presents an innovative approach to enhance dewaterability of anaerobic digestate（AD） harvested from a wastewater treatment plant. The combination of zero valent iron（ZVI, 0–4.0 g/g total solids（TS）） and hydrogen peroxide（HP, 0–90 mg/g TS） under pH 3.0 significantly enhanced the AD dewaterability. The largest enhancement of AD dewaterability was achieved at 18 mg HP/g TS and 2.0 g ZVI/g TS, with the capillary suction time reduced by up to 90%. Economic analysis suggested that the proposed HP and ZVI treatment has more economic benefits in comparison with the classical Fenton reaction process. The destruction of extracellular polymeric substances and cells as well as the decrease of particle size were supposed to contribute to the enhanced AD dewaterability by HP ＋ ZVI conditioning.

Environmental application and ecological significance of nano-zero valent iron

Toxicity studies considering both the bare and stabilized forms of zero valent iron nanoparticles（nZVI） could be timely, given that ecological risks identified are minimized through modification or with substitution of approaches in the synthesis, development and environmental application of the nanoparticles before succeeding to volume production.This review is focused on the fate, transport and toxicological implications of the bare nZVI and surface modified particles used for environmental applications.

Oxidative degradation of phenol by sulfidated zero valent iron under aerobic conditions:The effect of oxalate and tripolyphosphate ligands

After adding either organic or inorganic ligands,sulfidated nano-zero-valent iron(Sn ZVI)was used for aerobic degradation of phenol,and the effect of the ligand species on oxidation performance was investigated.We found that Sn ZVI hardly degraded phenol in the absence of ligand addition.Ligands initiated and promoted the degradation of pollutants by Sn ZVI.The data herein show that a characteristic inorganic ligand,tripolyphosphate(TPP),is more effective in enhancing oxidation than a characteristic organic ligand oxalate.In addition to the scavenging of reactive oxidants by the organic ligand,more ferrous ion(Fe(Ⅱ))dissolution from Sn ZVI in the TPP system is another cause for the superior enhancement by the inorganic ligand.In the oxalate system,as the sulfur content of Sn ZVI increased,the oxidation efficiency increased because Fe S shell promoted the transfer of electrons to produce more reactive oxygen species(ROS).In TPP system,the effect of sulfur content on oxidation performance is more complex.The Sn ZVI with low sulfur content showed poor oxidation performance compared with that of n ZVI.Further experiments proved that sulfidation might weaken the complexation of TPP with surface bound Fe,which would slow down the ionic Fe(II)dissolution rate.Therefore,sulfidation has the dual effects of enhancing electron transfer and inhibiting the complexation of inorganic ligands.In addition,the mechanisms of ROS generation in different ligand systems were investigated herein.Results showed that the critical ROS in both the oxalate and TPP systems are hydroxyl radicals,and that they are produced via one-electron activation of O_(2).

Quantification of changes in zero valent iron morphology using X-ray computed tomography

Morphological changes within the porous architecture of laboratory scale zero valent iron （ZVI） permeable reactive barriers （PRBs）, after exposure to different groundwater conditions, have been quantified experimentally for different ZVI/sand ratios （10%, 50% and 100%, W/W） with the aim of inferring porosity changes in field barriers. Column studies were conducted to simulate interaction with different water chemistries, a synthetic groundwater, acidic drainage and deionised （DI） water as control. Morphological changes, in terms of pore size and distribution, were measured using X-ray computed tomography （CT）. CT image analysis revealed significant morphological changes in columns treated with different water chemistries. For example, 100% ZVI （W/W） columns had a higher frequency of small pores （0.6 mm） was observed in ZVI grains reacted with typical groundwater, resulting in a porosity of 27%, compared to 32% when exposed to DI water. In comparison, ZVI grains treated with the acidic drainage had higher porosity （44%） and larger average pore size （2.8 mm）. 10% ZVI PRB barrier material had the highest mean porosity （56%） after exposure to any water chemistry whilst 100% ZVI （W/W） columns always had the lowest （34%） with the 50% ZVI （W/W） in between （40%）. These results agree with previously published PRB field data and simultaneously conducted geochemical monitoring and mass balance calculation, indicating that both the geochemical and hydraulic environment of the PRB play an important role in determining barrier lifespan. This study suggests that X-ray CT image analysis is a powerful tool for studying the detailed inter pores between ZVI grains within PRBs.

Synthesis of nanoscale zero-valent iron supported on exfoliated graphite for removal of nitrate

Nano ZVI particles supported on micro-scale exfoliated graphite were prepared by using KBH4 as reducing agent in the H2O/ethanol system. The supported ZVI materials generally have higher activity and greater flexibility for environmental remediation applications. The exfoliated graphite as the support was treated beforehand to hydrophilic material. Nano iron particles are deposited onto the rough graphite surface while those were formed by borohydride reduction. The possible nitrate reduction pathways were proposed. The TEM image shows that iron particles are highly dispersed on the surface of graphite and several of iron particles are imbedded in the pit of support surface. In this synthesis, iron particles have a nearly spherical shape with a grain size of 50?100 nm. The surface areas of materials with different iron loadings of 3.5%, 7.0%, 10.0%, 15.0% and 20.0%(mass fraction) are 2.89, 9.55, 8.45, 23.8 and 6.18 m2·g?1 by BET surface analyzer. The chemical reduction of nitrate by supported nano ZVI in aqueous solution were tested in series batch experiments. Experiment results suggest that NO3? can be more rapidly reduced to NH4+ at neutral pH and anaerobic conditions by supported nano ZVI than unsupported nano ZVI or ZVI scraps. The 15% nano Fe/graphite shows the best reduction efficiency contrasted with other Fe loading particles.

Treatment of simulated wastewater containing Reactive Red 195 by zero-valent iron/activated carbon combined with microwave discharge electrodeless lamp/sodium hypochlorite

A comparative study of treatment of simulated wastewater containing Reactive Red 195 using zero-valent iron/activated carbon （ZVI/AC）, microwave discharge electrodeless lamp/sodium hypochlorite （MDEL/NaCIO） and the combination of ZVI/AC- MDEL/NaCIO was conducted. The preliminary results showed the two steps method of ZVI/AC-MDEL/NaCIO had much higher degradation efficiency than both single steps. The final color removal percentage was nearly up to 100% and the chemical oxygen demand reduction percentage was up to approximately 82%. The effects of operational parameters, including initial pH value of simulated wastewater, ZVI/AC ratio and particle size of ZVI were also investigated. In addition, from the discussion of synergistic effect between ZVI/AC and MEDL/NaCIO, we found that in the ZVI/AC-MEDL/NaCIO process, ZVI/AC could break the azo bond firstly and then MEDLfNaCIO degraded the aromatic amine products effectively. Reversing the order would reduce the degradation efficiency.

Reductive transformation and detoxification mechanism of 2,4-dinitrochlorobenzene in combined zero valent iron and anaerobic-aerobic process

A combined zero valent iron （ZVI） and anaerobic-aerobic process was adopted for the treatment of 2,4-dinitrochlorobenzene （DNCB）- containing wastewater. The transformation pathway, reduction of acute toxicity and enhancement of biodegradability were investigated, After pretreatment by ZVI, DNCB in wastewater could be completely converted into 2,4-diaminochlorobenzene （DACB）. The ratio of BODs/COD increased from 0.005±0.001 to 0.168±0.007, while EC50,48hr （V/V） increased from 0.65% to 5.20%, indicating the enhancement of biodegradability and reduction of acute toxicity with the pretreatment by ZVI. DACB was further dechlorinated to m-phenylenediamine during the anaerobic process using methanol as electron donor, with EC50＇ 48 hr increasing from 5.20% to 48.2%. After the subsequent anaerobic-aerobic process, m-phenylenediamine was degraded completely, with effluent COD of 67.5±10.8 mg/L. This effluent of the subsequent anaerobic-aerobic process was not toxic to zebrafish. The combined ZVI and anaerobic-aerobic process offers bright prospects for the treatment of chlorinated nitroaromatic compound-containing wastewater.

Ligand-mediated contaminant degradation by bare and carboxymethyl cellulose-coated bimetallic palladium-zero valent iron nanoparticles in high salinity environments

The application of nanoscale zero-valent iron(nZVI) for the degradation of contaminants has been extensively investigated, however, few studies have focused on degradation in high salinity environments. In this study, the ability of bare and carboxymethyl cellulose(CMC)-coated bimetallic Pd-nZVI particles to degrade 33′44′-tetrachlorobiphenyl in high saline water(SW) is examined with particular attention given to the effects of ethylenediaminetetraacetic acid(EDTA) on the rate of degradation. EDTA enhances the reactivity of Pd-nZVI in SW, with evidence provided to link this to the removal of the passivating layer. Additionally, a conceptual model is proposed which provides a quantitative description of the removal of these iron oxide layers in the presence of EDTA. An optimum EDTA to bare Pd-nZVI molar ratio of 0.1 exists, with insufficient EDTA unable to remove the passivating layer whilst excess EDTA results in Fe loss and enhanced agglomeration due to magnetic attraction of the bare Fe(0) particles. In contrast, CMCcoating of Pd-nZVI assemblages actually impedes degradation, despite the coated particles displaying a smaller average size compared to uncoated particles, with even the presence of EDTA in this case not significantly improving degradation. The reduced reactivity in the presence of CMC is primarily attributed to the effect of CMC on the association of Pd with nZVI particles. In particular, the presence of CMC reduced the total amount of Pd incorporated with the stabilized particles compared to the non-stabilized particles.Additionally, the presence of CMC results in less Pd present in its reactive zero-valent oxidation state.

H₂Gas Charging of Zero-Valent Iron and TCE Degradation

Granular zero-valent iron (ZVI) has been widely used to construct permeable reactive barriers (PRB) for the in situ remediation of groundwater contaminated with halogenated hydrocarbons. In the anaerobic condition of most groundwater flow systems, iron undergoes corrosion by water and results in hydrogen gas generation. Several studies have shown that some of the hydrogen gas generated at the iron/water interface can diffuse into the iron lattice. Hydrogen gas also can be an electron donor for dechlorination of chlorinated compounds. In this study, the possibility of hydrogen gas bound in the lattice of ZVI playing a role in dehalogenation and improving the degradation efficiency of ZVI was evaluated. Two different granular irons were tested: one obtained from Quebec Metal Powders Ltd (QMP) and the other from Connelly-GPM. Ltd. For each type of iron, two samples were mixed with water and sealed in testing cells. Since the rate of hydrogen entry varies directly with the square root of the hydrogen pressure, one sample was maintained for several weeks under near-vacuum conditions to minimize the amount of hydrogen entering the iron lattice. The other sample was maintained for the same period at a hydrogen pressure of over 400 kPa to maximize the amount of hydrogen entering the iron lattice. The degradation abilities of the reacted ironsand the original iron materials were tested by running several sets of batch tests. The results of this study show little to no improvement of inorganic TCE degradation reactions due to the presence of lattice-stored hydrogen in iron material. This is probably due to the high energiesrequired to release hydrogen trapped in the iron lattice. However, there are certain chemical compounds that can promote hydrogen release from the iron lattice, and there may be bacteria that can utilize lattice-bound hydrogen to carry out dechlorination reactions.

Application of Iron Nanoparticles Synthesized by Green Tea for the Removal of Hexavalent Chromium in Column Tests

Nano zero valent iron particles (nZVI) are popular the last few years because of the numerous applications in remediation of a wide range of pollutants in contaminated soils and aquifers. The nZVI particles can be 10 - 1000 times more reactive than granular or micro-scale ZVI particles due to the small particle size, large specific surface area and high reactivity. An alternative green synthesis procedure was used for the production of nano zero valent iron particles (nZVI) using green tea (GT) extract, which is characterized by its high antioxidant content. Polyphenols in green tea extract possess double role in the synthesis of nZVI, because they not only reduce ferric cations, but also protect nZVI from oxidation and agglomeration as capping agents. The objective of current study was to simulate ata laboratory scale the attachment of GT-nZVI particles on soil material and study the effectiveness of attached nanoparticles for removing hexavalent chromium (Cr(VI)) from contaminated groundwater flowing through the porous soil bed. Column tests were carried out with various flowrates in order to examine the effect of contact time between the attached on porous medium nZVI and the flow-through solution on Cr(VI) reduction. After the completion of column tests the soil material in each column was split in 5 vertical sections, which were further subjected to chemical analyses and leaching tests. According to the results of the study increasing the contact time favors the reduction and removal of Cr(VI) from the aqueous phase. The reductive precipitation of Cr can be described as a reaction that follows a pseudo-first order kinetic law, with rate constant equal to k = 0.0243 ± 0.0011 min-1. Leaching tests indicated that precipitated chromium is not soluble. In the examined soil material, the total amount of precipitated Cr was found to range between 280 and 890 mg/(kg soil), while soluble Cr was less than 1.4 mg/kg and most probably it was due to the presence of residual Cr(VI) solution in the porosity of soil.

零价铁活化过硫酸盐降解土壤中邻苯二甲酸酯

为了探究零价铁(ZVI)活化过硫酸盐(PS)对土壤邻苯二甲酸二(2-乙基己基)酯(DEHP)的降解效率、最优降解条件及对土壤性质的影响,该文通过单因素实验和正交实验,研究初始pH值、水土比、PS浓度、ZVI添加量、反应时间对DEHP降解效率的影响,同时探讨了氧化体系对土壤理化性质和速效养分的影响。结果表明,5个因素对DEHP降解率的影响程度依次为PS>初始pH>ZVI添加量>水土比>反应时间。当初始pH为3、水土比4∶1、PS浓度为1 mmol/g、ZVI添加量为0.5 mmol/g、反应80 min时DEHP降解率在75.12%~80%之间,降解效果最佳。ZVI/PS氧化体系对土壤性质影响较大,随着PS浓度增加,土壤pH、土壤有机质含量呈现不同程度的降低,土壤电导率和氧化还原电位呈递增趋势。当同时加入PS和ZVI时,速效氮含量显著增大;单独向土壤溶液中添加ZVI或PS均使土壤速效磷含量显著增高,当土壤溶液中同时添加PS和ZVI后,速效磷含量急剧下降;而当ZVI或PS的浓度比≥1时,速效钾含量急剧下降,降幅达到76%。在实际修复PAEs污染土壤时要充分评估氧化剂添加量对土壤性质的影响,该研究可为ZVI活化PS去除土壤环境介质中的DEHP提供了理论和实践依据。