Concurrent adsorption and reduction of chromium(VI) to chromium(III) using nitrogen-doped porous carbon adsorbent derived from loofah sponge

• A high-efficiency N-doped porous carbon adsorbent for Cr(VI) was synthesized. • The maximum adsorption capacity of Cr(VI) reached up to 285.71 mg/g at 318K. • The potential mechanism for Cr(VI) adsorption by NHPC was put forward. • DFT analyzed the adsorption energy and interaction between NHPC and Cr(VI). To develop highly effective adsorbents for chromium removal, a nitrogen-doped biomass-derived carbon (NHPC) was synthesized via direct carbonation of loofah sponge followed by alkali activation and doping modification. NHPC possessed a hierarchical micro-/mesoporous lamellar structure with nitrogen-containing functional groups (1.33 at%), specific surface area (1792.47 m²/g), and pore volume (1.18 cm³/g). NHPC exhibited a higher Cr(VI) adsorption affinity than the HPC (without nitrogen doping) or the pristine loofah sponge carbon (LSC) did. The influence of process parameters, including pH, dosage, time, temperature, and Cr(VI) concentration, on Cr(VI) adsorption by NHPC were evaluated. The Cr(VI) adsorption kinetics matched with the pseudo-second-order model (R²≥0.9983). The Cr(VI) adsorption isotherm was fitted with the Langmuir isotherm model, which indicated the maximum Cr(VI) adsorption capacities: 227.27, 238.10, and 285.71 mg/g at 298K, 308K, and 318K, respectively. The model analysis also indicated that adsorption of Cr(VI) on NHPC was a spontaneous, endothermal, and entropy-increasing process. The Cr(VI) adsorption process potentially involved mixed reductive and adsorbed mechanism. Furthermore, computational chemistry calculations revealed that the adsorption energy between NHPC and Cr(VI) (−0.84 eV) was lower than that of HPC (−0.51 eV), suggesting that nitrogen doping could greatly enhance the interaction between NHPC and Cr(VI).     

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.     

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.     

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%.     

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.     

Removal of cadmium(II), lead(II), and chromium(VI) ions from aqueous solution using clay

Removal of cadmium(II), lead(II), and chromium(VI) from aqueous solution using clay, a naturally occurring low-cost adsorbent, under various conditions, such as contact time, initial concentration, temperature, and pH has been investigated. The sorption of these metals follows both Langmuir and Freundlich adsorption isotherms. The magnitude of Langmuir and Freundlich constants at 30°C for cadmium, lead, and chromium indicate good adsorption capacity. The kinetic rate constants (K _ad) indicate that the adsorption follows first order. The thermodynamic parameters: free energy change (ΔG ^o), enthalpy change (ΔH ^o), and entropy change (ΔS ^o) show that adsorption is an endothermic process and that adsorption is favored at high temperature. The results reveal that clay is a good adsorbent for the removal of these metals from wastewater.     

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.     

Removal of chromium(VI) by ZnCl2 activated coir pith carbon

The adsorption of chromium(VI) onto ZnCl₂ activated carbon developed from coir pith was investigated to assess the possible use of this adsorbent. The influence of contact time, adsorbent dose, Cr(VI) concentration, pH and temperature were investigated. The two theoretical adsorption isotherms, namely, Langmuir and Freundlich were used to describe the experimental results. The Langmuir adsorption capacity (Q ₀) was found to be 120.5?mg Cr(VI) per g of the adsorbent. The adsorption followed the second-order kinetics and was found to be maximum at pH 2.0. The pH effect and the desorption studies showed that ion exchange mechanism might be involved in the adsorption process. The effects of foreign ions such as chloride, sulphate, phosphate, selenite, molybdate, nitrate and perchlorate on the removal of Cr(VI) have been investigated. The removal of Cr(VI) from synthetic ground water was also tested. The results show that ZnCl₂ activated coir pith carbon is effective for the removal of Cr(VI) from water.     

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.     

Selective separation and preconcentration studies of chromium(VI) with Alamine 336 supported liquid membrane

Chromium compounds have received considerable attention because these are used extensively in such industrial applications as electroplating, steelmaking, tanning of leather goods, and corrosion inhibition. The use of supported liquid membranes (SLMs) to remove metals from wastewaters has actively been pursued by the scientific and industrial community. In the present work, the selective separation and preconcentration of Cr(VI) ions has been studied by using a commercial amine as the membrane liquid on the porous polypropylene support. Permeation experiments were conducted on a laboratory scale batch reactor made up of perspex, with a memberane fixed amid the two chambers. The flux of Cr(VI) ions was found to be maximum (3.15?×?10^?5?mol?cm^?2?s^?1) around pH 1. Above and below this pH the flux decreases. Distribution studies show that an increase in the amine concentration leads to higher distribution coefficients at fixed pH values. At pH around unity, the distribution of Cr(VI) ions into the organic phase was found to be maximum, of the order of 56.3. The Cr(VI) transport through the membrane increases with rise in temperature. In order to check the long-term efficiency of the flat sheet SLM, an experiment was conducted with higher Cr(VI) concentration (5000?ppm) for 24?h, at optimised parameters. It was observed that in 24?h, about 1/5th of the feed Cr(VI) is left over while the rest is transported. However, minute organic droplets were also seen in the feed and strip compartments, after 1 day. This observation suggested the loss of membrane liquid. The feasibility of preconcentration of Cr(VI) by using the proposed SLM parameters, was also studied by using the hollow fibre (HF) system. Highest enrichment factor (E.F) value was obtained for 50?mg?L^?1 whereby all of the metal was transported to the stripping phase and the resulting Cr concentration was 688?mg?L^?1 (E.F?=?13.8). It was observed that while treating more diluted solutions, the enrichment factor decreases. The values of E.F equal to 8.9 and 11.3 were found for initial Cr concentration of 10 and 30?mg?L^?1.     

Efficient water desalination using photo-responsive ZnO polyamide thin film nanocomposite membrane

Environmental Chemistry Letters - Membrane separation technology has become one of the most frequently used techniques to secure adequate water resources for human consumption and other...     

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     

Phytoextraction of Cr(VI) from soil using Portulaca oleracea

Cr(VI) represents an environmental challenge in both soil and water as it is soluble and bioavailable over a wide range of pH. In previous investigations, Portulaca oleracea (a plant local to the United Arab Emirates (UAE)) demonstrated particular ability for the phytoextraction of Cr(VI) from calcareous soil of the UAE. In this publication, the results of the evaluation of P. oleracea phytoextraction of Cr(VI) from UAE soil at higher concentrations are reported. P. oleracea was exposed to nine different concentrations of Cr(VI) in soil from 0 to 400 mg kg^?1. The uptake of Cr(VI) increased as its concentration in soil increased between 50 and 400 mg kg^?1, with the most efficient removal in the range from 150 to 200 mg kg^?1. The total chromium concentrations exceeded 4600 mg kg^?1 in roots and 1400 mg kg^?1 in stems, confirming the role of P. oleracea as an effective Cr(VI) accumulator. More than 95% of the accumulated Cr(VI) was reduced to the less toxic Cr(III) within the plant.