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1.
The removal of hexavalent chromium from wastewater streams has received an considerable attention in recent years, since it can cause harmful effects on the environment. Several approaches, including adsorption, are recognized to tackle this problem, but unfortunately most of these processes are impressed with practical conditions of the experiments. The main objective of this study was to recognize applicable conditions for Cr(VI) removal from an industrial drainage using nature-derived adsorbents (brown coal and modified zeolite) and to make the process more adaptive by using adsorbents conjointly. Batch experiments were carried out by agitating Cr(VI) stock solution with adsorbents at room temperature. The influence of main operating parameters was explored, and the best proportion of the adsorbents was determined. Maximum sorption of Cr(VI) onto brown coal was observed at pH = 4 by adding 60 g L?1 adsorbent to contaminated solution. In case of using zeolite, the modification process was required, and the pH indicated a weak influence in a wide range (2–8). Optimum dosage of modified zeolite for Cr(VI) removal was 10 g L?1. The hybrid application of adsorbents with the mass ratio of brown coal/modified zeolite at (3:1) was capable of removing more than 99% of Cr(VI) from contaminated wastewater in the natural pH range of the wastewater. The adsorption of Cr(VI) by brown coal and modified zeolite followed Langmuir and Freundlich isotherm models, respectively. Sorption of Cr(VI) onto both brown coal and modified zeolite fitted well to pseudo-second-order rate reaction.  相似文献   

2.
The aim of this work was to evaluate the usefulness of Lemna minuta Kunth for the simultaneous removal of Cr(VI) and phenol. The impact of these contaminants on plant growth and some biochemical processes have also been discussed for a better understanding and utilization of this species in the field of phytoremediation. The optimal growth conditions and plant tolerance to Cr(VI) and/or phenol as well as removal were determined. Plants exposed to Cr(VI) and phenol were able to efficiently grow and remove both contaminants at high concentrations (up to 2.5 and 250 mg/L, respectively) after 21 days, indicating that they were resistant to mixed contamination. There were no significant differences between chlorophyll, carotene and malondialdehyde content of treated plants with respect to the controls, which would be due to an efficient antioxidant response. L. minuta showed a higher biomass than control without contaminant when was exposed to low concentrations of Cr(VI), suggesting an hormesis effect. The main removal process involved in chromium phytoremediation would be sorption or accumulation in the biomass. Moreover, our results suggest that phenol could be used as a donor of carbon and energy by these plants. These findings demonstrated that Lemna minuta Kunth might be suitable for treatment of different solutions contaminated with Cr(VI) and phenol, showing a high potential to be used in the treatment of effluents containing mixed contamination.  相似文献   

3.

Background

Reductive precipitation of hexavalent chromium (Cr(VI)) with magnetite is a well-known Cr(VI) remediation method to improve water quality. The rapid (<a few hr) reduction of soluble Cr(VI) to insoluble Cr(III) species by Fe(II) in magnetite has been the primary focus of the Cr(VI) removal process in the past. However, the contribution of simultaneous Cr(VI) adsorption processes in aged magnetite has been largely ignored, leaving uncertainties in evaluating the application of in situ Cr remediation technologies for aqueous systems. In this study, effects of common groundwater ions (i.e., nitrate and sulfate) on Cr(VI) sorption to magnetite were investigated using batch geochemical experiments in conjunction with X-ray absorption spectroscopy.

Results

In both nitrate and sulfate electrolytes, batch sorption experiments showed that Cr(VI) sorption decreases with increasing pH from 4 to 8. In this pH range, Cr(VI) sorption decreased with increasing ionic strength of sulfate from 0.01 to 0.1 M whereas nitrate concentrations did not alter the Cr(VI) sorption behavior. This indicates the background electrolyte specific Cr(VI) sorption process in magnetite. Under the same ionic strength, Cr(VI) removal in sulfate containing solutions was greater than that in nitrate solutions. This is because the oxidation of Fe(II) by nitrate is more thermodynamically favorable than by sulfate, leaving less reduction capacity of magnetite to reduce Cr(VI) in the nitrate media. X-ray absorption spectroscopy analysis supports the macroscopic evidence that more than 75 % of total Cr on the magnetite surfaces was adsorbed Cr(VI) species after 48 h.

Conclusion

This experimental geochemical study showed that the adsorption process of Cr(VI) anions was as important as the reductive precipitation of Cr(III) in describing the removal of Cr(VI) by magnetite, and these interfacial adsorption processes could be impacted by common groundwater ions like sulfate and nitrate. The results of this study highlight new information about the large quantity of adsorbed Cr(VI) surface complexes at the magnetite-water interface. It has implications for predicting the long-term stability of Cr at the magnetite-water interface.
Graphical abstract Effects of background anions (sulfate and nitrate) on the Cr(VI) surface coverage at the magnetite-waterinterface at pH 4 and 9
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4.
This study reports the potential ability of non-living biomass of Cabomba caroliniana for biosorption of Cr(III) and Cr(VI) from aqueous solutions. Effects of contact time, biosorbent dosage, pH of the medium, initial concentration of metal ion and protonation of the biosorbent on heavy metal–biosorbent interactions were studied through batch sorption experiments. Cr(III) was sorbed more rapidly than Cr(VI) and the pH of the medium significantly affected the extent of biosorption of the two metal species differently. Surface titrations showed that the surface of the biosorbent is positively charged at low pH while it is negatively charged at pH higher than 4.0. Protonation of the biosorbent increased its capacity for removal of Cr(III), while decreasing that of Cr(VI). FT-IR spectra of the biosorbent confirmed the involvement of –OH groups on the biosorbent surface in the chromium removal process. Kinetic and equilibrium data showed that the sorption process of each chromium species followed pseudo second-order kinetic model and both Langmuir and Freundlich isothermal models. A possible mechanism for the biosorption of chromium species by non-living C. caroliniana is suggested.  相似文献   

5.
6.
Inorganic elements analyses of Carapicuíba lake reveal that As, Cr, Pb and Mn are above the recommended drinking water standards. The mean total concentrations of toxic elements in surface water decrease in the order Mn > Cr > Pb > As. At elevated concentrations, toxic elements like Cr can accumulate in soils and enter the food chain, leading to serious health hazards and threatening the long-term sustainability of the local ecosystem. Absorbing materials has often been used to improve water quality. In this investigation three types of material were studied: the natural zeolite (mordenite); synthetic goethite and the powdered block carbon modified. The adsorption of Pb2+ and Mn2+ onto natural zeolite as a function of their concentrations was studied at 24°C by varying the metal concentration from 100 to 400 mg L−1 while keeping all other parameters constant. The low-cost zeolites removed Pb from water without any pretreatment at pH values <6. The maximum adsorption attained was as follows: Pb2+ 78.7% and Mn2+ 19.6%. The modified powdered block carbon effectively removed As(V) and Cr(VI) while goethite removed more chromate than arsenate in the pH range 5–6. Results of this study will be used to evaluate the application these materials for the treatment of the Carapicuíba lake’s water.  相似文献   

7.
Sorption of U(VI) on Hanford fine sand (HFS) with varying Fe-oxide (especially ferrihydrite) contents showed that U(VI) sorption increased with the incremental addition of synthetic ferrihydrite into HFS, consistent with ferrihydrite being one of the most reactive U(VI) sorbents present in natural sediments. Surface complexation model (SCM) calculations for U(VI) sorption, using only U(VI) surface-reaction constants obtained from U(VI) sorption data on freshly synthesized ferrihydrite at different pHs, were similar to the measured U(VI) sorption results on pure synthetic ferrihydrite and on HFS with high contents of ferrihydrite (5 wt%) added. However, the SCM prediction using only U(VI) sorption reactions and constants for synthetic ferrihydrite overestimated U(VI) sorption on the natural HFS or HFS with addition of low amounts of added ferrihydrite (1 wt% added). Over-predicted U(VI) sorption was attributed to reduced reactivity of natural ferrihydrite present in Hanford Site sediments, compared to freshly prepared synthetic ferrihydrite. Even though the SCM general composite (GC) approach is considered to be a semi-quantitative estimation technique for contaminant sorption, which requires systematic experimental data on the sorbent–sorbate system being studied to obtain credible SCM parameters, the general composite SCM model was still found to be a useful technique for describing U(VI) sorption on natural sediments. Based on U(VI) batch sorption results, two simple U(VI) monodentate surface species, SO_UO2HCO3 and SO_UO2OH on ferrihydrite and phyllosillicate in HFS, respectively, can be successfully used to describe U(VI) sorption onto Hanford Site sediment contacting varying geochemical solutions.  相似文献   

8.
A sequential biological permeable reactive barrier (PRB) was determined to be the best option for remediating groundwater that has become contaminated with a wide range of organic contaminants (i.e., benzene, toluene, ethylbenzene, xylene and polyaromatic hydrocarbons), heavy metals (i.e., lead and arsenic), and cyanide at a former manufactured gas plant after 150 years of operation in Portadown, Northern Ireland. The objective of this study was to develop a modified flyash that could be used in the initial cell within a sequential biological PRB to filter complex contaminated groundwater containing ammonium. Flyash modified with lime (CaOH) and alum was subjected to a series of batch tests which investigated the modified cation exchange capacity (CEC) and rate of removal of anions and cations from the solution. These tests showed that a high flyash composition medium (80%) could remove 8.65 mol of ammonium contaminant for every kilogram of medium. The modified CEC procedure ruled out the possibility of cation exchange as the major removal mechanism. The medium could also adsorb anions as well as cations (i.e., Pb and Cr), but not with the same capacity. The initial mechanism for Pb and Cr removal is probably precipitation. This is followed by sorption, which is possibly the only mechanism for the removal of dichromate anions. Scanning electron microscopic analysis revealed very small (<1 μm) cubic highly crystalline precipitates on the flyash, although this new crystalline zeolite growth did not occur rapidly enough to enable productive zeolite formation. Surface area measurements showed that biofilm growth on the medium could be a major factor in the comparative reduction of surface area between real and synthetic contaminant groundwaters. The modified flyash was found to be a highly sorptive granular material that did not inhibit microbiological activity, however, leaching tests revealed that the medium would fail as a long-term barrier material.  相似文献   

9.
The effects of elevated pH, ionic strength, and temperature on sediments in the vadose zone are of primary importance in modeling contaminant transport and understanding the environmental impact of tank leakage at nuclear waste storage facilities like those of the Hanford site. This study was designed to investigate biotite dissolution under simulated high level waste (HLW) conditions and its impact on Cr(VI) reduction and immobilization. Biotite dissolution increased with NaOH concentrations in the range of 0.1 to 2 mol L-1. There was a corresponding release of K, Fe, Si, and Al to solution, with Si and Al showing a complex pattern due to the formation of secondary zeolite minerals. Dissolved Fe concentrations were an order of magnitude lower than the other elements, possibly due to the formation of green rust and Fe(OH)2. The reduction of Cr(VI) to Cr(III) also increased with increased NaOH concentration. A homogeneous reduction of chromate by Fe(II)aq released through biotite dissolution was probably the primary pathway responsible for this reaction. Greater ionic strengths increased biotite dissolution and consequently increased Fe(II)aq release and Cr(VI) removal. The results indicated that HLW would cause phyllosilicate dissolution and the formation of secondary precipitates that would have a major impact on radionuclide and contaminant transport in the vadose zone at the Hanford site.  相似文献   

10.
Adsorption of Cr(VI) on γ-alumina was investigated as a function of ionic strength (0.001, 0.01 and 0.1 M NaNO3), pH (4-10), Cr(VI) concentration (10−4 or 10−5 M with 5 g/L solid) and pCO2 (0, atmospheric, 2.5%). Cr(VI) sorption is significant at low pH and decreases with increasing pH, with 50% of the Cr(VI) adsorbed between pH ∼6.5 and 8. Adsorption varies little with ionic strength or pCO2 under most of the studied conditions. However, at low pH under high ionic strength and especially at high ionic strength and high pCO2, Cr(VI) sorption on γ-alumina is suppressed. The adsorption edge data were used to parameterize constant capacitance (CCM), diffuse double layer (DLM) and triple layer (TLM) surface complexation models. None of the models entirely captures the full range of observed adsorption dependence on ionic strength and sorbate/sorbent ratio. The best fits to the full dataset are produced by the CCM, mostly because it has ionic-strength dependent stability constants. The more sophisticated TLM, which requires the most fitting parameters, does not produce better fits than the simpler CCM or DLM approaches for the conditions tested in this study.  相似文献   

11.
The discharge of industrial effluents containing hexavalent chromium can be very harmful for the environment. Therefore, Cr(VI) should be removed from contaminated water, and especially from wastewater, to prevent its discharge into the environment. This study is aimed at analyzing the factors that affect the removal of Cr(VI) with the use of almond green hull and ash adsorbent. The effects of pH (2–10), adsorbent dose (2–24 g/L), Cr(VI) concentration (10–100 mg/L), exposure time (1–60 min), and temperature (5–50 °C) were examined. The surface morphology, pore size of adsorbent surfaces were characterized with SEM, EDX, FTIR. Maximum removal occurred at pH = 2. Results showed that the removal yield increased with the rise of exposure time and temperature. The data indicate that due to limited site on adsorbent surface, the removal efficiency decreased as initial Cr(VI) concentration increased. When the adsorbent dose was increased, the removal yield increased in the case of the bioadsorbent as well; however, in the ash adsorbent, there was an increase followed by a decreasing trend. The study highlights that almond green hull can be more efficient than its ash in the removal of Cr(VI) from aqueous solution. As a general result of study, it can be argued that almond green hull bioadsorbent and the obtained carbon are able to remove Cr(VI) from aqueous solutions; thus, they can be used as efficient and economical substitutes for existing adsorbents like activated carbon, for the removal of chromium from polluted aqueous solutions.  相似文献   

12.
Batch sorption system using co-immobilized (activated carbon and Bacillus subtilis) beads as adsorbent was investigated to remove Cr(VI) from aqueous solution. Fourier transform infrared spectroscopy analysis showed the functional groups of both bacteria and activated carbon in co-immobilized beads. Experiments were carried out as a function of contact time (5–300 min), initial metal concentration (50–200 mg L?1), pH (2–8), and adsorbent dose (0.2–1 g L?1). The maximum percentage of removal was found to be 99 %. Langmuir model showed satisfactory fit to the equilibrium adsorption data of co-immobilized beads. The kinetics of the adsorption followed pseudo-second-order rate expression, which demonstrates that chemisorption plays a significant role in the adsorption mechanism. The significant shift in the Fourier transform infrared spectroscopy peaks and a Cr peak in the scanning electron microscope–energy dispersive spectroscopy spectra further confirmed the adsorption. The results indicate that co-immobilized beads can be used as an effective adsorbent for the removal of Cr(VI) from the aqueous solution.  相似文献   

13.
This work describes a laboratory study concerning the adsorption of isopropylxanthate ions onto modified zeolites particles. The separation of the loaded carrier and their removal, from aqueous solutions, was conducted by flocculation followed by dissolved air flotation, DAF. The zeolite employed was a natural sample (approximately 48% clinoptilolite and 30% mordenite) which was previously treated with sodium ions (activation) and modified with copper ions (Cu–Z) before the xanthate ions uptake. Adsorption capacities (qm) for Cu–Z were 0.34 meq g− 1 for the powdered form, and 1.12 meq g− 1 for the floc form. The adsorption capacity for the floc form appears to involve an enhanced electrostatic adsorption due to the positive sites on the floc surface. In all cases, the isopropylxanthate concentration in the treated water was found to be negligible (< 0.04 mg L− 1). The flotation technique showed to be a fast process, requires a low recycle ratio (20%) in air saturated water, and the treated water ended up with a very low residual turbidity (6.8 NTU). It is believed that this adsorption–flotation technique, here named adsorptive particulate flotation, using activated and modified natural zeolite has a high potential as an alternative for pollutants removal (copper and isopropylxanthate ions) from waste mining effluents.  相似文献   

14.
《Applied Geochemistry》2004,19(7):1123-1135
About 200 samples from selected public supply, domestic, and observation wells completed in alluvial aquifers underlying the western Mojave Desert were analyzed for total dissolved Cr and Cr(VI). Because Cr(VI) is difficult to preserve, samples were analyzed by 3 methods. Chromium(VI) was determined in the field using both a direct colorimetric method and EPA method 218.6, and samples were speciated in the field for later analysis in the laboratory using a cation-exchange method developed for the study described in this paper. Comparison of the direct colorimetric method and EPA method 218.6 with the new cation-exchange method yielded r2 values of 0.9991 and 0.9992, respectively. Total dissolved Cr concentrations ranged from less than the 0.1 μg/l detection limit to 60 μg/l, and almost all the Cr present was Cr(VI). Near recharge areas along the mountain front pH values were near neutral, dissolved O2 concentrations were near saturation, and Cr(VI) concentrations were less than the 0.1 μg/l detection limit. Chromium(VI) concentrations and pH values increased downgradient as long as dissolved O2 was present. However, low Cr(VI) concentrations were associated with low dissolved O2 concentrations near ground-water discharge areas along dry lakes. Chromium(VI) concentrations as high as 60 μg/l occurred in ground water from the Sheep Creek fan alluvial deposits weathered from mafic rock derived from the San Gabriel Mountains, and Cr(VI) concentrations as high as about 36 μg/l were present in ground water from alluvial deposits weathered from less mafic granitic, metamorphic, and volcanic rocks. Chromium(III) was the predominant form of Cr only in areas where dissolved O2 concentrations were less than 1 mg/l and was detected at a median concentration of 0.1 μg/l, owing to its low solubility in water of near-neutral pH. Depending on local hydrogeologic conditions and the distribution of dissolved O2, Cr(VI) concentrations may vary considerably with depth. Samples collected under pumping conditions from different depths within wells show that Cr(VI) concentrations can range from less than the 0.1 μg/l detection limit to 36 μg/l in a single well and that dissolved O2 concentrations likely control the concentration and redox speciation of Cr in ground water.  相似文献   

15.
We have used synchrotron-based soft X-ray core-level photoemission and adsorption spectroscopies to study the reaction of aqueous sodium chromate solutions with freshly fractured pyrite surfaces. Pyrite surfaces were reacted with 50 μM sodium chromate solution at pH 7 for reaction times between 1 min and 37 hr. Additional experiments were performed at pH 2 and pH 4 with 50 μM sodium chromate solutions and at pH 7 with 5 mM solutions. At chromate concentrations of 50 μM, all chromium present on the pyrite surface was in the form of Cr(III), while at 5 mM, both Cr(III) and Cr(VI) were present at the pyrite surface. Minor quantities of oxidized sulfur species (sulfate, sulfite, and zero-valent sulfur) were identified as reaction products on the pyrite surface. The amount of oxidized sulfur species observed on the surface was greater when pyrite was reacted with 5 mM Cr(VI) solutions because the rate of chromium deposition exceeded the rate of dissolution of pyrite oxidation products, effectively trapping Cr(VI) and oxidized sulfur species in an overlayer of iron(III)-containing Cr(III)-hydroxide. This work shows that pyrite, an extremely cheap and readily available waste material, may be suitable for the removal of hexavalent chromium from acidic to circumneutral waste streams. The reduced chromium ultimately forms a coating on the pyrite surface, which passivates the pyrite surface towards further oxidation.  相似文献   

16.
The use of natural zeolites for environmental applications is gaining new research interests mainly due to their properties and significant worldwide occurrence. The present work describes the characterization of a natural Chilean zeolite and the results as adsorbent for ammonia from aqueous solutions. The zeolitic-rich tuff sample, mainly composed of clinoptilolite and mordenite, consisted of 13 μm mean volumetric particle diameter, 55 m2 g−1 (methylene blue adsorption) and 177 m2 g−1 (nitrogen adsorption) of specific surface area. Particles were negatively charged over a broad pH range (with or without ammonia) and 1.02 meq NH4+ g−1 cation-exchange capacity. The ammonia removal appears to proceed through ion-exchange and rapid kinetics (rate constant of 0.3 min−1) at neutral pH value, with removal capacities up to 0.68 meq NH4+ g−1. The Langmuir isotherm model provided excellent equilibrium data fitting (R2=0.97). Results indicate a significant potential for the Chilean natural zeolite as an adsorbent/ion-exchange material for wastewater treatment and water reuse applications.  相似文献   

17.
18.
This study deals with the use of the natural, low-cost sorbents bentonite and zeolite for the removal of lead from aqueous solutions. The mineral material is from large deposits of bentonite and zeolite that have been discovered recently in Iran. Experimental and modeling data from our kinetic and equilibrium investigations reveal that (1) the pseudo-second-order kinetic model gave the best fit, and (2) the Koble–Corrigan sorption model describes the interaction between Pb(II) and the two mineral materials better than the Freundlich and Langmuir models. However, the sorption of Pb(II) ions by zeolite and bentonite is complex and probably involves several mechanisms. The experimental data show that natural zeolite and bentonite used in this study exhibited a reasonable sorption capacity for Pb(II), and thus may be useful for the immobilization of Pb(II) from polluted sites.  相似文献   

19.
The effects of soil minerals on chromate (CrVIO4 2-, noted as Cr(VI)) reduction by sulfide were investigated in the pH range of 7.67 to 9.07 under the anoxic condition. The examined minerals included montmorillonite (Swy-2), illite (IMt-2), kaolinite (KGa-2), aluminum oxide (γ-Al2O3), titanium oxide (TiO2, P-25, primarily anatase), and silica (SiO2). Based on their effects on Cr(VI) reduction, these minerals were categorized into three groups: (i) minerals catalyzing Cr(VI) reduction – illite; (ii) minerals with no effect – Al2O3; and (iii) minerals inhibiting Cr(VI) reduction- kaolinite, montmorillonite, SiO2 and TiO2 . The catalysis of illite was attributed primarily to the low concentration of iron solubilized from the mineral, which could accelerate Cr(VI) reduction by shuttling electrons from sulfide to Cr(VI). Additionally, elemental sulfur produced as the primary product of sulfide oxidation could further catalyze Cr(VI) reduction in the heterogeneous system. Previous studies have shown that adsorption of sulfide onto elemental sulfur nanoparticles could greatly increase sulfide reactivity towards Cr(VI) reduction. Consequently, the observed rate constant, k obs, increased with increasing amounts of both iron solubilized from illite and elemental sulfur produced during the reaction. The catalysis of iron, however, was found to be blocked by phenanthroline, a strong complexing agent for ferrous iron. In this case, the overall reaction rate at the initial stage of reaction was pseudo first order with respect to Cr(VI), i.e., the reaction kinetics was similar to that in the homogeneous system, because elemental sulfur exerted no effect at the initial stage prior to accumulation of elemental sulfur nanoparticles. In the suspension of kaolinite, which belonged to group (iii), an inhibitive effect to Cr(VI) reduction was observed and subsequently examined in more details. The inhibition was due to the sorption of elemental sulfur onto kaolinite, which reduced or completely eliminated the catalytic effect of elemental sulfur, depending on kaolinite concentration. This was consistent with the observation that the catalysis of externally added elemental sulfur (50 μM) on Cr(VI) reduction would disappear with a kaolinite concentration of more than 5.0 g/L. In kaolinite suspension, the overall reaction rate law was:
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20.
The batch removal of Cr(VI) from aqueous solution using lignocellulosic solid wastes such as sawdust and pine leaves under different experimental conditions was investigated in this study. The influence of pH, temperature, contact time, initial concentration of Cr(VI) and particle size on the chromium removal was investigated. Adsorption of Cr(VI) is highly pH-dependent and the results indicate that the optimum pH for the removal is 2. The capacity of chromium adsorption at equilibrium by these natural wastes increased with absorbent concentration. Temperature in the range of 20–60 °C showed a restricted effect on the adsorption capacity of pine leaves, but had a considerable effect on the adsorption capacity of sawdust. The capacity of chromium adsorption at the equilibrium increased with the decrease in particle sizes. The suitability of adsorbents was tested with Langmuir and Freundlich isotherms and their constants were evaluated. Results indicated that the Freundlich model gave a better fit to the experimental data in comparison with the Langmuir equation. The study showed that lignocellulosic solid wastes such as sawdust and pine leaves can be used as effective adsorbents for removal of Cr(VI) from wastewater.  相似文献   

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