Taguchi DoE methodology for modeling of synthetic dye biosorption from aqueous effluents: parametric and phenomenological studies

Abstract

Biosorption technology has been acknowledged as one of the most successful treatment approaches for colored industrial effluents. The problems such as its high manufacturing cost and poor regeneration capability in the use of activated carbon as a biosorbent have prompted the environmental scientists to develop alternative biosorbent materials. In this context, as a sustainable green generation alternative biosorbent source, the discarded seed biomass from pepper (Capsicum annuum L.) processing industry was explored for the biotreatment of colored aqueous effluents in this study. To test the wastewater cleaning ability of biosorbent, Basic red 46 was selected as a typical model synthetic dye. Taguchi DoE methodology was employed to study the effect of important operational parameters, contact time, pH and synthetic dye concentration, on the biosorption process and to develop a mathematical model for the estimation of biosorption potential of biosorbent. The percentage contribution of each of these process variables on the dye biosorption was found to be 19.31%, 41.39%, and 38.74%, respectively. The biosorption capacity under the optimum environmental conditions, contact time of 360?min, pH of 8 and dye concentration of 30?mg L^?1, was estimated to be 92.878?mg g^?1 (R²: 99.45). This value was very close to the experimentally obtained dye removal performance value (92.095?mg g^?1). These findings indicated the high ability of Taguchi DoE technique in the optimization and simulation of dye biosorption system. The kinetic and equilibrium modeling studies showed that the pseudo-second-order and Langmuir models were the best models for the elucidation of dye removal behavior of biosorbent. The thermodynamic studies displayed that the dye biosorption was a feasible, spontaneous and exothermic process. This parametric and phenomenological survey revealed that the discarded pepper seed biomass can be introduced as a potential and efficient biosorbent for the bioremediation of colored industrial effluents.     

The biosorption of heavy metals from aqueous solution by Spirogyra and Cladophora filamentous macroalgae

The aim of this research was to develop a low cost adsorbent for wastewater treatment. The prime objective of this study was to search for suitable freshwater filamentous algae that have a high heavy metal ion removal capability. This study evaluated the biosorption capacity from aqueous solutions of the green algae species, Spirogyra and Cladophora, for lead (Pb(II)) and copper (Cu(II)). In comparing the analysis of the Langmuir and Freundlich isotherm models, the adsorption of Pb(II) and Cu(II) by these two types of biosorbents showed a better fit with the Langmuir isotherm model. In the adsorption of heavy metal ions by these two types of biosorbents, chemical and physical adsorption of particle surfaces was perhaps more significant than diffusion and adsorption between particles. Continuous adsorption-desorption experiments discovered that both types of biomass were excellent biosorbents with potential for further development.     

Modeling studies on mono and binary component biosorption of phenol and cyanide from aqueous solution onto activated carbon derived from saw dust

Biosorption is an effective treatment method for the removal of phenol and cyanide from aqueous solution by saw dust activated carbon (SDAC). Batch experiments were achieved as a function of several experimental parameters, i.e. influence of biosorbent dose (5–60 g/L) contact time (2–40 h), pH (4–12), initial phenol concentration (100–1000 mg/L) and initial cyanide concentration (10–100 mg/L) and temperature (20–40 °C). The biosorption capacities of the biosorbent were detected as 178.85 mg/g for phenol with 300 mg/L of initial concentration and 0.82 mg/g for cyanide with 30 mg/L of initial concentration. The optimum pH is found to be 8 for phenol and 9 for cyanide biosorption. The mono component biosorption equilibrium data for both phenol and cyanide were well defined by Redlich–Peterson model and binary component adsorption equilibrium data well fitted by extended Freundlich model. The percentage removal of phenol and cyanide using SDAC was 66.67% and 73.33%, respectively. Equilibrium established within 30 h for phenol and 28 h for cyanide. Kinetic studies revealed that biosorption of phenol followed pseudo second order indicating adsorption through chemisorption and cyanide followed pseudo first order kinetic model indicating adsorption through physisorption. Thermodynamic studies parameters, i.e., enthalpy (Δh₀), entropy (ΔS₀) and Gibb’s free energy (ΔG₀) have also been considered for the system. Thermodynamic modeling studies revealed that the process of cyanide biosorption was endothermic and phenol biosorption was exothermic in nature.     

Intensification of biosorption of copper ions from solution by the yeast Saccharomyces cerevisiae in magnetic field

We studied the possibility of intensification of biosorption of copper ions by the yeast Saccharomyces cerevisiae 1968 from a copper sulfate solution by immersing a metal 80-rod headpiece into the solution and applying an external magnetic field. The field was parallel or perpendicular to the axes of headpiece rods. It was shown that intensification of extraction of copper ions at various geometries of the system differed insignificantly and that copper ions were extracted from the solution via biosoprtion and cementation at the metal headpiece.     

Evaluation of a countercurrent biosorption system for the removal of lead and copper from aqueous solutions

Abstract: An automated bench-scale countercurrent biosorption system (CBS) has been designed for the removal of metals from aqueous effluents. The system has been tested with activated sludge microorganisms as a biosorbent and lead and copper as model metals. Nearly 5 1 of a lead nitrate solution at 100 mg l⁻¹ of lead have been treated down to a final concentration of 0.1 mg l⁻¹ (99.9% removal) by using 4.8 g of dry biosorbent. Under similar conditions, copper chloride solutions at 100 mg 1⁻¹ of copper were treated down to a final concentration of 35–45 mg l^−l representing 60% removal. The advantage of the CBS is to maximize metal concentration in the biosorbent, from which the metal may thereby be recovered if desired. In addition, the CBS minimizes metal concentration in the treated effluent, which is the first objective of the treatment.     

Mercury removal from aqueous solution by dried biomass of indigenous Vibrio parahaemolyticus PG02: Kinetic,equilibrium, and thermodynamic studies

In this study, for the first time the potential use of dried Vibrio parahaemolyticus PG02 to remove mercury from synthetic effluent was investigated by considering equilibrium, kinetic, and thermodynamic aspects. The results indicated that Hg²⁺ biosorption was best described by the pseudo-second order model. In addition, it was found that intraparticle diffusion was not the sole rate-limiting step. The ion-exchange mechanism was a predominant biosorption mechanism in the first 15 min of contact. The Langmuir isotherm better described the equilibrium data of Hg²⁺ biosorption than the Freundlich isotherm. According to this model, the maximum biosorption capacity was found to be 9.63 × 10⁻⁴ mol g⁻¹ at optimum conditions (pH = 6.0 and temperature =35 °C).     

Thiol pools and glutathione redox ratios as possible indicators of copper toxicity in the green macroalgae Enteromorpha spp. from the Scheldt Estuary (SW Netherlands,Belgium) and Thermaikos Gulf (Greece,N Aegean Sea)

Defence mechanisms against Cu toxicity were examined in two dominant Enteromorpha species from two coastal water types. The macroalgae were collected at three locations in the eulittoral of the Scheldt Estuary (Netherlands, Belgium) and the Thermaikos Gulf (Greece). For 10 days E. prolifera (Scheldt) and E. linza (Thermaikos) were incubated in seawater media of different salinities: 6, 9, 23 psu and 25, 30, 35 psu, respectively. In one series, media were enriched with 100 μg Cu l-1; responses were compared with those in controls with no extra Cu added. Enteromorpha, which is frequently used as a monitor species for heavy metal contamination, had relatively high Cu tissue levels (0.5–3.8 μmol Cu gdwt-1). Cu levels in E. prolifera controls (Scheldt) decreased with salinity; this was not the case with Cu levels in E. linza controls (Thermaikos). During the 10-d incubation algal protein contents and tissue Cu were rather stable. In E. linza (Thermaikos) algal protein contents were significantly lower than those of E. prolifera (Scheldt), although there was no indication for nitrogen limitation in E. linza. E. linza also had much lower glutathione pools than E. prolifera. Only under acute Cu stress (metal addition) did E. prolifera synthesise metal-binding thiols (phytochelatins). Phytochelatin pools are not suitable as an indicator of the Cu levels in these algae. The glutathione redox ratio GSH:(GSH + 0.5GSSG) was used as an indicator of (Cu-induced) oxidative stress. In E. prolifera (Scheldt) this ratio decreased with algal Cu content (P <0.05), from ~0.5 to ~0.2. The average glutathione ratios in Enteromorpha from the Scheldt and Thermaikos showed some oxidative stress induction with increasing algal Cu contents, however more clearly if Cu was added. As this redox ratio can also be influenced by environmental factors such as irradiance and desiccation, it may not be useful as an indicator for Cu-induced oxidative stress in situ. This revised version was published online in September 2006 with corrections to the Cover Date.     

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.     

Equilibrium and kinetic studies on biosorption potential of charophyte biomass to remove heavy metals from synthetic metal solution and municipal wastewater

The risk of heavy metal contamination in domestic water causes serious health and environmental problems. Biosorption has been considered as an efficient and alternative way for treatment of heavy metal–contaminated wastewater. The potentials of dried charophytes, Chara aculeolata and Nitella opaca, to biosorb lead (Pb), cadmium (Cd), and zinc (Zn) from synthetic solutions and municipal wastewater were investigated. The efficiency of metal removal was studied under varied conditions in different sorbent dosages, pH, and contact times. Biosorption isotherm and kinetics were used to clarify heavy metal preference and biosorption mechanism. C. aculeolata and N. opaca performed well in the biosorption of all three metal ions, with preference towards Pb, followed by Cd and Zn, in the single-metal solutions. Pb adsorption onto algal biomass followed first-order rate kinetics (N. opaca) and intraparticle diffusion (C. aculeolata and N. opaca). These results indicated physical adsorption process between Pb ions and both algal biomasses. Cd and Zn biosorption kinetics fitted the second-order rate model, indicating chemical adsorption between metal ions and both algae. The experimental data of three-metal biosorption fitted well to Langmuir isotherm model, suggesting that the metal ion adsorption occurred in a monolayer pattern on a homogeneous surface. C. aculeolata exhibited slightly higher maximum uptake of Pb, Cd, and Zn (105.3 mgPb/g, 23.0 mgCd/g, 15.2 mgZn/g) than did N. opaca (104.2 mgPb/g, 20.5 mgCd/g, 13.4 mgZn/g). In multi-metal solutions, antagonistic effect by metal competition was observed. The ability of charophytes to remove Pb and Zn was high in real municipal water (81–100%). Thus, the charophytic biomass may be considered for the treatment of metal contamination in municipal wastewater.     

Biosorption of Cu(II) and Pb(II) ions from aqueous solution by natural spider silk

Aside from its excellent mechanical properties, spider silk (SS) would offer an active surface for heavy metal interaction due to its rich protein structure. The present study describes the potential use of natural (SS) as a sorbent of heavy metals from aqueous solutions. Single and multi-species biosorption experiments of heavy metals by natural SS were conducted using batch and column experiments. The biosorption kinetics, in general, was found to follow the second-order rate expression, and the experimental equilibrium biosorption data fitted reasonably well to Freundlich isotherm. From the Freundlich isotherm, the biosorption capacities of Cu(II) and Pb(II) ions onto SS were found as 0.20 and 0.007 mmol g?1, respectively. The results showed a decrease in the extent of metal ion uptake with lowering the pH.     

Bioaccumulation and biosorption efficacy of Trichoderma isolate SP2F1 in removing copper (Cu(II)) from aqueous solutions

In our study, we isolated the isolate Trichoderma SP2F1 from sediment samples from the Penchala River, heavily contaminated with effluents from nearby industrial areas. Qualitative and quantitative screening using plate and broth assay, respectively, supplemented with various concentrations of Cu(II) showed the isolate was able to tolerate 6 mM CuSO₄, although growth was also detected in broths with 10 mM CuSO₄. Trichoderma spp. was able to remove Cu(II) in aqueous solutions in both viable and non-viable cell forms. Bioaccumulation capacity of viable SP2F1 cells removed 19.60 mg g⁻¹ of Cu(II) after 168 h incubation, while the maximum Cu(II) biosorption capacity for non-viable SP2F1 cells was 28.75 mg g⁻¹ of Cu(II). Results here showed that Trichoderma spp isolate SP2F1 has good potential for application in Cu(II) removal, can be used to treat sewage waste by applying either in viable or non-viable cell forms.     

Metals sorption from aqueous solutions by Kluyveromyces marxianus: Process optimization,equilibrium modeling and chemical characterization

The dead Kluyveromyces marxianus biomass, a fermentation industry waste, was used to explore its sorption potential for lead, mercury, arsenic, cobalt, and cadmium as a function of pH, biosorbent dosage, contact time, agitation speed, and initial metal concentration. The equilibrium data fitted the Langmuir model better for cobalt and cadmium, but Freundlich isotherm for all metals tested. At equilibrium, the maximum uptake capacity (Qmax) was highest for lead followed by mercury, arsenic, cobalt, and cadmium. The RL values ranged between 0–1, indicating favorable sorption of all test metals by the biosorbent. The maximum Kf value of Pb showed its efficient removal from the solution. However, multi-metal analysis depicted that sorption of all metals decreased except Pb. The potentiometric titration of biosorbent revealed the presence of functional groups viz. amines, carboxylic acids, phosphates, and sulfhydryl group involved in heavy metal sorption. The extent of contribution of functional groups and lipids to biosorption was in the order: carboxylic>lipids>amines>phosphates. Blocking of sulfhydryl group did not have any significant effect on metal sorption.     

Heavy metal uptake capacity of fresh water algae (Oedogonium westti) from aqueous solution: A mesocosm research

The green macroalgae present in freshwater ecosystems have attracted a great attention of the world scientists for removal of heavy metals from wastewater. In this mesocosm study, the uptake rates of heavy metals such as cadmium (Cd), nickel (Ni), chromium (Cr), and lead (Pb) by Oedogonium westi (O. westti) were measured. The equilibrium adsorption capabilities of O. westti were different for Cd, Ni, Cr, and Pb (0.974, 0.418, 0.620, and 0.261 mgg^–1, respectively) at 18°C and pH 5.0. Furthermore, the removal efficiencies for Cd, Cr, Ni and Pb were observed from 55–95%, 61–93%, 59–89%, and 61–96%, respectively. The highest removal efficiency was observed for Cd and Cr from aqueous solution at acidic pH and low initial metal concentrations. However, the removal efficiencies of Ni and Pb were higher at high pH and high concentrations of metals in aqueous solution. The results summarized that O. westti is a suitable candidate for removal of selected toxic heavy metals from the aqueous solutions.     

NMR and homology modeling studies of copper(II)-halocyanin from Natronobacterium pharaonis bacteria

Halocyanin from the haloalkaliphilic archaean Natronobacterium pharaonis is a peripheral membrane type 1 blue copper protein with a single polypeptide chain of 163 amino acid residues. Halocyanin participates as putative electron carrier protein associated to an electron acceptor role for a terminal oxidase and has the lowest redox potential value reported to date for a BCP. NMR studies and homology modeling calculations were performed to evaluate the electronic properties of Cu(II)-halocyanin from Natronobacterium pharaonis. The copper coordination site properties of Cu(II)-halocyanin are discussed. The ¹H NMR spectra, isotropic chemical shifts and relaxation times for halocyanin are compared with those of other BCPs such as azurin, amicyanin, plastocyanin and stellacyanin. The wild-type Cu(II)-halocyanin presents almost the same ¹H NMR spectra in comparison with Cu(II)-plastocyanin as expected from a similar coordination symmetry. However, minor differences were found. In order to get some insight on these differences, a computational model for Cu(II)-halocyanin from N. pharaonis was built. Model is based on sequential homology of halocyanin with two different families of proteins: plastocyanins and pseudoazurins. Homology modeling was performed using two different structural templates and copper ion was added for further refinement of the coordination site. Proposed structure was in good agreement with NMR experimental information and is the first three-dimensional model reported to date of an halocyanin. Small differences were found in the copper coordination site with respect to other BCP with known structure. This work is also an interesting example of expertise-driven homology modeling across different protein families.     

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.     

Rational design,synthesis, pharmacophore modeling,and docking studies for identification of novel potent DNA-PK inhibitors

Drugs of cancer based upon ionizing radiation or chemotherapeutic treatment may affect breaking of DNA double strand in cell. DNA-PK enzyme has emerged as an attractive target for drug discovery efforts toward DNA repair pathways. Hence, the search for potent and selective DNA-PK inhibitors has particularly considered state-of-the art and several series of inhibitors have been designed. In this article, a novel benchmark DNA-PK database of 43 compounds was built and described. Ligand-based approaches including pharmacophore and QSAR modeling were applied and novel models were introduced and analyzed for predicting activity test for DNA-PK drug candidates. Based upon the modeling results, we gave a report of synthesis of fifteen novel 2-((8-methyl-2-morpholino-4-oxo-4H-benzo[e][1,3]oxazin-7-yl)oxy)acetamide derivatives and in vitro evaluation for DNA-PK inhibitory and antiproliferative activities. These fifteen compounds overall are satisfied with Lipinski's rule of five. The biological testing of target compounds showed five promising active compounds 7c, 7d, 7f, 9e and 9f with micromolar DNA-PK activity range from 0.25 to 5 µM. In addition, SAR of the compounds activity was investigated and confirmed that the terminal aryl moiety was found to be quite crucial for DNA-PK activity. Moreover flexible docking simulation was done for the potent compounds into the putative binding site of the 3D homology model of DNA-PK enzyme and the probable interaction model between DNA-PK and the ligands was investigated and interpreted.     

Adsorption of ethidium bromide from aqueous solution onto nutraceutical industrial fennel seed spent: Kinetics and thermodynamics modeling studies

Dye pollutants from research laboratories are one of the major sources for environmental contamination. In the present study, a nutraceutical industrial fennel seed spent (NIFSS) was explored as potential adsorbent for removal of ethidium bromide (EtBr) from aqueous solution. The adsorbent was characterized by scanning electron microscopy (SEM) and Fourier transform infrared spectroscopy (FTIR). Through batch experiments, the operating variables like initial dye concentration, adsorbent dosage, temperature, contact time, and pH were optimized. Equilibrium data were analyzed using three number of two-parameter and six number of three-parameter isotherm models. The adsorption kinetics was studied using pseudo-first order and pseudo-second order. The diffusion effects were studied by film diffusion, Webber–Morris, and Dumwald–Wagner diffusion models. The thermodynamic parameters; change in enthalpy (ΔHº), entropy (ΔSº), and Gibbs free energy (ΔGº) of adsorption system were also determined and evaluated.     

Optimization and mathematical modeling of the transtubular bioreactor for the production of monoclonal antibodies from a hybridoma cell line

This report describes the use of a transtubular bioreactor to study the relative effects of diffusion versus perfusion of medium on antibody production by a hybridoma cell line. The study was performed with a high-density cell culture maintained in a serum-free, low-protein medium for 77 days. It was determined that the reactor possessed a macro-mixing pattern residence time distribution similar to a continuous stirred tank reactor (CSTR). However, due to the arrangement of the medium lines in the reactor, the flow patterns for nutrient distribution consist of largely independent medium path lengths ranging from short to long. When operated with cyclic, reversing, transtubular medium flow, some regions of the reactor (with short residence times) are more accessible to medium than others (with long residence times). From this standpoint, the reactor can be divided into three regions: a captive volume, which consists of medium primarily delivered via diffusion; a lapped volume, which provides nutrients through unilateral convection; and a swept volume, which operates through bilateral convection. The relative sizes of these three volumes were modified experimentally by changing the period over which the direction of medium flow was reversed from 15 min (larger captive volume) to 9 h (larger swept volume). The results suggest that antibody concentration increases as the size of the diffusion-limited (captive) volume is increased to a maximum at around 30 min with a sharp decrease thereafter. As reflected by changes in measured consumption of glucose and production of lactate, no significant difference in cellular metabolism occurred as the reactor was moved between these different states. These results indicate that the mode of operation of the transtubular bioreactor may influence antibody productivity under serum-free, low-protein conditions with minimal effects on cellular metabolism.