Ingenious bioorganic adsorbents for the removal of distillery based pigment-melanoidin: preparation and adsorption mechanism

Melanoidins are composite biopolymers which consist of amino carbonyl compounds which are the major coloring and polluting elements of distillery effluent. In this study, a synthetic melanoidin was used as a model for natural melanoidins, the chief colorant of the effluent. Deportations of melanoidins were investigated using both natural adsorbents and constructed microbial consortia based adsorbents and denoting it using the adsorption isotherms and SEM analysis. A review enabled us to assess about the valuation of the prepared low cost adsorbent and microbial coated adsorbents and for the treatment of the synthetic melanoidin solution. Based on the performances, both Microbial Coated Commercially Activated Carbon (MCCAC) and Commercially Activated Carbon (CAC) were better when compared with the other adsorbents at lower melanoidin concentrations; however, at higher melanoidin concentration, MCCAC performed better. The utilization of CAC for the removal of melanoidins may be cost competitive; hence Microbial Coated Procured Prosopsis Activated Carbon (MCPPAC) can be used as a substitute for the removal systems. Therefore, the microbial coated adsorbents can be a remedy for the removal of color through expatriation of melanoidin from the distillery effluents.     

Preparation and Performance of Polysulfone‐Cellulose Acetate Blend Ultrafiltration Membrane

In the development of high performance polymeric membranes, it is essential to design the molecular and morphological characteristics for specific applications. Polysulfone and cellulose acetate of blend membranes with various concentration of polymer pore former, PEG600 were prepared by phase inversion technique and used for ultrafiltration. Polymer blend composition, additive concentration, and casting conditions were optimized. The blend membranes were characterized in terms of compaction, pure water flux, water content, hydraulic resistance and separation of dextran studies. Surface morphology of the embranes was analyzed using scanning electron microscopy at different magnifications. Further, the characterized membranes were attempted for treatment of distillery effluents after secondary treatment and the results are discussed in detail.     

Application of Calcium Alginate–Starch Entrapped Bitter Gourd (<Emphasis Type="Italic">Momordica charantia</Emphasis>) Peroxidase for the Removal of Colored Compounds from a Textile Effluent in Batch as well as in Continuous Reactor

Calcium alginate–starch entrapped bitter gourd peroxidase has been employed for the treatment of a textile industrial effluent in batch as well as in continuous reactor. The textile effluent was recalcitrant to decolorization by bitter gourd peroxidase; thus, its decolorization was examined in the presence of a redox mediator, 1.0 mM 1-hydroxybenzotriazole. Immobilized enzyme exhibited same pH and temperature optima for effluent decolorization as attained by soluble enzyme. Immobilized enzyme could effectively remove more than 70% of effluent color in a stirred batch process after 3 h of incubation. Entrapped bitter gourd peroxidase retained 59% effluent decolorization reusability even after its tenth repeated use. The two-reactor system containing calcium alginate–starch entrapped enzyme retained more than 50% textile effluent decolorization efficiency even after 2 months of its operation. The absorption spectra of the treated effluent exhibited a marked difference in the absorption at various wavelengths as compared to untreated effluent. The use of a two-reactor system containing immobilized enzyme and an adsorbent will be significantly successful for treating industrial effluents at large scale, and it will help in getting water free from aromatic pollutants.     

利用粉状聚合物吸附剂脱除盐酸溶液中氯仿的研究

为了选择合适的吸附剂来脱除盐酸溶液中的氯仿,本文测定了几种聚合物吸附剂在298.15 K温度下对水溶液和20%盐酸溶液中氯仿的吸附等温线,考察了其吸附能力,并将其吸附能力与活性炭和固体石蜡进行了比较。所研究的吸附剂包括粉末状氯化橡胶,聚丙烯,氯化聚丙烯,聚氯乙烯,活性炭和固体石蜡。结果表明,这些吸附剂的吸附行为服从Langmuir 方程,其吸附能力的次序为活性炭>聚氯乙烯>氯化橡胶>聚丙烯 >氯化聚丙烯 >固体石蜡。该次序基本上与从聚氯乙烯到固体石蜡吸附剂中氯含量逐渐降低的次序相一致。聚氯乙烯与氯化橡胶的吸附能力与活性炭相当,其饱和吸附量大约为1.4g-CHCl3/g-吸附剂。所有吸附剂对氯仿的吸附能力均随着溶液中盐酸浓度的增加而降低。结果表明,工业级的粉状聚氯乙烯或氯化橡胶可以作为一种有效的吸附剂脱除水溶液中的氯仿,且具有成本低,吸附性好和易于通过热再生循环利用的特点。     

Pyrolysis/gas chromatography/mass spectrometry monitoring of fungal-biotreated distillery wastewater using Trametes sp. I-62 (CECT 20197)

Distillery wastewaters generated by ethanol production from fermentation of sugar-cane molasses, named vinasses, lead to important ecological impact due to their high content of soluble organic matter and their intense dark-brown color. Taking advantage of the well-known ability of white-rot fungi to degrade an extensive variety of organic pollutants, the capacity of Trametes sp. I-62 (CECT 20197) to detoxify this type of effluents was evaluated. In this work, pyrolysis/gas chromatography/mass spectrometry was applied to the chemical characterization of several fractions of Cuban distillery wastewater as well as to monitoring the changes which occurred after fungal treatment with this white-rot basidiomycete. Maximum effluent decolorization values and chemical oxygen demand reduction attained after seven days of fungal treatment were 73.3 and 61.7%, respectively, when 20% (v/v) of distillery vinasses was added to the culture medium. Under these conditions a 35-fold increase in laccase production by Trametes sp. I-62 was measured, but no manganese peroxidase activity could be detected. The pyrolysis/gas chromatography/mass spectrometry results showed a decrease in a number of pyrolysis products after seven days of fungal treatment, mainly furan derivatives. The decrease in the relative areas of these compounds could be related to the vinasse color-removal associated with melanoidin degradation. All these results indicated the potential use ofTrametes sp. I-62 in the detoxification of recalcitrant distillery vinasses.     

The Effect of Hydrotalcite and Zinc Oxide on Smoke Suppression of Commercial Rigid PVC

To reduce the smoke release of poly(vinyl chloride) (PVC) during burning, layered double hydroxides (LDHs) and zinc oxide (ZnO) powders were used to modify the polymer. The results indicated that the addition of LDHs‐ZnO had a significant effect on smoke suppression. The limiting oxygen index (LOI) reached a maximum value and the smoke density rank (SDR) exhibited a minimum value when the weight percentages of LDHs and ZnO in PVC were 3% and 2%, respectively. Thermal stabilities of the modified PVC and degradation products were investigated by means of thermogravimetry and pyrolysis‐gas chromatography‐mass spectra (Py‐GC‐MS). The LDHs‐ZnO obviously accelerated the decomposition of PVC to release hydrogen chloride, and the decomposed PVC consequently produced the trans‐conjugated polyene sequences, which easily formed crosslinked structures. However, a cyclization reaction in PVC chain without the additives produced aromatic compounds such as benzene, toluene, and naphthalene at 350°C. Even though, an amount of aromatic compounds was released from the PVC modified with LDHs‐ZnO at the temperature of 600°C, the content of the decomposed products is relatively lower compared to unmodified PVC.     

Extraction and Separation Properties of Hydrophilic Compounds Using Novel Water-Holding Adsorbents Bonded with a Zwitter-Ionic Polymer

A novel water-holding adsorbent was synthesized by introducing a zwitter-ionic polymer to a hydrophilic methacrylate base resin. The retention abilities of the hydrophilic compounds on the adsorbents with and without cross-link in the zwitter-ionic functional groups were examined. The amount of held water on the non-cross-linked adsorbent was higher than that of the cross-linked one. The extraction efficiencies of the hydrophilic solutes on the adsorbents were evaluated by the solid phase extraction method. These adsorbents showed high affinity for nucleosides and glycosides, and good recoveries for such hydrophilic compounds in the solid-phase extraction were obtained. Furthermore, the retention properties of the hydrophilic solutes on the adsorbents were also evaluated by LC. The hydrophilic solutes were retained on these adsorbents by a partition mode based on a hydrophilic interaction. The retention factors of the hydrophilic solutes showed good correlation to their log P _o/w (logarithm of octanol?Cwater partition coefficient) and good separation based on hydrophilic interaction was obtained for nucleobases and nucleosides.     

Electrochemical studies on PVC/PVdF blend-based polymer electrolytes

In recent years, special attention has been focused on the development of gel polymer electrolytes consisting of host polymers such as poly (acrylonitrile), PVC, poly (methyl methacrylate), poly (vinylidene fluoride) (PVdF), etc., as they may be found to have unique applications in consumer electronic and electric vehicle products. In the present study, blend-based polymer electrolytes composed of PVC, PVdF, NaClO₄, and propylene carbonate is prepared using the solvent casting technique. The thermal behaviors of PVC/PVdF polyblend films have been examined using differential scanning calorimetry and scanning electron microscopy. Miscibility studies were performed using X-ray diffraction and Fourier transform infrared. The role of interaction between polymer hosts on conductivity is discussed using the results of AC impedance studies.     

Aerobic Biodegradation Pathway for Remazol Orange by Pseudomonas aeruginosa

Removal of azo dyes from effluent generated by textile industries is rather difficult. Azo dyes represent a major class of synthetic colorants that are mutagenic and carcinogenic. Pseudomonas aeruginosa grew well in the presence of Remazol Orange (RO) and was able to decolorize and degrade it. In the present study, the decolorization and degradation efficiency using single culture P. aeruginosa with RO and textile wastewaters is studied. The elucidation of decolorization pathway for P. aeruginosa is of special interest. The degradation pathway and the metabolic products formed during the degradation were also predicted with the help of high performance liquid chromatography, Fourier transform infrared spectroscopy, and nuclear magnetic resonance spectroscopy analysis. The data show the cleavage of the azo dye RO to form both methyl metanilic acid and 4-aminobenzoic acid after decolorization and finally to oxidation forms benzoic acid, alkenes, aldehydes, and alkynes. The organism was able to decolorize the dye RO and wastewater effectively to the maximum of 82.4% and 62%, respectively.     

Adsorption of Reactive Blue 4 dye from water solutions by carbon nanotubes: experiment and theory

Multi-walled and single-walled carbon nanotubes were used as nanoadsorbents for the successful removal of Reactive Blue 4 textile dye from aqueous solutions. The adsorbents were characterised by infrared and Raman spectroscopy, N(2) adsorption/desorption isotherms and scanning and transmission electron microscopy. The effects of pH, shaking time and temperature on adsorption capacity were studied. In the acidic pH region (pH 2.0), the adsorption of the dye was favourable using both adsorbents. The contact time to obtain equilibrium isotherms at 298-323 K was fixed at 4 hours for both adsorbents. The general order kinetic model provided the best fit to the experimental data compared with pseudo-first order and pseudo-second order kinetic adsorption models. For Reactive Blue 4 dye, the equilibrium data (298 to 323 K) were best fitted to the Liu isotherm model. The maximum sorption capacity for adsorption of the dye occurred at 323 K, attaining values of 502.5 and 567.7 mg g(-1) for MWCNT and SWCNT, respectively. Simulated dyehouse effluents were used to check the applicability of the proposed nanoadsorbents for effluent treatment (removal of 99.89% and 99.98%, for MWCNT and SWCNT, respectively). The interaction of Reactive Blue 4 textile dye with single-walled carbon nanotubes (SWCNTs) was investigated using first principles calculations based on density functional theory. Results from ab initio calculations indicated that Reactive Blue 4 textile dye could be adsorbed on SWCNT through an electrostatic interaction; these results are in agreement with the experimental predictions.     

Quantification of deformed peaks in capillary gas chromatography (CGC): application to simultaneous analysis of free fatty acids and less polar compounds in aqueous distillery effluent

The purpose of this study was to find a simple and rapid method allowing the simultaneous quantification of some alcoholic fermentation inhibitors present in aqueous distillery effluent in order to evaluate its recycling properties. A capillary gas chromatography (CGC) method was tested for the quantification of both short chain fatty acids (acetic to hexanoic) and neutral compounds (butane 2,3-diol, 2-furaldehyde, phenyl-2-ethane1-ol). A polyvalent column coated with ^®trifluoro-propyl-polysiloxane, allowing water injection, was tested and experiments were performed directly on untreated samples. During the development of the method, a deformation of acid peaks was observed; that could be explained by a secondary equilibrium, added to the chromatographic equilibrium. Although the acid peaks were deformed, calibration curves were produced and rigorously validated, proving that quantification is possible even when the best chromatographic conditions have not been achieved. Eventually, the method enabled the concentration of eight major fermentation inhibitors in distillery effluent to be measured.     

Quantitative Sampling of Trace Organic Vapours by Gas Syringe and Porous Polymer Adsorbent Methods. A Comparative Study Using Naphthalene as a Reference Substance

Abstract

Two methods of sampling high molecular weight vapours, gas syringe sampling and porous polymer adsorbent sampling were studied. The methods were compared using a saturated naphthalene reference vapour of known concentration. The results showed that the porous polymer adsorbent method was more accurate than the gas syringe method. The accuracies of both methods were dependent on details in their respective techniques. For porous polymer adsorbents it was shown that the technique should be such that passive sampling did not occur. Sample volume, sampling rate, the number of fills before injecting and cleaning the syringe before sampling all influenced the accuracy of the gas syringe sampling method.     

Studies on the photooxidation mechanism of polymers. IV. Effect of ultraviolet light (2537 Å) on solid PVC particles suspended in different liquids

The photolysis of virgin PVC powder suspended in water, methanol, n-hexane, aqueous NH₄OH (30 wt-%), and 0.1 wt-% iodine in methanol and also as dry powder was studied. The mechanism of photolysis of PVC powder has been investigated by using ESR spectroscopy, conductivity titration, gel-permeation chromatography (GPC), and absorption spectroscopy. Photolysis of PVC has been found to occur by a free-radical mechanism. ESR spectroscopy permits a partial identification of several different types of free radicals in PVC such as alkyl, polyenyl, and peroxy radicals. An interpretation is proposed of the mechanism of formation of conjugated polyene structures, and also a new explanation of the crosslinking mechanism, in which transfer of unpaired electrons to double bonds occurs, is suggested. It has also been found that conjugated double bonds can photosensitize free-radical formation as a result of increased ultraviolet absorption due to polyene structures.     

Heterogeneous grafting on polymers containing chlorine: Grafting of amide groups in water suspension and the reactivity of the new polymer towards epoxy resins

Heterogeneous grafting on polyvinylchloride suspended in water was carried out using N-butyl-3-mercaptopropionamide as nucleophile. Over 50% graft was obtained by using a small amount of solvent as a swelling agent and tricapryl methyl ammonium chloride as a phase transfer catalyst. Elemental analysis of the grafted polymer shows that the chlorine displaced from the polymers is replaced by the thio-amide group. The above conclusion is supported by NMR and IR analysis. The kinetics of the chlorine displacement from PVC by the thio amide group obeys the Shell progressive mechanism. The rate at which an individual spherical particle reacts depends on the diffusion through the reacted layer. The grafted polymer is soluble in tetrahydrofuran or nitrobenzene. The films obtained from the grafted material are brittle due to excessive internal hydrogen bonding. The electrostatic charge which is a characteristic surface phenomena in PVC is diminished in the grafted polymer which may be due to the existence of the amide group near the surface. The amide groups attached to the side chains on the polymer may participate in various reactions, e.g., with epoxy resins. IR analysis of the cured film indicates the disappearance of the oxiran band at 913 cm^?1 and an increase in the hydroxyl band around 3300 cm^?1. Thus, grafting of amide groups on PVC enables us to further modify PVC by epoxy resins.     

Kinetic speciation of nickel in mining and municipal effluents

This study presents the results of kinetic speciation of nickel in undiluted mining and municipal effluents and effluents diluted with receiving freshwaters from the surrounding environment. The dilution ratios used for the dilution of the effluents were arbitrarily chosen, but were representative of the prevailing mining practices. The purpose of the this dilution was to mimic dilution with natural waters that result from dilution of the mining and municipal effluents with receiving freshwaters, so that this study would reveal environmental realities that are of concern to the managers and regulators of water resources. Ligand exchange kinetics using the competing ligand exchange method (CLEM) was studied using two independent techniques: graphite furnace atomic absorption spectrometry (GFAAS) with Chelex 100 resin as the competing ligand, and adsorptive cathodic stripping voltammetry (AdCSV) with dimethylglyoxime (DMG) as the competing ligand to determine the percentage of Ni metal released from Ni(II)–DOC complexes and the rate of dissociation of Ni(II)–DOC complexes. Using a sample containing a mixture of 30% Copper Cliff Mine effluent, 40% Sudbury municipal effluent and 30% Vermillion River water, both techniques gave results showing that the dilution of the effluent samples increased the percentage of nickel released from Ni(II)–DOC complexes. This increase in the release of nickel from the Ni(II)–DOC complexes may be of concern to managers and regulators of water resources. Agreement between the results of these two techniques has enhanced the validity of the competing ligand exchange method used by both techniques.     

Structure and Stability of Polyvinyl Chloride

Abstract

Polyvinyl chloride (PVC) was first prepared in the laboratory over a hundred years ago. Due to its inherent instability the commercial applications of the polymer could only be developed after the development of effective means for its stabilization. PVC started to gain commercial significance in the late thirties and since then has continued to gain in importance. By using modifying agents (plasticizers, fillers, stabilizers, and other additives), it can be modified to exhibit an extremely wide range of properties.     

Preparation of Mg–Al hydrotalcite from the effluent of Friedel–Crafts reaction and its application as a catalyst in Knoevenagel reaction

Abstract

Hydrotalcite containing magnesium and aluminium (Mg–Al HT) with a molar ratio of Mg(II)/Al(III) = 2.5 has been prepared by a co-precipitation method using the effluent of a Friedel–Crafts acylation reaction. The HT was calcined at 500°C and reconstructed with deionized water. The synthesized HT was characterized by XRD and FT-IR spectroscopy and was successfully used as a catalyst in the Knoevenagel reaction of aldehydes and active methylene compounds. The catalyst was found to be reusable.     

Patterning of cells on a PVC film surface functionalized by ion irradiation

Micropatterns of cells on a poly(vinyl chloride) (PVC) film surface were created by using ion irradiation. A PVC film was irradiated with H⁺ ions through a pattern mask in order to create patterns of the hydrophilic/hydrophobic regions on the PVC surface. The effect of ion irradiation on the surface properties of the PVC film was characterized by using Fourier transform‐infrared spectroscopy (FT‐IR), water contact angle measurement, and X‐ray photoelectron spectroscopy (XPS). The results revealed that the chemical environment of the PVC film surface was effectively changed by ion irradiation due to dehydrochlorination and oxidation. The in vitro cell culture on the patterned PVC film surface showed selective adhesion and proliferation of the cells on the ion‐irradiated regions. Well‐defined 50 µm patterns of the cells were obtained on the PVC film surface irradiated to 1 × 10¹⁵ ions/cm². Copyright © 2009 John Wiley & Sons, Ltd.     

The synthesis and adsorption properties of polyvinylchloride nanofilms with ligand groups

Polyvinylchloride (PVC) samples with a fairly developed surface were prepared by the spontaneous removal of the solvent (benzyl alcohol) from a polymer gel. The surface of the product was modified to obtain ethanolocyclame and sodium acetocyclame nanofilms. The structure and composition of the nanofilms were studied by IR Fourier spectroscopy. The adsorption of nitrogen vapor at ?196°C and benzene and water at 20°C on the nanofilms was investigated. Surface modification was shown to increase the stability of PVC in water and benzene and the specific surface area and volume of nanopores. The conclusion was drawn that nanofilm ligand groups could stoichiometrically interact with water and benzene molecules on PVC with a modified surface.     

Biotreatment of tannin-rich beer-factory wastewater with white-rot basidiomycete Coriolopsis gallica monitored by pyrolysis/gas chromatography/mass spectrometry

Some fractions of beer-factory wastewaters represent an important environmental concern owing to their high content of polyphenols and dark-brown color. The capacity of Coriolopsis gallica to preferentially degrade lignin has been successfully applied in our laboratory to the biotreatment and decolorization of paper-industry effluents. In this work, the ability of this white-rot fungus to degrade high-tannin-containing wastewaters is evaluated. Under all the conditions studied, effluent decolorization and chemical oxygen demand reduction achieved by C. gallica at day 12 of incubation were close to 50 and 65%, respectively. No adhesion of dark color to the fungal mycelium was observed suggesting that decolorization could be ascribed to C. gallica degradation systems. Mycelium dry-weight values showed that C. gallica is tolerant to relatively high tannin content present in the effluent samples. In the sample containing the highest effluent concentration (60% v/v), dry-weight values suggested an inhibition of fungal growth at day 6 of incubation and a further adaptation of the fungus to the stressing tannin effect at day 12 of fungal treatment. Pyrolysis/gas chromatography/mass spectrometry results showed a decrease of polyphenols pyrolysis products, mainly phenol and guaiacol, with the incubation time. All these results indicate the potential use of C. gallica in bioremediation of tannin-containing industrial wastewaters and in other applications where a reduction in polyphenols content is required.