Chromium (VI) uptake by grape stalks wastes encapsulated in calcium alginate beads: equilibrium and kinetics studies

Abstract

The removal of hexavalent chromium from aqueous solution using grape stalks wastes encapsulated in calcium alginate (GS–CA) beads was investigated. Cr(VI) sorption kinetics were evaluated as a function of chromium initial concentration and grape stalks (GS) content in the calcium alginate (CA) beads. The process follows pseudo second-order kinetics. Transport properties of hexavalent chromium on GS–CA beads was characterised by calculating chromium diffusion coefficient using the Linear Absorption Model (LAM). Langmuir isotherms, at pH 3.0 were used to describe sorption equilibrium data as a function of GS percentage in the CAbeads. Maximum uptake obtained was 86.42 mmol of Cr(VI) per L of wet sorbent volume. Results indicated that both kinetic and equilibrium models describe adequately the adsorption process.     

Biosorption of trivalent and hexavalent chromium from aqueous systems using shelled Moringa oleifera seeds

Abstract

The present study explores the sorption properties of shelled Moringa oleifera seeds (SMOS) for removal of two environmentally important oxidation states of chromium (trivalent and hexavalent) from an aqueous system on the laboratory scale. Sorption studies reveal the optimum conditions for the removal of 81.02%; Cr (III) and 88.15% Cr (VI) as follows: biomass dosage (4.0 g), metal concentration [25mg/L for Cr (III); 50mg/L for Cr (VI)], contact time (40 minutes) at pH 6.5 and 2.5 respectively. The adsorption data were found to fit well both the Freundlich and Langmuir isotherms. Characterization of the seed powder by FTIR showed the clear presence of amino acid moieties having both positively charged amino and negatively charged carboxylic groups and confirmed that biosorption involves amino acid-chromium interactions. SEM studies of native and exhausted [Cr(III) and Cr(VI)] treated SMOS revealed large spherical clusters having a pore area of 8.66 µm² in the case of native SMOS while dense agglomerated etched dendrite type morphology have a pore area of 0.80 µm² in Cr (III) and 0.78 µm² in Cr (VI) treated SMOS The spent biosorbent was regenerated and found to be effectively reusable for four cycles.     

Effect of organic Cr(III) complexes on chromium speciation

Abstract

Chromium speciation in the presence of organic chromium(III) complexes was investigated using solid-phase extraction. The adsorptions of Cr(VI) and Cr(III) on alumina and pumice powder were studied. Maximum sorption of Cr(VI) was obtained by alumina (90.22%), while Cr(III) was highly adsorbed onto pumice powder (86.65%). This result shows that pumice may be a new and promising adsorbent for Cr(III). The experimental equilibrium data for Cr(VI) adsorption onto alumina and Cr(III) sorption onto pumice were analysed using Langmuir and Freundlich isotherms. The separation and adsorption of Cr(VI), Cr(III) and five organic chromium(III) complexes onto pumice and alumina at different pH values were evaluated. Ethylenediaminetetraacetate (EDTA), oxalate, citrate, glycine, alanine and 8-hydroxyqinoline were used as ligands. Sorption of alanine and ethylenediaminetetraacetate complexes was higher onto alumina than pumice at pH>3. The enhancement of adsorption of chromium(III) complexes onto pumice was achieved by surface modification of pumice using a surfactant, namely hexadecyltrimethylammoniumbromür (HDTMA). The presence of surfactant enhanced the adsorption of Cr(III) citrate, oxalate, glycine and 8-hydroxyquinoline complexes onto pumice. However, the adsorption of EDTA and alanine complexes decreased, with ratio of 13.40% and 4.00% respectively. Here we demonstrate that chromium speciation methods depending on adsorption onto various adsorbents including alumina may lead erroneous results. Analytical measurements were performed by flame AAS, data were obtained by standard addition method.     

Chromium(VI) sorption efficiency of acid-activated banana peel over organo-montmorillonite in aqueous solutions

In the present study, we examined sorption of chromate (Cr(VI)) to acid-activated banana peel (AABP) and organo-montmorillonite (O-mont) as a function of pH, initial Cr(VI) concentration at a sorbent dose of 4 g L^?1 and at 20 ± 1°C in aqueous solutions. In sorption edge experiments, maximum Cr(VI) removal was obtained at pH 3 after 2 hours by AABP and O-mont (88% and 69%). Sorption isotherm data showed that the sorption capacity of AABP was higher than O-mont (15.1 vs. 6.67 mg g^?1, respectively, at pH 4). Freundlich and Langmuir models provided the best fits to describe Cr(VI) sorption onto AABP (R² = 0.97) and O-mont (R² = 0.96). Fourier transform infrared spectroscopy elucidated that for AABP mainly the –OH, –COOH, –NH₂, and for O-mont intercalated amines and –OH surface functional groups were involved in Cr(VI) sorption. The scanning electron microscopy combined with energy dispersive X-ray spectroscopy (SEM-EDX) analyses, although partly, indicate that the (wt. %) proportion of cations (e.g., Ca, Mg) in AABP decreased after Cr(VI) sorption. This may be due to ion exchange of chromite (Cr(III)) (produced from Cr(VI) reduction) with cationic elements in AABP. Also, Cr(VI) desorption (using phosphate solution) from AABP was lower (29%) than that from O-mont (51%) up to the third regeneration cycle. This bench scale comparative study highlights that the utilization of widely available and low-cost acid-activated biomaterials has a greater potential than organo-clays for Cr(VI) removal in aqueous media. However, future studies are warranted to precisely delineate different mechanisms of Cr(VI) sorption/reduction by acid-activated biomaterials and organo-clays.     

Removal of chromium from industrial waste by using eucalyptus bark

Several low cost biomaterials such as baggase, charred rice husk, activated charcoal and eucalyptus bark (EB) were tested for removal of chromium. All the experiments were carried out in batch process with laboratory prepared samples and wastewater obtained from metal finishing section of auto ancillary unit. The adsorbent, which had highest chromium(VI) removal was EB. Influences of chromium concentration, pH, contact time on removal of chromium from effluent was investigated. The adsorption data were fitted well by Freundlich isotherm. The kinetic data were analyzed by using a first order Lagergren kinetic. The Gibbs free energy was obtained for each system and was found to be -1.879 kJ mol(-1) for Cr(VI) and -3.885 kJ mol(-1) for Cr(III) for removal from industrial effluent. The negative value of deltaG0 indicates the feasibility and spontaneous nature of adsorption. The maximum removal of Cr(VI) was observed at pH 2. Adsorption capacity was found to be 45 mg/g of adsorbent, at Cr(VI) concentration in the effluent being 250 mg/l. A waste water sample containing Cr(VI), Cr(III), Mg, and Ca obtained from industrial unit showed satisfactory removal of chromium. The results indicate that eucalyptus bark can be used for the removal of chromium.     

Application of a hybrid biofilter column for the removal of Cr(VI) from aqueous solution using an indigenous bacterial strain Pseudomonas taiwanensis

In the present study, a laboratory-scale biofilter column was designed and fabricated. It was packed with a mixture of coal and compost as a packing medium. The column was enriched with an indigenous bacterial strain Pseudomonas taiwanensis isolated from aerobic mixed culture of Sewage Treatment Plant, BITS-Pilani, Pilani campus. The removal of hexavalent chromium [Cr(VI)] from aqueous solution was investigated in the biofilter column. The entire biofiltration operation was divided into five phases (I to V) for a period of 63 days. Biofilter column was subjected to shock loading conditions for 20 days immediately after 63 days of operation. The maximum removal efficiency of 89.4% was obtained during phase V for Cr(VI) inlet concentration of 40 mg L^?1. During shock loading, maximum removal efficiency was obtained as 90% for 48.5–50 mg L^?1 of initial Cr(VI) concentration. Kinetic parameters of biofiltration process for Cr(VI) removal were also determined by fitting Michaelis-Menten kinetic model with experimental data. The Michaelis-Menten kinetic constants were obtained as 0.258 mg L^?1 min^?1 and 26.83 mg L^?1. It was found that Ottengraf-Van den Oever model with zero-order diffusion limitation fit the experimental data quite well for phases III, IV, and V with coefficient of determination (R²) values .97, .99, and .984, respectively. A possible method for safe disposal of packing medium was also presented in this study.     

Bio-separation, speciation and determination of chromium in water using partially pyrolyzed olive pomace sorbent

Speciation of Cr(III)/Cr(VI) from water using olive pomace (OP) was improved by partial pyrolysis of OP. The sorbents were characterized by physicochemical techniques. Sorption of Cr(III) on raw and partially pyrolyzed OP sorbents followed Freundlich isotherm and second-order rate kinetics. OP pyrolyzed at 150 °C (sorbent OP-150) exhibited maximum sorption capacity, favorability and the lowest sorption energy. Sorption was exothermic and spontaneous for the raw-OP and OP pyrolyzed at 100 or 150 °C; but endothermic and non-spontaneous for OP pyrolyzed at 200, 250, 300 or 400 °C. A speciation method of chromium was proposed, in which Cr(III) was selectively retained at pH 3 on sorbent OP-150; while total Cr was determined after reduction of Cr(VI). The method was selective with a detection limit for Cr(III) of 1.58 μg L⁻¹. The method was applied on natural and industrial waters (recoveries >97.7%, RSD’s <9%) and on tobacco leaves certified reference material (INCT-PVTL-6).     

Microbial Waste Biomass for Removal of Chromium(VI) from Chrome Effluent

ABSTRACT

Microbial waste biomass, a by-product of the fermentation industry, was developed as a biosorbent to remove hexavalent chromium (Cr) from the acidic effluent of a metal processing industry. In batch sorption, 100% Cr(VI) removal was achieved from aqueous solution in 30 min contact at pH 4.0–5.0. The Cr(VI) sorption equilibrium was evaluated using the Langmuir and Freundlich models, indicating the involvement of ion exchange and physicochemical interaction. Fourier transform infrared (FTIR) analysis revealed the presence of amine, hydroxyl, and imine functional groups present on the surface of microbial biomass that are involved in Cr binding. In a continuous sorption system, 95 mg L^?1 of Cr(VI) was adsorbed before the column reached a breakthrough point of 0.1 mg L^?1 Cr(VI) at the column outlet. An overall biosorption capacity of 12.6 mg Cr(VI) g^?1 of dry microbial waste was achieved, including the partially saturated portion of the dynamic sorption zone. Insignificant change in metal removal was observed up to 10 cycles. In pilot-scale studies, 100% removal of Cr(VI) was observed up to 5 weeks, and the method was found to be cost-effective, commercially viable, and environmentally friendly, as it does not generate toxic chrome sludge.     

Evaluation of Cr(VI) Exposed and Unexposed Plant Parts of Tradescantia pallida (Rose) D. R. Hunt. for Cr Removal from Wastewater by Biosorption

Phytoremediation is an efficient method for the removal of heavy metals from contaminated systems. A productive disposal of metal accumulating plants is a major concern in current scenario. In this work, Cr(VI) accumulating Tradescantia pallida plant parts were investigated for its reuse as a biosorbent for the removal of Cr(VI) ions. The effect of pH, contact time, sorbent dosage, Cr(VI) concentration and temperature was examined to optimize these process parameters. Results showed that Cr(VI) exposed/unexposed T. pallida leaf biomass could remove 94% of chromium with a sorption capacity of 64.672 mg g^?1. Whereas the kinetics of Cr(VI) biosorption was well explained by the pseudo second-order kinetic model, the Langmuir model better described the data on Cr(VI) sorption isotherm compared with the Freundlich model. The changes in the free energy (ΔG°), entropy (ΔS°) and enthalpy (ΔH°) were found to be ?5.276 kJ mol^?1, 0.391 kJ mol^?1 K^?1 and 11.346 kJ mol^?1, respectively, which indicated the process to be spontaneous, feasible and endothermic in nature. FTIR spectra of T. pallida leaf biomass revealed the active participation of ligands, such as ?NH, amide, hydroxyl and sulphonate groups present in the biomass for Cr(VI) binding, SEM analysis revealed a porous structure of the biosorbent for an easy uptake of Cr(VI).     

Effect of Rhamnolipids on Chromium-Contaminated Kaolinite

Hexavalent chromium Cr(VI) is a common environmental pollutant that is treated by its reduction to the trivalent form Cr(III). The latter can be re-oxidized to the toxic form, Cr(VI), under specific conditions. A study was conducted on the removal of Cr(III) to eliminate the hazard imposed by its presence in soil as there has been some evidence that organic compounds can decrease its sorption. The effect of addition of negatively-charged biosurfactants (rhamnolipids) on chromium contaminated kaolinite was studied. Results showed that the rhamnolipids have the capability of extracting 25% portion of the stable form of chromium, Cr(III), from the kaolinite, under optimal conditions. The removal of hexavalent chromium was also enhanced compared to water by a factor of 2 using a solution of rhamnolipids. Results from the sequential extraction procedure showed that rhamnolipids remove Cr(III) mainly from the carbonate and oxide/hydroxide portions of the kaolinite. The rhamnolipids had also the capability of reducing close to 100% of the extracted Cr(VI) to Cr(III) over a period of 24 days. This study indicated that rhamnolipids could be beneficial for the removal or long–term conversion of chromium Cr(VI) to Cr(III).     

Kinetic and Equilibrium Studies of Cr(VI) Biosorption by Dead <Emphasis Type="Italic">Bacillus licheniformis</Emphasis> Biomass

Many studies have been carried out on the biosorption capacity of different kinds of biomass. However, reports on the kinetic and equilibrium study of the biosorption process are limited. In our experiments, the removal of Cr(VI) from aqueous solution was investigated in a batch system by sorption on the dead cells of Bacillus licheniformis isolated from metal-polluted soils. Equilibrium and kinetic experiments were performed at various initial metal concentrations, pH, contact time, and temperatures. The biomass exhibited the highest Cr(VI) uptake capacity at 50°C, pH 2.5 and with the initial Cr(VI) concentration of 300 mg/g. The Langmuir and Freundlich models were considered to identify the isotherm that could better describe the equilibrium adsorption of Cr(VI) onto biomass. The Langmuir model fitted our experimental data better than the Freundlich model. The suitability of the pseudo first-order and pseudo second-order kinetic models for the sorption of Cr(VI) onto Bacillus licheniformis was also discussed. It is better to apply the pseudo second-kinetic model to describe the sorption system.     

Advanced kinetic model of the Cr(VI) removal by biomaterials at various pHs and temperatures

Recently, a new and simple kinetic model was derived from a basic concept of the redox reaction between Cr(VI) and biomaterials, and successfully described the removal behavior of Cr(VI) under various Cr(VI) and biomaterial concentrations. However, this model did not consider the effects of pH and temperature on the Cr(VI) removal by biomaterials. In this study, a new efficient biomaterial, pine needle, capable of removing Cr(VI) was used as a model one to study the Cr(VI) removal by biomaterials. Analysis of chromium species in aqueous and solid phases revealed that the removal mechanism of Cr(VI) by pine needle was its reduction into Cr(III). The removal rate of Cr(VI) increased with a decrease in pH or with an increase of temperature. Finally, an advanced kinetic model in the form of -d[Cr(VI)]/dt = Ae(Ea/RT)[H+]n[Cr(VI)][OCs] was derived, and successfully predicted the time-dependent Cr(VI) concentration at various pHs (2-4) and temperatures (10-55 degrees C).     

Kinetic and equilibrium models for biosorption of Cr(VI) on chemically modified seaweed,Cystoseira indica

The biosorption data of hexavalent chromium by marine brown algae Cystoseira indica, which was chemically modified by crosslinking with epichlorohydrin (CB1, CB2), or oxidized by potassium permanganate (CB3), or only washed with distilled water (RB), has been used for kinetic studies based on fractional power, Elovich, pseudo-first order and pseudo-second order rate expressions. Five three parameter biosorption isotherm models, viz. Redlich–Peterson, Sips, Khan, Radke–Prausnitz and Toth are tested for their applicability apart from 6 two-parameter models. Non-linear curve fitting procedure was adopted for fitting the kinetic as well as equilibrium data in the kinetic and isotherm models and for the determination of parameters. The time-dependent Cr(VI) biosorption data were well-described by pseudo-second-order kinetic model. The intraparticle diffusion study revealed that film diffusion might be involved in Cr(VI) biosorption in the present case. Among the two-parameter models, the Langmuir model produces the best fit, while, among the three-parameter models, the best fit is produced by the Khan model, for the biosorption of Cr(VI) on all the four biosorbents studied.     

Removal of chromium (VI) using poly(methylacrylate) functionalized guar gum

Using persulfate/ascorbic acid redox pair, poly(methylacrylate) was grafted on to guar gum and the conditions for the grafting were optimized. The copolymer sample having maximum %G was evaluated for the removal of Cr(VI) and the sorption conditions were optimized. The sorption was found pH dependent, pH 1.0 being the optimum value. Sorption data at pH 1.0 were modeled using both the Langmuir and Freundlich isotherms where the data fitted better to Freundlich isotherm. The equilibrium sorption capacity of 29.67 mg/g was determined from the Langmuir isotherm. The sorption followed a pseudo-second-order kinetics with a rate constant 2.5 × 10^?4 g mg^?1 min^?1. The grafted product was also evaluated for Cr(VI) removal from local electroplating industrial waste water. The regeneration experiments revealed that the guar-graft-poly(methylacrylate) could be successfully reused for five cycles. In the present study conductivity measurements were used instead of conventional photometric method for determining Cr(VI) concentration in the equilibrium solutions and the results obtained have been compared with photometric method. Optimum Cr(VI) binding under highly acidic conditions indicated significant contribution of non electrostatic forces in the adsorption process.     

Effects of combining biological treatment and activated carbon on hexavalent chromium reduction

The objectives of the present work were: (a) to analyze the Cr(VI) removal by combining activated sludge (AS) with powdered activated carbon (PAC), (b) to analyze the effect of PAC and Cr(VI) on the growth kinetics of activated sludge, and (c) to determine if the combined method (AS-PAC) for Cr(VI) removal can be considered additive or synergistic with respect to the individual processes. Chromate removal was improved by increasing PAC concentrations in both PAC and AS-PAC systems. Cr(VI) removal using the AS-PAC system was higher than using AS or PAC. The increase of Cr(VI) caused longer lag phase and lower observed specific growth rate (μ_obs), biomass yield (Y_X/S), and specific growth substrate consumption rate (q_S) of activated sludge; additionally, PAC did not enhance the growth kinetic parameters (μ_obs, Y_X/S, q_S). Cr(VI) reduction in AS-PAC system was the result of the additive effect of each individual Cr(VI) removal process.     

Equilibrium and Kinetic Studies of Phosphate Removal from Solution onto a Hydrothermally Modified Oyster Shell Material

Phosphate removal to a hydrothermally modified fumed silica and pulverized oyster shell material for use in wastewater treatments were made. Sorption data modeling (pH’s 3–11, P concentrations of 3, 5, 10, 15, 20, & 25 mg/L, and at an ambient temperature of 23°C) indicate that an optimal removal of P occurs at pH 11. Three kinetic models were also applied (a pseudo-first-order Lagergren kinetic model, a pseudo-second-order (PSO) kinetic and Elovich) and indicate that a PSO model best describes P-removal. In addition, an application of the Weber and Morris intra-particle diffusion model indicates that external mass transfer and intra-particle diffusion were both involved in the rate-determining step. Langmuir, Freundlich modeling of the sorption data also indicate that the heterogeneous Freundlich sorption site model best describes the data although Langmuir data also fit with data tailing suggesting data are not linear. The data collected indicates that the hydrothermally modified fumed silica and pulverized oyster shell material is suitable for use in wastewater treatment, with P-removal to the solids being preferential and spontaneous.     

Hexavalent chromium removal by viable, granular anaerobic biomass

Hexavalent chromium in industrial wastewater is a major concern due to its extreme toxicity. This study investigates the removal of Cr(VI) using viable anaerobic granular biomass as a biosorbent. The effect of Cr(VI) concentration on biogas content and COD removal using batch studies indicated that the phase II (methanogenic-rich) culture was more sensitive than the phase I (acidogenic-rich) culture. Toxicity indices for both cultures using COD removal were developed based on linear-log interpolation. The median inhibition Cr(VI) concentration (IC(50)), for phase II cultures was found to be 263mg/L, while that for phase I cultures was 309mg/L. A sorption study was conducted on viable and non-viable (dried) phase I-rich biomass: both followed the Langmuir model. In addition, the biosorption capacity for metabolically inhibited biomass was 25% less indicating some level of cellular uptake associated with Cr(VI) removal. This study demonstrated the potential for a two-phase anaerobic treatment system for a Cr(VI)-contaminated effluent.     

Removal of Chromium (VI) from Aqueous Solution Using Mycelial Pellets of Penicillium simplicissimum Impregnated with Powdered Biochar

The mycelia pellets of Penicillium simplicissimum impregnated with powdered biochar (MPPSIPB) were synthesized and applied to remove chromium (VI) from aqueous solution. The effects of pH, MPPSIPB dosage, initial Cr(VI) concentration, and contact time were investigated via batch experiments. Results indicated that the percentage removal of Cr(VI) was significantly dependent on the pH of the solution. Ten grams mycelial pellets and 0.2 g powdered biochar could form the most stable pellets. The maximum value of biosorption of Cr(VI) was 28.0 mg/g. Scanning electron microscopy (SEM) analysis showed that the mycelia pellets of Penicillium simplicissimum had abundant filamentous network, which entrapped powdered biochar firmly. Fourier transform infrared (FTIR) analysis suggested that O?H, N?H, C?H, C?O, and C?OH groups from MPPSIPB were involved in chromium binding and the subsequent reduction. Kinetic studies indicated that the pseudo-second-order equation fit best for Cr(VI) removal from aqueous solution. Freundlich isotherm was found to apply better for the adsorption equilibrium data with respect to the Langmuir isotherm. Furthermore, MPPSIPB can be separated from aqueous solution completely by filtration. Both experimental study and modeling results indicated that MPPSIPB exhibited remarkable affinity for chromate and had a potential application in Cr(VI) removal from water.     

Chromium Biosorption from Cr(VI) Aqueous Solutions by Cupressus lusitanica Bark: Kinetics,Equilibrium and Thermodynamic Studies

The present study investigated the kinetics, equilibrium and thermodynamics of chromium (Cr) ion biosorption from Cr(VI) aqueous solutions by Cupressus lusitanica bark (CLB). CLB total Cr biosorption capacity strongly depended on operating variables such as initial Cr(VI) concentration and contact time: as these variables rose, total Cr biosorption capacity increased significantly. Total Cr biosorption rate also increased with rising solution temperature. The pseudo-second-order model described the total Cr biosorption kinetic data best. Langmuir´s model fitted the experimental equilibrium biosorption data of total Cr best and predicted a maximum total Cr biosorption capacity of 305.4 mg g^-1. Total Cr biosorption by CLB is an endothermic and non-spontaneous process as indicated by the thermodynamic parameters. Results from the present kinetic, equilibrium and thermodynamic studies suggest that CLB biosorbs Cr ions from Cr(VI) aqueous solutions predominantly by a chemical sorption phenomenon. Low cost, availability, renewable nature, and effective total Cr biosorption make CLB a highly attractive and efficient method to remediate Cr(VI)-contaminated water and wastewater.