Biosorption of three textile dyes from contaminated water by filamentous green algal Spirogyra sp.: Kinetic,isotherm and thermodynamic studies

A freshwater filamentous green alga Spirogyra sp. was used as an inexpensive and efficient biosorbent for the removal of C.I. Acid Orange 7 (AO7), C.I. Basic Red 46 (BR46) and C.I. Basic Blue 3 (BB3) dyes from contaminated water. The effects of various physico–chemical parameters on dye removal efficiency were investigated, e.g. contact time, pH, initial dyes concentration, the amount of alga, temperature and biosorbent particle size. Dyes biosorption was a quick process and reactions reached to equilibrium conditions within 60 min. The biosorption capacity of three dyes onto alga was found in the following order: BR46 > BB3> AO7. The values of thermodynamic parameters, including ΔG, ΔH and ΔS, indicated that the biosorption of the dyes on the dried Spirogyra sp. biomass was feasible, spontaneous and endothermic. The pseudo-first order, pseudo-second order and the intraparticle diffusion models were applied to the experimental data in order to kinetically describe the removal mechanism of dyes, with the second one showing the best fit with the experimental kinetic biosorption data (R² = 0.99). It was also found that the adsorption process followed the Freundlich isotherm model with the highest value of correlation coefficients (0.99) and the biosorption capacity being estimated to be 13.2, 12.2 and 6.2 mg g⁻¹ for BR46, BB3 and AO7, respectively.     

Biosorption of methylene blue from aqueous solution using free and polysulfone-immobilized Corynebacterium glutamicum: batch and column studies

The amino acid fermentation industry waste, Corynebacterium glutamicum, has been found to possess excellent biosorption capacity towards methylene blue (MB). Due to practical difficulties in solid-liquid separation and biomass regeneration, C. glutamicum was immobilized in a polysulfone matrix. The pH edge experiments revealed that neutral or alkaline pH values favored MB biosorption. Isotherm experiments indicated that C. glutamicum, when in immobilized state, exhibited slightly inferior dye uptake compared to free biomass. Also considering the two forms, immobilized biomass took a long time to attain equilibrium. An attempt to identify the diffusion limitations in immobilized beads was successful, with the Weber-Morris model clearly indicating intraparticle as the rate controlling step. Regeneration of the free biomass was not possible as it tended to become damaged under strong acidic conditions. On the other hand, immobilized biomass performed well with 99% desorption of MB from the biosorbent with the aid of 0.1 mol/l HCl. The immobilized biomass was also successfully regenerated and reused for three cycles without significant loss in sorption capacity. An up-flow packed column loaded with immobilized biomass was employed for the removal of MB. The column performed well in the biosorption of MB, exhibiting a delayed and favorable breakthrough curve with MB uptake and % removal of 124 mg/g biomass and 70.1%, respectively.     

Biosorption of tetradecyl benzyl dimethyl ammonium chloride on activated sludge: kinetic, thermodynamic and reaction mechanisms

The biosorption of tetradecyl benzyl dimethyl ammonium chloride (C₁₄BDMA) onto activated sludge was examined in aqueous solution with respect to the contact time, temperature and particle size. Equilibrium reached in about 2 h contact time. An decrease in the temperature increases of biosorption capacity of C₁₄BDMA onto activated sludge, which also increases with decreasing particle size. The experimental data fit the pseudo-second-order kinetics model well. The Langmuir and Freundlich models were applied to describe equilibrium isotherms, and the equilibrium partitioning data was described well by both models. Thermodynamic data showed that C₁₄BDMA biosorption onto activated sludge was feasible, spontaneous and exothermic. The Fourier transform infrared (FT-IR) spectrophotometry results show that both physisorption and chemisorption were involved. The measured zeta potential values and the enhanced cation concentration indicate the presence of electrostatic interactions, hydrophobic interactions and ion exchange.     

1,3‐Propanediol adsorption on a cation exchange resin: Adsorption isotherm,thermodynamics, and mechanistic studies

1,3‐Propanediol (1,3‐PD) is widely used in cosmetics, foods, antifreezes, and polyester. A low‐cost cation exchange resin, 001×7 H‐form resin, was selected for 1,3‐PD adsorption obtained from microbial fermentation of crude glycerol. The thermodynamics and kinetics of adsorption were studied. To identify the characteristics of the adsorption process, the influence of 1,3‐PD concentration, temperature, and resin particle diameters was studied. The temperature dependence of the adsorption equilibrium in the range of 288 to 318 K was observed to satisfy the Langmuir isotherm well. The thermodynamic parameters, adsorption enthalpy, entropy, and Gibbs free energy, were determined as 36.2 kJ·moL^?1, 160 mol^?1·K^?1, and ?11.2 kJ·moL^?1, respectively, which indicated that the adsorption was spontaneous and endothermic. The adsorption kinetics was accurately represented by the shell progressive model and indicated that the particle diffusion was the rate‐limiting step. Based on the kinetic simulation, the rate constant of exchange (k₀), order reaction (α), and the apparent activation energy reaction (E_a) were obtained as 3.11×10^?3, 0.644, and 11.5 kJ·moL^?1, respectively. This kinetic and thermodynamic analysis of 1,3‐PD recovery presented in this article is also applicable for the separation of other polyols by resin adsorption, which will promote value‐added utilization of glycerol.     

Improvement of pectinase,xylanase and cellulase activities by ultrasound: Effects on enzymes and substrates,kinetics and thermodynamic parameters

Ultrasound effects were investigated on pectinase (PE), xylanase (XLN) and cellulase (CE) activities at different pH, temperatures, and by sonication pre-treatment, comparing the reaction at ultrasound bath (US) and at a mechanical stirring (MS). In general, US increased the activity of the enzymes by 5% for PE, 30 % for XLN and 25% for CE compared to MS. US provided a higher activity at extremes pH (pH 3 and 7), mainly for XLN and CE. The substrate and enzyme pre-sonication enhanced the activities. The previous sonication of xylan increased the xylanase activity in almost 30% under US and almost 20% under MS. On the other hand, cellulase pre-sonication increased the activity in 50% under US and 40% under MS. The catalytic efficiency (V_max/K_M) increase 25% for PE and 17% for higher XLN and CE under US. US affected the PE activity at low temperature improving 10% the PE activity, while its effect was more representative at high temperatures, where the enzymatic activities of XLN and CE were 33% and 15% higher. Our results demonstrated that ultrasound can affect enzymes and substrates, making it a powerful tool for enzymatic-catalyzed reactions.     

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.     

Biosorption of nickel(II) ions by baker's yeast: kinetic, thermodynamic and desorption studies

In this study, the biosorption of nickel(II) ion on deactivated protonated yeast was investigated as a function of temperature at different initial metal ion concentrations. The effect of temperature on the sorption was more significant at lower nickel(II) ion concentrations compared to higher concentrations. The protonated yeast biomass exhibited the highest nickel(II) ion uptake capacity at 27 degrees C at an initial nickel(II) ion concentration of 400mg/l and an initial pH of 6.75. The biosorption capacity decreased from 9.8 to 9.3mg/g at an initial nickel(II) ion concentration of 400mg/l, while at a lower initial concentration of 100mg/l, it decreased from 8.2 to 4.9 mg/g, as the temperature was increased from 27 degrees C to 60 degrees C. The equilibrium data fit better to the Freundlich and Redlich-Peterson isotherm models compared to the Langmuir model in the concentration range studied (10-400mg/l). Kinetic models applied to the sorption data at different temperatures showed that nickel(II) ion uptake process followed the pseudo-second order rate model and the adsorption rate constants decreased with increasing temperature. The activation energy of biosorption (Ea) was determined to be -13.3 kJ/mol using the pseudo-second order rate constants. The results indicated that the biosorption of nickel(II) ion on to baker's yeast was spontaneous and exothermic in nature. Desorption studies revealed that the protonated yeast biomass can be regenerated using 0.1N HCl and reused.     

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.     

磷酸盐在土壤中的竞争吸附与解吸机制

本文概述了近年来国内外有关磷酸盐的竞争吸附与解吸的研究成果。土壤中许多阴离子都能与磷竞争吸附点位,使得磷的吸附下降。有机质可促进或抑制磷的吸附,pH是影响竞争吸附的主要因子。磷被吸附后大多固持在表面而难于解吸,往往呈现明显的滞后现象。通常只有拟物理吸附的磷能被解吸,化学吸附的磷因与表面金属离子作用形成双齿配位而极难被淋洗下来。解吸受多种因素的影响,其中解吸剂的类型是主要因子之一。     

Improved adsorption of cadmium ions from aqueous solution using chemically modified apple pomace: Mechanism,kinetics, and thermodynamics

Apple pomace (AP), before and after chemical modification (CM), was assessed for the removal of cadmium (Cd²⁺) ions from aqueous solution by equilibrium, kinetics, and thermodynamics studies. The chemical modification of AP was done with succinic anhydride by a simple ring opening mechanism for providing a large surface area for cadmium adsorption. The surface area of chemically modified apple pomace (CMAP) increased about 18% after the treatment. The amount of CMAP required for cadmium removal was 50 times less than the unmodified AP. The Langmuir adsorption isotherm equation was found to be more suitable for the AP and CMAP adsorption experimental data with a correlation coefficient of r² = 0.99 than was the Freundlich isotherm. The FTIR spectra of CMAP, with or without cadmium loading, indicated that ester (–COO), carboxyl (–CO), and amine (–NH₂) groups were involved in the cadmium adsorption mechanism. The adsorption of cadmium ions onto AP and CMAP followed pseudo-second-order kinetics. The ΔG^° value, at different temperatures, was calculated by applying the Van't Hoff equation and found to be negative, indicating that the reaction is spontaneous in nature. The value of ΔH^° indicated that the adsorption was exothermic (−6.93 KJ mol⁻¹) and endothermic (3.171 KJ mol⁻¹) for AP and CMAP, respectively. CMAP could be reutilized for up to three cycles with a removal efficiency of 76.6%, while AP efficiency lessened significantly after a single cycle.     

红螺菌吸附铜的动力学与脱附研究

研究了红螺菌(Rhodospirillum)对Cu~(2 )的吸附动力学行为,在一定的条件下,吸附在45 min达到平衡,吸附平衡时最大吸附量为48.23 mg·g~(-1)。应用准一级和准二级反应动力学模型进行数据分析,结果表明菌体对Cu~(2 )的吸附符合准二级动力学模型。比较分析了多种脱附剂对菌体脱附,EDTA和柠檬酸是较有效的洗脱剂,脱附率分别为86.4％、66.9％;无机酸及无机盐对菌体的脱附效果很差,脱附率在20％左右。X-射线衍射分析表明,菌体吸附Cu~(2 )后没有形成新晶相,并且菌体部分晶相转变为非晶相。     

A versatile noninvasive method for adsorber quantification in batch and column chromatography based on the ionic capacity

Within the Quality by Design (QbD) framework proposed by the International Conference on Harmonisation (ICH), high‐throughput process development (HTPD) and mechanistic modeling are of outstanding importance for future biopharmaceutical chromatography process development. In order to compare the data derived from different column scales or batch chromatographies, the amount of adsorber has to be quantified with the same noninvasive method. Similarly, an important requirement for the implementation of mechanistic modeling is the reliable determination of column characteristics such as the ionic capacity Λ for ion‐exchange chromatography with the same method at all scales and formats. We developed a method to determine the ionic capacity in column and batch chromatography, based on the adsorption/desorption of the natural, uv‐detectable amino acid histidine. In column chromatography, this method produces results comparable to those of classical acid?base titration. In contrast to acid?base titration, this method can be adapted to robotic batch chromatographic experiments. We are able to convert the adsorber volumes in batch chromatography to the equivalent volume of a compressed column. In a case study, we demonstrate that this method increases the quality of SMA parameters fitted to batch adsorption isotherms, and the capability to predict column breakthrough experiments. © 2016 American Institute of Chemical Engineers Biotechnol. Prog., 32:666–677, 2016     

Sorption of heavy metals from electroplating effluent using immobilized biomass Trichoderma viride in a continuous packed-bed column

The sorption of heavy metals ions by immobilized Trichoderma viride biomass in a packed-bed column was studied. Fungal biomass T. viride was immobilized to Ca-alginate used for removal of Cr(VI), Ni(II) and Zn(II) ions from synthetic solutions and electroplating effluent. The experiments were conducted to study the effect of important design parameters such as bed height, flow rate and initial concentration of metal ions. The maximum sorption capacity was observed at flow rate 5 ml/min, bed height 20 cm and metal ions concentration 50 mg/L with immobilized biomass. Whereas, breakthrough time and saturation time decreased with increase flow rate and metal ions concentration and an inverse condition was found in bed height. The bed depth service time (BDST) Adams-Bohart model was used to analyze the experimental data. The regeneration efficiency was observed 40.1%, 75% and 53% for Cr(VI), Ni(II) and Zn(II) without any significant alteration in sorption capacity after 5th sorption-desorption cycles.     

Effects of proanthocyanidins on porcine pancreatic lipase: Conformation,activity, kinetics and thermodynamics

The interactions between proanthocyanidins (PC) and porcine pancreatic lipase (PL) were investigated from variant aspects of lipase conformation, activity, kinetics, and thermodynamics. Results show that 34% inhibitory rate of PC on PL is achieved after about 30-min incubation, and the inhibitory rate increases with the increase of PC concentration and then plateaus at the PC/PL ratio of 200. Circular dichroism and fluorescence spectroscopic analyses demonstrate that PC decreases the α-helix content while increases the β-sheet content of PL, but does not change the microenvironment of Trp, and PC quenches the fluorescence of PL both dynamically and statically through the formation of PL–PC complex. PC induces PL aggregation and then stabilizes the lipase aggregates. Kinetic studies reveal that PC does not change the K_m value while decreases the V_max value, implying that PC non-competitively inhibits the PL activity.     

Biosorption and desorption studies of chromium (III) by free and immobilized Rhizobium (BJVr 12) cell biomass

Experiments with free cell biomass (cells + exopolysaccharides) ofRhizobium BJVr 12 (mungbean isolate) showed that amount ofCr³⁺ ion sorbed is influenced by the amount of biomass toCr³⁺ concentration ratio and time of contact. A ratio of 0.5 gfresh biomass to 10.0 ml 5.03 ppm Cr³⁺ sorbed 0.0275 mg Crequivalent to an uptake of 2.86 mg Cr g-¹ dry biomass and 1.0g: 10.0 ml sorbed 0.0366 mg Cr equivalent to an uptake of 1.9 mg Crg-¹ biomass. Immobilized cell biomass in ceramic beads and inaquacel (a porous cellulose carrier with a charged surface) were moreefficient than free cell biomass in adsorbing Cr(III). A reduction of49.7percnt; of Cr(III) for free cells, 95.6% for cells immobilized inceramic beads and 94.6% for cells in aquacel was achieved after 48hours under shaken conditions. Sorption capacities of immobilized cellbiomass in ceramic beads and aquacel ranged from 5.01 to 5.06 mg Crg^-1 dry cell biomass. The biosorption of Cr³⁺follows generally the Langmuir and Freundlich models of adsorption at lowCr³⁺ concentrations. The Langmuir constant for immobilizedcells in ceramic beads are: Q₀, 0.065 mmol Crg^-1 biomass; b (affinity constant), - 694 lmmol^-1 Cr and for cells in aquacel Q, 0.07 mmol Crg^-1 biomass; b, - 694 l mmol Cr g^-1 Cr. TheFreundlich constants are: K, 0.071 mmol Cr g^-1 biomass; n,0.13 g^-1 biomass l^-1 and for aquacel: K, 0.074mmol g^-1 biomass; n, 0.13 g^-1 biomass. Biotrapsmade up of immobilized cells in ceramic beads and aquacel were tested foradsorbing Cr(III) using two different flow rates: 0.5 ml/min and 1.5 ml/min.A significantly higher amount of Cr(III) was adsorbed at the lower flow rateof 0.5 ml/min. Biosorption of Cr³⁺ is competitive. Thetreatment of a waste water sample containing 6.03 ppm Cr³⁺ andother cations with the biomass reduced the Cr³⁺ concentrationto that much lower than for the test solution containing only Cr. Recoveryof biosorbed Cr(III) was by treatment at a different pH using dilute HClsolution. Recovery was higher for cells imbibed in ceramic beads thanaquacel. Percentage recoveries for cells in aquacel are 46.4% at pH1.0, 33.0% at pH 3.0 and 6.6% at pH 6.0–7.0. For cellsin ceramic beads, percentage recoveries are: 93.1% at pH 1.0,75.6% at pH 3.0 and 16.4% at pH 6.0–7.0. Biosorption ofCr³⁺ by cells immobilized in ceramic beads is reversible butonly partially for cells in aquacel.     

红壤中镉在有机酸作用下的解吸行为

采用平衡批处理法,研究了3种有机酸及其两两混合液在序列pH值梯度下（pH 3.0～7.0）对华南山地红壤Cd解吸行为的影响.结果表明,草酸与苹果酸不利于Cd的解吸,反而促进了吸附,其中草酸只是在较高浓度(20 mmol·L^-1)且土壤溶液pH＞5.0时促进解吸.随着pH值升高,草s酸、苹果酸以及不含有机酸的对照溶液对红壤中Cd的解吸率都快速下降.柠檬酸在pH＜5.0时不利于Cd解吸;在pH＞5.0时显著促进Cd解吸,但两种浓度柠檬酸解吸特征有所不同,在低浓度(2 mmol·L^-1)下对镉的解吸率呈降低-升高-降低变化,在高浓度(20 mmol·L^-1)下呈降低-升高变化.在低pH条件下（pH 3.0、4.0）,苹果酸最有利于Cd的解吸,但3种酸对Cd解吸率差别不大,在较高pH条件下(pH 5.0～7.0),柠檬酸最有利于解吸,且解吸率大大高于草酸与苹果酸.有机酸混合没有明显的交互作用,对Cd的解吸率介于相应单独有机酸之间.     

Fast pyrolysis of palm kernel cake in a closed-tubular reactor: product compositions and kinetic model

In this study, fast pyrolysis of palm kernel cake (PKC) was carried out in a closed-tubular reactor over a temperature range of 550 to 750 °C with various retention times. The pyrolyzing gas products mainly included CO, CO₂, and light hydrocarbons; it is noted that no hydrogen was detected in the product. In order to investigate the reaction pathway, the kinetic lump model of Liden was applied to verify and calculate all rate constants. The results obtained at different temperatures indicated that the rate constant increased with pyrolysis temperature. Furthermore, the experimental results were in good agreement with the proposed mechanism.     

Biosorption of chromium(III) by two brown algae Macrocystis pyrifera and Undaria pinnatifida: Equilibrium and kinetic study

Two brown algae, Macrocystis pyrifera and Undaria pinnatifida, were employed to remove Cr(III) from aqueous solutions. Both seaweeds were characterized in terms of alginate yields. The alginate contents were 20 and 30% of the dry weight for M. pyrifera and U. pinnatifida, respectively. Kinetics experiments were carried out at different initial pH values. Cr(III) biosorption was affected by the solution pH. The highest metal uptake was found at pH 4 for both biosorbents. Different models were applied to elucidate the rate‐controlling mechanism: pseudo‐first‐order, pseudo‐second‐order, external mass transfer and intra‐particle diffusion. The application of Langmuir, Freundlich and Dubinin–Radushkevich models to the equilibrium data showed a better fitting to the first model. The maximum Cr(III) sorption capacity (q_m) and the affinity coefficient (b) were very similar for both biosorbents: 0.77 mmol/g and 1.20 L/mmol for M. pyrifera and 0.74 mmol/g and 1.06 L/mmol for U. pinnatifida. The free energy of the sorption process was estimated using the Dubinin–Radushkevich isotherm. The values indicate that the processes are chemical sorptions. To evaluate the significance of the ion‐exchange mechanism, the light metals (Ca²⁺, Na⁺, Mg²⁺ and K⁺) and pH were measured during the experiments.     

Kinetic analysis of a monoclonal therapeutic antibody and its single-chain homolog by surface plasmon resonance

Monoclonal antibodies (mAbs) and antibody fragments have become an emerging class of therapeutics since 1986. Their versatility enables them to be engineered for optimal efficiency and decreased immunogenicity, and the path to market has been set by recent regulatory approvals. One of the initial criteria for success of any protein or antibody therapeutic is to understand its binding characteristics to the target antigen. Surface plasmon resonance (SPR) has been widely used and is an important tool for ligand-antigen binding characterization. In this work, the binding kinetics of a recombinant mAb and its single-chain antibody homolog, single-chain variable fragment (scFv), was analyzed by SPR. These two proteins target the same antigen. The binding kinetics of the mAb (bivalent antibody) and scFv (monovalent scFv) for this antigen was analyzed along with an assessment of the thermodynamics of the binding interactions. Alternative binding configurations were investigated to evaluate potential experimental bias because theoretically experimental binding configuration should have no impact on binding kinetics. Self-association binding kinetics in the proteins’ respective formulation solutions and antigen epitope mapping were also evaluated. Functional characterization of monoclonal and single-chain antibodies has become just as important as structural characterization in the biotechnology field.     

Effect of fouling on the capacity and breakthrough characteristics of a packed bed ion exchange chromatography column

This study examined the impact of fouling with yeast homogenate on capacity and breakthrough performance of an ion exchange packed bed column. Column performance was assessed by analysis of breakthrough curves obtained with BSA as a test protein. The overall impact of fouling on breakthrough performance depended heavily on the level of clarification of the feed stream. Challenging the column with particulate-free homogenate caused no change in column performance. Loading successive small volumes of poorly clarified homogenate, interspersed with frequent column salt washes, did not alter significantly the column capacity. By contrast, when the column was challenged with an equivalent cumulative volume of poorly clarified homogenate, dynamic binding capacity decreased significantly and changes in breakthrough curves suggested increased intraparticle and external mass transfer limitations. These changes were ascribed to deposition of solid particulates in void spaces in the bed and colloidal contaminants in the bead pores.