Hexavalent chromium reduction with scrap iron in continuous-flow system Part 1: effect of feed solution pH

The reduction of hexavalent chromium by scrap iron was investigated in continuous system, using long-term column experiments, for aqueous Cr(VI) solutions having low buffering capacities, over the pH range of 2.00-7.30. The results showed that the initial pH of Cr(VI) solution significantly affects the reduction capacity of scrap iron. The highest reduction capacity was determined to be 19.2 mg Cr(VI)/g scrap iron, at pH 2.50, and decreased with increasing the initial pH of Cr(VI) solution. A considerable decrease in scrap iron reduction capacity (25%) was also observed at pH 2.00, as compared to pH 2.50, due to the increased contribution of H(+) ions to the corrosion of scrap iron, which leads to a rapid decrease in time of the scrap iron volume. Over the pH range of 2.50-7.30, hexavalent chromium concentration increases slowly in time after its breakthrough in column effluent, until a steady-state concentration was observed; similarly, over the same pH range, the amount of solubilized Cr(III) in treated column effluent decreases in time, until a steady-state concentration was observed. The steady-state concentration in column effluent decreased for Cr(VI) and increased for Cr(III) with decreasing the initial pH of Cr(VI) solution. No steady-state Cr(VI) or Cr(III) concentrations in column effluent were observed at pH 2.00. Over the entire studied pH range, the amount of Fe(total) in treated solution increases as the initial pH of column influent is decreased; the results show also a continuously decrease in time of Fe(total) concentration, for a constant initial pH, due to a decrease in time of iron corrosion rate. Cr(III) concentration in column effluent also continuously decreased in time, for a constant initial pH, over the pH range of 2.50-7.30. This represents an advantage, because the amount of precipitant agent used to remove Fe(total) and Cr(III) from the column effluent will also decrease in time. The optimum pH for Cr(VI) reduction with scrap iron in continuous-flow system was established at the value of 2.50.     

Effects of pH and dissolved oxygen on Cr(VI) removal in Fe(0)/H2O systems

The effects of pH and dissolved oxygen (DO) on aqueous Cr(VI) removal by micro-scale zero-valent iron (Fe(0)/H(2)O system) were investigated. Batch experiments were conducted at pH 4.0, 5.0 and 6.0 under oxic and anoxic conditions. Column experiments were performed at pH 5.0 and 7.5 under oxic condition. Spectroscopic analyses were applied to explain the mechanism of Cr(VI) removal using X-ray absorption near-edge structure (XANES), X-ray diffraction (XRD), and scanning electron microscopy (SEM). Results showed that the kinetics of Cr(VI) removal were fastest at pH 5 under both oxic and anoxic conditions. As a rule, Cr(VI) removal were faster under oxic conditions than under anoxic conditions. Column experiments showed that Cr(VI) removal was about 1.7-fold higher at pH 5 than at pH 7.5. XANES (X-ray absorption near edge structures) results showed that Fe(0) reduced Cr(VI) to Cr(III) under both oxic and anoxic conditions. X-ray diffraction patterns of the Cr(VI)-Fe(0) reaction products suggested partial formation of chromite (FeCr(2)O(4)) at pH 5 and 6 under oxic conditions. However, nano-sized clusters of Cr(III)/Fe(III) hydroxide/oxyhydroxide were formed on the surface of Fe(0) under anoxic conditions. These results indicate that the presence of oxygen in solution plays an important role in control of the kinetic of Cr(VI) removal and in development of various Cr(VI) reduction products.     

Simultaneous photocatalytic reduction of Cr(VI) and oxidation of bisphenol A induced by Fe(III)-OH complexes in water

Simultaneously photocatalytic reduction of Cr(VI) and oxidation of bisphenol A (BPA) in aqueous solution in the presence of Fe(III)-OH complexes were investigated under a 250 W metal halide lamp (lambda>or=365 nm). Synergy effect of the simultaneous photocatalytic oxidation and reduction of both pollutants was achieved. The effects of initial pH value, initial concentration of BPA, Cr(VI) and Fe(III) were preliminarily investigated. The results showed that both photocatalytic reduction of Cr(VI) and degradation of BPA could occur simultaneously in the Fe(III)/Cr(VI)/BPA ternary system, and the rates of photocatalytic reduction of Cr(VI) and the oxidation of BPA were more rapid at a low pH range of 2.0-3.0. The increase of the initial concentration of Fe(III) was favorable to both photocatalytic reduction of Cr(VI) and oxidation of BPA. The reduction efficiency of Cr(VI) decreased with increasing initial concentrations of Cr(VI) and BPA, but the degradation efficiency of BPA was not changed obviously at different Cr(VI) concentrations.     

In situ stabilization of chromium(VI) in polluted soils using organic ligands: the role of galacturonic, glucuronic and alginic acids

Laboratory batch sorption and column experiments were performed to investigate the role of organic ligands such as galacturonic, glucuronic and alginic acids (main constituents of bacterial exopolymeric substances (EPS)) on Cr(VI) uptake and transport in heterogeneous subsurface media. Our batch sorption experiments demonstrate the addition of galacturonic, glucuronic and alginic acids to soils enhances Cr(VI) uptake by soil at pH values <7.7 depending on the concentration of the ligand and pH used. The enhanced Cr(VI) uptake at pH values <7.7 may be explained through either the catalytic reduction of Cr(VI) to Cr(III) by the surface-bound organic matter/Fe oxides and/or the dissolved metal ions (e.g., Fe(III)) from the soil. On the other hand, organic ligands have no or little effect on Cr(VI) uptake under highly alkaline pH conditions since the catalytic Cr(VI) reduction decreases with increasing pH. Similarly, the results from column experiments show that, depending on the concentration of organic ligands, the Cr(VI) breakthrough curves were significantly retarded relative to the organic acid-free systems at pH 7.6. A significant portion of Cr(VI) initially added to the feed solution was not readily recoverable in the effluent, indicating Cr(VI) reduction in columns, most probably catalyzed by surface-bound metal-oxides (e.g., Fe oxides) or dissolved metal ions such as Fe(II; III). The overall results suggest that EPS constituents such as glucuronic, galacturonic and alginic acids may play a significant role on Cr(VI) stabilization in subsurface systems under acidic to slightly alkaline pH conditions.     

The role of iron in hexavalent chromium reduction by municipal landfill leachate

The function of iron (ferric (Fe(III)) and ferrous (Fe(II))) in the hexavalent chromium (Cr(VI)) reduction mechanism by bacteria in municipal landfill leachate (MLL) was assessed. Evidence of an "electron shuttle" mechanism was observed, whereby the Cr(VI) was reduced to trivalent chromium (Cr(III)) by Fe(II) with the resulting Fe(III) bacterially re-reduced to Fe(II). Typically, investigations on this electron shuttle mechanism have been performed in an artificial medium. As MLL comprises an elaborate mixture of bacteria, humic materials and organic and inorganic species, additional complexities were evident within the cycle in this study. Bioavailability of the Fe(III) for bacterial reduction, availability of bacterially produced Fe(II) for chemical Cr(VI) reduction and hydrolysis of Fe(II) and Fe(III) become prevalent during each phase of the shuttle cycle when MLL is present. Each of these factors contributes to the overall rate of bacterial Cr(VI) reduction in this media. This work highlights the need to consider local environmental conditions when assessing the bacterial reduction of Cr(VI).     

Cr(VI) removal from aqueous solution using chemically reduced and functionalized graphene oxide

Chemically reduced and functionalized graphene oxide (GO) was prepared by refluxing of GO with ethylenediamine (ED) using dimethyl formamide (DMF) as solvent. It was confirmed that both ED and DMF contributed to the reduction and functionalization of GO. The resulting adsorbent (ED–DMF–RGO) with amine groups was highly efficient in removing Cr(VI) from its aqueous solution and could be easily separated by filtration. The optimum pH for total Cr removal was observed at pH 2.0 and the Cr(VI) removal capacity of ED–DMF–RGO at this pH was 92.15 mg g^?1, which was about 27 times higher than that of activated carbon, even nearly 4–8 times higher than that of various modified activated carbons. The presence of other ions such as Na⁺, K⁺, Ca²⁺, Cl^?, and Br^? had little effect on the removal of Cr(VI). Interestingly, Cr(VI) was reduced to low-toxic Cr(III) during the adsorption process, which followed an indirect reduction mechanism. Both the Cr(VI) adsorption and subsequent reduction of adsorbed Cr(VI) to Cr(III) contributed to the Cr(VI) removal. The obtained ED–DMF–RGO may be applicable in Cr(VI) removal if they are produced on a large scale and at low price in near future.     

Grape waste as a biosorbent for removing Cr(VI) from aqueous solution

Grape waste generated in wine production is a cellulosic material rich in polyphenolic compounds which exhibits a high affinity for heavy metal ions. An adsorption gel was prepared from grape waste by cross-linking with concentrated sulfuric acid. It was characterized and utilized for the removal of Cr(VI) from synthetic aqueous solution. Adsorption tests were conducted in batch mode to study the effects of pH, contact time and adsorption isotherm of Cr(VI), which followed the Langmuir type adsorption and exhibited a maximum loading capacity of 1.91 mol/kg at pH 4. The adsorption of different metal ions like Cr(VI), Cr(III), Fe(III), Zn(II), Cd(II) and Pb(II) from aqueous solution at different pH values 1-5 has also been investigated. The cross-linked grape waste gel was found to selectively adsorb Cr(VI) over other metal ions tested. The results suggest that cross-linked grape waste gel has high possibility to be used as effective adsorbent for Cr(VI) removal.     

Removal of chromium ions from [corrected] aqueous solutions by adsorption on activated carbon and char

Adsorption isotherms of chromium ions in aqueous solution have been experimentally measured on a granular activated carbon (GAC) and on a char of South African coal (CSAC). Experimental results show that the adsorption capacity for the GAC strongly depends on solution pH and salinity, with maximum values around 7mg/g at neutral pH and low salinity levels. On the contrary, the CSAC shows a smaller adsorption capacity, near 0.3mg/g, which slightly decreases by increasing pH and salinity levels. Chromium adsorption mainly depends on the availability of chromium ions in solution and on the occurrence of redox reactions between the surface groups and the Cr(VI) which lead to the formation of Cr(III). The reduction of Cr(VI) and the following sorption of Cr(III) cations appears as the leading mechanism for chromium uptake on the CSAC. A similar behaviour can be observed for the GAC at pH below 3. On the contrary, at pH>7, the multicomponent competitive adsorption of Cr(VI), OH(-) and Cl(-) has to be considered.     

Characterization of Cr(VI) removal from aqueous solutions by a surplus agricultural waste--rice straw

The removal of Cr(VI) from aqueous solution by rice straw, a surplus agricultural byproduct was investigated. The optimal pH was 2.0 and Cr(VI) removal rate increased with decreased Cr(VI) concentration and with increased temperature. Decrease in straw particle size led to an increase in Cr(VI) removal. Equilibrium was achieved in about 48 h under standard conditions, and Cr(III), which appeared in the solution and remained stable thereafter, indicating that both reduction and adsorption played a part in the Cr(VI) removal. The increase of the solution pH suggested that protons were needed for the Cr(VI) removal. A relatively high level of NO(3)(-) notably restrained the reduction of Cr(VI) to Cr(III), while high level of SO(4)(2-) supported it. The promotion of the tartaric acid modified rice straw (TARS) and the slight inhibition of the esterified rice straw (ERS) on Cr(VI) removal indicated that carboxyl groups present on the biomass played an important role in chromium remediation even though were not fully responsible for it. Isotherm tests showed that equilibrium sorption data were better represented by Langmuir model and the sorption capacity of rice straw was found to be 3.15 mg/g.     

Mechanisms of the removal of hexavalent chromium by biomaterials or biomaterial-based activated carbons

Three papers published during recent 2 years in Journal of Hazardous Materials made a mistake in analyzing chromium species in aqueous solution, resulting in incorrect elucidation of Cr(VI) biosorption; the Cr(VI) was removed from aqueous solution systems by 'anionic adsorption'. However, it has been proved that Cr(VI) is easily reduced to Cr(III) by contact with organic materials under acidic conditions because of its high redox potential value (above +1.3 V at standard condition). Therefore, it is strongly possible that the mechanism of Cr(VI) removal by biomaterials or biomaterial-based activated carbons is not "anionic adsorption" but "adsorption-coupled reduction". Thus, for researches of Cr(VI) biosorption, researchers have to analyze not only Cr(VI) but also total Cr in aqueous solution and to check the oxidation state of chromium bound on the biomaterials or activated carbons.     

Characteristics and mechanisms of hexavalent chromium removal by biochar from sugar beet tailing

Removal of Cr(VI) from aqueous solutions using biochar from sugar beet tailing (SBT) was investigated as a function of pH, contact time, and biochar mass via batch experiments. The surface characteristics of SBT biochar before and after Cr(VI) sorption was investigated with scanning electron microscopy equipped with energy dispersive X-ray spectroscopy and Fourier transform infrared spectroscopy. Desorption and X-ray photoelectron spectroscopy studies showed that most of the Cr bound to SBT biochar was Cr(III). These results indicated that the electrostatic attraction of Cr(VI) to positively charged biochar surface, reduction of Cr(VI) to Cr(III) ion, and complexation between Cr(III) ion and SBT's function groups were probably responsible for Cr(VI) removal by SBT biochar. An initial solution with a pH of 2.0 was most favorable for Cr(VI) removal. The sorption process can be described by the pseudo-second order equation and Langmuir isotherm. The maximum sorption capacity for Cr(VI) was 123 mg/g under an acidic medium, which was comparable to other low-cost sorbents.     

Hexavalent chromium removal by ferrochromium slag

The aim of this study is to demonstrate the potential of Cr(VI) generation during jigging operation applied for ferrochrome recovery from slag. The Cr(VI) concentrations of water contacted with ferrochromium slag (W/FS=10) in a closed cycle after 50 batches were found as 0.61 mg/l. Also, reduction of Cr(VI) to Cr(III) and a subsequent precipitation of Cr(III) by using ferrochrome slag (FS) in a model solution has been aimed. The effects of amount of acid, contact time, FS dosage, initial Cr(VI) concentration and temperature on the Cr(VI) reduction have been studied through the batch runs. The amount of acid has been found to be the most effective parameter affecting the Cr(VI) reduction. A 10 g/l FS dosage and 3.5 ml/l H2SO4 (5M) are sufficient to reduce all Cr(VI) in the model solution containing 10mg/l Cr(VI) and for contact time of 60 min at 25 degrees C. In reduced solutions, precipitation of metal ions has been studied by using extra FS. A 60 g/l dosage of fresh FS can precipitate all Cr(III) and Fe ions in the reduced solution. Thus, it has been demonstrated that the treatment of jigging water stream to be generated in a ferrochrome plant containing Cr(VI) can be accomplished by using ferrochromium slag and sulphuric acid. Also, it has been determined that solid residues of the process are environmentally stable by applying TCLP test.     

The effectiveness of ferrous iron and sodium dithionite for decreasing resin-extractable Cr(VI) in Cr(VI)-spiked alkaline soils

Ferrous iron, Na(2)S(2)O(4), and a mixture of Fe(II) and Na(2)S(2)O(4) (4:1 mol/mol) were tested for their effectiveness for decreasing resin-extractable Cr(VI) in alkaline Cr(VI)-spiked soils. The results indicated that adding those reductants greatly decreased the amount of resin-extractable Cr(VI) when the application rate of reductants equaled the number of equivalents of dichromate added to the Cr(VI)-spiked soils. This was mainly as a result of the Cr(VI) reduction into Cr(III), as supported by the XANES spectra. Among the tested reductants, a mixture of Fe(II) and Na(2)S(2)O(4) was the most effective to decrease resin-extractable Cr(VI). The extent to which resin-extractable Cr(VI) and soil pH were decreased was affected by the pH of the reductants. Among the tested reductants at various pH, FeSO(4) at pH below 1 was the most effective in decreasing resin-extractable Cr(VI) in alkaline soils. However, the soil pH was the most decreased as well. On the other hand, the mixtures of ferrous iron and dithionite at a wide range of pH were all efficient (>70% efficiency) in decreasing resin-extractable Cr(VI). Moreover, the extent of the decrease in soil pH was much smaller than that by FeSO(4) (pH<1) alone, and thus the possibility of the Cr(III) hazard can be avoided.     

A mechanism study of light-induced Cr(VI) reduction in an acidic solution

The mechanisms of photo-catalytic reduction of Cr(VI) were investigated in acidic solutions with and without Fe(III). In a system without Fe(III), no Cr(VI) reduction was observed in dark conditions; conversely, under light conditions, the reduction reaction rate increased to 0.011 and 0.020microM min(-1) at pH 2 and pH 1, respectively, indicating the occurrence of Cr(VI) photo-reduction. The Cr(VI) photo-reduction reaction was induced by the photolysis of water molecules, leading to O(2) production. Upon the addition of Fe(III), the photo-reduction rate of Cr(VI) was significantly enhanced due to the formation of Fe(II), which is the photolytic product of FeCl(2)(+) and the electron donor for Cr(VI) reduction. However, with the same concentration of FeCl complexes, a strong inhibition of Cr(VI) reduction at pH 2 was observed, compared with pH 1. A possible explanation is that FeOH(2+) becomes predominant with increasing pH and that its photolytic product, the OH free radical, is an oxidant for Fe(II) and Cr(III) and can compromise Cr(VI) reduction. The kinetic result of each photo-reduction reaction pathway shows zero-order kinetics, suggesting that the photolysis reaction of H(2)O or FeCl(2+) is the rate-determining step in each pathway. The results also show the potential of developing a homogeneous photo-catalytic method to treat Cr(VI)-containing water.     

Study of the removal of mercury(II) and chromium(VI) from aqueous solutions by Moroccan stevensite

The objective of the present study was to investigate the adsorption of the heavy metals mercury(II) and chromium(VI), from aqueous solutions, onto Moroccan stevensite. A mineralogical and physicochemical characterization of natural stevensite was carried out. In order to improve the adsorption capacity of stevensite for Cr(VI), a preparation of stevensite was carried out. It consists in saturating the stevensite by ferrous iron Fe(II) and reducing the total Fe by Na(2)S(2)O(4). Then, the adsorption experiments were studied in batch reactors at 25+/-3 degrees C. The influence of the pH solution on the Cr(VI) and Hg(II) adsorption was studied in the pH range of 1.5-7.0. The optimum pH for the Cr(VI) adsorption is in the pH range of 2.0-5.0 while that of Hg(II) is at the pH values above 4.0. The adsorption kinetics were tested by a pseudo-second-order model. The adsorption rate of Hg(II) is 54.35 mmol kg(-1)min(-1) and that of Cr(VI) is 7.21 mmol kg(-1)min(-1). The adsorption equilibrium time for Hg(II) and Cr(VI) was reached within 2 and 12 h, respectively. The adsorption isotherms were described by the Dubinin-Radushkevich model. The maximal adsorption capacity for Cr(VI) increases from 13.7 (raw stevensite) to 48.86 mmol kg(-1) (modified stevensite) while that of Hg(II) decreases from 205.8 to 166.9 mmol kg(-1). The mechanism of Hg(II) and Cr(VI) adsorption was discussed.     

Enhanced abiotic reduction of Cr(VI) in a soil slurry system by natural biomaterial addition

Among various plant-based natural biomaterials, pine bark was chosen as an efficient biomaterial capable of removing toxic Cr(VI) from aqueous solution. XPS spectra indicated that Cr(VI) was abiotically reduced to Cr(III) in both liquid and solid phases. The Cr(VI)-reducing capacity of pine bark was determined as 545 (±1.3) mg-Cr(VI) g⁻¹ of it, which was 8.7 times higher than that of a common chemical Cr(VI)-reductant, FeSO₄·7H₂O. Because pine bark could completely reduce toxic Cr(VI) to less toxic or nontoxic Cr(III) even at neutral pH, it was used as an organic reductant to remediate Cr(VI)-contaminated soil in this study. Soil slurry system using a bottle roller was applied to ex situ slurry-phase remediation experiments. In the soil slurry system, pine bark completely reduced Cr(VI) to Cr(III) and adsorbed the reduced-Cr(III) on its surface. Abiotic remediation rate of Cr(VI)-contaminated soil increased with the increase of pine bark dosage and with the decreases of Cr(VI) and water contents. In conclusion, pine bark can be used to remediate Cr(VI)-contaminated soil efficiently and environmentally friendly.     

Kinetics of hexavalent chromium reduction by scrap iron

The kinetics of Cr(VI) reduction by scrap iron was investigated in batch system, for aqueous solutions having low buffering capacities, as a function of pH (2.10-7.10), temperature (10-40 degrees C) and Cr(VI) concentration (19.2-576.9 microM). The results obtained using only the experimental data at initial times indicate zero-order kinetics at pH 2.10 and first-order kinetics over the pH range of 2.98-7.10. The reaction order with respect to H(+) concentration, over the pH range of 4.17-7.10 and Cr(VI) concentration range of 19.2-38.4 microM, was found to be 0.31. The effects of pH, Cr(VI) initial concentration and temperature were investigated; the observed Cr(VI) reduction rates increased with decreasing pH, increasing temperature and decreasing initial Cr(VI) concentration. The observed and overall rate coefficients were determined, and a kinetic expression was developed to describe reduction of chromium by scrap iron over the pH range of 4.17-7.10 and Cr(VI) concentration range of 19.2-38.4 microM.     

Cr(VI) reduction in aqueous solutions by siderite

Hexavalent chromium is a common and toxic pollutant in soils and wastewaters. Reduction of the mobile Cr(VI) to less mobile and less toxic Cr(III) is a solution for decontamination of industrial effluents. In this study, the reduction of hexavalent chromium in aqueous solutions by siderite was investigated. The influences of amount of acid, contact time, siderite dosage, initial Cr(VI) concentration, temperature and particle size of siderite have been tested in batch runs. The process was found to be acid, temperature and concentration dependent. The amount of acid is the most effective parameter affecting the Cr(VI) reduction since carbonaceous gangue minerals consume acid by side reactions. The highest Cr(VI) reduction efficiency (100%) occurred in the 50 mg/l Cr(VI) solution containing two times acid with respect to stoichiometric amount of Cr(VI) and at the conditions of siderite dosage 20 g/l, contact time 120 min and temperature 25 degrees C. Reduction efficiency increased with increase in temperature and decrease in particle size. The reduction capacity of siderite was found to be 17 mg-Cr(VI)/g.     

The comprehensive investigation on removal mechanism of Cr(VI) by humic acid-Fe(II) system structured on V,Ti-bearing magnetite surface

The Cr(VI) could be adsorbed and reduced by the humic acid (HA)-Fe(II) system structured on the V, Ti-magnetite (VTM) surface. The Cr(VI) removal process included adsorption and reduction stages. First, the Cr(VI) was adsorbed on the VTM-HA surface via the ionic bonds between the Ti atoms of VTM core and the O atoms of the HCrO₄^?. The adsorption of Cr(VI) is uniform, monolayer, and controlled by Cr(VI) diffusion. Subsequently, the adsorbed Cr(VI) was reduced by the HA-Fe(II) system on the VTM-HA surface. During the Cr(VI) reduction process, the HA and Fe(II) have a synergistic effect. The Cr(VI) was reduced to the Cr(III) by the HA and Fe(II). Meanwhile, the HA could also reduce Fe(III) to Fe(II), making Fe(II) continue to participate in the Cr(VI) reduction. The olefin, hydroxyl, and aldehyde groups of HA were the primary electron donors during the Cr(VI) reduction. The Fe(II) acted as an electron bridge, transferring the electron from HA to Cr(VI). The reduced Cr(III) was deposited on the VTM-HA surface via the complexation with the carboxyl and hydroxyl groups of HA. The results demonstrated that the Cr(VI) could be adsorbed, reduced and complexed by the HA-Fe(II) system on the VTM-HA surface synchronously.     

Simultaneous removal of chromium and leather dye from simulated tannery effluent by photoelectrochemistry

The feasibility of the photobleaching of a leather acid dye, acid red 151, simultaneously to degradation of anionic surfactant, Tamol^®, and reduction of Cr(VI) to the less toxic Cr(III) was investigated by photoelectrocatalytic oxidation. The best experimental conditions were found to be pH 2.0 and 0.1 mol L⁻¹ sodium sulfate when the nanoporous Ti/TiO₂ photo anode was biased at +1.0 V and submitted to UV-irradiation. The photoelectrocatalytic oxidation promotes 100% discoloration, reducing around 98–100% of Cr(VI) and achieving an abatement of 95% of the original total organic carbon. The effect of pH, the applied potential, the Cr(VI) concentration and the complexation reaction between Cr(VI) and acid red dye were evaluated as to their effect on the kinetics of the reaction.