Biosorption of chromium(VI) by spent cyanobacterial biomass from a hydrogen fermentor using Box-Behnken model

The study explores utilization of waste cyanobacterial biomass of Nostoc linckia from a lab-scale hydrogen fermentor for the biosorption of Cr(VI) from aqueous solution. The biomass immobilized in alginate beads was used for removal of the metal in batch mode optimizing the process conditions adopting response surface methodology (RSM). Kinetic studies were done to get useful information on the rate of chromium adsorption onto the cyanobacterial biomass, which was found to follow pseudo second-order model. Four important process parameters including initial metal concentration (10-100 mg/L), pH (2-6), temperature (25-45 °C) and cyanobacterial dose (0.1-2.0 g) were optimized to obtain the best response of Cr(VI) removal using the statistical Box-Behnken design. The response surface data indicated maximum Cr(VI) biosorption at pH 2-4 with different initial concentrations of the metal in the aqueous solution. The biosorbent could remove 80-90% chromium from solutions with initial metal concentration of 10-55 mg/L. Involvement of the surface characteristics of the biomass was studied through its scanning electron micrographs and Fourier transform infrared (FTIR) analysis.     

Isotherm Modelling,Kinetic Study and Optimization of Batch Parameters Using Response Surface Methodology for Effective Removal of Cr(VI) Using Fungal Biomass

Biosorption is a promising alternative method to replace the existing conventional technique for Cr(VI) removal from the industrial effluent. In the present experimental design, the removal of Cr(VI) from the aqueous solution was studied by Aspergillus niger MSR4 under different environmental conditions in the batch systems. The optimum conditions of biosorption were determined by investigating pH (2.0) and temperature (27°C). The effects of parameters such as biomass dosage (g/L), initial Cr(VI) concentration (mg/L) and contact time (min) on Cr(VI) biosorption were analyzed using a three parameter Box–Behnken design (BBD). The experimental data well fitted to the Langmuir isotherm, in comparison to the other isotherm models tested. The results of the D-R isotherm model suggested that a chemical ion-exchange mechanism was involved in the biosorption process. The biosorption process followed the pseudo-second-order kinetic model, which indicates that the rate limiting step is chemisorption process. Fourier transform infrared (FT-IR) spectroscopic studies revealed the possible involvement of functional groups, such as hydroxyl, carboxyl, amino and carbonyl group in the biosorption process. The thermodynamic parameters for Cr(VI) biosorption were also calculated, and the negative ∆Gº values indicated the spontaneous nature of biosorption process.     

Biosorption of Methylene Blue by De-Oiled Algal Biomass: Equilibrium,Kinetics and Artificial Neural Network Modelling

The main objective of the present study is to effectively utilize the de-oiled algal biomass (DAB) to minimize the waste streams from algal biofuel by using it as an adsorbent. Methylene blue (MB) was used as a sorbate for evaluating the potential of DAB as a biosorbent. The DAB was characterized by SEM, FTIR, pH_PZC, particle size, pore volume and pore diameter to understand the biosorption mechanism. The equilibrium studies were carried out by variation in different parameters, i.e., pH (2–9), temperature (293.16–323.16 K), biosorbent dosage (1–10 g L⁻¹), contact time (0–1,440 min), agitation speed (0–150 rpm) and dye concentration (25–2,500 mg L⁻¹). MB removal was greater than 90% in both acidic and basic pH. The optimum result of MB removal was found at 5–7 g L⁻¹ DAB concentration. DAB removes 86% dye in 5 minutes under static conditions and nearly 100% in 24 hours when agitated at 150 rpm. The highest adsorption capacity was found 139.11 mg g⁻¹ at 2,000 mg L⁻¹ initial MB concentration. The process attained equilibrium in 24 hours. It is an endothermic process whose spontaneity increases with temperature. MB biosorption by DAB follows pseudo-second order kinetics. Artificial neural network (ANN) model also validates the experimental dye removal efficiency (R² = 0.97) corresponding with theoretically predicted values. Sensitivity analysis suggests that temperature and agitation speed affect the process most with 23.62% and 21.08% influence on MB biosorption, respectively. Dye adsorption capacity of DAB in fixed bed column was 107.57 mg g⁻¹ in preliminary study while it went up to 139.11 mg g⁻¹ in batch studies. The probable mechanism for biosorption in this study is chemisorptions via surface active charges in the initial phase followed by physical sorption by occupying pores of DAB.     

The Suitability of Jatropha Seed Press Cake as a Biosorbent for Removal of Hexavalent Chromium from Aqueous Solutions

Jatropha seed press cake (JPC), a biodeisel waste, was investigated for its use as biosorbent for Cr(VI) removal from wastewater. The acid-pretreated biomass exhibited 1.9-fold higher biosorption efficiency for Cr(VI). The Cr(VI) biosorption efficiency was found to increase with decrease in pH of aqueous medium. The adsorption capacity of biosorbent for Cr(VI) increased with increasing concentration of Cr(VI). The biosorption of Cr(VI) by acid-treated JPC followed a pseudo-second-order kinetics. The results of equilibrium studies showed that the biosorption process fitted the Langmuir isotherm model, with a maximum adsorption capacity of 22.727 mg of Cr(VI)/g of biosorbent at 30°C. The activation energy was found to be 27.114 kJ/mol, suggesting that the adsorption process was mainly a physical process. The important thermodynamic parameters of adsorption (ΔG, ΔH, andΔS) were determined, which indicated that the Cr(VI) sorption by JPC is a spontaneous and endothermic process.     

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.     

Biosorption of chromium (Cr(III)/Cr(VI)) on the residual microalga Nannochloris oculata after lipid extraction for biodiesel production

In order to increase the economic feasibility of biodiesel production from microalgae, the residual biomass after biodiesel production can be utilized as biosorbent for heavy metal removal. In this study, biosorption of chromium by residual Nannochloris oculata after lipid extraction was investigated. Increased surface area of N. oculata was observed after lipid extraction. Cr(III) removal increased as the pH increased from 2 to 6, while Cr(VI) removal was highest at pH 2 and it decreased with the increase in pH. Cr(VI) was reduced to Cr(III) in the presence of biomass under acidic conditions; X-ray photoelectron spectroscopy revealed that the converted Cr(III) was bound to the biomass. Chromium removal was significantly enhanced at high chromium concentrations, which indicates that surface reactions may occur at high chromium/biomass ratios. FTIR study indicated that phosphate and carboxyl functional groups of the biomass were mainly responsible for chromium binding.     

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).     

Potential use of green algae as a biosorbent for hexavalent chromium removal from aqueous solutions

The hexavalent chromium Cr(VI) poses a threat as a hazardous metal and its removal from aquatic environments through biosorption has gained attention as a viable technology of bioremediation. We evaluated the potential use of three green algae (Cladophora glomerata, Enteromorpha intestinalis and Microspora amoena) dry biomass as a biosorbent to remove Cr(VI) from aqueous solutions. The adsorption capacity of the biomass was determined using batch experiments. The adsorption capacity appeared to depend on the pH. The optimum pH with the acid-treated biomass for Cr(VI) biosorption was found to be 2.0 at a constant temperature, 45?°C. Among the three genera studied, C. glomerata recorded a maximum of 66.6% removal from the batch process using 1.0?g dried algal cells/100?ml aqueous solution containing an initial concentration of 20?mg/L chromium at 45?°C and pH 2.0 for 60?min of contact time. Langmuir and Freundlich isotherm equations fitted to the equilibrium data, Freundlich was the better model. Our study showed that C. glomerata dry biomass is a suitable candidate to remove Cr(VI) from aqueous solutions.     

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.     

Chromium Removal from Aqueous System and Industrial Wastewater by Agricultural Wastes

This study involved the development of formaldehyde-treated, deseeded sunflower head waste–based biosorbent (FSH) for the biosorption of Cr(VI) from aqueous solution and industrial wastewater. Batch-mode experiments were conducted to determine the kinetics, sorption isotherms, effect of pH, initial Cr(VI) concentration, biosorbent dose, and contact time. The results demonstrated that FSH can sequester Cr(VI) from the aqueous solution. The maximum sorption occurred at pH = 2.0, biosorbent dose = 4.0 g/L, concentration of 100 mg/L at 25°C at 180 rpm after 2 h contact time. The FSH had an adsorption capacity of 7.85 mg/g for Cr(VI) removal at pH 2.0. The rate of adsorption was rapid, and equilibrium was attained within 2 h. The equilibrium sorption data fitted the Langmuir isotherm model, which was further confirmed by the chi-square test.     

Biosorption of chromium(VI) from aqueous solution by cone biomass of Pinus sylvestris

Biosorption of chromium(VI) on to cone biomass of Pinus sylvestris was studied with variation in the parameters of pH, initial metal ion concentration and agitation speed. The biosorption of Cr(VI) was increased when pH of the solution was decreased from 7.0 to 1.0. The maximum chromium biosorption occurred at 150 rpm agitation. An increase in chromium/biomass ratio caused a decrease in the biosorption efficiency. The adsorption constants were found from the Freundlich isotherm at 25 degrees C. The cone biomass, which is a readily available biosorbent, was found suitable for removing chromium from aqueous solution.     

Biosorption of Cr(VI) onto marine Aspergillus niger: experimental studies and pseudo-second order kinetics

The removal of hexavalent chromium from aqueous solution was studied in batch experiments using dead biomass of three different species of marine Aspergillus after alkali treatment. All the cultures exhibited potential to remove Cr(VI), out of which, Aspergillus niger was found to be the most promising one. This culture was further studied employing variation in pH, temperature, metal ion concentration and biomass concentration with a view to understand the effect of these parameters on biosorption of Cr(VI). Higher biosorption percentage was evidenced at lower initial concentration of Cr(VI) ion, while the sorption capacity of the biomass increased with rising concentration of ions. Biomass as low as 0.8 g l⁻¹ could biosorb 95% Cr(VI) ions within 2,880 min from an aqueous solution of 400 mg l⁻¹ Cr(VI) concentration. Optimum pH and temperature for Cr(VI) biosorption were 2.0 and 50°C, respectively. Kinetic studies based on pseudo second order models like Sobkowsk and Czerwinski, Ritchie, Blanchard and Ho and Mckay rate expressions have also been carried out. The nature of the possible cell–metal ion interactions was evaluated by FTIR, SEM and EDAX analysis.     

Biosorption of Acid Black 172 and Congo Red from aqueous solution by nonviable Penicillium YW 01: Kinetic study, equilibrium isotherm and artificial neural network modeling

The main objective of this work was to investigate the biosorption performance of nonviable Penicillium YW 01 biomass for removal of Acid Black 172 metal-complex dye (AB) and Congo Red (CR) in solutions. Maximum biosorption capacities of 225.38 and 411.53 mg g⁻¹ under initial dye concentration of 800 mg L⁻¹, pH 3.0 and 40 °C conditions were observed for AB and CR, respectively. Biosorption data were successfully described with Langmuir isotherm and the pseudo-second-order kinetic model. The Weber-Morris model analysis indicated that intraparticle diffusion was the limiting step for biosorption of AB and CR onto biosorbent. Analysis based on the artificial neural network and genetic algorithms hybrid model indicated that initial dye concentration and temperature appeared to be the most influential parameters for biosorption process of AB and CR onto biosorbent, respectively. Characterization of the biosorbent and possible dye-biosorbent interaction were confirmed by Fourier transform infrared spectroscopy and scanning electron microscopy.     

Removal of hexavalent chromium by fungal biomass of <Emphasis Type="Italic">Mucor racemosus</Emphasis>: influencing factors and removal mechanism

This study reported the hexavalent chromium removal by untreated Mucor racemosus biomass and the possible mechanism of Cr (VI) removal to the biomass. The optimum pH, biomass dose, initial Cr (VI) concentration and contact time were investigated thoroughly to optimize the removal condition. The metal removal by the biomass was strongly affected by pH and the optimum pH ranged from 0.5 to 1.0. The residual total Cr was determined. It was found that dichromate reduction occurred at a low very low pH value. At biomass dose 6 g/l, almost all the Cr (VI) ions were removed in the optimum condition. Higher removal percentage was observed at lower initial concentrations of Cr (VI) ions, while the removal capacity of the biomass linearly depended on the initial Cr (VI) concentration. More than half of Cr (VI) ions were diminished within 1 h of contact and removal process reached a relative equilibrium in approximately 8 h. Almost all of the Cr (VI) ions were removed in 24 h when initial concentrations were below 100 mg/l. The equilibrium data were fitted in to the Langmuir and the Freundlich isotherm models and the correlated coefficients were gained from the models. A Fourier transform infrared spectra was employed to elucidate clearly the possible biosorption mechanism as well.     

Experimental and theoretical approaches for Cd(II) biosorption from aqueous solution using Oryza sativa biomass

Biomass of Oryza sativa (OS) was tested for the removal of Cd(II) ions from synthetic and real wastewater samples. Batch experiments were conducted to investigate the effects of operating parameters on Cd(II) biosorption. Fourier transform infrared spectroscopy, scanning electron microscopy, and energy-dispersive x-ray spectroscopy were used to examine the surface characteristics of the Cd(II)-loaded biomass. The maximum removal efficiency of Cd(II) was 89.4% at optimum pH 6.0, biosorbent dose 10.0 g L^?1, initial Cd(II) 50 mg L^?1, and biosorbent particle size 0.5 mm. The applicability of Langmuir and Freundlich isotherms to the sorbent system implied the existence of both monolayer and heterogeneous surface conditions. Kinetic studies revealed that the adsorption process of Cd(II) followed the pseudo-second-order model (r2: 0.99). On the theoretical side, an adaptive neuro-fuzzy inference system (ANFIS) was applied to select the operating parameter that mostly influences the Cd(II) biosorption process. Results from ANFIS indicated that pH was the most influential parameter affecting Cd(II) removal efficiency, indicating that the biomass of OS was strongly pH sensitive. Finally, the biomass was confirmed to adsorb Cd(II) from real wastewater samples with removal efficiency close to 100%. However, feasibility studies of such systems on a large-scale application remain to be investigated.     

Biosorption of hexavalent chromium from aqueous solution by a tropical basidiomycete BDT-14 (DSM 15396)

Summary A tropical white-rot basidiomycete, BDT-14 (DSM 15396) was investigated for its chromium (VI) biosorption potential from an aqueous solution. Pre-treatment of fungal biomass with acid resulted in 100% metal adsorption compared to only 26.64% adsorption without any pre-treatment. Chromium adsorption was a rapid process at early exposure resulting in 60% chromium removal within the first 2 h of exposure. An increase in biomass showed an increase in the total metal ions adsorption but a decrease in specific uptake of metal ions. The concentrations of chromium had a pronounced effect on the rate of adsorption. The adsorption efficiency was 100% when the initial Cr (VI) concentration was 100 mg l⁻¹ with 1,000 mg biomass. Only 47.5% adsorption was observed with 500 mg l⁻¹ Cr (VI) concentration. The adsorption data fit well with the Langmuir and Freundlich isotherm models. Comprehensive characterization of parameters indicates BDT−14 biomass as a promising material for Cr (VI) adsorption.     

Process optimization studies of lead (Pb(II)) biosorption onto immobilized cells of Pycnoporus sanguineus using response surface methodology

A central composite design (CCD) was employed to optimize the biosorption of Pb(II) ions onto immobilized cells of Pycnoporus sanguineus. The independent variables were initial Pb(II) concentration, pH and biomass loading. The combined effects of these variables were analyzed by response surface methodology (RSM) using quadratic model for predicting the optimum point. Under these conditions the model predicted a maximum of 97.7% of Pb(II) ions removal at pH 4, 200mg/L of initial Pb(II) concentration with 10g/L of biosorbent. The experimental values are in good agreement with predicted values within +0.10 to +0.81% error.     

Process optimization of batch biosorption of lead using <Emphasis Type="Italic">Lactobacillius bulgaricus</Emphasis> in an aqueous phase system using response surface methodology

Response surface methodology (RSM) based on central composite rotatable design was used to investigate the effects of operating variable, mainly, pH, weight of biomass, and initial lead ion concentration on the lead adsorption capacity at ambient temperature using dried cells of Lactobacillius bulgaricus. Using RSM, quadratic polynomial equation was obtained for predicting the percent of lead ion removal. Analysis of variance showed that the effects of pH and weight of dried biomass were concluded to be the key factors influencing the capacity of lead ion removal. At pH lower than 2 (high acidic condition) and in alkaline condition, there is no significant biosorption. The optimum percent of lead ion removal was found at pH of 6.78, biomass concentration of 6.58 g/l and initial lead concentration 36.22 ppm. In this condition, percent of lead ion removal was 86.21%. This study showed RSM effectiveness for modeling of biosorption 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.     

Senna auriculata L. flower petal biomass: An alternative green biosorbent for the removal of fluoride from aqueous solutions

Fluoride contamination in groundwater is a major concern in many parts of India and all over the world. Researches paying attention for the removal of fluoride through the application of biosorbents prepared from different parts of plants are finding greater scope and importance. The present research work focuses on Senna auriculata L., flower petal biomass as biosorbent, and evaluated its feasibility for fluoride ion elimination from aqueous solutions. Batch experiments were conducted to remove fluoride under different experimental conditions have been optimized for the maximum removal of fluoride; 80% removal was observed at pH: 6, sorbent dosage: 0.25 g/100 mL, time of agitation: 90 min, and initial concentration of the fluoride ions: 5 mg/L. Characterization studies of the biosorbent revealed its favorability towards the sorption of fluoride. In the isothermal modeling studies, Langmuir isotherm model was obeyed by the biosorption process with R² value of 0.98 and from a kinetic perspective, the biosorption of fluoride onto the biosorbent observed the pseudo-second-order reaction with R² value of 0.98. The developed biosorbent has been applied to real field fluoride-contaminated water samples and found to be successful.