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1.
Photo-reduction of Cr(VI) in a solution with single or multi-inorganic anions was evaluated. The results show that 38.5 microM Cr(VI) is photo-reduced in the presence of NO(3)(-) at pH 1. The photolysis of NO(3)(-), producing NO(2)(-) or H(2)O(2), may contribute to Cr(VI) reduction. The addition of 0.001-0.1 M chlorite to NO(3)(-) enhanced Cr(VI) photo-reduction when 35.8 microM Fe(III) was present. This enhancement was the combinative result of photolysis of NO(3)(-) and Fe-Cl complexes, leading to the formation of NO(2)(-) and Fe(II), respectively, for Cr(VI) reduction. On the contrary, a significant decrease in Cr(VI) photo-reduction was observed with the addition of PO(4)(3-) and SO(4)(2-). This decrease was due to their strong competition with Fe(III) from Cl(-), resulting in a marked decrease in the concentrations of Fe-Cl complexes. The results suggest that a direct irradiation of acidic wastewaters containing Cl(-), NO(3)(-), and Fe(III) is a feasible strategy for eliminating Cr(VI).  相似文献   

2.
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.  相似文献   

3.
Fluidized zero valent iron (ZVI) process was conducted to reduce hexavalent chromium (chromate, CrO(4)(2-)) to trivalent chromium (Cr(3+)) from electroplating wastewater due to the following reasons: (1) Extremely low pH (1-2) for the electroplating wastewater favoring the ZVI reaction. (2) The ferric ion, produced from the reaction of Cr(VI) and ZVI, can act as a coagulant to assist the precipitation of Cr(OH)(3(s)) to save the coagulant cost. (3) Higher ZVI utilization for fluidized process due to abrasive motion of the ZVI. For influent chromate concentration of 418 mg/L as Cr(6+), pH 2 and ZVI dosage of 3g (41 g/L), chromate removal was only 29% with hydraulic detention time (HRT) of 1.2 min, but was increased to 99.9% by either increasing HRT to 5.6 min or adjusting pH to 1.5. For iron species at pH 2 and HRT of 1.2 min, Fe(3+) was more thermodynamically stable since oxidizing agent chromate was present. However, if pH was adjusted to 1.5 or 1, where chromate was completely removed, high Fe(2+) but very low Fe(3+) was present. It can be explained that ZVI reacted with chromate to produce Fe(2+) first and the presence of chromate would keep converting Fe(2+) to Fe(3+). Therefore, Fe(2+) is an indicator for complete reduction from Cr(VI) to Cr(III). X-ray diffraction (XRD) was conducted to exam the remained species at pH 2. ZVI, iron oxide and iron sulfide were observed, indicating the formation of iron oxide or iron sulfide could stop the chromate reduction reaction.  相似文献   

4.
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.  相似文献   

5.
This work investigated the effect of co-existing organic matters on aqueous Cr(VI) reduction by electrodeposited zero-valent iron (ED Fe(0)) at neutral pH. The ED Fe(0) prepared in a solution containing mixture of saccharin, L-ascorbic acid and sodium dodecyl sulfate showed higher activity in reducing the aqueous Cr(VI) at neutral pH than that prepared without any organic presence. XRD and SEM indicated that the structure of ED Fe(0) was significantly improved to nano-scale by the presence of organic mixture in the preparation solution. Further, the ED Fe(0) activity in the Cr(VI) reduction at neutral pH was increased by the co-existence of citric acid or oxalic acid in the chromate solution. Electrochemical impedance spectroscopy (EIS) demonstrated that the corrosive current increased with the concentration of organic matter in the reaction solution. With the co-existing organic matters in the preparation solution, the ED Fe(0) corroded more rapidly due to its nano-size, thus the Cr(VI) reduction by the ferrous iron was accelerated. With the co-existing organic matters in the reaction solution, the Cr(VI) reduction was accelerated by a Fe(II) complex as the main electron donor, and a prevention of the passivation due to the Fe(III) and Cr(III) complexes also accelerated the Cr(VI) reduction.  相似文献   

6.
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.  相似文献   

7.
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).  相似文献   

8.
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.  相似文献   

9.
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.  相似文献   

10.
Dai R  Yu C  Gou J  Lan Y  Mao J 《Journal of hazardous materials》2011,186(2-3):2110-2116
In the present study, exposure of Cr(III)-tar to full light of medium pressure mercury lamps and a xenon lamp was conducted in batch reaction systems at 25°C and different pH values to predict the potential for Cr(III) oxidation. The results indicated that the more intense irradiation and higher pH facilitated Cr(III)-tar oxidation. It appears that a ligand-to-metal charge-transfer occurs for Cr(III)-tar after irradiation, leading to the generation of Cr(II) and tar· or ·OH. The accompanying photochemical decomposition of tar·/or tar, together with O(2), further caused the formation of ·OH through multiple pathways, which ultimately converted Cr(II) to Cr(VI) step by step. H(2)O(2), a direct source of ·OH under irradiation, significantly enhanced photooxidation of Cr(III)-tar, but not obviously of aqueous Cr(III) or Cr(III)-tar in dark, implying that Cr(II) acts as a precursor of Cr(III) oxidization to Cr(VI).  相似文献   

11.
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.  相似文献   

12.
TiO(2) and sulfated TiO(2) (SO(4)(2-)/TiO(2)) catalysts with different textural properties were prepared under different calcination temperatures and the photo-reduction of Cr(VI) to Cr(III) catalyzed by these catalysts was investigated. For the photocatalytic reduction of Cr(VI), the photocatalytic activities of the TiO(2) samples were found to be strongly dependent of the calcination temperature and TiO(2) calcined at 400 degrees C showed a higher catalytic activity compared to other TiO(2) catalysts. In contrast, sulfation of TiO(2) stabilized the catalytic activities of SO(4)(2-)/TiO(2) catalysts. At low calcination temperature, SO(4)(2-)/TiO(2) catalysts exhibited catalytic activities almost comparable with that of TiO(2) and the catalytic activities of SO(4)(2-)/TiO(2) catalysts were markedly higher than TiO(2) under high calcination temperature. In addition, the removal of surface SO(4)(2-) of SO(4)(2-)/TiO(2) catalyst led to a marked decrease of the catalytic activity for Cr(VI) photo-reduction, suggesting that the presence of surface SO(4)(2-) provided an acid environment over the catalyst surface and favored the photo-reduction of Cr(VI).  相似文献   

13.
Immobilized titania (TiO2) batch reactors reduced hexavalent chromium (Cr(VI)) in the form of potassium dichromate (K2Cr2O7) to trivalent chromium (Cr(III)) in aqueous solution at pH 3 under 171 W/m2 light intensity. The light source was a 125-W ultraviolet (UV) lamp. The Cr(VI) reduction showed zero-order kinetics (k0), while the Cr(VI) adsorption fitted with first-order kinetics (k(1st)). Adsorption capacity increased with increasing initial Cr(VI) concentration, and the area of immobilized TiO2 limited the reduction efficiency. The lifetime of fresh immobilized TiO2 was approximately 14 h. In addition, the regeneration of TiO2 with 3M sodium hydroxide (NaOH) was necessary to improve adsorption reaction.  相似文献   

14.
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.  相似文献   

15.
Grape waste as a biosorbent for removing Cr(VI) from aqueous solution   总被引:3,自引:0,他引:3  
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.  相似文献   

16.
In this study a new method for chromium speciation in water using solid phase extraction coupled to a flow injection system and flame atomic absorption spectrometry was developed. The adsorption behavior of Cr(III) and Cr(VI) on Nb2O5-SiO2 allowed the selective separation of Cr(III) from Cr(VI) in the pH range of 6-9. Thus, a method for Cr(III) preconcentration and extraction using Nb2O5-SiO2 was developed. Total chromium was determined after the reduction of Cr(VI) to Cr(III) using sodium sulfite in acidic medium. The operational variables of the preconcentration and reduction procedures were optimized through full factorial and Doehlert designs. The limit of detection for Cr(III) was 0.34microgL(-1) and the precision was below 4.6%. Results for recovery tests using different environmental samples were between 90 and 105%. Certified reference materials (NIST 1640 and NIST 1643e) were analyzed in order to check the accuracy of the proposed method, and the results were in agreement with the certified values.  相似文献   

17.
In this paper, the facilitating role of biogenetic jarosite in the reduction of Cr(VI) by sulfide and its mechanism were investigated through batch experiments and analysis of X-ray photoelectron spectrum (XPS). To study the effects of operational parameters on the reduction of Cr(VI) by sulfide, four operational parameters (pH of solution, operation temperature, loading of jarosite and reaction time) were considered as input variables for response surface methodology (RSM). Graphical response surfaces and contour plots were used to evaluate the effect of interaction between operational parameters on the reduction of Cr(VI). The results suggest that a cycle process of converting Fe(III) to Fe(II) occurred on the surface of jarosite and markedly accelerated the reduction of Cr(VI) by sulfide. For example, the efficiency of Cr(VI) reduced by sulfide increased from 20.5% to 100% when jarosite (1 g/L) was added to the homogenous reaction system at pH = 8 within 40 min. The analysis of variance (ANOVA) revealed a high coefficient of determination (p-value < 0.0001, R2 = 97.99%, Adj-R2 = 95.98%) between experimental Cr(VI) removal efficiency and predicted one by RSM developed model. The Pareto analysis results demonstrated that the pH of solution was the most significant term of the developed model. Operation temperature, loading of jarosite and reaction time exhibited synergistic effects on the reduction of Cr(VI), and the effect of interaction between independent factors on the response factor can't be ignored.  相似文献   

18.
The kinetics and stoichiometry of the reduction of hexavalent chromium (Cr(VI)) with ferrous iron (Fe(II)) were examined in systems with and without aquifer solids. Cr(VI) reduction was rapid in the absence of solids, but demonstrated slower and more complex kinetics in the presence of aquifer solids. The aquifer solids removed Fe(II) from solution and a portion of the reducing capacity of Fe(II) was transferred to the aquifer solids. The solid phases were then able to continue to remove Cr(VI). This suggests in situ treatment of Cr(VI) by Fe(II) injection would be feasible in the aquifer environment. In general, re-oxidation of reduced chromium by molecular oxygen was not observed in our systems over time periods of nearly 1 year, suggesting that the potential for chromium solubilization under these oxidizing conditions will be low. An empirical model was developed to describe the reduction kinetics of Cr(VI) in the presence of solids. The model assumes that the reaction is brought about by pseudo-species of iron that react instantaneously, rapidly and slowly with Cr(VI). A fourth pseudo-species is assumed to be non-reactive. Model coefficients were determined by non-linear regression. The model was able to describe observed concentrations of chromium well, but analysis of model errors indicated the potential existence of a distribution of species with different reaction rates rather than just three distinct species. Another model was developed to predict concentrations of different pseudo-species depending on the total amount of Fe(II) added and the amount of aquifer solids present. This model assumed that pseudo-species could result from intrinsic characteristics of the aquifer solids as well as being formed by addition of Fe(II), which could sorb to the aquifer solids.  相似文献   

19.
The photolysis and photo-catalysis of ferrioxalate in the presence of hydrogen peroxide with UV irradiation (UV/ferrioxalate/H(2)O(2) process) for treating the commercial azo dye, reactive Black B (RBB), is examined. An effort is made to decolorize textile effluents at near neutral pH for suitable discharge of waste water. pH value, light source, type of initial catalyst (Fe(3+) or Fe(2+)) and concentration of oxalic acid (Ox) strongly affected the RBB removal efficiency. The degradation rate of RBB increased as pH or the wavelength of light declined. The optimal molar ratio of oxalic acid to Fe(III) is three, and complete color removal is achieved at pH 5 in 2h of the reaction. Applying oxalate in such a photo process increases both the RBB removal efficiency and the COD removal from 68% and 21% to 99.8% and 71%, respectively.  相似文献   

20.
Recently, Cr(VI) removal by grape stalks has been postulated to follow two mechanisms, adsorption and reduction to trivalent chromium. Nevertheless, the rate at which both processes take place and the possible simultaneity of both processes has not been investigated. In this work, kinetics of Cr(VI) sorption onto grape stalk waste has been studied. Experiments were carried out at different temperatures but at a constant pH (3 ± 0.1) in a stirred batch reactor. Results showed that three steps take place in the process of Cr(VI) sorption onto grape stalk waste: Cr(VI) sorption, Cr(VI) reduction to Cr(III) and the adsorption of the formed Cr(III). Taking into account the evidences above mentioned, a model has been developed to predict Cr(VI) sorption on grape stalks on the basis of (i) irreversible reduction of Cr(VI) to Cr(III) reaction, whose reaction rate is assumed to be proportional to the Cr(VI) concentration in solution and (ii) adsorption and desorption of Cr(VI) and formed Cr(III) assuming that all the processes follow Langmuir type kinetics. The proposed model fits successfully the kinetic data obtained at different temperatures and describes the kinetics profile of total, hexavalent and trivalent chromium.The proposed model would be helpful for researchers in the field of Cr(VI) biosorption to design and predict the performance of sorption processes.  相似文献   

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