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1.
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.  相似文献   

2.
《分离科学与技术》2012,47(11-12):3200-3220
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.  相似文献   

3.
BACKGROUND: This work fulfils the need to develop an eco‐friendly biosorbent, elucidating the mechanism of biosorption. Removal of Cr(VI) by Rhizopus arrhizus was investigated in batch mode. Enhancement in the performance of the biosorbent was attempted by pre‐treating the biomass with inorganic and organic acids, chelating agent, cross‐linker and an organic solvent followed by autoclaving. The surface characterization of the biomass was carried out by potentiometric titration, surface area analysis, infrared spectroscopy, chemical modification of the biomass and scanning electron microscopy. RESULTS: All the physico‐chemical treatments of the biosorbent improved Cr(VI) uptake compared with the native biomass (21.72 mg g?1). The highest biosorption capacity (31.52 mg g?1) was achieved after pre‐treating the biomass with 0.5 mol L?1 HNO3 followed by autoclaving. Surface characterization of the biomass using pHzpc, potentiometry and Fourier transform infrared (FTIR) analysis revealed the role of amino and carboxyl groups in Cr(VI) removal by electrostatic attraction. Chemical modification of amino and carboxyl groups significantly decreased Cr(VI) uptake capacity confirming their role in biosorption. SEM analysis showed adsorption of Cr(VI) on the biosorbent surface. CONCLUSION: Rhizopus arrhizus biomass proved to be an effective and low cost alternative biosorbent for removal of Cr(VI) from aqueous solutions. Copyright © 2011 Society of Chemical Industry  相似文献   

4.

While atmospheric particles can have adverse health effects, the reasons for this toxicity are largely unclear. One possible reason is that the particles can contain toxic metals such as chromium. Chromium exists in the environment in two major oxidation states: III, which is an essential nutrient, and VI, which is highly toxic and carcinogenic. Currently little is known about the speciation of chromium in airborne particles or how this speciation is altered by atmospheric reactions. To investigate the potential impacts of atmospheric aging on the speciation and toxicity of chromium-containing particles, we collected chromium and chromium-iron combustion ultrafine particles on Teflon filters and exposed the particles to a combination of light, ozone, water vapor, and, in some cases, basic or acidic conditions. After the aging process, the aged and not-aged samples were analyzed for Cr oxidation state using X-ray Absorption Near Edge Spectroscopy (XANES). We found that the aging process reduced Cr(VI) by as much as 20% in chromium particles that had high initial Cr(VI)/Cr(total) ratios. This reduction of Cr(VI) to Cr(III) appears to be due to reactions primarily with light and hydroperoxyl radical (HO 2 ) in the chamber. Particles that had low initial Cr(VI)/Cr(total) ratios experienced no significant change in Cr oxidation states after aging. Compared to particles containing only Cr, the addition of Fe to the flame decreased the Cr(VI)/Cr(total) ratio in fresh Cr-Fe particles by ~60%. Aging of these Cr-Fe particles had no additional effects on the Cr(VI)/Cr(total) ratio.  相似文献   

5.
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  相似文献   

6.
The galvanic reaction of metallic copper in Cr(VI)-laden aqueous solutions of varying pH was examined by in situ u.v.–visible spectrophotometry, rotating disc electrode chronopotentiometry and cyclic voltammetry. The galvanic reaction in 0.2 M H2SO4 solutions was pseudo first order in Cr(VI) concentration. Experiments with both magnetically stirred solutions and a copper mesh or a copper film in a rotating disc electrode configuration revealed the reaction to be diffusion-controlled with respect to Cr(VI) transport to the copper surface. Finally, cyclic voltammetry data in Cr(VI)-laden media of varying pH underline the important role of protons in the galvanic reaction.  相似文献   

7.
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 Km (Kmapp) of approx. 650 µmol dm?3 and Vmax 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  相似文献   

8.
A metal surface is chromatized with a chromic acid solution to obtain a good adherence of polymer coatings. In this process Cr(VI) is reduced to Cr(III). The oxidation strength of the solution decreases during use. The chrome solution needs to be regenerated and purified. A new anode material, namely boron-doped diamond, was used to investigate the oxidation of Cr(III) to Cr(VI). It was found that the current efficiency for Cr(III) oxidation decreases with increasing total current density. The current density of Cr(III) oxidation increases linearly with increasing Cr(III) concentration and is practically independent of the Cr(VI) concentration. It was concluded that the diffusion of Cr(III) is the rate-determining step for the Cr(III) oxidation at Cr(III) concentrations form 40 to 160 mol m–3. The surface of the boron-doped diamond shows no signs of chemical corrosion or mechanical destruction. A filter-press type cell divided into two compartments by a cation exchange membrane was proposed. A cost calculation was carried out for the oxidation of 1.28 mmol s–1 Cr(III) in a 40 mol m–3 chrome(III) solution. Factors affecting the feasibility of this process include the costs of chemical waste disposal, the costs of chromic acid, government legislation and to a great extent the costs of the new anode material.  相似文献   

9.
The use of fly ash-based geopolymer binders to immobilize chromium is investigated in detail, with particular regard to the role of the sulfide ion as a reductant for Cr(VI) treatment. In the absence of sulfide, Cr added as Cr(VI) is highly leachable. However, addition of a small quantity of Na2S reduces the Cr to Cr(III), and enables leaching efficiencies in excess of 99.9% to be reached after 90 days' exposure to deionized water, Na2CO3 or MgSO4 solutions. Leaching in H2SO4 is somewhat greater than this, due most probably to the oxidation of the Cr(III) present. Addition of the Cr(VI) as a highly soluble salt is preferable to its addition as a sparingly soluble salt, because a higher salt solubility means the Cr(VI) is more available for reduction prior to geopolymeric setting. The potential value of geopolymer technology as an immobilization process for problematic heavy metal waste streams is highlighted by these results, and the need for a full understanding of binder chemistry in any immobilization system outlined.  相似文献   

10.
The aim of this study is to demonstrate the potential of coals as a low-cost reactive barrier material for environmental protection applications, with the ability to prevent leaching of toxic Cr(VI) and other transition metals. Depending upon the type of ion and the surface functionalities, the uptake can involve ion sorption, ion exchange, chelation and redox mechanisms with the surface functionalities being considered as partners in electron transfer processes. The capacity for Cr(VI) uptake of low rank coals and oxidized bituminous coals has been found to lie within the range 0.2-0.6 mM g−1. Air oxidation of bituminous coals can increase their Cr(VI) removal capacities. The effect of air oxidation of coals on uptake capacity was more pronounced for Cr(VI) than Cr(III), but less than for Hg(II) and the other ions (Ca2+, Ba2+, Zn2+, Cd2) investigated. As previously found for Hg(II), redox mechanisms play an important role in Cr(VI) uptake, with sorption of the resultant Cr(III) being aided by the functionalities arising from oxidation of the coal surface. In acidic media, much of the resultant Cr(III) is exchanged back into solution by hydrogen ions, but some of the sorbed chromium is irreversibly bound to the coal. The reduction of Cr(VI) alone is often considered a satisfactory solution in view of Cr(III) being essentially non-toxic.  相似文献   

11.
Iron oxide coated sand (IOCS) as an adsorbent medium for removing hexavalent chromium (Cr(VI)) from industrial wastewater, as well as in permeable reactive barriers for remediation of Cr(VI) in aquifers is investigated in this study. An important feature was the use of a mathematical model for performance forecasting and process upscaling of IOCS fixed‐bed adsorber systems for Cr(VI) removal. Another significance aspect was the elucidation of IOCS surface mechanisms and interactions responsible for Cr(VI) sorption and reduction to the less toxic Cr(III). The adsorption equilibrium and mass‐transfer parameters for modeling were obtained from independent laboratory studies. Adsorber studies validated the predictive model and established the effectiveness of IOCS for Cr(VI) removal under different conditions. Model simulation studies demonstrated that adsorbent capacity, surface diffusion, and film transfer significantly influenced process dynamics. The study showed that IOCS can be used to remove Cr(VI) from contaminated waters, meeting the overall objectives of regulatory agencies. © 2016 American Institute of Chemical Engineers AIChE J, 62: 3717–3729, 2016  相似文献   

12.
BACKGROUND: The reduction of highly mobile and toxic hexavalent chromium by bacterial strains is considered to be a viable alternative to reduce Cr(VI) contamination, in soils and water bodies, emanating from the overburden dumps of chromite ores and mine drainage. The present study reports the isolation of Cr(VI) resistant bacterial strains from an Indian chromite mine soil and their potential use in reduction of hexavalent chromium. RESULTS: Among the isolates, a bacterial strain (CSB‐4) was identified as Bacillus sp. based on standard biochemical tests and partial 16SrRNA gene sequencing, which was tolerant to as high as 2000 mg L?1 Cr(VI) concentration. The strain was capable of reducing Cr(VI) to Cr(III) in different growth media. Under the optimized conditions pH ~7.0, 100 mg L?1 Cr(VI), 35 °C temperature and stirring speed 100 rpm, CSB‐4 reduced more than 90% of Cr(VI) in 144 h. The time course reduction data fitted well an exponential rate equation yielding rate constants in the range 3.22 × 10?2 to 6.5 × 10?3 h?1 for Cr(VI) concentration of 10–500 mg L?1. The activation energy derived from temperature dependence rate constants between 25 and 35 °C was found to be 99 kJ mol?1. The characterization of reduced product associated with bacterial cells by SEM‐EDS, FT‐IR and XRD was also reported. CONCLUSION: Reasonably high tolerance and reduction ability of indigenous Bacillus sp. (CSB‐4) for Cr(VI) under a wide range of experimental conditions show promise for its possible use in reclamation of chromite ore mine areas including soils and water bodies. Copyright © 2010 Society of Chemical Industry  相似文献   

13.
The photocatalytic reduction of Cr(VI) to the less toxic Cr(III) is presented in the presence of the polyoxometalates (POM) PW12O403− or SiW12O404− as photocatalyst and an organic substrate (salicylic acid or propan-2-ol) as electron donor. Cr(VI), as dichromate, is reduced to Cr(III), according to the 6:1 stoichiometry of PW12O404− versus Cr2O72− indicated from experiments in the dark. Increase of POM or salicylic acid (SA) concentration accelerates, till a saturation value, both the reduction of metal and the oxidation of the organic, suggesting that these two conjugate reactions act synergistically. The photocatalytic action of POM is not so important in the case of highly concentrated solutions of organics that exhibit direct photochemical reduction of Cr(VI), i.e. propan-2-ol (i-prOH), while it becomes important at low concentrations of i-prOH, especially for organics that do not react directly photochemically with Cr(VI), such as SA. Increase of Cr(VI) concentration enhances consumption of SA and Cr(VI) till an optimum value, due to inner filter effect. The method is suitable for a range of chromium concentration from 5–100 ppm achieving complete reduction of Cr(VI) to Cr(III) up to non-detected traces (>98%). The presence of oxygen does not influence the efficiency of SA and Cr(VI) consumption. In contrast to the semiconductor-based heterogeneous photocatalysis, the POM-based homogeneous process seems superior in the frame that: (i) it remains catalytic throughout illumination by providing more active sites and (ii) among the two POM used, the one that is more efficient in the degradation of the organic, that is PW12O403− compared to SiW12O404−, is also more efficient in reducing Cr(VI), due to a kinetic effect, and a compromise is not needed.  相似文献   

14.
A new solid extractant (designated PS-DETA-JS) in which sulfur-chlorinated jojoba wax is bound via an amine spacer group to polystyrene beads was synthesized. The absorption of mercury cations from acidic solutions and of chromate anions from saline solutions onto PS-DETA-JS was investigated. The sorption of mercury ions by the solid extractant was compared with that by liquid-sulfurized jojoba wax impregnated inside macroporous resins. The static and dynamic properties of dichromate sorption from 2–20 g/L NaCl solutions at pH 4.1 were studied. Selective sorption of Cr(VI) was obtained at low chromate concentrations (∼ 6 ppm) in saline aqueous solutions. Complete regeneration of the PS-DETA-JS resin was achieved after the reduction of Cr(VI) to Cr(III) and the elution of the Cr(III) with 1N HCl. © 1997 John Wiley & Sons, Inc.  相似文献   

15.
Adsorption of chromium by activated carbon from aqueous solution   总被引:3,自引:0,他引:3  
Adsorption isotherms of Cr(III) and Cr(VI) ions on two samples of activated carbon fibres and two samples of granulated activated carbons from aqueous solutions in the concentration range 20–1000 mg/l have been studied. The adsorption isotherms have been determined after modifying the activated carbon surfaces by oxidation with nitric acid, ammonium persulphate, hydrogen peroxide and oxygen gas at 350°C and after degassing at different temperatures. The adsorption of Cr(III) ions increases on oxidation and decreases on degassing. On the other hand, the adsorption of Cr(VI) ions decreases on oxidation and increases on degassing. The increase of Cr(III) and the decrease of Cr(VI) on oxidation and the decrease of Cr(III) and the increase of Cr(VI) on degassing have been attributed to the fact that the oxidation of the carbon surface enhances the amount of acidic carbon–oxygen surface groups while degassing eliminates these surface groups. Thus while the presence of acidic surface groups enhances the adsorption of Cr(III) cations, it suppresses the adsorption of Cr(VI) anions.  相似文献   

16.
BACKGROUND: Bioaccumulation and biosorption by Pichia stipitis yeast has not yet been explored. This paper evaluates, for the first time, the use of both viable and nonviable P. stipitis yeast to eliminate Cu(II) and Cr(III) from aqueous solutions. The effect of Cu(II) and Cr(III) ions on the growth and bioaccumulation properties of adapted and nonadapted biomass is investigated as a function of initial metal concentration. Binding capacity experiments using nonviable biomass are also performed as a function of temperature. RESULTS: The addition of Cu(II) and Cr(III) had a significant negative effect on the growth of yeast. Nonadapted cells could tolerate Cu(II) and Cr(III) ions up to a concentration of 75 ppm. The growth rate of nonadapted and adapted cells decreased with the increase in Cu(II) and Cr(III) concentration. Adapted P. stipitis biomass was capable of removing Cu(II) and Cr(III) with a maximum specific uptake capacity of 15.85 and 9.10 mg g−1, respectively, at 100 ppm initial Cu(II) and Cr(III) concentration at pH 4.5. Adsorption data on nonviable cells were found to be well modeled by the Langmuir and Temkin isotherms. The maximum loading capacity of dry biomass predicted from Langmuir isotherm for Cu(II) and Cr(III) at 20 °C were 16.89 and 19.2 mg g−1, respectively, at pH 4.5. Biosorptive capacities were dependent on temperature for Cu(II) and Cr(III) solutions. CONCLUSION: Cu(II)‐ and Cr(III)‐adapted cells grow and accumulate these ions at high ratios. On the other hand, nonviable P. stipitis was found to be an effective biosorbent for Cu(II) and Cr(III) biosorption. Copyright © 2008 Society of Chemical Industry  相似文献   

17.
《分离科学与技术》2012,47(4):555-561
The transport of Cr(VI) from acidic media through pseudo-emulsion based membrane strip dispersion (PEMSD) containing the ionic liquid (PJMTH+Cl?) as carrier in the form of a pseudo-emulsion with sodium hydroxide has been investigated. The ionic liquid was generated in situ by reaction of the primary amine Primene JMT and HCl. The transport of Cr(VI) is evaluated as a function of various experimental variables: stirring speed in the feed phase, concentration of Cr(VI) and HCl in the feed phase, carrier concentration, and organic diluents in pseudo-emulsion, and NaOH concentration in pseudo-emulsion as strippant. In PEMSD, pseudo-emulsion is an emulsion that is formed temporarily between the organic and the stripping solutions. Both solutions are separated when the stirring device is stopped. The value of the overall permeation coefficient obtained under standard experimental conditions was 3.1 × 10?3 cm s?1, whereas the transport process is controlled by diffusion of chromium species in the stagnant film of the feed phase. The performance of the system against other carriers (amines, quaternary phosphonium salt and quaternary ammonium salt) was also evaluated.  相似文献   

18.
Mixed oxide electrodes of Ti(IV) and Cr(III) were prepared by calcining Cr(OH)3 layers deposited on metallic titanium supports. This treatment produced a mixed oxide film of TiO2–Cr2O3 covered with a layer of pure Cr2O3. The electrochemical response (cyclic voltammetry) shows the presence of two or three oxidation peaks depending on the electrode preparation conditions. One peak may be interpreted as the oxidation of Cr(III) to Cr(VI) species and the appearance of other peaks is due to the presence of chromium atoms in oxidation states higher than (III). The results of chemical analyses, electrophoretic mobilities and acid-base potentiometric titrations on calcined Cr(OH)3 powders shows that the calcination step in air produced the decomposition of the Cr(III) hydroxide to the Cr(VI) oxide. Soluble Cr(VI) compounds were found in equilibrium with the suspended powder oxide which markedly affected the shape of the titrations curves. From the amount of Cr(VI) present in solution it was possible to correct the experimental 0-pH curves. These corrected data indicated that Cr(VI) soluble species adsorbed at the Cr2O3/electrolyte interface.  相似文献   

19.
Various organisms such as fungus are capable of reducing Cr(VI) to less toxic Cr(III). However, light-induced Cr(VI) reduction by fungus is less reported and needs to be explored since anthropogenic or natural activities may bring these two reactants into a sunlit environment. In this study, the interactions and reaction mechanisms of Cr(VI) on a model fungus, Neurospora crassa, were evaluated in the presence or absence of light. The influence of ferric ion, a widely distributed metal, on Cr(VI) reduction by the fungus was also investigated under illumination. The results show that 20–54% of added Cr(VI) (96.2 μM) was removed by 1 g of dead fungal biomass (i.e., 1–2.7 mg Cr(VI) reduction by 1 g biomass) at pH 1–3, after 6 h reaction in the dark. However, 96.2 μM Cr(VI) disappeared completely (i.e., 5 mg Cr(VI) reduction by 1 g biomass) under the same reaction time and experimental conditions when light was present. The rapid disappearance of Cr(VI) in solution was due to the reduction of Cr(VI) by the excited biomass upon light absorption, and the rates of redox reactions increased with a decrease at pH. Cr(VI) reduction could be further increased with the addition of 89.5 μM Fe(III) because the formation of Fe(II) from the photolysis of Fe–organic complexes enhanced Cr(VI) reduction. Spectroscopic studies indicated that the amide, NH, and carboxyl groups of N. c.-biomass may be responsible for initiating Cr(VI) reduction; comparatively, the cyclo-carbons of chitin, glucan, and their derivatives were more persistent to the oxidation by Cr(VI). Accordingly, fungi containing high amount of carboxyl, amide, and NH groups may be preferable as efficient reductants for scavenging Cr(VI) from environment. Upon the absorption of a renewable light source, Cr(VI) could be converted rapidly by the biomaterials to the less toxic Cr(III).  相似文献   

20.
BACKGROUND: This study compared the removal of aqueous Cr(VI) by multi‐walled carbon nanotubes (CNTs) modified by sulfuric acid, titanium dioxide (TiO2) and composite of CNTs and TiO2. RESULTS: More than 360 h contact time was needed to completely adsorb 3 mg L?1 of Cr(VI) by CNTs, indicating that the rate of adsorption by CNTs alone was slow. The reaction time approaching equilibrium depended on the Cr(VI) concentration. XPS analysis of CNTs after adsorbing Cr(VI) showed that the Cr(VI) on the surface of CNTs was partially reduced to Cr(III). A 3 mg L?1 solution of Cr(VI) was fully photocatalyzed by commercial TiO2 (Degussa P25) in less than 0.5 h under UV irradiation. Unlike P25, reduction by another commercial TiO2 (Hombikat UV100) took 4 h and more than 2 h were necessary for reduction by the composite. Thus the efficiency of Cr(VI) photo‐reduction by the composite was lower than by TiO2, but higher than that by CNTs. XPS analysis of TiO2 and composite showed the existence of both Cr(VI) and Cr(III) on their surfaces. CONCLUSION: In contrast to TiO2, the reduction rate of aqueous Cr(VI) using CNTs as adsorbent was slow. P25 had a markedly higher photocatalytic efficiency than the composite or UV100 alone. Using P25 to reduce aqueous Cr(VI) has a higher potential for practical application. The diameters of TiO2 and CNTs and the ratio of TiO2/CNTs are key problems in the preparation of TiO2/CNTs composite. Copyright © 2011 Society of Chemical Industry  相似文献   

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