Investigation on effects of operating conditions in combined activation of char to develop the pore structure

In this study, activation of pistachio shell char was investigated by chemical, physical and combined activation experimentally using a TGA instrument and lab scale reactor. The effects of operating conditions such as activation time, temperature and impregnation ratio in the activation methods were studied via the weight loss and iodine number of the samples. The results showed that combined activation is the premium activation method. In addition, in this method. a temperature of 800 °C, a dwell time of 45 min and an impregnation ratio of 50 % are the optimum conditions which give a product with an iodine number of 2433 mg/g and a weight loss 52 %. A high iodine number of this activated carbon was developed at a moderate temperature and dwell time, and the weight loss confirms the advantages of the combined activation method. The products were characterized by SEM and FTIR analyses.     

Nanocellulose for biosorption of chlorpyrifos from water: chemometric optimization,kinetics and equilibrium

The study explores the biosorption potential of nanocellulose (NC) to remove an insecticide, chlorpyrifos (CP), from aqueous solutions using the batch method. Biosorption kinetics were very fast and reached equilibrium in 60 min, and the experimental kinetic data had fit well with the pseudo-second-order model. Film diffusion was the rate-limiting step for the biosorption of CP onto crystalline nanocellulose (CNC). The equilibrium sorption was well described by the Sips and Langmuir isotherm models. The values of maximum sorption capacities (7.237–5.017 mg/g for the Sips and 12.325–7.247 mg/g for the Langmuir model) decreased with an increase in temperature from 288 to 308 K, signifying biosorption of CP is an exothermic process. Based on the central composite design (CCD), two-factor interaction (2FI) and quadratic models, the correlation between the effects of variable parameters on the CP biosorption onto NC was evaluated. The chemometric analyses suggested that 1.5 g/l NC required 20 min to biosorb 5 mg/l CP to yield an efficiency of 99.3%. Overall, the results demonstrated that NCs can be a promising biosorbent for the removal of pesticides from aqueous streams.     

The use of microwave radiation for obtaining carbonaceous adsorbents from biomass and their use in elimination of inorganic pollutants

A new technology of obtaining activated carbons by physical and direct activation of biomass with the use of microwave radiation is described. The effect of activation temperature (700 and 800 °C) and two periods of time (15 and 30 min) on the textural parameters, acid–base character of the surface and sorption properties of activated carbons was tested. The resulting carbons were characterized by low-temperature nitrogen sorption and determination of pH as well as the number of surface oxygen groups. The sorption properties of the activated carbons obtained were characterized by determination of nitrogen dioxide and hydrogen sulphide adsorption in dry and wet conditions as well as by iodine removal from aqueous solution. The final products were adsorbents of surface area ranging from 291 to 368 m²/g and pore volume from 0.20 to 0.26 cm³/g, showing basic character of the surface. The results obtained in our study have proved that suitable choice of the pyrolysis and activation procedure for hay with the use of microwave radiation permit producing adsorbents with good capacity toward toxic gases of acidic character as well as inorganic pollutants of molecules of size similar to that of iodine molecules.     

Estimation of total as well as bioaccessible levels and average daily dietary intake of iodine from Japanese edible seaweeds by epithermal neutron activation analysis

An epi-thermal instrumental neutron activation analysis (EINAA) method in conjunction with Compton suppression spectrometry (EINAA-CSS) was used for the determination of total iodine in eight different species of edible seaweeds from Japan. This method gave an absolute detection limit of about 2 μg. The accuracy of the method was evaluated using various reference materials and found to be generally in agreement within ±6% of the certified values. The longitudinal distributions of iodine at different growing stages in Japanese sea mustard and tangle seaweeds were investigated. For a 150-cm-high tangle, the highest concentration (5,360 mg/kg) of iodine was found at the root, then decreased slowly to 780 mg/kg in the middle portion (60–75 cm), and increased to 2,300 mg/kg at the apex. On the other hand, for a 190-cm-high sea mustard the highest levels of iodine were found both at the roots (164 mg/kg) and apex (152 mg/kg) with lower values (98 mg/kg) in the middle section. In order to estimate the bioaccessible fraction of iodine, seaweeds were digested by an in vitro enzymolysis method, dietary fibre separated from residue, and both fractions analyzed by EINAA-CSS. The average daily dietary intakes of total (0.14 mg) as well as bioaccessible fraction (0.12 mg) of iodine from the consumption of sea mustards were estimated.     

Preparation of activated carbon from organic fraction of municipal solid wastes by ZnCl2 activation method and use it for elimination of chromium(VI) from aqueous solutions

In this study, the use of the organic fraction of municipal solid waste as an abundant and low-cost raw material for producing activated carbon was investigated. For this purpose, ZnCl₂ was used as a chemical activation agent and the carbonization process took place at 800 °C in N₂ atmosphere. Seven sorbents were prepared by chemical activation (pyrolysis under N₂ atmosphere at temperature of 800 °C after impregnation with ZnCl₂) with different ratios of ZnCl₂. The optimum ratio of organic fraction of municipal solid waste to ZnCl₂ was inspected via methylene blue number and iodine number (ASTM Designation: D4607–94). The results showed that the adsorbent with 60 % ZnCl₂/raw material was the most appropriate one with a satisfactory adsorption capacity, 112.4 mg g^?1 for methylene blue and 134.0 mg g^?1 for iodine. In addition, the structural analysis of this sorbent was performed using FT-IR, BET surface area, SEM–EDX and thermal analysis. Application of this sorbent to remove Cr(VI) from wastewater was studied to find an adsorption capacity of 66.7 mg g^?1. The experimental adsorption equilibrium data were fitted to Langmuir adsorption model with an acceptable adsorption capacity of 66.7 mg g^?1.     

Modeling and optimization of densification of nanocrystalline Al<Subscript>2</Subscript>O<Subscript>3</Subscript> powder prepared by a sol–gel method using response surface methodology

Response surface methodology (RSM) based on central composite design (CCD) was successfully applied to the optimization and modeling of densification of nanocrystalline Al₂O₃ powder prepared by sol–gel method. The effects of three operating variables, sintering temperature, calcination temperature and milling time on the densification of nanocrystalline Al₂O₃ were systematically evaluated. A quadratic model for densification was proposed. Analysis of variance (ANOVA) indicated that the proposed quadratic model could be used to navigate the design space. The simulated values obtained from the statistical model were in conformity with the experimental results within an average error of ±1.5%. The optimum operating conditions for densification were found to be 1,579 °C of sintering temperature, 909 °C of calcination temperature and 117 min of milling time. The obtained density under the optimum conditions determined by RSM was 98.5%. The results confirmed that RSM based on central composite design was an accurate and reliable method to optimize the densification conditions of nanocrystalline Al₂O₃ powder.     

Transport parameters of I− and IO3 − determined in crushed granitic rock columns and groundwater system under dynamic flow conditions

Transport of two principal inorganic iodine anions separately in two crushed crystalline granitic rocks, gabbro and tonalite, have been investigated. The rocks were crushed and sieved, and finally a fraction between 0.25 and 0.80 mm was filled in 5 cm³ PET columns (medical syringes) of 5.40 cm length and 1.24 cm in inner diameter. NaI and NaIO₃ were dissolved in synthetic groundwater (SGW) in a concentration as low as 10^?4 mol/dm³. The SGW was pumped into the columns at a seepage velocity of 0.031 ± 0.001 cm/min using a multi-head peristaltic pump. Iodine concentration in the outflow SGW from the columns was determined by UV–Vis spectrophotometry at 510 nm absorption maximum in CHCl₃ using redox reactions. By the use of a dependence of concentration on the number of pore volumes from the outflow and the linear isotherm model, based on erfc-function, breakthrough curves were constructed and the principal transport parameters were calculated. The values of sorption and desorption retardation coefficients of about 1 for both iodide and iodate have been obtained, which show evidence of practically non-sorption behavior of these chemical forms of iodine in the tested granitic rocks. The values of hydrodynamic dispersion coefficients and corresponding Peclet numbers were about 0.0077 ± 0.0006 and 21.6 ± 1.8 cm²/min, respectively, for both anions and rocks under given conditions.     

A Statistical Approach for Optimization of Polyhydroxybutyrate Production by Bacillus sphaericus NCIM 5149 under Submerged Fermentation Using Central Composite Design

The aim of this work was to statistically optimize the cultural and nutritional parameters for the production of polyhydroxybutyrate (PHB) under submerged fermentation using jackfruit seed hydrolysate as the sole carbon source. On the basis of results obtained from “one variable at a time” experiment, inoculum age, jackfruit seed hydrolysate concentration, and pH were selected for response surface methodology studies. A central composite design (CCD) was employed to get the optimum level of these three factors to maximize the PHB production. The CCD results predicted that jackfruit seed hydrolysates containing 2.5% reducing sugar, inoculum age of 18 h, and initial medium pH 6 could enhance the production of PHB to reach 49% of the biomass (biomass 4.5 g/l and PHB concentration 2.2 g/l). Analysis of variance exhibited a high coefficient of determination (R ²) value of 0.910 and 0.928 for biomass and PHB concentration, respectively, and ensured that the quadratic model with the experimental data was a satisfactory one. This is the first report on PHB production by Bacillus sphaericus using statistical experimental design and RSM in submerged fermentation with jackfruit seed hydrolysate as the sole source of carbon.     

Optimization of oxalic acid pretreatment of moso bamboo for textile fiber using response surface methodology

In this article, samples of moso bamboo were pretreated with oxalic acid under various process conditions. Response surface methodology was applied to optimize the pretreatment conditions. A three-variable quadratic polynomial regression model was obtained to predict the cellulose content, lignin removal and hemicellulose solubilization. The reliability of the model was also evaluated by the key elements obtained from analysis of variance of the coefficients. The surface response plot and contour plot of the effects were studied to further examine the interactions of the three factors and determine the optimum levels of each factor. Finally, the optimized conditions for oxalic acid pretreatment were temperature 178.4 °C, 3.68 % oxalic acid and 28.4 min, respectively. The maximum predicted value of cellulose content in the residue fraction was 64.98 %, along with 79.43 % lignin removal and 96.71 % hemicellulose solubilization after the oxalic acid pretreatment.     

Optimization of temperature-controlled ionic liquid homogenous liquid phase microextraction followed by high performance liquid chromatography for analysis of diclofenac and mefenamic acid in urine sample

In this work, a temperature-controlled ionic liquid homogeneous liquid phase microextraction (TCIL-HLPME) technique followed by HPLC–UV was applied for preconcentration and determination of diclofenac (DIC) and mefenamic acid (MEF) in urine samples. 1-butyl-3-methylimidazolium hexafluorophosphate ([C₄mim][PF₆]) was used as the optimum extraction solvent. Experimental design and response surface methodology was used for the optimization process. Firstly, a screening step, using Plackett-Burman design, was carried out to find the significant factors on the extraction efficiency and subsequently, a central composite design (CCD) was employed to find the optimum values of these parameters. The optimal conditions were obtained as extraction solvent volume of 105 µL; sample pH of 2.0, extraction time of 6 min, centrifugation time of 5 min; heating time of 2 min; heating temperature of 50 °C and 20 % of NaCl. Under optimized conditions, the preconcentration factors of 82 and 60 were obtained for DIC and MEF, respectively. The detections limits of 20 and 30 ng mL^?1 were achieved for DIC and MEF by the proposed method, respectively. The calibration curves were linear in the range of 40–1000 and 60–1000 ng mL^?1 for DIC and MEF, respectively. The intra- and inter-assay precisions (RSD %, n = 3) were in the range of 3.5–4.4 % and 7.3–8.0 % at the concentration level of 100 ng mL^?1, respectively. The validated method was successfully applied for the analysis of target analytes in some urine samples.     

Study of the polymer concentration and polymer/crosslinker ratio effect on gelation time of a novel grafted polymer gel for water shutoff using a central composite design method

In this research article, a hydrogel was prepared by crosslinking of carboxymethyl cellulose‐g‐polyacrylamide copolymer aqueous solution with chromium(III) acetate for the purpose of a water shutoff job in the oil reservoir. The experiments were conducted to investigate the main effects of copolymer concentration and crosslinker/copolymer ratio on gelation time of the hydrogel system. Then the effects of these two factors and their interactions on the gelation time were determined by using a central composite design (CCD) of the response surface method. CCD was used to generate the quadratic mathematical model for the gelation time response as a function of copolymer concentration, crosslinker/copolymer ratio, and their interaction. Furthermore, the analysis of variance (ANOVA) was used to evaluate the quality of the quadratic model. The ANOVA result of the developed model showed that the model was highly significant. The result also showed that the crosslinker/polymer ratio had more effects on the gelation time than did the polymer concentration and their interaction. A response surface method provides an optimum gel formulation. Core flooding experiments reveal that a significant permeability reduction on the sand pack cores can be achieved at reservoir conditions, when it is treated with an optimum gel formulation. Hence, this gel system may be suitable in the water shutoff job required for enhanced oil recovery from the oil fields. Copyright © 2015 John Wiley & Sons, Ltd.     

Preparation and characterization of activated carbon from pine cone by microwave-induced ZnCl2 activation and its effects on the adsorption of methylene blue

In this work, activated carbon prepared from pine cone (PCAC) with ZnCl₂ as an activation agent under microwave radiation was investigated. The activation step was performed at the microwave input power of 400 W and radiation time of 5 min. The properties of activated carbon were characterized by N₂ adsorption Brunauer–Emmett–Teller (BET), scanning electron microscopy and Fourier transform infrared spectroscopy. Results showed that the BET surface area, Langmuir surface area, and total pore volume of PCAC were 939, 1,486 m²/g and 0.172 cm³/g, respectively. Adsorption capacity was demonstrated by the iodine numbers. The adsorptive property of PCAC was tested using methylene blue dye. Equilibrium data was best fitted by the Langmuir isotherm model, showing a monolayer adsorption capacity of 60.97 mg/g. The pseudo-first- and pseudo-second-order kinetic models were examined to evaluate the kinetic data, and the rate constants were calculated. Adsorption of the dyes followed pseudo-first order kinetics. Thermodynamic parameters such as free energy, enthalpy and entropy of dye adsorption were obtained.     

Pb(II) removal from aqueous solution by polyacrylic acid stabilized zero-valent iron nanoparticles: process optimization using response surface methodology

Optimization and modeling of Pb(II) removal using polyacrylic acid stabilized zero-valent iron nanoparticles (PAA-ZVINs) from aqueous solution was performed. Central composite design (CCD) as the most applicable method in response surface methodology (RSM) was employed for optimization of Pb(II) removal. ZVINs were synthesized using the borohydride reduction method in the presence of PAA as a stabilizer and characterized via scanning electron microscopy (SEM) and X-ray diffraction (XRD). The independent variables for CCD optimization of Pb(II) removal were initial solution pH, ZVINs concentration (g/L), and initial concentration of Pb(II) (mg/L). Results showed a significant correlation between predicted values obtained from second-order polynomial model and experimental values (R ² = 93.19 and adj-R ² = 87.07). Maximum removal of Pb(II) (90.09 %) was observed at the optimal conditions of ZVINs concentration of 3 g/L, initial Pb(II) concentration of 10 mg/L, and initial solution pH of 5.     

Evaluation and Optimization of Water-in-Oil Microemulsion Using Ternary Phase Diagram and Central Composite Design

In the present study, water-in-oil (w/o) microemulsions were prepared, evaluated, and optimized using pseudoternary phase diagram and central composite design (CCD). Ternary phase diagrams were designed to determine the microemulsion region whereas face-centered CCD helped in the determination of the effect of variables like oil type and surfactant ratio on globule size and viscosity of w/o microemulsion. The design exhibited that the factors have statistically significant effects (p < 0.0001) on the selected responses. The actual responses showed excellent agreement with the predicted values as suggested by the CCD with lower residual standard error. Similarly, the optimized values were found within the range as predicted by the model. Furthermore, other characteristics of microemulsions like pH, conductivity, refractive index, and transmittance were also analyzed. Overall, the primary objective of the research was to fabricate water-in-oil microemulsions which could facilitate effective delivery of hydrophilic molecules and drugs.     

Sodium alginate/HPMC/liquid paraffin emulsified (o/w) gel beads,by factorial design approach; and in vitro analysis

The present study involved development of a novel sodium alginate (SA)/HPMC/light liquid paraffin emulsified (o/w) gel beads containing Diclofenac sodium (DS) as an active pharmaceutical ingredient and its site specific delivery by using hard gelatin capsule fabricated by enteric coated Eudragit L-100 polymer. Emulsified gel beads were formulated by 3-level factorial design, ionic gelatin method. The obtained beads were characterized by Fourier transform infrared, X-ray diffraction and Field emission scanning electron microscope analysis. The variables such as SA (X₁), HPMC (X₂), were optimized for drug loading and in vitro drug release with the help of response surface methodology (RSM). The RSM analysis predicted that SA was significant for both drug loading (p = 0.0005) and drug release (p = 0.0041). HPMC was only significant for drug release (p = 0.0154). The cross-product contribution (2FI) and quadratic model were found to be adequate and statistically accurate with correlation value (R²) of 0.9054 and 0.9450 to predict the drug loading and drug release respectively. An increase in concentration of HPMC and SA decreases the drug loading as well as the drug release. The obtained optimum values of drug loading and DS released were 7.43 % and 85.54 % respectively, which were well in agreement with the predicted value by RSM.     

Chemically activated Ipomoea carnea as an adsorbent for the copper sorption from synthetic solutions

An indigenously prepared zinc chloride activated Ipomoea carnea (morning glory), a low-cost and abundant adsorbent, was used for removal of Cu(II) ions from aqueous solutions in a batch adsorption system. The chemical activating agent ZnCl₂ was dissolved in deionised water and then added to the adsorbent in two different ratios 1:1 and 1:0.5 adsorbent to activating agent ratio by weight. Studies were conducted as a function of contact time, initial metal concentration, dose of adsorbent, and pH. Activated Ipomoea carnea (AIC) were characterised using scanning electron microscopy (SEM), iodine number and methylene blue number. High iodine numbers indicates development of micro pores with zinc chloride activation. Maximum adsorption was noted within pH range 6.0(±0.05). Adsorption process is fast initially and reaches equilibrium after about 4 hours. The kinetic data were analysed using pseudo-first-order and pseudo-second-order models. The pseudo-second-order kinetic model was found to agree well with the experimental data. Adsorption equilibrium data were analyzed using Langmuir and Freundlich isotherm models. The Langmuir model represented the sorption process better than the Freundlich model. Based on the Langmuir isotherm, the monolayer adsorption capacity of Cu(II) ions was 7.855 mg?g^?1 for AIC (1:1) and 6.934 mg?g^?1 for AIC (1:0.5).     

Optimizing mass spectrometric detection for ion chromatographic analysis. I. Common anions and selected organic acids

We describe a systematic method of optimizing mass spectrometric (MS) detection for ion chromatographic (IC) analysis of common anions and three selected organic acids using response surface methodology (RSM). RSM was utilized in this study because it minimized the number of experiments required to achieve the optimum MS response and included the interactions between individual parameters for multivariable optimization. Five MS parameters, including probe temperature, nebulizer gas, assistant makeup flow, needle voltage and cone voltage, were screened and systematically optimized by two steps. Central composite design (CCD) was used to design the experiment points and a quadratic model was applied to fit the experimental data. Analysis of variance (ANOVA) was carried out to evaluate the validity of the statistical model and to determine the most significant parameters for MS response. The optimum MS conditions for each analyte were summarized and the method optimum condition was achieved by applying desirability function. Our observation showed good agreements between statistically predicted optimum response and the responses collected at the predicted optimum condition. Operable range of each parameter (with normalized MS response greater than 0.8 for each analyte) was provided for general anionic IC/MS applications. Copyright © 2009 John Wiley & Sons, Ltd.     

Synthesis of molecular imprinted polymer nanoparticles followed by application of response surface methodology for optimization of metribuzin extraction from urine samples

A molecular imprinted polymer was prepared with precipitation polymerization technique and applied as a sorbent for selective extraction and enrichment of metribuzin herbicide prior to high performance liquid chromatography. Optimization of critical variables affecting the efficiency of molecularly imprinted solid-phase extraction (MISPE), such as sorbent mass, sample pH and flow rate of sample, volume, concentration, and flow rate of elution solvent was done by employing central composite design (CCD) of the response surface methodology. Two separate models were developed for the adsorption and recycling steps. The analysis of variance (ANOVA) demonstrated that, experimental data were excellently fitted to the proposed response models. The optimum operating conditions were: a sorbent mass of 25 mg, sample pH 6.19, sample flow rate of 2.15 mL/min, and a 5 mL portion of methanol/acetic acid with 92.7:7.3 (v/v) ratio and flow rate of 2.1 mL/min for the extraction process. Under the optimized conditions, the linear range was obtained from 20 to 120 µg/L (R²?=?0.999) and the lowest detectable concentration (LOD) and the lowest quantitative concentration (LOQ) were calculated as 5.75 and 19.86 µg/L, respectively. Finally, the designed MISPE method was successfully applied to determine trace amount of metribuzin in real samples. The diluted urine samples were spiked with metribuzin at 4 levels and extracted with recoveries ranging from 93.82 to 97.84% and the relative standard deviation (RSD) less than 4.8%.     

Crossed D-Optimal Experimental Design Methodology for the Chromatographic Separation of Antihypertensive Drugs

An efficient, isocratic, reversed-phase high performance liquid chromatography method was developed, optimized, and validated to separate nine antihypertensive drugs by experimental design methodology and the Crossed D-Optimal process. In order to find the most suitable separation conditions, twenty-three experiments were carried out, based on the simultaneous effects of three solvent (methanol, acetonitrile, and water) compositions in combination with different pH values of the mobile phase. The components were cross-combined with a pH factor (quadratic x quadratic process), whereas optimal adjusted models were used for the eight individually chosen responses. The optimal mobile phase consisted of methanol, acetonitrile, and 0.05 M aqueous ammonium acetate at pH 3.1 (18:26: 56 v/v/v, pH adjustment with formic acid). Analysis was carried out on a C₁₈ column (150 × 4.6 mm, 5 µm) at 40 °C using photodiode array detection at 242 nm. The system was found to produce sharp and well resolved peaks for all analytes while the retention times ranged from 2.3 to 31 min. The method was linear (r² > 0.999) and reliable since the accuracy (recovery = 100 ± 2.9) and the precision (relative standard deviation < 2%) met International Conference on Harmonization guidelines. The technique was shown to be a useful tool for separating complex mixtures using experimental design methodology.     

Studies of total, organic and inorganic iodine in Canadian bovine milk samples with varying milk fat content using ion-exchange chromatography and neutron activation analysis

Chemical separation methods in conjunction with instrumental neutron activation analysis (INAA) were developed for measuring iodine levels in commercially available bovine milk with varying milk fat (MF) content. Samples of homogenized (3.25 % MF), partly skimmed (2 % MF), partly skimmed (1 % MF), partly skimmed calcium enriched (1 % MF + Ca), and skim (<0.05 %) milk were purchased from local supermarkets. Ion exchange chromatography, solvent extraction, and ammonium sulfate precipitation methods were applied to the separation of the inorganic, lipidic and proteic fractions of iodine in milk. The levels of iodine were measured by INAA in total reactor and epi-cadmium (EINAA) neutron flux in conjunction with conventional gamma-ray and Compton suppression spectrometry (CSS). A pseudo-cyclic INAA method coupled with CSS (PC-INAA-CSS) was also explored as an instrumental option to further lower the detection limit of iodine. The detection limits of 0.06, 0.06 and 0.02 μg mL^?1 for iodine were obtained using INAA-CSS, EINAA-CSS, and PC-INAA-CSS methods, respectively. Although the PC-INAA-CSS method provided the lowest detection limit, the INAA-CSS method was sufficient for the determination of total iodine in almost all samples analyzed in this work. The total iodine concentrations (μg mL^?1) were: 0.40 ± 0.01 (in 3.25 % MF), 0.40 ± 0.01 (2 % MF), 0.42 ± 0.01 (1 % MF), 0.42 ± 0.01 (<0.05 %), and 0.96 ± 0.01 (1 % MF + Ca) milk samples. Iodine bound to various fractions of the milk samples analyzed, in percent of total iodine content, ranged: (0.05–1.8), (1.9–4.8), (90–95) for the lipidic, proteic and anionic inorganic fractions respectively. Iodine recovery in all cases was higher than 96 %.