Removal of chromium (VI) from water streams: a thermodynamic study

The chemical speciation of water solutions containing chromium oxyanions in various ratios is calculated (with the aid of available computer code Mineql Plus, Geochemist Workbench and Visual Minteq) and discussed. The effect of solution pH, total concentration of each species studied, and the presence of other species in solution are calculated and presented in the form of thermodynamic speciation diagrams. Electrochemical diagram (correlating pH to Eh) has been calculated as well. The conditions of Cr(VI) reduction to Cr(III) and the subsequent solid phase precipitation are given as a function of redox potential and pH. Surface reactions that might occur between the chromate ions in the solution and redox couples as Fe²⁺/Fe³⁺ on the surface of sorbents are also discussed. Moreover, experimental sorption data of hexavalent chromium onto synthetic magnetite are presented and discussed with the aid of the calculated diagrams. A mechanism is elucidated for the efficient removal of Cr(VI) from water streams at low pH values, and zeta potential data of synthetic magnetite with and without Cr(VI) are presented, which agree well with the mechanism proposed.     

Coordination chemistry and the carcinogenicity and mutagenicity of chromium(VI)

Chromate is a known carcinogen, it is only in recent years that the molecular mechanisms by which this toxicity may be expressed have been investigated. The toxicity of chromate may be mediated by the reaction of chromium(VI) with glutathione (GSH) to generate relatively stable chromium(V) complexes and other more reactive intermediates. The conditions favouring the formation of such complexes have been studied. Reactive intermediates generated during the reduction of chromate by GSH include thionyl radicals and at least two relatively stable chromium(V) species (g -1.996 and g -.986). Mixtures of chromium(VI) and glutathione and a chromium(V) complex of glutathione, which we have isolated from the reaction (g = 1.996), are capable of causing strand breaks in bacteriophage PM2 DNA. In contrast a chromium(III) complex of GSSG, one of the final products of the reaction between GSH and chromium(VI), does not damage DNA in closed circle assays. These observations support the suggestion that reactive intermediates generated during the reduction of chromium(VI) provide one route by which the genotoxicity of chromate may be expressed.     

Biosorption of chromium(VI), nickel(II) and copper(II) ions from aqueous solutions using Pithophora algae

The biosorption of heavy metals is considered to be one of the best alternatives for the treatment of wastewater. The metal binding capacity of algae and acid-treated algae is investigated to find out the removal characteristics of Cr(VI), Ni(II) and Cu(II) ions from single metal solutions. Batch experiments are conducted and the study is extended to investigate the effect of pH, amount of adsorbent and adsorbate concentration on the extent of biosorption. The results indicate that the adsorption capacity of algae depends strongly on pH. The maximum adsorption of Cr(VI), Ni(II) and Cu(II) occurs at pH values of 2, 7 and 4.3, respectively. The adsorption process follows first-order kinetic equation. The data obtained are correlated with Freundlich and Langmuir adsorption isotherms.     

Preparation of magnetic nanocomposite beads and optimizing the conditions for effective removal of U(VI) from aqueous solutions

Magnetic ion-imprinted polymers (IIPs) were prepared by precipitate polymerization and leached with HCl to remove uranium. Their ability to remove hexavalent uranium from wastewater effluents was studied. Batch adsorption studies to determine the optimum conditions of U(VI) removal were conducted at different levels of sample pH, sorbent amount, agitation time, and initial uranium concentration. It was observed that, under optimum conditions (i.e. pH 4, adsorbent amount of 50 mg, 45 min agitation time, and initial U(VI) concentration of 2 mg L^?1), the maximum removal of U(VI) cations was >98% and 80% for the magnetic IIP and the corresponding magnetic non-imprinted polymers (NIP), respectively. Langmuir and Freundlich isotherms were used to describe the adsorption of U(VI) onto magnetic IIP and NIP. The adsorption capacity of U(VI) was determined to be 1.06 and 0.85 mg g^?1 for the two isotherms, respectively. The order of selectivity was found to be U(VI) > Fe(III) > Pb(II). For six cycles of regeneration and reuse, the magnetic polymers maintained their stabilities with only a 4% loss in the extraction efficiency. The average extraction efficiencies of the magnetic polymers for the spiked acid mine drainage and sewage wastewater effluents were 71% and 58% for the magnetic IIP and NIP, respectively. From powder X-ray diffraction analysis, application of the Scherrer equation yielded magnetic nanoparticles of an average mean diameter of 11.9 nm. Thermo-gravimetric analysis revealed that the HCl-leached magnetic polymers had a magnetite residual weight of 5%.     

Removal of toxic chromium(VI) from aqueous solution by activated carbon using Casuarina equisetifolia

Highly activated carbon from the seed husk of Casuarina Casuarinas equisetifolia, a worldwide famous plant, have been prepared and tested for the removal of toxic Cr(VI) from its aqueous solution. The adsorbent was investigated for influences of initial chromium concentration (75, 100, 125, and 150 mg l^-1), pH, contact time, and quantity of carbon on removal of Cr(VI) from aqueous solution at room temperature (25±2 °C). The adsorption kinetic of Cr(VI) was studied, and the rates of sorption were found to conform to pseudo-second-order kinetics with a good correlation (R²≥0.99). The Langmuir and Freundlich models fit the isotherm data well. Furthermore, the Gibbs free energy was obtained for each system and was found to be-5.29 kJ mol^-1 for removal of Cr(IV). The negative value of Δ G° indicates the feasibility and spontaneous nature of adsorption. The results indicate that acidic pH (1.05) supported the adsorption of Cr(IV) on activated carbon. The maximum adsorption capacity of Cr(VI) on activated carbon was about 172.4 mg g^-1 at pH 1.05.     

Mass-transfer processes of chromium(VI) adsorption onto guava seeds

The chromium(VI) biosorption onto guava seeds, as an alternative method for Cr⁶⁺ removal from aqueous solutions, was investigated. The parameters affecting kinetics and equilibrium of Cr⁶⁺ adsorption onto guava seeds were studied. An external mass-transfer diffusion coefficient k and intra-particle diffusion coefficient k_i were determined to measure the rate-limiting step of adsorption. A single external mass-transfer diffusion model and intra-particle diffusion models were used. The effects of initial pH, sorbent mass, and initial Cr⁶⁺ concentrations on mass-transfer coefficients were investigated. The external mass-transfer coefficient has an average value of 7.2×10^-3 cm s^-1, while the intra-particle mass-transfer diffusion coefficient was 0.34 mg g^-1 min^-0.5. This indicates that external diffusion to the guava seeds surface and intra-particle diffusion are both involved in the sorption process. The isotherm equilibrium data were well fitted by the Langmuir and Freundlich models with an average correlation coefficient R²=0.98. The maximum removal of Cr⁶⁺ was obtained at pH 1 (about 100% for adsorbent dose of 15 g l^-1 and 25 mg l^-1 initial concentration of Cr⁶⁺). The results indicated that the guava seeds exhibit acceptable sorption capacity.     

Evaluation of metabisulfite and a commercial steel wool for removing chromium(VI) from wastewater

Efficiency of metabisulfite and a commercial steel wool as reducing agents in the removal of Cr(VI) from wastewaters was evaluated. Chromium(VI) was converted to Cr(III), precipitated with NaOH, and removed by filtration. A reduction of more than 1.0 × 10⁵ and 4.0 × 10⁵ fold in total Cr and the Cr(VI) concentrations, respectively, was observed by employing steel wool masses as low as 0.4420 g to 30-mL solutions of wastewater. Chromium(III) hydroxide obtained after the treatment was recycled and used as marker in cattle nutrition studies. The liquid residue obtained after the treatment was reused as precipitation agent replacing NaOH.     

Behavioural toxicity in zebrafish (Danio rerio) exposed to waterborne zinc and chromium(VI)

This study is to investigate the behavioural responses of zebrafish to the toxic effects of waterborne zinc and chromium(VI). Swimming performance of fish was tracked by a real-time toxicity bio-monitoring system and transformed into data to calculate individual and fish school behavioural endpoints. Behavioural responses under metals were in accordance with the Stepwise Behavioural Response model. Significant and concentration-dependent effects on swimming speed and turning times were found at concentrations equal to or higher than 3.5 mg L^-1 for zinc and 0.7 mg L^-1 for chromium. Swimming height significantly declined in concentrations equal to or higher than 3.5 mg L^-1 under zinc exposure, while for the chromium treatment, it significantly increased in lower concentration exposures and decreased in higher concentration exposures. Average distance and dispersion of fish school decreased at the beginning but there were no obvious changes during the whole exposure period. Behavioural responses under metal exposures were time-dependent: avoidance (increased speed and turning times and decreased average distance and dispersion) might be the first response and followed by height changes. Changes in behavioural endpoints ‘swimming speed and height’ can be used as early stress responses for acute aquatic metal contamination as part of ecological risk assessment.     

Changes in chromium distribution during the electrodialytic remediation of a Cr (VI)-contaminated soil

A laboratory study has been carried out to determine the feasibility of in situ remediation of chromium (VI)-contaminated soil using electrodialysis in relation to its speciation in soil. This technique is best suited for low-permeability soils or sediments, which may be difficult to remediate by other means and implies the application of a low-intensity direct current to the soil, which is separated from the electrode compartments by ion-exchange membranes. A clayey soil was prepared for use in the experiments and was characterized before being mixed with a solution of potassium dichromate for several days to produce a final Cr content of 4,056 mg/kg of soil dry wt. Remediation tests were carried out under constant-voltage conditions for periods of 7–14 days and the evolution of applied current to the cell, pH, and conductivity of the electrolytes were recorded periodically. Fractionation of chromium was determined for soil samples before and after remediation using a standardized four-step sequential extraction procedure (SEP) with acetic acid, hydroxylamine, hydrogen peroxide, and aqua regia solutions. Results show that chromium is mobilized from the most labile phases (soluble/exchangeable/carbonate). In a 15 V test, SEP results show that the amount of chromium extracted in the first step drops from 80% to 9%, but also that changes in the total chromium distribution occur during the treatment with some transferred to other soil phases that are more difficult to mobilize.     

Ferrate(VI) oxidation of ibuprofen: A kinetic study

The kinetics of ferrate(VI) (Fe^VIO₄ ²⁻, Fe(VI)) oxidation of an antiphlogistic drug, ibuprofen (IBP), as a function of pH (7.75–9.10) and temperature (25–45°C) were investigated to see the applicability of Fe(VI) in removing this drug from water. The rates decrease with an increase in pH and the rates are related to protonation of ferrate(VI). The rates increase with an increase in temperature. The E _a of the reaction at pH 9.10 was calculated as 65.4±6.4 kJ mol⁻¹. The rate constant of the HFeO₄ ⁻ with ibuprofen is lower than with the sulphur drug, sulfamethoxazole. The use of Fe(VI) to remove ibuprofen is briefly discussed.     

Cr (VI) and Fe (III) removal using Cajanus cajan husk

Husk of tur dal (Cajanus cajan) was investigated as a new biosorbent for the removal of Fe (III) and Cr (VI) ions from aqueous solutions. Parameters like agitation time, adsorbent dosage and pH were studied at different initial Fe (III) and Cr (VI) concentrations. The biosorptive capacity of the Tur dal husk was dependent on the pH of the chromium and iron solution, with pH 2 and 2.5 respectively being optimal. The adsorption data fit well with Langmuir and Freundlich isotherm models. The practical limiting adsorption capacity (qmax) calculated from the Langmuir isotherm was 96.05 mg of Cr(VI)/ g of the biosorbent at an initial pH of 2.0 and 66.65 mg/g at pH 2.5. The infrared spectra of the biomass revealed that hydroxyl, carboxyl and amide bonds are involved in the uptake of Cr (VI) and Fe (III) ions. Characterisation of tur dal husk has revealed that it is an excellent material for treating wastewaters containing low concentration of metal ions.     

Kinetics of the oxidation of endocrine disruptor nonylphenol by ferrate(VI)

The kinetics of the oxidation of endocrine disruptor nonylphenol (NP) by potassium ferrate(VI) (K₂FeO₄) in water as a function of pH 8.0–10.9 at 25°C is presented. The observed second-order rate constants, k _obs, decrease with an increase in pH 269–32 M^?1 s^?1. The speciation of Fe(VI) (HFeO ₄ ^? and FeO ₄ ^2? ) and NP (NP–OH and NP–O^?) species was used to explain the pH dependence of the k _obs values. At a dose of 10 mg L^?1 (50 μM) K₂FeO₄, the half-life for the removal of NP by Fe(VI), under water treatment conditions, is less than 1 min.     

Biosorption of Cr(VI) using low cost sorbents

Waste products from industrial operations, such as yohimbe bark, grape stalks, cork and olive stones were investigated for the removal of Cr(VI) from aqueous solutions. Equilibrium batch experiments at room temperature were performed. Metal uptake showed a pH-dependent profile and optimum uptake at initial pH between 2.0–3.0. Slight influence of NaCl on metal uptake was observed. The sorption data fitted well to the Langmuir model within the concentration range studied. Grape stalks proved to be the most efficient sorbent followed by yohimbe bark, cork and olive stones. N. Fiol is the recipient of the 2002 ACE Environmental Chemistry Award     

Metabolic responses in zebrafish (Danio rerio) exposed to zinc and cadmium by nuclear magnetic resonance -based metabolomics

Heavy metals are common marine and soil pollutants that are mainly the result of industrial activity, and are a threat to the environment and human health. In this study, ¹H nuclear magnetic resonance (NMR)-based metabolomics was applied to adult Danio rerio to monitor the metabolic change as a response to ZnCl₂ and CdCl₂ exposure at different concentrations for 72?h. NMR spectroscopy was used to identify and quantify the metabolites extracted from D. rerio. The metabolite profiles of the control and heavy metal exposed group were classified by partial least squares – discriminant analysis (PLS-DA) analysis, and potential contaminant-specific biomarkers were suggested. For the ZnCl₂-exposed zebrafish, the levels of ATP, aspartate and NAD⁺ were increased, whereas the levels of formate, inosine, hypoxanthine and succinate decreased. In addition, the CdCl₂-exposed zebrafish showed an increase in the levels of ATP and formate and a decrease in the levels of glutamate, inosine and glutathione. Overall, Zn and Cd may lead to neurotoxicity, disturbances in the energy metabolism and oxidative stress. Our finding demonstrated that the application of NMR-based metabolomics might be useful for detecting the toxicity caused by sub-lethal concentrations of heavy metal contaminants in the environment.     

The effects of KI/Se(VI) molar ratio and initial concentration of Se(VI) on the reduction of Se(VI) to Se(IV) by KI

In this study, potassium iodide (KI) was found to be capable of reducing selenium(VI) to selenium(IV). When KI was added to Se(VI) solution, the Se(VI) concentration rapidly decreased with an increase in the KI/Se(VI) molar ratio. By using the potential-pH equilibrium diagram for the selenium/water system, we confirmed that Se(VI) reduced to Se(IV) because the potential of the solution shifted to the stable Se(IV) region upon the addition of KI. This reduction accompanies the oxidation of I⁻ to I₃⁻. The reduction of Se(VI) by KI was found to be effective for concentrated Se(VI) solutions.     

Removal of Cr(VI) from aqueous solution using waste weed, Salvinia cucullata

Biosorption studies of Cr(VI) were carried out using waste weed, Salvinia cucullata. Various adsorption parameters were studied, such as agitation speed, contact time, pH, particle size, and concentrations of adsorbent and adsorbate. The equilibrium was achieved in 12 h. A lower pH favoured adsorption of Cr(VI). The kinetics followed pseudo-second-order rate equations. The adsorption isotherm obeyed both the Langmuir and Freundlich models. The calculated activation energy (1.1 kJ mol^-1) suggested that the adsorption followed a diffusion-controlled mechanism. Various thermodynamic parameters such as Δ G^°, Δ H^°, and Δ S^° were also calculated. The positive values of enthalpy indicated the endothermic nature of the reaction, and Δ S^° showed the increasing randomness at the solid liquid interface of Cr(VI) on the adsorbent, which revealed the ease of adsorption reaction. These thermo-dynamic parameters showed the spontaneity of the reaction. The maximum adsorption of uptake (232 mg g^-1) compared well with reported values of similar adsorbents. The rate-determining step was observed to follow an intra-particle diffusion model.     

北固山芦苇湿地土壤对铜铬(VI)的吸附研究

北固山芦苇(Phragmites communis)湿地是长江中下游典型湿地类型之一,沿江工业化和城市化的快速发展使其面临严重的重金属污染威胁.然而,目前有关湿地重金属污染的吸附尤其竞争吸附的研究还少见报道.该文以北固山芦苇湿地为对象,采用平衡法对Cu2+、Cr(VI)在湿地土壤中的吸附行为进行了研究,旨在服务于湿地重金属污染的修复与生物学效应评价.研究结果表明(1)湿地土壤吸附Cu2+、Cr(VI)的过程符合Langmuir等温模型;二者的表观最大吸附量(xm)分别为36.10 g·kg-1和178.57 g·kg-1(初始液质量浓度c0＜500 g·m-3),平均吸附率分别达到99.82%± 0.35%和93.17%±1.14%.(2)无论单一吸附或竞争吸附体系,当c0(Cu2+)＞250 g·m-3时,平衡液Cu2+质量浓度快速升高.(3)c0相等的Cu2+、Cr(VI) 竞争吸附体系中,平衡液中Cu2+质量浓度升高,Cr(VI)质量浓度下降;但xm的变化表现为Cu2+增加了2.7倍,Cr(VI)降低了2.4倍.(4)Cu2+、Cr(VI) 的竞争吸附体系中,随Cr(VI)初始液质量浓度的变化(c0(Cu2+)恒定),Cr(VI)的xm下降至其单一吸附时的6%;而随Cu2+初始液质量浓度的变化(c0(Cr(VI))恒定),Cu2+的xm仅为其单一吸附时的1/3.