Capacity of Cr(VI) reduction in an aqueous solution using different sources of zerovalent irons

Zerovalent iron (ZVI) has drawn intense interest as an effective and inexpensive tool to enhance degradation of various environmental contaminants. Reduction of Cr(VI) to Cr(III) by ZVI merits environmental concern as a hazardous species is transformed into a non-hazardous one. Objectives of this research were to assess kinetics and capacity of Cr(VI) reduction by different sources of ZVIs, of which chemical parameters can base in situ application of ZVI to treat Cr(VI) contaminated water. Reduction kinetics were first-order and rapid showing that 50% of the initial Cr(VI) was reduced within 7.0 to 347 min depending on Cr(VI) concentration, temperature and ZVI source. The reduction rates were increased with decreasing the initial Cr(VI) concentrations and increasing the reaction temperatures. The J ZVI (Shinyo Pure Chemical Co., Japan) was more effective in Cr(VI) reduction than PU (Peerless Metal Powders, USA). The maximum reduction capacities of J and PU ZVIs at 25°C were 0.045 and 0.042 mmol g⁻¹ Fe⁰, respectively. A relatively higher value of the net reaction energy (E _a ) indicated that Cr(VI) reduction by ZVI was temperature dependent and controlled by surface properties of ZVI. Chemical parameters involved in the Cr(VI) reduction by ZVI such as temperature quotient, kinetic rates, and stoichiometry indicated that the ZVI might be effective for in situ treatment of the Cr(VI) containing wastewater.     

Removal behavior of Cu(II) during Cr(VI) reduction by cast iron powder in absence and presence of ultrasound

ABSTRACT

Cu(II) is an important and typical heavy metal ion in the wastewater containing Cr(VI), and its removal during Cr(VI) reduction by zero valent iron (ZVI) may make it separately be recovered as a kind of copper resource. In this study, the removal behavior of Cu(II) during Cr(VI) reduction by cast iron powder in absence and presence of ultrasound was investigated by atomic absorption spectrometry (AAS), X-ray powder diffractometer (XRD), scanning electron microscope-energy dispersion spectrum (SEM-EDS) and X-ray photoelectron spectroscopy (XPS). The AAS tests indicated that the ultrasound could not only obviously enhance the removal of Cu(II) but also improve the reduction rate of Cr(VI). The XRD and SEM-EDS analyses showed that Cu(II) in the solution was reduced to metallic copper and then was deposited at the surface of ZVI. The ultrasound could remove the Fe-Cr oxides and hydroxides at the ZVI surfaces, resulting in the active surfaces of iron increased. The XPS analyses demonstrated that the surface of metallic copper would be transformed into the film of copper oxide (CuO) in the ultrasound system. The obtained metallic copper and copper oxide could be recovered alone by traditional method of the acid pickling.     

Removal of Cr(VI) from wastewater by adsorption on iron nanoparticles

Due to rapid industrialisation, the presence of heavy metals in water and wastewater is a matter of environmental concern. Though some of the metals are essential for our system but if present beyond their threshold limit value (TLV), they are harmful and their treatment prior to disposal becomes inevitable. The present communication has been addressed to the removal of Cr(VI) from aqueous solutions by nanoparticles of iron. Nanoparticles of iron were prepared by sol–gel method. The characterisation of the nanoparticles was carried out by XRD and TEM analysis. Batch experiments were adopted for the adsorption of Cr(VI) from its solutions. The effect of different important parameters such as contact time and initial concentration, pH, adsorbent dose, and temperature on removal of chromium was studied. The removal of chromium increased from 88. 5% to 99.05% by decreasing its initial concentration from 15 to 5 mg L^?1 at optimum conditions. Removal of Cr(VI) was found to be highly pH dependent and a maximum removal (100%) was obtained at pH 2.0. The process of removal was governed by first and pseudo‐second‐order kinetic equations and their rate constants were determined. The process of removal was also governed by intraparticle diffusion. Values of the thermodynamic parameters viz. ΔG°, ΔH°, and ΔS° at different temperatures were determined. The data generated in this study can be used to design treatment plants for chromium rich industrial effluents. Adsorption results indicate that nanoiron particles can be effective for the removal of chromium from aqueous solutions.     

Electrospinning of polyacrylonitrile nanofibers embedded with zerovalent iron and cerium oxide nanoparticles,as Cr(VI) adsorbents for water treatment

Zerovalent iron (ZVI) and cerium oxide (CeO₂) nanoparticles (NPs) embedded in polyacrylonitrile nanofibers (NFs) were obtained via electrospinning. Each NF was characterized using Fourier transform infrared spectroscopy and X-ray diffraction. The scaffold morphology and average diameter of the NFs were determined using scanning electron microscopy (SEM). Energy dispersive X-ray spectroscopy (EDS) mapping and Raman spectroscopy were used to characterize the NPs dispersion in the NFs. The Cr(VI) removal efficiency (%E) of ZVI and CeO₂ NPs was compared with the efficiency of their corresponding NFs. CeO₂ NPs showed 79% Cr(VI) removal; the efficiency was better for their NFs (96%). Regeneration of ZVI NFs was 98 %E. ZVI NPs were the best adsorbent with 99.9% efficiency. An adsorption mechanism was proposed using Langmuir, Freundlich, and Temkin isotherm models. SEM–EDS analyses revealed that Cr adsorbed on the NP and NF surfaces. © 2019 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2019 , 137, 48663.     

Reduction of Cr(VI) by palladized biomass of Desulfovibrio vulgaris NCIMB 8303

Palladized biomass of Desulfovibrio vulgaris (Bio‐Pd(0)) reduced Cr(VI) to Cr(III) at an initial rate four‐fold higher than chemically‐prepared Pd(0) metal. Optimal Cr(VI) reduction by suspended Bio‐Pd(0) occurred at pH 3, whereas pH did not affect the rate of Cr(VI) reduction by Bio‐Pd(0) immobilized in agar beads. The rate of Cr(VI) reduction was concentration‐dependent below 300 µmol dm^?3, and application of enzyme kinetics, considering Bio‐Pd(0) as an ‘artificial enzyme’, gave an apparent K_m (K_mapp) of approx. 650 µmol dm^?3 and V_max of 1667 nmol h^?1 mg Pd(0) for suspended Bio‐Pd(0). The potential of Bio‐Pd(0) as a method for the treatment of Cr(VI)‐wastes is discussed. Copyright © 2005 Society of Chemical Industry     

A simple mathematical analysis on the effect of sand in Cr(VI) reduction using zero valent iron

A simple mathematical model was proposed to analyze the enhancement of Cr(VI) reduction when sand materials are added to the zero valent iron (ZVI). Natural decay of Cr(VI) in a control experiment was analyzed by using a zero-order decay reaction. Adsorption kinetics of Cr(VI) to sand was modeled as a first-order reversible process, and the reduction rate by ZVI was treated as a first-order reaction. Natural decay of Cr(VI) was also included in other experiments, i.e., the adsorption to sand, the reduction by ZVI, and both adsorption and reduction when sand and ZVI are present together. The model parameters were estimated by fitting the solution of each model to the corresponding experimental data. To observe the effect of sand addition to ZVI, both adsorption and reduction rate models were considered simultaneously including the natural decay. The solution of the combined model was fitted to the experimental data to determine the first-order adsorption and reduction rate constants when sand as well as ZVI is present. The first-order reduction rate constant in the presence of sand was about 35 times higher than that with ZVI only.     

Removal of Chromium(VI) and Chromium(III) from Aqueous Solution by Grainless Stalk of Corn

Abstract

Grainless stalk of corn (GLSC) was tested for removal of Cr(VI) and Cr(III) from aqueous solution at different pH, contact time, temperature, and chromium/adsorbent ratio. The results show that the optimum pH for removal of Cr(VI) is 0.84, while the optimum pH for removal of Cr(III) is 4.6. The adsorption processes of both Cr(VI) and Cr(III) onto GLSC were found to follow first-order kinetics. Values of k _ads of 0.037 and 0.018 min^?1 were obtained for Cr(VI) and Cr(III), respectively. The adsorption capacity of GLSC was calculated from the Langmuir isotherm as 7.1 mg g^?1 at pH 0.84 for Cr(VI), and as 7.3 mg g^?1 at pH 4.6 for Cr(III), at 20°C. At the optimum pH for Cr(VI) removal, Cr(VI) reduces to Cr(III). EPR spectroscopy shows the presence of Cr(V) + Cr(III)-bound-GLSC at short contact times and adsorbed Cr(III) as the final oxidation state of Cr(VI)-treated GLSC. The results indicate that, at pH ≈ 1, GLSC can completely remove Cr(VI) from aqueous solution through an adsorption-coupled reduction mechanism to yield adsorbed Cr(III) and the less toxic aqueous Cr(III), which can be further removed at pH 4.6.     

Influence of photoirradation on reduction of hexavalent chromium by zero-valent iron in the presence of organic acids

Reduction of hexavalent chromium (Cr(VI)) by zero-valent iron (Fe⁰) was investigated systematically in the present study. No change in Cr(VI) concentration occurs using untreated Fe⁰ powders even after a long contact time. The Fe⁰ powders treated with acid washing shows a weak activity and a poor long-term performance to reduction of Cr(VI). The activity and long-term performance of treated Fe⁰ powders is not effectively improved in the presence of citric acid. In contrast, introduction of photoirradiation not only dramatically increases the reduction rate of Cr(VI) in the presence of citric acid but also effectively stabilizes the activity of Fe⁰ powders and films. Such enhancement should be attributed to photoreductive dissolution of the oxide layer on Fe⁰ surface. For this newly developed system, effective reduction of Cr(VI) is favored at low pH values and oxalic and tartaric acid are also effective as complex reagents.     

Adsorption Characteristics of Chromium(VI) Ions onto Fe(III)-Coordinated Amino-Functionalized Poly(glycidylmethacrylate)-Grafted TiO2-Densified Cellulose

An investigation was conducted with a newly developed adsorbent, iron(III)- coordinated amino-functionalized poly(glycidylmethacrylate)-grafted TiO₂-densified cellulose (Fe(III)-AM-PGDC) on the removal of chromium(VI) from aqueous solution. Batch experiments were performed under various conditions of time, pH, concentration, dose, ionic strength, and temperature. Adsorption of Cr(VI) on Fe(III)-AM-PGDC was dominated by ion exchange or outer-sphere complexation. The maximum adsorption capacity was found to be 109.76 mg g^?1. Thermodynamic study showed that adsorption of Cr(VI) onto Fe(III)-AM-PGDC is more favored. The complete removal of Cr(VI) from electroplating wastewater was achieved by the adsorbent. The adsorbent did not lose its adsorption capacity even after the fourth regeneration.     

Dynamical modeling of the electrochemical process to remove Cr (VI) from wastewaters in a tubular reactor

This work is aimed at obtaining and calibrating a dynamical model of the electrochemical reduction of Cr(VI) in a tubular continuous reactor with a spiral wire shaped anode at different conditions of pH (1.0 to 2.0) and residence times. An industrial wastewater sampled from a Mexican electroplating industry with about 1000 mg dm^?3 of Cr(VI) was used for the experiments. It was found that pH exerts a strong influence on the performance of electrochemical reduction of Cr(VI). Thus at a wastewater influent pH = 1.0 and a residence time in the reactor of 38.5 min it is possible to reduce the Cr(VI) concentration from 1000 to 0.37 mg dm^?3. However at an influent pH higher than 1.5, an effluent Cr(VI) concentration lower than 0.5 mg dm^?3 cannot be obtained. A more complete dynamic model was applied incorporating pH and the dispersion effects that affect the electrochemical Cr(VI) removal. The model, which adequately describes the performance of the electrochemical process, can be used to optimize the performance of this kind of reactor with more reliability. Copyright © 2007 Society of Chemical Industry     

Chromium (VI) removal from water using starch coated nanoscale zerovalent iron particles supported on activated carbon

Starch coated nanoscale zerovalent iron (S-nZVI) was immobilized in activated carbon (AC) and its Cr (VI) removal characteristics were studied. Macroscopic evidence and mechanism analysis proved that S-nZVI and AC were closely linked and mutual complementary. Different factors including pH of the original solution, reaction time, and mass ratio (S-nZVI@AC/Cr =10:1, 20:1, 30:1, 50:1, 60:1, 70:1) were studied to analyze the removal rate. Results showed that the removal rate of Cr (Ⅵ) could reach 99.96% under the condition of pH of 5, and temperature =25?°C, when the mass ratio of S-nZVI@AC/Cr was 60:1. The removal of Cr(Ⅵ) by S-nZVI@AC followed pseudo-second-order kinetics. X-ray diffraction (XRD) resulted demonstrate that S-nZVI@AC existed in a Fe₃C state before reaction and in a Fe(III) state after reaction. XPS (X-ray photoelectrons spectroscopy) analysis suggested that the mechanism of Cr (VI) removal by S-nZVI@AC is adsorption and reduction. S-nZVI@AC might be a potential composite material for the purification and detoxification of Cr (VI) in water because of its efficiency and stability.     

Boron-Doped Diamond Electrode Performance in Cr(VI) Reduction Using Synthetic and Plating Wastewater

The goal of this work was to evaluate the effectiveness of iron and boron-doped-diamond (BDD) as cathodic electrodes on the reduction of Cr(VI) in synthetic and wastewater samples. The pH and electrolyte composition were varied, and the effect on the Cr(VI) reduction rate was measured. The optimized conditions from the synthetic water Cr(VI) reduction experimental data, were tasted on electroplating wastewater. The results indicated that both a pH of 2 and the use of NaCl as an electrolyte significantly increase the Cr(VI) reduction rate for all synthetic systems, especially the iron-BDD system. The Cr(VI) reduction rate in Fe-BDD systems was also affected by nitrate and sulfate ions. In the case of electroplating wastewater, Cr(VI) reduction by BDD cathodes was faster than with iron cathodes, achieving a complete reduction of 180 mg Cr(VI)/L in 25 min, with 40% less sludge produced. The elemental composition of sludge was analyzed using SEM/EDS and X-ray spectroscopy to confirm that iron and chromium precipitated out of the solution. The sludge had a chemical composition of (31.9%) Fe₂O₃, (29.6%) FeOOH, (21%) FeO, and (17.4%) FeSO₄. Therefore, BDD as an electrode material effectively reduces Cr(VI) in electroplating wastewater, and can be effectively scaled up to industrial applications.     

颗粒活性炭载纳米零价铁去除水中的Cr(Ⅵ)

以Fe2+溶液为原料、NaBH4为还原剂,采用传统液相还原技术合成了颗粒活性炭(GAC)载纳米零价铁(nZVI)复合材料GAC-nZVI,用扫描电镜对GAC-nZVI进行表征,通过间歇实验考察了其对去除Cr(VI)的影响。结果表明,GAC能阻止nZVI颗粒聚集,合成的GAC-nZVI能有效去除水中的Cr(VI)。在Cr(VI)初始浓度50 mg/L、温度40℃和pH=2.0、投加GAC-nZVI 3.0 g/L的条件下反应5 min,Cr(VI)去除率为99.4%。pH=2.0?4.0时,处理后水中总铬浓度均低于1 mg/L,表明残留少量Cr(III)。随pH值和Cr(VI)浓度增加,Cr(VI)去除率降低;随反应温度和GAC-nZVI投加量增加,Cr(VI)去除率增加。准一级动力学模型可用于描述Cr(VI)的去除过程。相同条件下,GAC-nZVI去除Cr(VI)的反应速率常数达0.19797 min?1,为原颗粒活性炭反应速率常数0.0023 min?1的86倍。随pH值降低或反应温度和GAC-nZVI投加量增加,反应速率常数增加。     

Synthesis,characterization of Fe3O4@glycine doped polypyrrole magnetic nanocomposites and their potential performance to remove toxic Cr(VI)

Fe₃O₄ coated glycine doped polypyrrole magnetic nanocomposite (Fe₃O₄@gly-PPy NC) was prepared via coating of suspended Fe₃O₄ nanoparticles with gly-PPy. FE-SEM and HR-TEM images indicated that Fe₃O₄ nanoparticles were encapsulated by precipitating gly-PPy moieties. Chromium(VI) adsorption followed a Langmuir isotherm with maximum capacity of 238–303 mg/g for a temperature range of 25–45 °C at pH 2. The adsorption process was governed by the ionic interaction and the reduction of Cr(VI) to Cr(III) by the PPy moiety. Results showed that NCs are effective adsorbents for the removal of Cr(VI) from wastewater and can be separated by external magnetic field from the reactor.     

A new bioinorganic process for the remediation of Cr(VI)

Palladised biomass of Desulfovibrio desulfuricans ATCC 29577 (bio‐Pd(0)) effected reduction of Cr(VI) to Cr(III) under conditions where biomass alone or chemically‐prepared Pd(0) were ineffective. Reduction of 500 µmol dm^?3 Cr(VI) by 0.4 mg cm^?3 bio‐Pd(0) (Pd : biomass ratio of 1:1) was achieved from 1 mol dm^?3 formate/acetate buffer at pH 1–7 at room temperature; the optimum pH was 3.0. The ratio of mass of Pd : dry mass of biomass, and the need for finely ground bio‐Pd(0) were important parameters for optimal Cr(VI) reduction, with a ratio of 1:1 giving 100% reduction of 500 µmol dm^?3 Cr(VI) within 6 h at room temperature, decreasing to 30 min following heat treatment of the Pd(0)‐loaded biomass. The reduced Cr was recovered quantitatively as soluble Cr(III) at pH 3.0 with no poisoning of the bioinorganic catalyst with respect to continued reduction of Cr(VI). © 2002 Society of Chemical Industry     

Removal of hexavalent chromium in wastewater by polyacrylamide modified iron oxide nanoparticle

Iron oxide nanoparticle has been successfully modified by polyacrylamide and the polyacrylamide modified magnetic nanoparticles (PMMNs) were applied to remove Cr(VI) in wastewater. The vibrating sample magnetometer (VSM) spectra indicated the large saturation magnetization and superparamagnetic property of the PMMNs. This made the polyacrylamide modified iron oxide easily separate with liquid phase. Scanning electron microscope (SEM) results showed that both the synthesized iron oxide and the PMMNs were nanoscale. Batch adsorption studies had been carried out to determine the effect of pH, contact time, Cr(VI) initial concentration, and coexisting salts on the adsorption of Cr(VI). Maximum removal (98.30%) was observed from an initial concentration of 100 mg L^?1 Cr(VI) at pH 3.0, 30°C. This process followed pseudo‐second‐order kinetics model and the equilibrium time was 40 min. The experimental data fitted the Langmuir isotherm better than Freundlich. Maximum adsorption amount of Cr(VI) by PMMN was 35.186 mg g^?1. The effect of coexisting salts on Cr(VI) removal was not apparent even the concentration of salt was 10 times as big as the low concentration, 0.01M. It had been proposed that the mechanism of Cr(VI) uptake onto PMMN was adsorption‐coupled reduction. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 40945.     

Electrocatalytic reduction of chromium by poly(aniline-co-o-aminophenol): An efficient and recyclable way to remove Cr(VI) in wastewater

Poly(aniline-co-o-aminophenol) (PANOA)-modified glassy carbon electrode (GCE) was first used to investigate the electrocatalytic reduction of dichromate in a NaCl solution of pH 5.0. The results of cyclic voltammograms and UV–vis spectra demonstrated that the reduction of Cr(VI) occurred at PANOA-modified GCE. The FT-IR, ESR and XPS results showed that the Cr(VI) can be doped in the PANOA films and can convert to less-toxic Cr(III). The doping level Cr/N was 78.2% and trace amount of Cl (0.42%) was detected in the doped PANOA, which indicated that the doping process is effective and PANOA had rather good ion selectivity in the 0.10 M NaCl supporting electrolyte. The factors influenced the reduction were also considered. Various initial concentrations of Cr(VI) had different removal rates. The maximum removal rate of Cr(VI) at 20 mg L⁻¹ (32.3%) was better than that of at 5 mg L⁻¹ (22.9%). The solution pH had little effect on Cr(VI) reduction and doping process of the PANOA because PANOA had good electrochemical activity and stability in a wide range of pHs (from pH 4 to pH 8).     

Effect of pH on the removal of Cr(III) and Cr(VI) from aqueous solution by modified polyethyleneimine

A novel flocculant with the capacities of reduction and chelation was prepared in this paper. The flocculant, called polyethyleneimine–sodium xanthogenate (PEX), was synthesized by modifying polyethyleneimine with carbon disulfide and sodium hydroxide. The effect of pH on the removal of Cr(III) and Cr(VI) from aqueous solution with PEX was investigated by using flocculation experiments. The results showed that in the single-ion system (only including Cr(III) or Cr(VI) in the solution), the final Cr(III) decreased with the increase in pH from 2.0 to 10.0, while the final Cr(VI) increased at first and then decreased with the increase in this pH range studied. The removal of Cr(III) was not desirable at pH lower than 7.0, whereas the final Cr(VI) concentration reached the minimum value of 0.145 mg/L at pH 2.0. In the mixture system of Cr(III) and Cr(VI), the variation tendency for the removal of Cr(III) or Cr(VI) was very similar to that obtained in the single-ion system. The oxidation–reduction potential, zeta potential, and final pH in the supernatant were also measured to analyze the above results. Furthermore, FTIR spectra revealed that dithiocarboxylic acid groups on the macromolecular chains of PEX played a major role in the Cr(VI) reduction and Cr(III) chelation.     

Removal of Cr(VI) from Aqueous Solution: Electrocoagulation vs Chemical Coagulation

Abstract

Hydrolyzed products of Al(III) have affinity below pH_zpc for oppositely charged mono and bi‐nuclear species of hexavalent chromium. This study investigates the comparative performance of electrocoagulation (EC) and chemical coagulation (CC) for the removal of Cr(VI) from aqueous solution. The highest removal of Cr(VI) achieved with EC was about 42% with 4.36 mA/cm² current density. Cathodic adsorption of chromium boosted up Cr(VI) removal during EC. Simultaneous electro‐ and chemical‐dissolution lead to high current efficiency of about 178%. Both the pH and the coagulant dosage have a significant impact on Cr(VI) removal in the pH ranges from 4.9 to 7.0. CC with alum and aluminum sulfate (AS) removed about 11% and 12% of Cr(VI). Co‐adsorption of divalent SO₄ ^2? ions with Cr(VI) is responsible for the lower removal observed with chemical coagulants. About 0.061 and 0.099 mole of SO₄ ^2? was adsorbed per mole Al in the precipitate in the pH range 4.9 to 7.0 with AS and alum. A higher coagulant dosage increases the removal of Cr(VI) but adversely affects the removal efficiency (Cr(VI) removed per unit of Al dosing). Cell current density (CD) has shown little effect on Cr(VI) removal and the pH elevation at the same charge density. Higher initial Cr(VI) concentration improves the removal efficiency as the species of Cr(VI) is acidic in solution and decreases the pH elevation rate.     

Biological Cr(VI) reduction in a trickling filter under continuous operation with recirculation

BACKGROUND: Hexavalent chromium (Cr(VI)) is toxic to humans, animals and plants. Conventional treatment technologies reduce Cr(VI) to the less toxic and mobile Cr(III), but these methods are usually expensive and generate secondary waste. Microbial Cr(VI) reduction has recently gained attention as a detoxification process, since it enables Cr(VI) reduction through relatively cheap and simple methods. The aim of this work was to investigate the mechanism and the performance of biological Cr(VI) reduction using mixed cultures originated from industrial sludge under continuous operation with recirculation in a pilot‐scale trickling filter. RESULTS: Biological Cr(VI) reduction was studied using a pilot‐scale trickling filter filled with plastic media under continuous operation with recirculation and the use of indigenous bacterial population. The effect of the organic carbon (electron donor) concentration was examined for constant Cr(VI) influent concentration at about 5.5 mg L^?1 and volumetric flow rates ranging from 60 to 900 mL min^?1. The highest reduction rate achieved was 1117 g Cr(VI) m^?2 d^?1 for a volumetric flow rate of 900 mL min^?1. The system's reduction capacity was significantly affected by chromate loadings, resulting in frequent backwashing of the filter. The determination of the reduction mechanism was also studied using batch cultures of free suspended cells and culture supernatant. CONCLUSION: The high reduction rates combined with the low operating cost indicate that the above technology can be a viable solution for the treatment of industrial chromate effluents. Copyright © 2008 Society of Chemical Industry