Autohydrogenotrophic denitrification of drinking water using a polyvinyl chloride hollow fiber membrane biofilm reactor

A hollow fiber membrane biofilm reactor (MBfR) using polyvinyl chloride (PVC) hollow fiber was evaluated in removing nitrate form contaminated drinking water. During a 279-day operation period, the denitrification rate increased gradually with the increase of influent nitrate loading. The denitrification rate reached a maximum value of 414.72 g N/m³ d (1.50 g N/m² d) at an influent NO₃⁻–N concentration of 10 mg/L and a hydraulic residence time of 37.5 min, and the influent nitrate was completely reduced. At the same time, the effluent quality analysis showed the headspace hydrogen content (3.0%) was lower enough to preclude having an explosive air. Under the condition of the influent nitrate surface loading of 1.04 g N/m²d, over 90% removal efficiencies of the total nitrogen and nitrate were achieved at the hydrogen pressure above 0.04 MPa. The results of denaturing gel gradient electrophoresis (DGGE), 16S rDNA gene sequence analysis, and hierarchical cluster analysis showed that the microbial community structures in MBfR were of low diversity, simple and stable at mature stages; and the beta-Proteobacteria, including Rhodocyclus, Hydrogenophaga, and beta-Proteobacteria HTCC379, probably play an important role in autohydrogenotrophic denitrification.     

Impedance spectroscopy measurements of charge carrier mobility in 4,4'-N,N'-dicarbazole-biphenyl thin films doped with tris(2-phenylpyridine) iridium

The charge carrier mobility of green phosphorescent emissive layers, tris(2-phenylpyridine) iridium [Ir(ppy)₃]-doped 4,4'-N,N'-dicarbazole-biphenyl (CBP) thin films, has been determined using impedance spectroscopy (IS) measurements. The theoretical basis of mobility measurement by IS rests on a theory for single-injection space-charge limited current. The hole mobilities of the Ir(ppy)₃-doped CBP thin films were measured to be 10^− 10–10^− 8 cm²V^− 1 s^− 1 in the 2–7 wt.% Ir(ppy)₃-doped CBP from the frequency dependence of both conductance and capacitance. These hole mobility values are much lower than those of the undoped CBP thin films (~ 10^− 3 cm²V^− 1 s^− 1) because the Ir(ppy)₃ molecules act as trapping centers in the CBP host matrix. These mobility measurements in the Ir(ppy)₃-doped CBP thin films provide insight into the hole injection process.     

Photoluminescence and electrochemistry behavior of well-dispersible poly-N-[5-(8-quinolinol)ylmethyl]aniline/nano-TiO2 composite

Well-dispersible poly-N-[5-(8-quinolinol)ylmethyl]aniline/nano-TiO₂ composite was synthesized by the surface modification of nano-TiO₂ particles using poly-N-[5-(8-quinolinol)ylmethyl] (PANQ), and it was characterized by Fourier-transform infrared spectroscopy, photoluminescence spectroscopy, thermogravimetric analysis and scanning electron microscope, as well as conductivity and cyclic voltammogram were given. The conductivity of this composite was 2.1 × 10⁻² S cm⁻¹ at 25 °C, and showed good redox reversibility. It was easy to cast a transparent conducting film with photoluminescent property.     

Kinetics of zero-valent iron reductive transformation of the anthraquinone dye Reactive Blue 4

The effect of operational conditions and initial dye concentration on the reductive transformation (decolorization) of the textile dye Reactive Blue 4 (RB4) using zero-valent iron (ZVI) filings was evaluated in batch assays. The decolorization rate increased with decreasing pH and increasing temperature, mixing intensity, and addition of salt (100 g L⁻¹ NaCl) and base (3 g L⁻¹ Na₂CO₃ and 1 g L⁻¹ NaOH), conditions typical of textile reactive dyebaths. ZVI RB4 decolorization kinetics at a single initial dye concentration were evaluated using a pseudo first-order model. Under dyebath conditions and at an initial RB4 concentration of 1000 mg L⁻¹, the pseudo first-order rate constant (k_obs) was 0.029 ± 0.006 h⁻¹, corresponding to a half-life of 24.2 h and a ZVI surface area-normalized rate constant (k_SA) of 2.9 × 10⁻⁴ L m⁻² h⁻¹. However, as the initial dye concentration increased, the k_obs decreased, suggesting saturation of ZVI surface reactive sites. Non-linear regression of initial decolorization rate values as a function of initial dye concentration, based on a reactive sites saturation model, resulted in a maximum decolorization rate (V_m) of 720 ± 88 mg L⁻¹ h⁻¹ and a half-saturation constant (K) of 1299 ± 273 mg L⁻¹. Decolorization of RB4 via a reductive transformation, which was essentially irreversible (2–5% re-oxidation), is believed to be the dominant decolorization mechanism. However, some degree of RB4 irreversible sorption cannot be completely discounted. The results of this study show that ZVI treatment is a promising technology for the decolorization of commercial, anthraquinone-bearing, spent reactive dyebaths.     

The bromination kinetics of phenolic compounds in aqueous solution

The purpose of this study was to investigate the bromination kinetics of selected phenolic compounds in aqueous solutions over the pH range of 5–11. The experiment results indicated that the reaction of hypobromous acid with the phenoxide ions controlled the overall reaction rate, whereas the reaction between hypobromite ion and the phenoxide ions and the reaction between hypobromous acid and the undissociated phenolic species were considered to be negligible respectively in the pH range of 7–9. The apparent second-order rate constants of the reaction of hypobromous acid with the phenoxide ions ranged from 7.9 × 10⁶ M⁻¹ s⁻¹ for 3-chlorophenol to 6.5 × 10⁸ M⁻¹ s⁻¹ for 3-methoxyphenol, respectively. The Hammett correlation could be successfully used to estimate the reactivity of bromine with substituted phenols and the linear regression was log(k₂) = −2.85б + 8.00. The rate constants of the reaction of bromine with phenol-like organic compounds were about three orders of magnitude higher than with chlorine and two to three orders of magnitude lower than with ozone.     

Sorption behavior of nano-TiO2 for the removal of selenium ions from aqueous solution

Titanium dioxide nanoparticles were employed for the sorption of selenium ions from aqueous solution. The process was studied in detail by varying the sorption time, pH, and temperature. The sorption was found to be fast, and to reach equilibrium basically within 5.0 min. The sorption has been optimized with respect to the pH, maximum sorption has been achieved from solution of pH 2–6. Sorbed Se(IV) and Se(VI) were desorbed with 2.0 mL 0.1 mol L⁻¹ NaOH. The kinetics and thermodynamics of the sorption of Se(IV) onto Nano-TiO₂ have been studied. The kinetic experimental data properly correlate with the second-order kinetic model (k₂ = 0.69 g mg⁻¹ min⁻¹, 293 K). The overall rate process appears to be influenced by both boundary layer diffusion and intraparticle diffusion. The sorption data could be well interpreted by the Langmuir sorption isotherm. The mean energy of adsorption (14.46 kJ mol⁻¹) was calculated from the Dubinin–Radushkevich (D–R) adsorption isotherm at room temperature. The thermodynamic parameters for the sorption were also determined, and the ΔH⁰ and ΔG⁰ values indicate exothermic behavior.     

Electrical and optical properties of 12CaO·7Al2O3 electride doped indium tin oxide thin film deposited by RF magnetron co-sputtering

12CaO·7Al₂O₃ electride (C12A7:e⁻) doped indium tin oxide (ITO) (ITO:C12A7:e⁻) thin films were fabricated on a glass substrate by an RF magnetron co-sputtering system with increasing number of C12A7:e⁻ chips (from 1 to 7) and at various oxygen partial pressure ratios. The optical transmittance of the ITO:C12A7:e⁻ thin film was higher than 70% in the visible wavelength region. In the electrical properties of the thin film, a decrease of the carrier concentration from 2.6 × 10²⁰ cm^− 3 to 2.1 × 10¹⁸ cm^− 3 and increase of the resistivity from 1.4 × 10^− 3 Ω cm to 4.1 × 10^− 1 Ω cm were observed with increasing number of C12A7:e⁻ chips and oxygen partial pressure ratios. It was also observed that the Hall mobility was decreased from 17.27 cm²·V^− 1·s^− 1 to 5.13 cm²·V^− 1·s^− 1. The work function of the ITO thin film was reduced by doping it with C12A7:e⁻.     

Coupling extraction–flotation with surfactant and electrochemical degradation for the treatment of PAH contaminated hazardous wastes

The performance of a two-stage process combining extraction of polycyclic aromatic hydrocarbons (PAHs) with an amphoteric surfactant (CAS) followed by electro-oxidation of PAH-foam concentrate was studied for the decontamination of aluminum industry wastes (AIW) and polluted soils. The PAH suspensions extracted from AIW and soils were treated in a 2 L-parallelepipedic electrolytic cell containing Ti/RuO₂ anodes and stainless steel cathodes. Current densities varying from 4.6 to 18.5 mA cm⁻² have been tested with and without addition of a supporting electrolyte (6.25 to 50 kg Na₂SO₄ t⁻¹ of dry waste). The best performance for PAH degradation was obtained while the electrolytic cell was operated during 90 min at a current density of 9.2 mA cm⁻², with a total solids concentration of 2.0%, and in presence 12.5 kg Na₂SO₄ t⁻¹. The application of the process on AIW (initial PAH content: 3424 mg kg⁻¹) allowed extracting 42% of PAH, whereas 50% of PAH was electrochemically degraded in the resulting foam suspensions. By comparison, 44% to 60% of PAH was extracted from polluted soils (initial PAH content: 1758 to 4160 mg kg⁻¹) and 21% to 55% of PAH was oxidized in the foam suspensions. The electrochemical treatment cost (including only electrolyte and energy consumption) recorded in the best experimental conditions varied from 99 to 188 USD $ t⁻¹ of soils or AIW treated.     

Bacterial biosurfactant in enhancing solubility and metabolism of petroleum hydrocarbons

Biosurfactant can make hydrocarbon complexes more mobile with the potential use in oil recovery, pumping of crude oil and in bioremediation of crude oil contaminant. In the investigation, bacterial isolates capable of utilizing poly-cyclic aromatic hydrocarbons like phenanthrene, pyrene and fluorene were used. A gradual decrease of the supplemented hydrocarbons in the culture medium was observed with corresponding increase in bacterial biomass and protein. The medium having the combined application of fluorine and phenanthrene caused better biosurfactant production (0.45 g l⁻¹) and (0.38 g l⁻¹) by Pseudomonas aeruginosa strains MTCC7815 and MTCC7814. The biosurfactant from MTCC7815 (41.0 μg ml⁻¹) and MTCC7812 (26 μg ml⁻¹) exhibited higher solubilization of pyrene; whereas, MTCC8165 caused higher solubilization of phenanthrene; and that of MTCC7812 (24.45 μg ml⁻¹) and MTCC8163 (24.49 μg ml⁻¹) caused more solubilzation of fluorene. Higher solubilization of pyrene and fluorene by the biosurfactant of MTCC7815 and MTCC7812, respectively enhanced their metabolism causing sustained growth. Biosurfactants were found to be lipopeptide and protein–starch–lipid complex in nature and they could reduce the surface tension of pure water (72 mN m⁻¹) to 35 mN m⁻¹. The critical micelle concentration (CMC) was also lower than the chemical surfactant sodium dodecyl sulphate (SDS). They differed in quantity and structure. The predominant rhamnolipids present in biosurfactants were Rha–C₈–C₁₀ and Rha–C₁₀–C₈.     

Effect of potential electron acceptors on anoxic ammonia oxidation in the presence of organic carbon

A novel route of anoxic ammonia removal in the presence of organic carbon was identified recently from ecosystems contaminated with ammonia. Sequencing batch reactor (SBR) studies were carried out in anoxic condition at oxidation–reduction potential varied from −185 to −275 mV for anoxic ammonia oxidation with adapted biomass (mixed culture). SBR studies were carried out in absence and in the presence of externally added organic carbon and/or in the presence of inorganic electron acceptors like NO₂⁻, NO₃⁻ and SO₄²⁻. The results showed anoxic ammonia oxidation to nitrate (in contrast to reported anammox process) in the presence of organic carbon available through endogenous respiration whereas anoxic ammonia oxidation was effective in the presence of externally added organic compound for nitrogen removal. The presence of externally added inorganic electron acceptors like NO₂⁻, NO₃⁻ and SO₄²⁻ was effective in anoxic ammonia oxidation, but failed to follow the reported anammox reaction's stoichiometry in nitrogen removal in the presence of organic carbon. However, the presence of NO₂⁻ affected best in total nitrogen removal compared to other electron acceptors and maximum ammonia removal rate was 100 mg NH₄⁺/g MLVSS/d. Based on the results, it is possible to suggest that rate of anoxic ammonia oxidation depends up on the respiration activities of mixed culture involving organic carbon, NO₂⁻, NO₃⁻ and SO₄²⁻. The process shows possibilities of new pathways of ammonia oxidation in organic contaminated sediments and/or wastewater in anoxic conditions.     

Interactive behavior of caffeine at a platinum electrode surface

Interactive behavior of caffeine at a charged platinum/solution interface was investigated in a wide temperature range, from 295 to 333 K, in a phosphate buffer solution pH 7.0. It was shown that the amount of adsorbed caffeine (surface concentration) is directly proportional to the measured adsorption surface charge density resulting from caffeine oxidation to theophilline. At low temperatures, a monolayer of caffeine molecules laying in a flat orientation on the Pt surface is adsorbed, while at higher temperatures, conformational changes occur, resulting in tilting of the adsorbed molecules to allow for higher surface concentrations to be achieved. A highly negative Gibbs energy of adsorption, ranging from −51.1 kJ mol⁻¹ at 295 K to −60.6 kJ mol⁻¹ at 333 K, demonstrated a high affinity of caffeine for the Pt surface. Although the adsorption process was found to be endothermic (ΔH_ADS = 20 kJ mol⁻¹), it was determined that a large positive change in the adsorption entropy (TΔS_ADS = 75 ± 3 kJ mol⁻¹) represents the driving force for the strong interaction of caffeine with Pt.     

Meteorological variations of PM2.5/PM10 concentrations and particle-associated polycyclic aromatic hydrocarbons in the atmospheric environment of Zonguldak, Turkey

Airborne particulate matter (PM_2.5 and PM₁₀) concentrations were measured in Zonguldak, Turkey from January to December 2007, using dichotomous Partisol 2025 sampler. Collected particulate matter was analyzed for 14 selected polycyclic aromatic hydrocarbons (PAHs) by high-performance liquid chromatography with fluorescence detection (HPLC-FL). The seasonal variations of PM_2.5 and PM₁₀ concentrations were investigated together with their relationships with meteorological parameters. The maximum daily concentrations of PM_2.5 and PM₁₀ reached 83.3 μg m⁻³ and 116.7 μg m⁻³ in winter, whereas in summer, they reached 32.4 μg m⁻³ and 66.7 μg m⁻³, respectively. Total concentration of PM₁₀-associated PAHs reached 492.4 ng m⁻³ in winter and 26.0 ng m⁻³ in summer times. The multiple regression analysis was performed to predict total PM_2.5- and PM₁₀-associated PAHs and benzo(a)pyrene-equivalent (BaPE) concentrations with respect to meteorological parameters and particulate mass concentrations with the determination coefficients (R²) of 0.811, 0.805 and 0.778, respectively. The measured mean values of concentrations of total PM_2.5- and PM₁₀-associated PAHs were found to be 88.4 ng m⁻³ and 93.7 ng m⁻³ while their predicted mean values were found to be 92.5 ng m⁻³ and 98.2 ng m⁻³, respectively. In addition, observed and predicted mean concentration values of PM_2.5-BaPE were found to be 14.1 ng m⁻³ and 14.6 ng m⁻³. The close annual mean concentrations of measured and predicted total particulate related PAHs imply that the models can be reliably used for future predictions of particulate related PAHs in urban atmospheres especially where fossil fuels are mainly used for heating.     

Fluorescence and nonlinear optical properties of non-aggregating hexadeca-substituted phthalocyanine

Highly non-aggregating hexadeca-substituted phthalocyanine (Pc) complexes were prepared and their fluorescence and nonlinear optical properties were studied. Three visible fluorescence bands were observed when the Pc complexes were excited at 355 nm and found to be concentration dependent. They are attributed to the optical transitions S₂ → S₀ at 415 nm, T₂ → T₁ at 630 nm, and S₂ → S₁ at 755 nm. Nonlinear absorptive and refractive effects were measured with the help of Z-scan technique. Saturation absorption was observed at 632.8 nm where the nonlinear absorption coefficient is found to be very large (β = −2.8 × 10⁻² cm/W) and the refractive nonlinear coefficient γ = −9.5 × 10⁻¹¹ cm²/W. In the transparency domain at 532 nm, reverse absorption saturation is observed and β and γ are found to be 17.5 and 15.5 times smaller, respectively. Optical limiting performances are measured in the absorption and transparency domains. Purely refractive-based optical limiting at 632.8 nm is found to have a threshold of 0.16 kW/cm², lower than the reverse absorption saturation and refractive-based optical limiting of 0.90 kW/cm² at 532 nm.     

The structural and electrical property of CuCr1 − xNixO2 delafossite compounds

A series of CuCr_1 − xNi_xO₂ (0 ≤ x ≤ 0.06) polycrystalline samples was prepared. The electrical conductivity was measured in the temperature range of 160–300 K. It was found that the electrical conductivity (σ) increases rapidly with the doping of Ni²⁺ ions. At room temperature, the σ is 0.047 S cm^− 1 for the sample with x = 0.06, which is two orders of magnitude larger than that of the CuCrO₂ sample (9.49E− 4 S cm^− 1). The Seebeck coefficients are positive for all samples, which indicate p-type conducting of the samples. The experimental results imply that it is possible to get higher electrical conductivity p-type transparent conducting oxides (TCO) from CuMO₂ by doping with divalent ions.     

Growth and optical characterizations of (Ba0.32Sr0.68)5Nb4O15 crystal

(Ba_0.32Sr_0.68)₅Nb₄O₁₅ crystal with sizes of Ø 17 × 35 mm was grown successfully by Czochralski technique method. The thermal anisotropy was discussed. The principal coefficients of thermal expansion along (100), (010), (001) directions were precisely measured to be 1.308 × 10^− 5, 1.288 × 10^− 5, 1.478 × 10^− 5 K^− 1, respectively. Its optical transparency range has been measured and found to span from 323 to 5500 nm. The bands present in the IR spectra were identified and assigned to the corresponding vibration modes of NbO₆ anions.     

Growth, thermal and spectroscopic characteristics of LiNd(WO4)2 crystal

Crystal growth, thermal and optical characteristics of LiNd(WO₄)₂ crystal have been investigated. The LiNd(WO₄)₂ crystal up to Ø15 × 32 mm³ has been grown by Czochralski technique. The hardness is about 5.0 Mohs’ scale. The specific heat at 50 °C is 0.42 J g⁻¹ K⁻¹. The thermal expansion coefficient for c- and a- axes is 1.107 × 10⁻⁵ and 2.104 × 10⁻⁵ K⁻¹, respectively. The absorption and fluorescence spectra and the fluorescence decay curve of LiNd(WO₄)₂ crystal were measured at room temperature. Some spectroscopic parameters such as the intensity parameters, the spontaneous transition probabilities, the fluorescence branching ratios, the radiative lifetimes and emission cross sections were estimated.     

Preparation of double-doped BaCeO3 and its application in the synthesis of ammonia at atmospheric pressure

Perovskite-type oxides BaCe_0.90Sm_0.10O_3−δ (BCS) and BaCe_0.80Gd_0.10Sm_0.10O_3−δ (BCGS) were synthesized by the sol–gel method and characterized by thermal analysis (TG-DTA), X-ray diffraction (XRD), scanning electron microscopy (SEM), and transmission electron microscopy (TEM). Using the sintered samples as solid electrolytes and silver–palladium alloy as electrodes, ammonia was synthesized from nitrogen and hydrogen at atmospheric pressure in a solid-state proton-conducting cell reactor. The maximum rate of production of ammonia was 5.82×10⁻⁹ mol s⁻¹ cm⁻².     

A novel route for the synthesis of processable conducting poly(m-aminophenol)

Polymerization of m-aminophenol (mAP) in aqueous NaOH solution was done chemically by using ammonium persulfate (APS) as an oxidative initiator. The product poly(m-aminophenol) (PmAP) was found to be highly soluble in aqueous sodium hydroxide, dimethyl sulfoxide (DMSO) and N,N-dimethyl formamide (DMF). From the intrinsic viscosity measurement, the optimum condition for the polymerization was established with 0.6 M NaOH medium with the ratio of monomer to oxidant as 1:1.5 (mol:mol). The polymer was characterized by FTIR and ¹H NMR spectroscopy, elemental (CHNS) and thermogravimetric (TGA) analyses. From the spectroscopic analysis the structure of the polymer was found to resemble that of hydroxy polyaniline as the polymer contains free –OH groups attached to o/m position in the phenyl ring. The elemental analysis of the polymer also confirmed the same. From TGA study, the polymer was found to be thermally stable. A freestanding film of poly(m-aminophenol) was cast in DMSO solution followed by solvent removal and drying of the film at 100 °C for 7–8 h in an oven. A dc conductivity of 4.8 × 10⁻⁴ S cm⁻¹ was obtained for the synthesized polymer film after doping with H₂SO₄ solution.     

Preparation, characterization and applications of novel iminodiacetic polyurethane foam (IDA-PUF) for determination and removal of some alkali metal ions from water

The new type of ion chelating resin (IDA-PUF) has iminodiacetic group that was prepared from polyurethane foam (PUF) by the reaction between primary amine of PUF and monochloro-acetic acid. The IDA-PUF was characterized using infrared spectra, elemental and thermal analysis. The exchange properties and chromatographic behaviour of the new chelating resin were investigated for removal of some alkali metal ions (lithium, sodium and potassium) using batch and column processes. The maximum distribution coefficient (K_D) of trace alkali metal ions was in the pH range of 8–10. The kinetics of sorption of the alkali metal ions was found to be fast with average values of half-life of sorption (t_1/2) of 4.93 min. The values of ΔG, ΔS and ΔH were −3.86 kJ mol⁻¹, 57.73 J mol⁻¹ K⁻¹ and 14.41 kJ mol⁻¹, respectively, which reflects the spontaneous and endothermic nature of ion exchanger process. The average sorption capacity of IDA-PUF is 4.8 mmol/g for alkali metal ions, enrichment factors ≈40 and the recovery 95–100% were also achieved with average value of RSD% = 1.67. The proposed method has been successfully applied to preconcentrate, determinate and remove the alkali metal ions from different samples of water.     

Electrochemical reclamation of silver from silver-plating wastewater using static cylinder electrodes and a pulsed electric field

Silver was reclaimed from silver-plating wastewater by using a pulsed electric field (PEF) combined with static cylinder electrodes (SCE). The conditions that produced the maximal silver recovery rate (RR_Ag) (99%) were as follows: average retention time of 10 min, interelectrode gap of 50 mm, solution pH of 9.0, temperature of 45 °C, initial Ag(I) concentration of 1000 mg L⁻¹, PEF pulse frequency of 1200 Hz, current density of 5.0 A m⁻² and a pulse duty cycle of 60%. Compared with the conventional direct current (DC) technology, the PEF process exhibited improvements in the silver recovery rate (RR_Ag), total energy consumption (TEC) and physical properties of the silver deposits, especially for low Ag(I) concentrations, for example, from 500 to 1000 mg L⁻¹. For an initial Ag(I) concentration of 500 mg L⁻¹, the PEF process produced an RR_Ag of up to 99%, and the TEC was 4.56 kWh (kg Ag)⁻¹. In comparison, the RR_Ag and TEC were 90% and 5.66 kWh (kg Ag)⁻¹, respectively, in the DC process. The results of SEM observation and XRD analysis indicated that the silver deposits formed by the PEF process were smaller, denser, and of a higher purity than those produced by the DC process. Therefore, the presented method was effective for reclaiming silver from silver-plating wastewater.