Biosorption of hexavalent chromium from aqueous solution onto pomegranate seeds: kinetic modeling studies

Hexavalent chromium has been proved to be the reason of several health hazards. This study aimed at evaluating the application of pomegranate seeds powder for chromium adsorption (VI) from aqueous solution. Chromium adsorption percentage (VI) increased with increasing the adsorbent dosage. Chromium adsorption capacity (VI), at pH = 2 and 10 mg/L initial metal concentration, decreased from 3.313 to 1.6 mg/g through increasing dosage of adsorbent from 0.2 to 0.6 g/100 ml. The adsorption rate increased through increase in chromium initial concentration (VI). However, there was a removal percentage reduction of chromium (VI). Chromium adsorption kinetics by different models (pseudo-first-order, modified pseudo-first-order, pseudo-second-order, Elovich, intraparticle diffusion, Boyd kinetic) was investigated as well. Studies on adsorption kinetic indicated that the experimental data were matched by pseudo-second-order model (R ² = 0.999) better. Obtained results demonstrated the pomegranate seeds can be used as an effective biomaterial and biosorbent for hexavalent chromium adsorption from aqueous solutions.     

Significance of co-immobilized activated carbon and Bacillus subtilis on removal of Cr(VI) from aqueous solutions

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.     

Fast,green and effective chromium bio-speciation using <Emphasis Type="Italic">Sepia pharaonis</Emphasis> endoskeleton nano-powder

The development of a fast, effective, simple and low-cost procedure for chromium speciation is an analytical challenge. In this work, a new and simple method for speciation and determination of chromium species in different matrices was developed. Sepia pharaonis endoskeleton nano-powder was used as an adsorbent for the dispersive micro-solid-phase extraction. Finally, the desorbed chromium was determined using a graphite furnace atomic absorption spectrometer. The experimental results showed that Cr(III) could be quantitatively extracted by the adsorbent, while Cr(VI) adsorption was negligible. Concentrated H₂SO₄ and ethanol reduced Cr(VI)–Cr(III), and total chromium content was assessed as Cr(III). Then, the Cr(VI) concentration in the sample was calculated as the difference. The optimum conditions were obtained in terms of pH, adsorbent amount, contact time, and type, concentration and volume of eluent. Under the optimum conditions that involved the speciation of chromium ions from 25 mL of the water samples at pH 7.0 using 0.025 g of the adsorbent with contact time of 5 min, the method was validated in terms of linearity, precision and accuracy. The calibration curve was linear over the concentration range of 0.01–25.00 μg L^?1 for Cr(III). The obtained limit of detection for the proposed method was 0.003 µg L^?1. The maximum adsorption capacity of the adsorbent was found to be 995.57 mg g^?1. The proposed method was validated by the speciation of Cr(III) and Cr(VI) in different real water and wastewater samples with satisfactory results.     

Utilization of agro-waste for removal of toxic hexavalent chromium: surface interaction and mass transfer studies

Abundantly available agricultural waste materials (banana bunch, sorghum stem and casuarinas fruit) are processed with negligible cost and are found to be highly suitable as biosorbents for chromium(VI) removal from aqueous environment due to high surface area and functional groups of adsorbents. The equilibrium data have been analyzed for the adsorbate–adsorbate/adsorbent interactions and found to be fitted to the data in the order, Hill–de Boer ≥ Fowler–Guggenheim ? Frumkin > Kiselev. To determine the characteristic parameters for process design, mass transfer studies have been carried out using two-parameter isotherm models (Harkins–Jura, Halsey, Smith, El-Awady and Flory–Huggins) and three-parameter isotherm models (Redlich–Peterson and Sips) which are applied to the experimental data. The fitness of the isotherms describes that both mono- and multilayer adsorptions occur in the present studied three biosorbents in preference to the latter. The mechanism of adsorption has been studied using diffusion kinetic models (viz. liquid film diffusion, Dunwald–Wagner intra-particle diffusion model and moving boundary model) and described the possibility of diffusion in the order of banana bunch–stem powder > sorghum stem powder > casuarinas fruit powder in terms of diffusion coefficients. In essence of all the results, the selected adsorbents can be used as a potential adsorbent for the removal of Cr(VI) from aqueous solutions.     

Characterization and evaluation of a tropical peat for the removal of Cr(VI) from solution

Tropical peat soils present higher ash content than those generated at temperate climate areas. Therefore, this study evaluated the characteristics of a Brazilian organic soil (OS), commercialized as peat, as well as its capacity in removing Cr(VI) from contaminated waters. The OS is composed of 35.5 wt% of organic matter and 56 wt% of inorganic fraction (ash), which is formed by minerals and phytoliths rich in silica (29.2 wt%) and alumina (23.6 wt%). The Cr(VI) removal tests were carried out in batch and column systems using OS and solutions of Cr(VI) prepared with distilled water and groundwater. Batch tests revealed that the organic substances in the OS caused the reduction of Cr(VI) to Cr(III), with an efficiency depending on solution pH. At pH 5.0 the Cr(VI) removal was 0.45 mg g^?1 in 24 h; whereas at pH 2.0, this removal increased to 1.10 mg g^?1. Since this redox reaction is very slow, the removal of Cr(VI) at pH 5.0 increased to around 2 mg g^?1 after 5 days. The removal of Cr(VI) was more effective in the column tests than in the batch test due to the greater solid/solution ratio, and their half-lives were 4.4 and 26.2 h, respectively. Chemical analysis indicated that Cr(VI) was reduced by the humic substances of OS, followed by the precipitation and/or adsorption of Cr(III) into the organic and inorganic components, as anatase. The presence of Cr(III) increased the stability of anatase structure, avoiding its transformation into rutile, even after being heated at 800 °C/2 h.     

Removal of hexavalent chromium from aqueous solution by barium ion cross-linked alginate beads

Barium ion cross-linked alginate beads have shown great affinity to toxic hexavalent chromium ions in aqueous solution, in contrast to the traditionally used calcium alginate beads. Our adsorption experiments were carried out by the batch contact method. The optimal pH for removal was found to be pH 4. The equilibrium was established in 4 h, and the removal efficiency of chromium(VI) was found to be 95 %. The adsorption data were applied to Langmuir, Freundlich, Dubinin–Redushkevich (D–R), and Temkin isotherm equations. Both Langmuir and Freundlich isotherm constants indicated a favorable adsorption. The value of mean sorption energy calculated from D–R isoterm indicates that the adsorption is essentially physical. The high maximum chromium(VI) adsorption capacity was determined from the Langmuir isotherm as 36.5 mg/g dry alginate beads. The chromium(VI) adsorption data were analyzed using several kinetic models such as the pseudo-first-order, pseudo-second-order, intraparticle diffusion, and Elovich models, and the rate constants were quantified. Our study suggests that barium alginate beads can be used as cost-effective and efficient adsorbents for the removal of chromium(VI) from contaminated waters.     

Comparative study on adsorption of chromium(VI) from industrial wastewater onto nature-derived adsorbents (brown coal and zeolite)

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.     

A novel adsorbent for heavy metal remediation in aqueous environments

The objective of this study was to investigate the possibility of using maize tassel as an alternative adsorbent for the removal of chromium (VI) and cadmium (II) ions from aqueous solutions. The effect of pH, solution temperature, contact time, initial metal ion concentration and adsorbent dose on the adsorption of chromium (VI) and cadmium (II) by tassel was investigated using batch methods. Adsorption for both chromium (VI) and cadmium (II) was found to be highly pH dependent compared to the other parameters investigated. Obtained results gave an adsorption capacity of 79.1 % for chromium (VI) at pH 2, exposure time of 1h at 25 °C. Maximum capacity of cadmium of 88 % was obtained in the pH range of 5-6 at 25 °C after exposure time of 1 h. The adsorption capacities of tassel for both chromium (VI) and cadmium (II) were found to be comparable to those of other commercial adsorbents currently in use for the removal of heavy metals from aqueous wastes. These results have demonstrated the immense potential of maize tassel as an alternative adsorbent for toxic metal ions remediation in polluted water and wastewater.     

Removal of hexavalent chromium from aqueous solution by lignocellulosic solid wastes

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.     

Ionic solid-impregnated sulphate-crosslinked chitosan for effective adsorption of hexavalent chromium from effluents

Microwave-assisted tetrabutyl ammonium-impregnated sulphate-crosslinked chitosan was synthesized for enhanced adsorption of hexavalent chromium. The adsorbent obtained was extensively characterized using Fourier transform infrared, X-ray diffraction, scanning electron microscopy and energy-dispersive X-ray studies. Various isotherm models such as Langmuir, Freundlich and Dubinin–Radushkevich were studied to comprehend the adsorption mechanism of hexavalent chromium by the adsorbent. Maximum adsorption capacity of 225.9 mg g^?1 was observed at pH 3.0 in accordance with Langmuir isotherm model. The sorption kinetics and thermodynamic studies revealed that adsorption of hexavalent chromium followed pseudo-second-order kinetics with exothermic and spontaneous behaviour. A column packed with 1 g of adsorbent was found to give complete adsorption of Cr(VI) up to 900 mL of 200 mg L^?1 solution which discerns the applicability of the adsorbent material for higher sample volumes in column studies. The effective adsorption results were obtained due to both ion exchange and ion pair interaction of adsorbent with hexavalent chromium. Greener aspect of overall adsorption was regeneration of the adsorbent which was carried out using sodium hydroxide solution. In the present study, the regenerated adsorbent was effectively reused up to ten adsorption–desorption cycles with no loss in adsorption efficiency.     

Retention studies of chromium (VI) from aqueous solution on the surface of a novel carbonaceous material

In the present study, the retention capacity of carbonaceous material obtained from the diesel engine exhaust mufflers for Cr(VI) removal has been investigated. The physicochemical properties such as density, pH of aqueous slurry, pH at point of zero charge, ash content, moisture content, volatile matter, surface area, scanning electron microscopy and electron dispersive spectroscopy of the carbonaceous material were determined. The capacity of adsorbent for removal of Cr(VI) from aqueous solution was observed under different experimental condition like contact time, initial concentration of metal ions, pH and temperatures on the adsorption capacity of the adsorbent. Maximum adsorption of Cr(VI) ions was found at low pH. The adsorption process was found to follow second-order kinetics. The rate constant was evaluated at different temperatures along with other thermodynamic parameters like activation energy, Gibbs free energy change, enthalpy change and entropy change. Both Langmuir and Freundlich isotherms were used to describe the adsorption equilibrium of carbonaceous material at different temperatures. Langmuir isotherm shows better fit than Freundlich isotherm at given conditions. The result shows that low-cost carbonaceous material from diesel engine exhaust mufflers can be efficiently used for wastewater treatment containing Cr(VI) ions.     

Potential biosorbents for treatment of chromium(VI)-contaminated water discharged into Asopos River

The present study reports on the preliminary investigation of three low-cost natural materials with respect to their chromium(VI) removal efficiency from contaminated water. The tested materials were reed, in milled and chopped form, compost, and dewatered sludge from a municipal wastewater treatment plant. The chromium(VI) removal capacity of the aforementioned materials was investigated by simulating the physicochemical conditions prevailing in a stormwater outfall flowing into the Asopos River in Inofyta, Central Greece. Thus, batch and column experiments were carried out using solutions of 3–5 mg/L chromium(VI) and pH value 8.5 ± 0.5. The results showed that the tested materials were capable of removing 3 mg/L chromium(VI), however by allowing different contact times for each material. The chromium(VI) removal kinetics were studied through batch experiments, and reed was found to be the most efficient material. Therefore, at a second series of batch and up-flow column experiments, the effect of the liquid-to-solid ratio, pH, and contact time on chromium(VI) removal using chopped reed was investigated. Chromium(VI) removal took place through both reduction and adsorption mechanisms, while the released soluble organic matter from reed seemed to favor the reduction mechanism. As a result, reed is a potential biosorbent capable of treating heavily chromium(VI)-contaminated water flows, although a high mass of reed is required for a treatment process, such in the case of the stormwater discharged into Asopos River.     

Biosorption of Cr(III) and Cr(VI) species from aqueous solution by Cabomba caroliniana: kinetic and equilibrium study

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.     

Antioxidants and chromium reductases by <Emphasis Type="Italic">Penibacillus</Emphasis> species enhance the growth of soybean under chromium stress

Hexavalent chromium [Cr(VI)] is used in various industries, but its improper and uncontrolled discharge contaminates the environment. In order to circumvent chromium toxicity, several physicochemical and biological strategies have been employed. Among biological approach, microbes convert toxic Cr(VI) to less soluble Cr(III) form and hence can be used to detoxify/remove Cr(VI) from contaminated environment. Considering these, present study was designed to assess the effect of chromium reductases and antioxidants secreted by Penibacillus species to detoxify Cr(VI) and concurrently to augment soybean growth. Bacterial strains (MAI1 and MAI2) were identified as Penibacillus sp. using 16S rRNA gene. Penibacillus species reduced Cr(VI) significantly at pH 7. Maximum Cr(VI) was reduced at 50 and 100 µg/ml of Cr(VI) concentrations. Penibacillus sp. also reduced Cr(VI) significantly at 25 and 35 °C as well as 1 g sodium alginate in 1 g polyvinyl alcohol. Bacterial strains reduced Cr(VI) into Cr(III) which were detected as 33 ± 1 and 35 ± 1 µg/ml in supernatant and 67 ± 2.5 and 65 ± 1 µg/ml in cell debris, respectively, after 120 h. Chromium reductase found in cell-free extract reduced almost all Cr(VI) compared to those observed in cell debris. Both malondialdehyde and antioxidant levels were increased with gradual increase in Cr(VI) concentration. Penibacillus species inoculated soybean plants had better growth and photosynthetic pigments under Cr(VI) stress.     

Hexavalent chromium removal from aqueous solutions by using low-cost biological wastes: equilibrium and kinetic studies

The batch removal of hexavalent chromium from aqueous solutions using almond shell, activated sawdust, and activated carbon, which are low-cost biological wastes under different experimental conditions, was investigated in this study. The influences of initial concentration, adsorbent dose, adsorbent particle size, agitation speed, temperature, contact time, and pH of solution were investigated. The adsorption was solution pH dependent and the maximum adsorption was observed at a solution pH of 2.0. The capacity of chromium adsorption under equilibrium conditions increased with the decrease in particle sizes. The equilibrium was achieved for chromium ion after 30?min. Experimental results showed that low-cost biosorbents are effective for the removal of pollutants from aqueous solution. The pseudo-second-order kinetic model gave a better fit of the experimental data as compared to the pseudo-first-order kinetic model. Experimental data showed a good fit with the Freundlich isotherm model. Changes in the thermodynamic parameters, including Gibbs free energy (??G_o), enthalpy (??H_o), and entropy (??S_o), indicated that the biosorption of hexavalent chromium onto almond shell, activated sawdust, and activated carbon was feasible, spontaneous, and endothermic in the temperature range 28?C50?°C.     

Removal of chromium (VI) from aqueous solutions using Lewatit FO36 nano ion exchange resin

The removal of the chromium (VI) ion from aqueous solutions with the Lewatit FO36 ion-exchange resin is described at different conditions. The effects of adsorbent dose, initial metal concentration, contact time and pH on the removal of chromium (VI) were investigated. The batch ion exchange process was relatively fast and it reached equilibrium after about 90 min of contact. The ion exchange process, which is pH dependent showed maximum removal of chromium (VI) in the pH range 5.0–8.0 for an initial chromium (VI) concentration of 0.5 mg/dm³. The equilibrium related to Lewatit FO36 ion- exchange capacity and the amounts of the ion exchange were obtained using the plots of the Langmuir adsorption isotherm. It was observed that the maximum ion exchange capacity of 0.29 mmol of chromium (VLVg for Lewatit FO36 was achieved at optimum pH value of 6.0. The ion exchange of chromium (VI) on this cation-exchange resin followed first-order reversible kinetics.     

Adsorption of chromium (VI) from aqueous solution by the iron (III)-impregnated sorbent prepared from sugarcane bagasse

An iron (III)-impregnated sorbent was prepared from sugarcane bagasse and ferric chloride solution via carbonization/activation in a muffle furnace at 500?°C for 4?h. The adsorption removal of chromium (VI) from aqueous solution by the iron (III)-impregnated sorbent was then studied in a batch system. With increasing initial chromium (VI) concentration from 25 to 130?mg/L at an adsorbent dose of 300?mg/50?mL, the amount of adsorbed chromium (VI) increased from 4.15 to 12.20?mg/g at 20?°C, from 4.16 to 12.50?mg/g at 30?°C, and from 4.16 to 13.72?mg/g at 40?°C. The dynamical data fit very well with the pseudo-second-order kinetic model, and the calculated adsorption capacities of 4.16, 8.37, and 13.37?mg/g were equal to the actual values of the experiments at the initial chromium (VI) concentrations of 25, 50, and 100?mg/L, respectively. The Langmuir isotherm could yield better fits than the Freundlich isotherm. The calculated isotherm parameters confirmed the favorable adsorption of chromium (VI) on the iron (III)-impregnated sorbent.     

Chromium(VI) adsorption from aqueous solution by prepared biochar from <Emphasis Type="Italic">Onopordom Heteracanthom</Emphasis>

In this research, the stems of Onopordom Heteracanthom which is a kind of weed were converted to biochar particles, and their characteristics were investigated. The morphology and purity of these particles were examined by SEM and EDX techniques, respectively. Specific surface area was obtained as 5.73 m² g^?1 by BET method. The biochar particles obtained from Onopordom Heteracanthom were evaluated as an adsorbent to remove Cr(VI) from aqueous environments. The effect of some parameters such as initial concentration of Cr(VI), dosage of adsorbent, and pH were investigated on the adsorption capacity of Cr(VI) onto the adsorbent. The equilibrium data were analyzed by various isotherm models. The results revealed that in this process, the adsorption isotherm and kinetics have more conformity with Langmuir isotherm and pseudo-second-order kinetics, respectively. The multi-linearity of the Weber and Morris adsorption kinetic model indicates that the intra-particle diffusion is not merely the rate-controlling step for the whole adsorption process.     

Removal of chromate from aqueous solution using treated natural zeolite

This paper present the possible alternative removal options for the development of safe drinking water supply in the chromium-affected areas. The Cr (VI) state is of particular concern because of its toxicity. The mordenite has suitable mineralogical properties that enable them to be used for ion-exchange processes. This includes total cation exchange capacity. However, in the present work, the modified-natural zeolite was used as an adsorbent for the removal of Cr (VI) from aqueous solution. The ability of modified natural zeolite (mordenite) to remove inorganic anion was investigated. Laboratory experiments were conducted examining the effect of the sorption of cationic surfactants. On the basis of the results of this study, the HDTMA-HSO₄ modified zeolite appears suitable as a sorbent for hexavalent chromium whereas EHDDMA-modified zeolite were not removed with the same efficiency. The sorption of chromate on HDTMA-zeolite results from a combination of entropic, coulombic, hydrophobic effects, and HDTMA counterion.     

Comparison of fast elimination of Cr(VI) by alumina nanofiber and alumina nanoporous

The goal of this study is examination of the mixture between adsorption and permeation process for removing chromium (VI) from the water. Two types of supported membranes are developed: The first one which was made by sol–gel method is called nanoporous and the second one which was made by electrospinning is called nanofiber. The sorption capacity of nanoporous and nanofiber is examined in single batch experiments at various pH values, and it is found that maximum chromium removal is observed for both nanoporous and nanofiber at pH 3.5. Adsorption studies illustrated that the Cr(VI) adsorption onto alumina nanoporous and nanofiber is affected by changes in pH, contact time, dosage of adsorbent, concentration of chromium and solution volume. Langmuir and Freundlich isotherms can be used to explain the adsorption equilibria of Cr(VI) onto alumina nanoporous and nanofiber. It was found that balance adsorption data adequate Langmuir isotherm more than Freundlich model. Adsorption kinetics was found to be fitted to pseudo-second order and Weber and Morris model. The output of multiple linear regressions was run for the second-order response surface model implied that the linear agents of pH, sorbent dosage and Cr(VI) concentration are more significant factors. Manufacturing electrospun alumina nanofiber and sol–gel nanoporous with these cheap materials, renewable and fast methods are so important although the removal percentage is significant.