Polyethersulfone‐Modified Montmorillonite Hybrid Beads for the Removal of Bisphenol A

Abstract

Na‐Montmorillonite (Na‐MMT) was modified by cetyltrimethylammonium bromide first, then polyethersulfone (PES)‐MMT hybrid beads were prepared using a liquid‐liquid phase separation technique for the removal of bisphenol (BPA). The interlayer spacing of the MMT increased after the modification. Adsorption data showed that the modified MMT had excellent adsorption ability to BPA due to the hydrophobic interaction and large porosity. An adsorption dynamics model for the beads was constructed using concentration decrease data. Also, the experimental data of BPA adsorption were adequately fitted with both Langmuir and Freundlich equations. These results indicated that the PES‐MMT hybrid particles have the potential to be used in the environmental application.     

A Comparative Approach to the Application of a Physico‐Chemical and Advanced Oxidation Combined System to Natural Water Samples

Abstract

Natural organic matter removal (NOM) efficiencies of samples from three major drinking water sources (Elmali, Omerli, and Buyukcekmece) of Istanbul were compared using different treatment systems. Enhanced coagulation as a physico‐chemical method was applied using ferric chloride and aluminum sulphate as the coagulating agents. Moreover, the application of enhanced coagulation in combination with photocatalytic oxidation using TiO₂ was investigated. The efficiency of NOM removal relevant to each treatment step was assessed through DOC removal, UV₂₅₄ removal, and fluorescence measurements.

Irrespective of the treatment applied as enhanced coagulation, photocatalytic oxidation or their combinations, the highest removal efficiency was determined for Elmali followed by Omerli and Buyukcekmece samples both in terms of DOC and UV₂₅₄. Enhanced alum coagulation leads to significant variation in DOC removals as 44%, 28% and 26% for Elmali, Omerli, and Buyukcekmece water samples, respectively. Upon application of ferric chloride as the coagulant, the DOC removals achieved were found to be slightly higher as compared to alum. Moreover, the combined treatment incorporating photocatalytic oxidation subsequent to alum coagulation leads to 36%, 37%, and 50% of DOC removal for Omerli, Buyukcekmece, and Elmali respectively. The improvement of removal efficiencies in combined treatment systems were scrutinized with an emphasis on induced water properties as supported by the specific fluorescence intensities of the samples.     

A Novel Sponge‐Submerged Membrane Bioreactor (SSMBR) for Wastewater Treatment and Reuse

Abstract

Membrane fouling has been regarded as one of the biggest challenges to widespread application of membrane bioreactor (MBR). This study focuses on minimizing the membrane fouling and improving the performance of submerged membrane bioreactor (SMBR) by porous sponge addition. The effects of sponge addition on sustainable flux and membrane fouling were investigated. Acclimatized sponge could significantly increase the suspended growth in SMBR with biomass of 16.7 g/L_(sponge). With the sponge volume fraction of 10%, SSMBR could enhance sustainable flux up to 50 L/m² · h compared with sustainable flux of SMBR (only 25 L/m² · h). SSMBR also exhibited excellent results in terms of DOC removal (over 95%), COD removal (over 97%), lower transmembrane pressure development, and oxygen uptake rate. Over 89% of NH₄‐N and 98% of PO₄‐P were removed when SSMBR was operated with a MLSS concentration of 15 g/L.     

Application of N,N′‐Dimethyl‐N,N′‐Di(4‐Chlorophenyl)Tetradecyl Malonamide for the Selective Recovery of Iron(III) from Concentrated Chloride Solutions

Abstract

The feasibility of using two new diamides namely; N,N′‐dimethyl‐N,N′‐di(4‐chlorophenyl)malonamide (DMDPhClMA) and N,N′‐dimethyl‐N,N′‐di(4‐chlorophenyl)tetradecylmalonamide (DMDPhClTDMA), as agents for the selective extraction of iron(III) from chloride solution was investigated. A systematic investigation has been carried out on the detailed extraction properties of iron(III) with these extractants from chloride media. The extraction of iron(III) from an aqueous chloride solution in the presence of metal ions, such as Zn(II), Co(II), Mn(II) Cu(II), Pb(II), Ni(II) and Ag(I) was carried out using DMDPhClMA or DMDPhClTDMA in binary and multicomponent mixtures. The quantitative extraction of iron(III) with DMDPhClMA and DMDPhClTDMA in toluene is observed at 4 and 7 M HCl, respectively. The quantitative stripping of Fe(III), from the loaded organic phase was successfully achieved by simple contact with water.     

Hybrid Properties of Alginate‐PEI Adsorbent for Chromium (VI) Removal from Aqueous Solutions

Abstract

An adsorbent consisting of polyethyleneimine (PEI) immobilized in calcium alginate gel beads was synthesized and evaluated for Cr⁶⁺ removal. An evaluation of the synthesis process showed the importance of the PEI molecular weight on the immobilization efficiency. Polyethyleneimine of 70,000 Da molecular weight displayed the highest immobilization percentage at 52%. Batch kinetics and equilibrium tests showed that alginate‐PEI (APEI) resin displayed considerable affinity for negatively charged Cr⁶⁺ complexes at low pH conditions ranging from pH 1.5‐pH 3. The results also indicated the reduction of Cr⁶⁺ to less toxic Cr³⁺ species by the APEI adsorbent. The column adsorption experiments showed the ability of APEI resin to treat a 10 mg/L Cr⁶⁺ solution with pH influent adjustment from pH 1.5 to pH 3 to concentrations that satisfy effluent standards for Cr⁶⁺ (<0.1 mg/L) and total Cr (<0.5 mg/L). Finally, comparisons with a highly aminated commercial resin Chitopearl CS‐03 highlighted the unique ability of the hybrid APEI beads with its amine and carboxylic groups for the adsorption of Cr⁶⁺ as well as the retention of generated Cr³⁺ ions.     

Stereo-Preference in the Degradation of the Erythro and Threo Isomers of β‐O‐4‐Type Lignin Model Compounds in Oxidation Processes: Part 1: In the Reaction with Active Oxygen Species Under Oxygen Delignification Conditions

We examined whether or not active oxygen species (AOS) stereo-preferentially attack the erythro or threo isomer of non-phenolic β-O-4 -type lignin model compounds under oxygen delignification conditions. When AOS were generated in situ by the reaction between O₂ and co-existing 4-hydroxy-3-methoxybenzyl alcohol (vanillyl alcohol), the obtained results could be explained on the basis of the hypothesis that an electrostatic repulsion exists between the negatively charged oxyl anion radical and the side-chain of the erythro isomer carrying the α-alkoxide anion. This repulsion prevents the reaction between the two species and, consequently, the erythro isomer is degraded less than the threo isomer. When 2,4,6-trimethylphenol (TMPh) was used to generate AOS, the reverse stereo-preference was observed. This reversal could be attributed to the neutral nature of a peroxyl radical that is an important AOS in the TMPh system and can attack the side-chain of the erythro isomer carrying the negatively charged α-alkoxide anion.     

A Hybrid Membrane of Poly(vinyl alcohol) and Phosphotungstic Acid for Fuel Cells

Proton conducting membranes composed of phosphotungstic acid (PWA) and poly(vinyl alcohol) (PVA) were prepared. Conductivity and Fourier transform infrared spectrometer(FTIR) measurements show that most of the acid embedded are stable in the PVA matrix when the membrane is immerged in water or methanol solution at room temperature. Conductivity of the composite membranes scatters around 10-3S·cm-1 at room temperature. The methanol crossover through the membranes is about an order of magnitude lower than that through Nafion 117 membrane.     

Synthesis,Characterization, and Evaluation of Gel‐Type Poly(4‐Vinylpyridine) Resins for Plutonium Sorption

Abstract

Three different cross‐linked (4, 8, and 12%) gel‐type strong‐base poly(4‐vinylpyridine) resins (PVP) have been synthesized and characterized by elemental analysis, IR, exchange capacity, and moisture content. The uptake of plutonium and uranium was measured as a function of nitric acid concentration using all the three PVP resins. Plutonium sorption and elution kinetics experiments were also performed on all three PVP resins and compared with the benchmark, a gel‐type quarternary ammonium type anion‐exchange resin. The plutonium sorption rate decreases with the increase in cross‐linkage of the resin. All the three PVP resins exhibit better elution kinetics compared to the benchmark. The results on kinetic experiments performed on all three‐gel‐type resins indicated 8% gel‐type PVP resin with 50–100 mesh as a better candidate for plutonium processing or purification. Radiation degradation studies were carried out on the 8% PVP resin by gamma irradiation up to 200 MRad. The irradiated resins were characterized by IR, TGA, and SEM.

The exchange capacity, moisture content, and plutonium uptake were also evaluated for the irradiated PVP resins in comparison with the benchmark. The results indicated a better radiation stability for PVP resin over the benchmark.     

Structure of the Extracted Complex in the Ni(II)‐LIX84I System and the Effect of D2EHPA Addition

Abstract

The structure of the Ni(II) complex extracted with the commercial hydroxyoxime, LIX84I, and the effect of adding bis(2‐ethylhexyl) phosphoric acid (D2EHPA) to LIX84I on the extraction rate and the coordination of Ni(II) were investigated by solvent extraction and XAFS methods. The XANES spectrum and the curve fits of the EXAFS spectrum of the Ni‐LIX84I complex showed that the complex is four‐coordinate square‐planar with a 1:2 stoichiometry. In the Ni(II)–D2EHPA–LIX84I system, the coordination geometry changes from square‐planar to six‐coordinate octahedral with an increase in the D2EHPA concentration. Although the rate of Ni(II) extraction from the model spent electroless nickel plating bath with LIX84I is significantly accelerated by adding a small amount of D2EHPA ([LIX84I]: 0.5 M, [D2EHPA]: 0.05 M), most of the Ni(II) complexes extracted with this organic solution remain square‐planar. This indicates that the increase in the extraction rate does not depend on the change in the coordination structure of the extracted complex.     

Application of Poly(acetic Acid)–Based Graft Copolymer as a Compatibilizer for Poly(L-lactic Acid)/Poly(butylenesuccinate) Blend System

Poly(L-lactic acid) (PLLA) was blended with poly(butylenesuccinate) (PBS) using a single-screw extruder to modify the poor characteristics of these polymers. Furthermore, when both polymers were blended, the graft copolymer that was synthesized by partially saponified poly(vinyl alcohol) (PSPVA) and ?-caprolactone (?-CL) was used as a novel compatibilizer. The structure of the synthesized compatibilizer was determined by ¹H or ¹³C NMR. From this result, the ring-opening polymerization of the ?-CL occurred at the hydroxyl group of PSPVA. The structures of the PLLA/PBS solvent-cast blended films could be observed via an optical microscope. From the optical microscopic observation, the structures of the solvent-cast blended films with the synthesized compatibilizer were more homogeneous than those of the solvent-cast blended films without the compatibilizer. The mechanical properties of the PLLA/PBS extruded blended films were determined by a tensile test. The result showed the tensile strength of the blended films with the synthesized compatibilizer was greater than that of the blended films without the compatibilizer.     

6,6′‐Bis(5,5,8,8‐tetramethyl‐5,6,7,8‐tetrahydro‐benzo[1,2,4]triazin‐3‐yl) [2,2′]bipyridine,an Effective Extracting Agent for the Separation of Americium(III) and Curium(III) from the Lanthanides

Abstract

The extraction of americium(III), curium(III), and the lanthanides(III) from nitric acid by 6,6′‐bis(5,5,8,8‐tetramethyl‐5,6,7,8‐tetrahydro‐benzo[1,2,4]triazin‐3‐yl)‐[2,2′]bipyridine (CyMe₄‐BTBP) has been studied. Since the extraction kinetics were slow, N,N′‐dimethyl‐N,N′‐dioctyl‐2‐(2‐hexyloxy‐ethyl)malonamide (DMDOHEMA) was added as a phase transfer reagent. With a mixture of 0.01 M CyMe₄‐BTBP+0.25 M DMDOHEMA in n‐octanol, extraction equilibrium was reached within 5 min of mixing. At a nitric acid concentration of 1 M, an americium(III) distribution ratio of approx. 10 was achieved. Americium(III)/lanthanide(III) separation factors between 50 (dysprosium) and 1500 (lanthanum) were obtained. Whereas americium(III) and curium(III) were extracted as disolvates, the stoichiometries of the lanthanide(III) complexes were not identified unambiguously, owing to the presence of DMDOHEMA. In the absence of DMDOHEMA, both americium(III) and europium(III) were extracted as disolvates. Back‐extraction with 0.1 M nitric acid was thermodynamically possible but rather slow. Using a buffered glycolate solution of pH=4, an americium(III) distribution ratio of 0.01 was obtained within 5 min of mixing. There was no evidence of degradation of the extractant, for example, the extraction performance of CyMe₄‐BTBP during hydrolylsis with 1 M nitric acid did not change over a two month contact.     

Unraveling the Early Events of Amyloid-β Protein (Aβ) Aggregation: Techniques for the Determination of Aβ Aggregate Size

The aggregation of proteins into insoluble amyloid fibrils coincides with the onset of numerous diseases. An array of techniques is available to study the different stages of the amyloid aggregation process. Recently, emphasis has been placed upon the analysis of oligomeric amyloid species, which have been hypothesized to play a key role in disease progression. This paper reviews techniques utilized to study aggregation of the amyloid-β protein (Aβ) associated with Alzheimer's disease. In particular, the review focuses on techniques that provide information about the size or quantity of oligomeric Aβ species formed during the early stages of aggregation, including native-PAGE, SDS-PAGE, Western blotting, capillary electrophoresis, mass spectrometry, fluorescence correlation spectroscopy, light scattering, size exclusion chromatography, centrifugation, enzyme-linked immunosorbent assay, and dot blotting.     

Synthesis and Characterization of Perovskite-Type Oxides La1−xMxCoO3 (M = Ce,Sr) for the Selective CO Oxidation (SELOX)

Perovskite-type oxides La_1?xM_xCoO₃ (M = Ce, Sr) were prepared by citrate method, characterized and evaluated in the selective CO oxidation (SELOX-CO). The insertion of low Cerium or Strontium content generated solids with a single phase related LaCoO₃ perovskite. For higher contents we observed segregation of CeO₂ and SrCO₃. The iso-structural substitution favors the formation of vacancies. The SELOX-CO showed 100 % CO conversion at 200 °C. Higher temperatures favored hydrogen oxidation and methanation.     

Mixed Micelles of Surface Active Ionic Liquid (SAIL)–Octylphenol Ethoxylate: A Novel Reaction Medium for Selective Oxidation of Toluene to Benzaldehyde

Ionic liquids have been found to be suitable alternatives to volatile organic solvents in chemical transformation. Through a proper choice of cations and anions, the properties of an ionic liquid can be tuned so that it resembles an amphiphile. Such specially designed molecules are known as surface-active ionic liquids (SAIL). Like conventional surfactants, SAIL also form aggregates in an aqueous medium. Studies show that the mixing of SAIL with conventional surfactants leads to synergistic micellization. However, very few reports are available on the application of such systems as reaction media. Present study focuses on the application of mixed micelles of 1-tetradecyl-3-methylimidazol-1-ium bromide, ([C₁₄mim]Br) with nonionic surfactant, Octylphenol ethoxylate with 10 moles of ethylene oxide (OPE-10). Enhanced solubilization and selective catalytic oxidation of toluene using hydrogen peroxide as an oxidant and tungstic acid as a catalyst have been studied in detail using this system.     

Synthesis and Photocatalytic Activity of Ni–Fe Layered Double Hydroxide Modified Sulphur Doped Graphitic Carbon Nitride (SGCN/Ni–Fe LDH) Photocatalyst for 2,4-Dinitrophenol Degradation

In this work, visible light-active sulphur doped graphitic carbon nitride coupled with Ni–Fe layered double hydroxide (SGCN/Ni–Fe LDH) was prepared through co-precipitation procedure using commercially available thiourea, nickel nitrate, and ferric nitrate. The surface morphology characterization showed LDH crystallite growth onto the surface of SGCN, exploiting the delocalized π-electrons of graphitic structure to attain chemical stability. The synthesized photocatalyst exhibited 98% 2,4-dinitrophenol (DNP) photodegradation within 120 min of visible light irradiations, which was surprisingly high compared to 60 and 55% obtained for bare GCN and Ni–Fe LDH samples. This photo removal efficiency could be due to suitable bandgap energy, layered graphitic and brucite Ni–Fe layered structures, and sufficient pollutant adherence to active sites provided by incorporation of S dopant into bare GCN. The characterization results obtained by cyclic voltammetry graph photoluminescence and electrochemical impedance spectra indicated minimum charge carrier recombination due to the type-II charge transfer route along with an active generation of ?O₂^? and h⁺ as dominant reactive species participating in DNP mineralization into more unaffected inorganic ions. The photocatalytic activity enhanced in an acidic medium at optimized parameters, i.e., pH 4, photocatalyst dosage 50 mg in 50 mL solution, and DNP concentration 1.0?×?10^?4 mol/dm³, due to ionic interactions between negatively charged DNP and positive intercalated structure of Ni–Fe LDH. The as-prepared photocatalyst photodegradation ability was retained after 5 catalytic cycles, confirming its environmentally-compatible usage in water treatment.

     

Kinetics of Y(III) Stripping for the System Y/HCl/Cyanex 272‐P507/Heptane with Constant Interfacial Area Cell with Laminar Flow

Abstract

Kinetics and mechanism of stripping of yttrium(III) previously extracted by mixtures of bis(2,4,4‐trimethylpentyl)phosphinic acid (Cyanex 272, HA), and 2‐ethylhexyl phosphonic acid mono‐2‐ethylhexl ester (P507, HB) dissolved in heptane have been investigated by constant interfacial‐area cell by laminar flow. The corresponding equilibrium stripping equation and equilibrium constant were obtained. The studies of effects of the stirring rate and temperature on the stripping rate show that the stripping regime is dependent on the stripping conditions. The plot of interfacial area on the rate has shown a linear relationship. This fact together with the strong surface activity of mixtures of Cyanex 272 and P507 at heptane‐water interfaces makes the interface the most probable locale for the chemical reactions. The stripping rate constant is obtained, and the value is compared with that of the system with Cyanex 272 and P507 alone. It is concluded that the stripping ability with the mixtures is easier than that of P507 due to lower the activation energy of the mixtures. The stripping rate equation has also been obtained, and the rate‐determining steps are the two‐step interfacial chemical reactions as predicted from interfacial reaction models.     

Extraction Behavior of the Synergistic System 2,6‐ bis ‐(Benzoxazolyl)‐4‐ Dodecyloxylpyridine and 2‐Bromodecanoic Acid Using Am and Eu as Radioactive Tracers

Abstract

In this study, the extraction properties of a synergistic system consisting of 2,6‐bis‐(benzoxazolyl)‐4‐dodecyloxylpyridine (BODO) and 2‐bromodecanoic acid (HA) in tert‐butyl benzene (TBB) have been investigated as a function of ionic strength by varying the nitrate ion and perchlorate ion concentrations. The influence of the hydrogen ion concentration has also been investigated. Distribution ratios between 0.03–12 and 0.003–0.8 have been found for Am(III) and Eu(III), respectively, but there were no attempts to maximize these values. It has been shown that the distribution ratios decrease with increasing amounts of ClO₄ ^?, NO₃ ^?, and H⁺. The mechanisms, however, by which the decrease occurs, are different. In the case of increasing perchlorate ion concentration, the decrease in extraction is linear in a log–log plot of the distribution ratio vs. the ionic strength, while in the nitrate case the complexation between nitrate and Am or Eu increases at high nitrate ion concentrations and thereby decreases the distribution ratio in a non‐linear way. The decrease in extraction could be caused by changes in activity coefficients that can be explained with specific ion interaction theory (SIT); shielding of the metal ions, and by nitrate complexation with Am and Eu as competing mechanism at high ionic strengths. The separation factor between Am and Eu reaches a maximum at ～1 M nitrate ion concentration. Thereafter the values decrease with increasing nitrate ion concentrations.     

A new family of “ligated” anionic initiators for the “living” polymerization of (meth)acrylic esters

Summary A new family of ligands (dual - ligand), i.e. chelating lithium alkoxides, Li-O-(CH₂-CH₂O)_nCH₃, is shown to be very effective in promoting the living anionic polymerization of methacrylic and acrylic esters, including a number of primary alkyl acrylates such as n-butyl acrylate and 2-ethylhexylacrylate.     

A Lack of Evidence for an Ecological Role of the Putative Allelochemical (±)-Catechin in Spotted Knapweed Invasion Success

Allelopathy is a notoriously difficult mechanism to demonstrate. There has been a recent resurgence of interest in allelopathy because of the work done on the invasive weed spotted knapweed and its putative allelochemical, (±)-catechin. In this study we collected and analyzed soil samples taken from three, long-term knapweed infested sites in Montana, USA during the summer and fall of 2005. We only detected catechin in all the soil cores at one time point (August, 2005) at two of the sites. Field levels from these two sites were nearly three orders of magnitude lower than what has previously been reported to cause reduced growth in a sensitive native species. Fourteen percent of the remaining soil cores contained low but detectable levels (<0.11 ppm) of (±)-catechin. Additional experiments indicated that soil moisture appears to play a significant role in whether or not catechin degrades rapidly or remains in the soil. Adding to previous work, this paper sheds doubt on the importance of this chemical in spotted knapweed invasion success.