Development and characterization of a titanosilicate ETS-10-coated optical fiber reactor towards the photodegradation of methylene blue

An optical fiber reactor (OFR) system containing uniformly distributed quartz fibers coated with titanosilicate ETS-10 crystals was investigated. Optimum ETS-10 film thickness (～1.5 μm) and coating length (15 cm) were determined from the light propagation analysis in a single ETS-10-coated fiber. The nearly constant value of the attenuation coefficient (α ≈ 0.10 cm^?1) for films with different thickness indicated uniform fiber surface coverage with these films. The extinction coefficient, ?, decreased from ～1.6 to ～1.0 μm^?1 with ETS-10 film thickness increasing from ～0.5 to ～1.5 μm, which suggested less contact per unit film thickness between light and ETS-10 crystals inside thicker films, likely due to their lower crystal packing density. Photodegradation of methylene blue (MB) conducted in the OFR showed higher photocatalytic activity for thicker ETS-10 films. Although higher MB photodegradation rates were obtained at higher light intensity, the apparent quantum efficiency, Φ, decreased with increasing light intensity. This is consistent with the charge separation mechanism for MB photodegradation in the UV light range investigated. All ETS-10 samples investigated showed ～4–5 times higher Φ values in the OFR than in the slurry reactor, likely due to the unique light/photocatalyst/reactant contact and high fiber packing density in the OFR.     

A microtubular all CNT gas diffusion electrode

We report a microtubular gas diffusion electrodes made of multi-walled carbon nanotubes (MWCNT). The electrodes were prepared by inside-out cake filtration of an aqueous MWCNT suspension onto a microfiltration hollow fiber (HF) membrane, followed by washing out the surfactant, drying and removal of the all CNT microtube from the HF membrane. Length, outer diameter, and wall thickness of the tubular electrodes are: up to 44 cm, ~ 1.7 mm and 275 μm, respectively. The BET surface area is 200 m²/g with a porosity of 48–67% and an electrical conductivity of ~ 20 S/cm. Application of this microtubular Gas Diffusion Electrodes (GDE) was studied for the oxygen reduction reaction (ORR) in divided and undivided electrochemical cells. Oxygen supply into the lumen of the tubular electrodes resulted in much higher current densities for ORR than in experiments where the electrolyte was saturated by bubbling with pure oxygen. Within the 0.25–1.0 bar pressure (gauge) region, higher ORR rates were achieved at lower pressure. We also show that H₂O₂ production is possible using the new GDE. We propose to use such novel electrodes for the fabrication of tubular electrochemical reactors, e.g. fuel cells, H₂O₂ generators, CO₂ reduction and other processes that involve GDE application.     

Removal of trace organics from water using a pumped bed-membrane bioreactor with powdered activated carbon

A pumped bed-membrane bioreactor (PB-MBR) combining powdered activated carbon (PAC) adsorption with bacterial degradation was studied for the purification of tap water, spiked with 2 mg/l of phenanthrene, to sub-ppm levels. The feedwater was supplemented with nitrogen and phosphorous to reach a COD:N:P ratio of 100:10:1. PAC concentration was maintained at 5 g/l. Polyacrylonitrile (PAN) flat-sheet membranes of 250 and 1500 kDa MWCO were tested. The overall efficiency during long term operation was tested at different hydraulic conditions with intermittent biosolids wastage and high frequency-chemical cleaning (every 2–3 days) or without chemical cleaning and without sludge removal. With intermittent PAC dosage-high frequency chemical cleaning steady fluxes of 150–200 l/m² h were maintained. With no chemical cleaning-no solids wastage, steady fluxes of 22.5±3.8 and 28.8±4.8 l/m² h were achieved for the 250 and 1500 kDa membranes, respectively. An almost complete removal of phenanthrene was observed in all cases, regardless the type of membrane, operating protocols or hydraulic conditions applied (permeate concentration was consistently below 5 μg/l). The relatively high permeate fluxes and constant filterability observed are attributed to the turbulent flow regime and high PAC-slurry recirculation ratio generated.     

Optimization of parameters of sampling and determination of reduced sulfur compounds using cryogenic capture and gas chromatography in tropical urban atmosphere

Reduced sulfur compounds, RSCs (H₂S, COS, CH₃SH, CH₃SCH₃, CS₂ and CH₃S₂CH₃) play a role in global cycle and acid rain formation. At trace levels RSCs in air are difficult to collect, store and analyze because of their highly adsorptive and reactive properties. This work optimizes parameters of sampling and instrumental determination of RSCs for urban measurements. The method used is based on cryogenic sampling and gas chromatography provided with a cryofocusing trap and flame photometric detection.Greater sampling efficiency was obtained with liquid argon as freezing fluid and air flow rate of 150 mL min^? 1 for two hours. Best results have been obtained with preconcentration for 3 min and injection volume of 3 ml. For H₂S, CH₃SH and CH₃S₂CH₃ the method showed a precision of 89%, limit of detection of 0.10 µg m^? 3 and limit of quantification 0.3 µg m^? 3. For CH₃SCH₃ and CS₂ the corresponding values were 89%, 0.15 µg m^? 3 and 0.5 µg m^? 3 and for COS were 75%, 0.18 µg m^? 3 and 0.8 µg m^? 3 respectively. Sampling efficiency varied between 70–80% for all the RSCs. Accuracy of H₂S from field measurements obtained with parallel measurements using a continuous monitor varied between 88 and 98%. The optimized methodology proved to be suitable for field measurements in urban tropical atmospheres with different characteristics.     

Formation and characterization of magnetic barium ferrite hollow fibers with high specific surface area via sol–gel process

The magnetic barium ferrite (BaFe₁₂O₁₉) hollow fibers with a high specific surface area about 22–38 m² g^?1, diameters around 1 μm and a ratio of the hollow diameter to the fiber diameter estimated about 1/2–2/3 have been prepared by the gel-precursor transformation process. The precursor and resulting ferrite hollow fibers were analyzed by thermo-gravimetric and differential scanning calorimetry, infrared spectroscopy, scanning electron microscopy and X-ray diffraction. The specific surface area was measured by the Brunauer–Emmett–Teller method. The gel formed at pH 5.5 has a good spinnability. A pure barium ferrite phase is formed after calcined at 750 °C for 2 h and fabricated of nanograins about 38 nm with a hexagonal plate-like morphology, which are increased to about 72 nm with the calcination temperature increased up to 1050 °C. The barium ferrite hollow fibers obtained at 750 °C for 2 h have a specific surface area 38.1 m² g^?1 and average pore size 6.5 nm and then the specific surface area and average pore size show a reduction tendency with the calcination temperature increasing from 750 to 1050 °C owing to the particle growth and fiber densification. These barium ferrite hollow fibers exhibit typical hard-magnetic materials characteristics and the formation mechanism for hollow structures is discussed.     

New ceramic microfiltration membranes from mineral coal fly ash

This work aims to develop a new mineral porous tubular membrane based on mineral coal fly ash. Finely ground mineral coal powder was calcinated at 700 °C for about 3 h. The elaboration of the mesoporous layer was performed by the slip casting method using a suspension made of the mixture of fly ash powder, water and PVA. The obtained membrane was submitted to a thermal treatment which consists in drying at room temperature for 24 h then a sintering at 800 °C. SEM photographs indicated that the membrane surface was homogeneous and did not present any macro defects (cracks, etc.). The average pore diameter of the active layer was 0.25 μm and the thickness was around 20 μm. The membrane permeability was 475 l/h m² bar.This membrane was applied to the treatment of the dying effluents generated by the washing baths in the textile industry. The performances in term of permeate flux and efficiency were determined and compared to those obtained using a commercial alumina microfiltration membrane. Almost the same stabilised permeate flux was obtained (about 100 l/h m²). The quality of permeate was almost the same with the two membranes: the COD and color removal was 75% and 90%, respectively.     

Fixed-bed study for adsorptive removal of furfural by activated carbon

In our previous study [A.K. Sahu, V.C. Srivastava, I.D. Mall, D.H. Latye, Sep. Sci. Technol. 43 (5) (2008) 1239], commercial grade activated carbon (ACC) was used for adsorptive removal of furfural from aqueous solution using batch studies. In the present study, continuous fixed-bed adsorption was carried out in ACC packed bed for the removal of furfural from aqueous solution. The effects of important factors namely bed height (Z = 15–60 cm), influent concentration of furfural (C_o = 50–200 mg/l), the flow rate (Q = 0.02–0.04 l/min) and column diameter (D = 2–4 cm) were studied. Capacity of the bed to adsorb furfural was found to increase with an increase in the value of Z, C_o and D; and with decrease in the value of Q. Adams–Bohart, Bed-Depth Service-Time, Thomas, Yoon–Nelson, Clark and Wolborska models were applied to the experimental data for the prediction of the breakthrough point, and to determine the characteristic parameters of the column. Error analysis showed that the Yoon–Nelson model best described the experimental breakthrough curve, while Wolborska model showed good prediction of breakthrough curve for the relative concentration region up to 0.5.     

Visualization and characterization of SPG membrane emulsification

Shirasu-porous-glass (SPG) membrane emulsification is highly attractive for various fields of foods, cosmetics, and pharmaceuticals because this technique produces monodispersed emulsions. However, there are few reports on the observation of membrane emulsification at the membrane surface. In the present work, we aimed to visualize the membrane emulsification using a microscope high-speed camera system. The direct observation made it possible to measure the mean rate of droplet formation and the percentage of active pores. The mean rate of droplet formation ranged 0.3–12 s⁻¹ and the percentage of active pores ranged 0.3–0.5% under the dispersed-phase flux of 0.58×10⁻⁶–5.8×10⁻⁶ m³/(m² s). We also observed that the droplets were formed without continuous-phase flow and the droplets were also formed by shear force at the continuous-phase flow under different experimental conditions. The balance among the dispersed-phase flux and the continuous-phase flow velocity influenced droplet formation.     

Operation of industrial-scale electron beam wastewater treatment plant

Textile dyeing processes consume large amount of water, steam and discharge filthy and colored wastewater. A pilot scale e-beam plant with an electron accelerator of 1 MeV, 40 kW had constructed at Daegu Dyeing Industrial Complex (DDIC) in 1997 for treating 1,000 m³ per day. Continuous operation of this plant showed the preliminary e-beam treatment reduced bio-treatment time and resulted in more significant decreasing TOC, COD_Cr, and BOD₅. Convinced of the economics and efficiency of the process, a commercial plant with 1 MeV, 400 kW electron accelerator has constructed in 2005. This plant improves the removal efficiency of wastewater with decreasing the retention time in bio-treatment at around 1 kGy. This plant is located on the area of existing wastewater treatment facility in DDIC and the treatment capacity is 10,000 m³ of wastewater per day. The total construction cost for this plant was USD 4 M and the operation cost has been obtained was not more than USD 1 M per year and about USD 0.3 per each m³ of wastewater.     

Copper removal from aqueous solution using biochar: Effect of chemical activation

The main aim of this study was to test the efficiency of biochar for Cu removal from synthetic and soil solutions, respectively.The biochar was produced from brewers draff via pyrolysis. Additionally, the prepared biochar was also activated using 2 M KOH to enhance its sorption efficiency to remove Cu from both solutions. Two different aqueous solutions were prepared for these experiments: (i) a synthetic using Cu-nitrate salt with 0.01 M NaNO₃ and (ii) soil solution obtained from a Cu-contaminated soil using 0.01 M CaCl₂ leaching procedure. Batch sorption and column experiments were used to evaluate the efficiency of both biochar (BC) and activated biochar (BC_act) to remove Cu from the solutions.Results showed that both biochar samples are pure amorphous carbon and the Cu sorption is thus mainly a result of physical sorption on the biochar surface. Next, chemical activation, using 2 M KOH, significantly increased the total volume of all pores in biochar (from 0.01 ± 0.002 to 8.74 ± 0.18 mL g⁻¹). On the other hand, the BET surface area was similar for both sorbents (BC = 9.80 ± 0.62 m² g⁻¹ and BC_act = 11.6 ± 0.4 m² g⁻¹). Results also demonstrate enhanced sorption efficiency of the BC_act (10.3 mg g⁻¹) in comparison with the BC (8.77 mg g⁻¹). Additionally, enhanced Cu removal during column retention test was observed for the BC_act in both synthetic and soil solutions, respectively.In summary, the results showed that biochar prepared from brewers draff was able to remove Cu from both aqueous solutions.     

Advanced oxidation of aromatic VOCs using a pilot system with electron beam–catalyst coupling

The decomposition of volatile organic compounds (VOCs) using a pilot system of electron beam (EB)–catalyst coupling was investigated. Two aromatic VOCs, toluene (1800 ppmC) and o-xylene (1500 ppmC), were irradiated with a dose range of 0–10 kGy at room temperature. The removal efficiencies for toluene and o-xylene were 92.4% and 94.5%, respectively, under a 10 kGy absorbed dose condition, which were higher than the results of 45.7% and 52.3% when EB-only was used, respectively. The CO₂ selectivity approached 100% for both toluene and o-xylene using the EB-catalyst coupling system, while the concentrations of O₃ formed were 0.02 ppm (toluene) and 0.003 ppm (o-xylene) at 10 kGy. The aerosol concentration was also measured as 43.2 μg/m³ (toluene) and 53.4 μg/m³ (o-xylene) at 10 kGy absorbed dose.     

Chemical bath deposition of CdS quantum dots on vertically aligned ZnO nanorods for quantum dots-sensitized solar cells

Formation of CdS quantum dots (Q dots) on the vertically aligned ZnO nanorods electrode was carried out by chemical bath deposition. The diameter and thickness of ZnO nanorods are ～100–150 nm and ～1.6 μm, respectively, and CdS Q dots on ZnO nanorods have a diameter of smaller than 15 nm. In application of the Q dots-sensitized solar cells, composite film exhibited a power conversion efficiency of 0.54% under air mass 1.5 condition (80 mW/cm²), and incident-photon-to-current conversion efficiency showed 18.6%.     

Viscosity of {xCO2 + (1 − x)CH4} with x = 0.5174 for temperatures between (229 and 348) K and pressures between (1 and 32) MPa

A vibrating wire instrument, in which the wire was clamped at both ends, was used to measure the viscosity of {xCO₂ + (1 − x)CH₄} with x = 0.5174 with a combined uncertainty of 0.24 μPa · s (a relative uncertainty of about 0.8 %) at temperatures T between (229 and 348) K and pressures p from (1 to 32) MPa. The corresponding mass density ρ, estimated with the GERG-2008 equation of state, varied from (20 to 600) kg · m⁻³. The measured viscosities were consistent within combined uncertainties with data obtained previously for this system using entirely different experimental techniques. The new data were compared with three corresponding states-type models frequently used for predicting mixture viscosities: the Extended Corresponding States (ECS) model implemented in REFPROP 9.1; the SUPERTRAPP model implemented in MultiFlash 4.4; and a corresponding states model derived from molecular dynamics simulations of Lennard Jones fluids. The measured viscosities deviated systematically from the predictions of both the ECS and SUPERTRAPP models with a maximum relative deviations of 11 % at (229 K, 600 kg · m⁻³) and −16 % at (258 K, 470 kg · m⁻³), respectively. In contrast, the molecular dynamics based corresponding states model, which is predictive for mixtures in that it does not contain any binary interaction parameters, reproduced the density and temperature dependence of the measured viscosities well, with relative deviations of less than 4.2 %.     

Viscosity measurements of hydrogen at high temperatures up to 573 K by a curved vibrating wire method

The viscosities of hydrogen were measured at temperatures of (296 to 573) K and at pressures up to 0.7 MPa by the vibrating wire method. In this study, a tungsten wire 50 μm in diameter and 24 mm in length is bent into semicircular form. The direction of the vibrating motion is fixed using the curved wire, and a more compact sample vessel can be used than in a traditional straight vibrating wire method requiring weight for the tension in the wire. Alternating voltages with different frequencies were supplied to the curved wire, which was set between samarium cobalt magnets. The generated induced voltages depending on the supplied frequencies were measured by a lock-in amplifier, and the resonant curve was obtained. The resonant frequency and half-width of the resonant curve were determined by curve fitting. The wire’s effective diameter and internal friction coefficient, which represents the damping from the wire material and the magnetic force, are very important parameters for evaluating the viscosities, and they were precisely calibrated by measuring helium and nitrogen as reference fluids. Finally, the viscosities of hydrogen were obtained with an uncertainty of 1.4% (k = 2).     

The solubility measurements of sodium dicarboxylate salts; sodium oxalate,malonate, succinate,glutarate, and adipate in water from T = (279.15 to 358.15) K

The solubility measurements of sodium dicarboxylate salts; sodium oxalate, malonate, succinate, glutarate, and adipate in water at temperatures from (278.15 to 358.15 K) were determined. The molar enthalpies of solution at T = 298.15 K were derived: Δ_solH_m (m = 2.11 mol · kg^?1) = 13.86 kJ · mol^?1 for sodium oxalate; Δ_solH_m (m = 3.99 mol · kg^?1) = 14.83 kJ · mol^?1 for sodium malonate; Δ_solH_m (m = 2.45 mol · kg^?1) = 14.83 kJ · mol^?1 for sodium succinate; Δ_solH_m (m = 4.53 mol · kg^?1) = 16.55 kJ · mol^?1 for sodium glutarate, and Δ_solH_m (m = 3.52 mol · kg^?1) = 15.70 kJ · mol^?1 for sodium adipate. The solubility value exhibits a prominent odd–even effect with respect to terms with odd number of sodium dicarboxylate carbon numbers showing much higher solubility. This odd–even effect may have implications for the relative abundance of these compounds in industrial applications and also in the atmospheric aerosols.     

Field emission investigation of single Fe-doped SnO2 wire

Tin oxide submicronwires doped with Fe element were prepared by the thermal evaporation method. Morphological and structural characterizations revealed wires with sub micron size and crystalline in nature. The field electron emission from the single Fe:SnO₂ wire was carried out in conventional field emission microscope. The Fowler–Nordheim plot obtained from I–V characteristics of the wire showed a linear behavior typical that of metal. The field enhancement factor estimated from the slope of the F–N plot is 7455 cm^?1, indicating that the field emission is from nanometric features of the emitter. A current density of 10 A/cm² has been obtained at an applied field of 4.845 × 10³ V/μm. The field emission current–time record at a current level of 1 μA for more than 3 h duration is promising for various field emissions based applications.     

Study of the chemical composition of particulate matter from the Rio de Janeiro metropolitan region,Brazil, by inductively coupled plasma-mass spectrometry and optical emission spectrometry

Air quality in the metropolitan region of Rio de Janeiro was evaluated by analysis of particulate matter (PM) in industrial (Santa Cruz) and rural (Seropédica) areas. Total suspended particles (TSP) and fine particulate matter (PM_2.5) collected in filters over 24 h were quantified and their chemical composition determined. TSP exceeded Brazilian guidelines (80 μg m^− 3) in Santa Cruz, while PM_2.5 levels exceeded the World Health Organization guidelines (10 μg m^− 3) in both locations. Filters were extracted with water and/or HNO₃, and the concentrations of 20 elements, mostly metals, were determined by inductively coupled plasma mass spectrometry (ICP-MS) and optical emission spectrometry (ICP OES). Water soluble inorganic anions were determined by ion chromatography (IC). To estimate the proportion of these elements extracted, a certified reference material (NIST SRM 1648a, Urban Dust) was subjected to the same extraction process. Concordant results were obtained by ICP-MS and ICP OES for most elements. Some elements could not be quantified by both techniques; the most appropriate technique was chosen in each case. The urban dust was also analyzed by the United States Environmental Protection Agency (US EPA) method, which employs a combination of hydrochloric and nitric acids for the extraction, but higher extraction efficiency was obtained when only nitric acid was employed. The US EPA method gave better results only for Sb. In the PM samples, the elements found in the highest average concentrations by ICP were Zn and Al (3–6 μg m^− 3). The anions found in the highest average concentrations were SO₄^2 − in PM_2.5 (2–4 μg m^− 3) and Cl⁻ in TSP (2–6 μg m^− 3). Principal component analysis (PCA) in combination with enrichment factors (EF) indicated industrial sources in PM_2.5. Analysis of TSP suggested both anthropogenic and natural sources. In conclusion, this work contributes data on air quality, as well as a method for the analysis of PM samples by ICP-MS.     

Emission color tuning of copolymers containing polyfluorene,benzothiadiazole, porphyrin derivatives

Copolymer containing benzothiadiazole (BT) and porphyrin (POR) derivatives as dopants (<0.3 mol%) was synthesized to polyfluorene (PF) backbone using Suzuki coupling reaction. The synthesized polymer was thermally stable and soluble in general organic solvents. UV–vis spectra of the polymer showed the similar behaviors in solution and on film. However, PL spectra was similar to PF in solution, but its peak increased around 520 and 612 nm as BT and POR, the dopants, went up in casting film. The more POR increased, the more effective Forster energy transfer was observed by POR than BT in PF. The device was made in ITO/PEDOT:PSS/polymer/BaF₂/Ba/Al structure. For PFB02P05 polymer, the luminous efficiency was 0.66 cd/A, the power efficiency 0.29 lm/W and the maximum brightness 936 cd/m². CIE coordinate (0.36, 0.34) was closer to pure white. For PFB15P20, the luminous efficiency was 1.40 cd/A, the power efficiency 0.32 lm/W, the maximum brightness 5997 cd/m². PFB15P20 demonstrated the best performance as green emission.     

Radon concentration in hot springs of the touristic city of Sarein and methods to reduce radon in water

The aim of this research was to measure the efficiency of various simple methods to decrease the concentration of radon in hot springs of the touristic city of Sarein (a touristic city in northwest Iran). With the aid of “RAD7” radon detector, concentrations in water varied from 212 Bq m^?3 to 3890 Bq m^?3. Using 250 mL vials half-filled with water samples, our research showed that when the temperature of the water increased from 17 °C to 27 °C, the radon concentration decreased from 3230 Bq m^?3 to 745 Bq m^?3. The mixing of the sample at a speed of 500 rpm for 12 min led to a radon reduction of about 70%. Aerating the water sample with 0.2 L min^?1 of ambient air resulted in a 90% decrease in radon concentration in 6 min. Strong exponential correlations (>95%) were reported, which verified that the effectiveness of these methods in reducing dissolved gas in the waters used would be high.     

Effects of the feed solution concentration on the separation degree in Donnan dialysis for binary systems of amino acids

The separations of amino acids by Donnan dialysis using an ion-exchange membrane were studied. Donnan dialytic experiments were carried out using an anion-exchange membrane, glutamic acid–phenylalanine or glutamic acid–alanine mixed solutions as the feeds, and sodium hydroxide solutions as the stripping ones. The initial concentrations of the two kinds of amino acids in the feed solutions were equal and in the range of 0.5–50 mol m⁻³. The amino acid fluxes were measured for each feed solution. Above the feed concentration of 10 mol m⁻³, the glutamic acid flux was over 100 times greater than that of the other amino acid, and it was found that the Donnan dialysis was applicable to the separation of the amino acids. On the other hand, below 10 mol m⁻³, the amino acid fluxes varied in a complicated manner with the concentration, and below 1 mol m⁻³ there was little difference between the fluxes of the two amino acids.Furthermore, after soaking the membrane in solutions having the same concentrations as the feed in the Donnan dialysis, uptake of the amino acids into the membrane was also measured. By comparing the experimental results of both the flux and uptake of the amino acids, the reason why the flux varied in a complicated manner with the concentration was discussed.