Application of acidogenic fixed-bed reactor prior to anaerobic membrane bioreactor for sustainable slaughterhouse wastewater treatment

High rate anaerobic treatment systems such as anaerobic membrane bioreactors (AMBR) are less popular for slaughterhouse wastewater due to the presence of high fat oil and suspended matters in the effluent. This affects the performance and efficiency of the treatment system. In this work, AMBR has been tried for slaughterhouse wastewater treatment. After the start up period, the reactor was operated with an average organic loading rate (OLR) of 4.37 kg TCOD m⁻³ d⁻¹ with gradual increase to an average of 13.27 kg TCOD m⁻³ d⁻¹. At stable conditions, the treatment efficiency was high with an average COD and BOD₅ reduction of 93.7 and 93.96%, respectively. However, a reduction in the AMBR performance was shown with the increase of the OLR to 16.32 kg TCOD m⁻³ d⁻¹. The removal efficiencies of SCOD and BOD₅ were drastically decreased to below 53.6 and 73.3%, respectively. The decrease of the AMBR performance was due to the accumulation of VFAs. Thus, a new integrated system composed of a FBR for the acidogenesis step followed by the AMBR for methanogenesis step was developed. At high ORL, the integrated system improved the performance of the anaerobic digestion and it successfully overcame the VFA accumulation problem in the AMBR. The anaerobic treatment led to a total removal of all tested pathogens. Thus, the microbiological quality of treated wastewater fits largely with WHO guidelines.     

Scintillation and optical properties of Pb-doped YCa4O(BO3)3 crystals

This communication reports optical properties and radiation responses of Pb²⁺ 0.5 and 1.0 mol%-doped YCa₄O(BO₃)₃ (YCOB) single crystals grown by the micro-pulling-down (μ-PD) method for neutron scintillator applications. The crystals had no impurity phases according to the results of X-ray powder diffraction. These Pb²⁺-doped crystals demonstrated blue-light luminescence at 330 nm because of Pb²⁺¹S₀-³P_0,1 transition in the photoluminescence spectra. The main emission decay component was determined to be about 250-260 ns under 260 nm excitation wavelength. When irradiated by a ²⁵²Cf source, the relative light yield of 0.5% Pb²⁺-doped crystal was about 300 ph/n that was determined using the light yield of a reference Li-glass scintillator.     

The influence of Na2CO3 content and Ni concentration on the physicochemical properties of nanometer Y-substituted nickel hydroxide

Nanometer Y-substituted nickel hydroxide was prepared by supersonic co-precipitation method with Na₂CO₃ as a buffer and NiCl₂ as a nickel source. The crystal structure, morphology, particle size distribution and electrochemical performance affected by the buffer (Na₂CO₃) content and Ni²⁺ concentration are characterized. The results indicate most of the samples are co-existence with α and β phases and the proportion of α-Ni(OH)₂ increases with the increase of Na₂CO₃, but decreases with the increase of Ni²⁺ concentration. The primary particles of samples are nanometer particles and the shape of primary particles transform from acicular to quasi-spherical with increasing Na₂CO₃ content, but converse process for the increase of Ni²⁺ concentration. The average particle size decreases initially and then increases. Complex electrodes were prepared by mixing 8 wt.% nickel hydroxides with commercial micro-size spherical nickel. The discharge capacities of samples increase initially and then decrease with increasing Na₂CO₃ content or decreasing Ni²⁺ concentration. When Na₂CO₃ content is 0.08 g and Ni²⁺ concentration is 0.2 mol/L, the sample has better electrochemical performance, such as larger discharge capacity (316.3 mAh/g at 0.2 C rate), lower charge voltage and higher discharge plateau, than those of other samples.     

Application of accelerated carbonation with a combination of Na2CO3 and CO2 in cement-based solidification/stabilization of heavy metal-bearing sediment

The efficient remediation of heavy metal-bearing sediment has been one of top priorities of ecosystem protection. Cement-based solidification/stabilization (s/s) is an option for reducing the mobility of heavy metals in the sediment and the subsequent hazard for human beings and animals. This work uses sodium carbonate as an internal carbon source of accelerated carbonation and gaseous CO₂ as an external carbon source to overcome deleterious effects of heavy metals on strength development and improve the effectiveness of s/s of heavy metal-bearing sediment. In addition to the compressive strength and porosity measurements, leaching tests followed the Chinese solid waste extraction procedure for leaching toxicity – sulfuric acid and nitric acid method (HJ/T299-2007), German leaching procedure (DIN38414-S4) and US toxicity characteristic leaching procedures (TCLP) have been conducted. The experimental results indicated that the solidified sediment by accelerated carbonation was capable of reaching all performance criteria for the disposal at a Portland cement dosage of 10 wt.% and a solid/water ratio of 1:1. The concentrations of mercury and other heavy metals in the leachates were below 0.10 mg/L and 5 mg/L, respectively, complying with Chinese regulatory level (GB5085-2007). Compared to the hydration, accelerated carbonation improved the compressive strength of the solidified sediment by more than 100% and reduced leaching concentrations of heavy metals significantly. It is considered that accelerated carbonation technology with a combination of Na₂CO₃ and CO₂ may practically apply to cement-based s/s of heavy metal-bearing sediment.     

(Eu-Nb)-codoped TiO2 nanopowders synthesized via Ar/O2 radio frequency thermal plasma oxidation processing: Phase composition and photoluminescence properties through energy transfer

(Eu³⁺-Nb⁵⁺)-codoped TiO₂ nanopowders have been prepared by Ar/O₂ radio frequency (RF) thermal plasma oxidizing liquid precursor mists, with various addition contents of dopants (molar ratio of Eu³⁺:Nb⁵⁺ = 1:1). Characterizations have been performed by the combined studies of XRD, TEM, Raman spectra, UV-vis spectroscopy, and excitation and PL spectra. The plasma-generated nanopowders mainly consist of anatase and rutile polymorphs. Doping Nb⁵⁺ cannot have appreciable influence on Eu³⁺ solubility (0.5 at.%) in the TiO₂ host lattice, but can significantly inhibit the increase of rutile weight fraction for TiO₂. 617 nm PL intensity at 350 nm indirect excitation through energy transfer is considerably weaker than that at 467 nm direct excitation, indicating that a defect state level in the TiO₂ host lattice might be lowered below the excited state of Eu³⁺ by doping Nb⁵⁺, which is conceivable from a relatively large amount of oxygen deficiencies yielded in the TiO₂ host lattice.     

Enhanced G4 emission in NaLaF4: Pr, Yb and charge transfer in NaLaF4: Ce, Yb studied by fourier transform luminescence spectroscopy

A high resolution luminescence study of NaLaF₄: 1%Pr³⁺, 5%Yb³⁺ and NaLaF₄: 1%Ce³⁺, 5%Yb³⁺ in the UV to NIR spectral range using a InGaAs detector and a fourier transform interferometer is reported. Although the Pr³⁺(³P₀ → ¹G₄), Yb³⁺(²F_7/2 → ²F_5/2) energy transfer step takes place, significant Pr³⁺¹G₄ emission around 993, 1330 and 1850 nm is observed. No experimental proof for the second energy transfer step in the down-conversion process between Pr³⁺ and Yb³⁺ can be given. In the case of NaLaF₄: Ce³⁺, Yb³⁺ it is concluded that the observed Yb³⁺ emission upon Ce³⁺ 5d excitation is the result of a charge transfer process instead of down-conversion.     

Dynamical processes of energy transfer in red emitting phosphor CaMoO4:Sm, Eu

Upon ⁴K_11/2 excitation of Sm³⁺ at 405 nm, the performance of energy transfer from Sm³⁺ to Eu³⁺ in the red emitting phosphor CaMoO₄:Eu³⁺, Sm³⁺ significantly extends its excitation region for better matching the near-UV LED. Photoluminescence spectra indicate that the energy transfer pathway concerns the relaxation from ⁴K_11/2 to ⁴G_5/2 of Sm³⁺ and subsequent transfer to ⁵D₀ of Eu³⁺ rather than ⁵D₁ of Eu³⁺. The fluorescent decay pattern of Sm³⁺⁴G_5/2 level in CaMoO₄:0.5% Sm³⁺, 2% Eu³⁺ is studied at 77 K based on the Inokuti-Hirayama formula, revealing an electronic dipole-dipole interaction between Sm³⁺ and Eu³⁺. The coefficient for the energy transfer is obtained to be 8.5 × 10⁻⁴⁰ s⁻¹ cm⁶. The fluorescence rise and decay pattern of Eu³⁺⁵D₀ level as Sm³⁺ is only excited at 77 K is well described by the dynamical processes of the energy transfer.     

Preparation and upconversion property of TeO2:Er/Yb nanoparticles

Different crystal structure of TeO₂ nanoparticles were used as the host materials to prepare the Er³⁺/Yb³⁺ ions co-doped upconversion luminescent materials. The TeO₂ nanoparticles mainly kept the original morphology and phase after having been co-doped the Er³⁺/Yb³⁺ ions. All the as-prepared TeO₂:Er³⁺/Yb³⁺ nanoparticles showed the green emissions (525 nm, 545 nm) and red emission (667 nm) under 980 nm excitation. The green emissions at 525 nm, 545 nm and red emission at 667 nm were attributed to the ²H_11/2 → ⁴I_15/2, ⁴S_3/2 → ⁴I_15/2 and ⁴F_9/2 → ⁴I_15/2 transitions of the Er³⁺ ions, respectively. For the α-TeO₂:Er³⁺/Yb³⁺ (3/10 mol%) nanoparticles, three-photon process involved in the green (²H_11/2 → ⁴I_15/2) emission, while two-photon process involved in the green (⁴S_3/2→⁴I_15/2) and red (⁴F_9/2 → ⁴I_15/2) emissions. For the β-TeO₂:Er³⁺/Yb³⁺ (3/10 mol%) nanoparticles, two-photon process involved in the green (²H_11/2 → ⁴I_15/2), green (⁴S_3/2 → ⁴I_15/2) and red (⁴F_9/2 → ⁴I_15/2) emissions. It suggested that the crystal structure of TeO₂ nanoparticles had an effect on transition processes of the Er³⁺/Yb³⁺ ions. The emission intensities of the α-TeO₂:Er³⁺/Yb³⁺ (3/10 mol%) nanoparticles and β-TeO₂:Er³⁺/Yb³⁺ (3/10 mol%) nanoparticles were much stronger than those of the (α + β)-TeO₂:Er³⁺/Yb³⁺ (3/10 mol%) nanoparticles.     

Influence of excitation wavelengths on luminescent properties of Sr3Al2O6:Eu, Dy phosphors prepared by sol-gel-combustion processing

Eu²⁺ and Dy³⁺ ion co-doped Sr₃Al₂O₆ red-emitting long afterglow phosphor was synthesized by sol-gel-combustion methods using Sr(NO₃)₂, Al(NO₃)₃·9H₂O, Eu₂O₃, Dy₂O₃, H₃BO₃ and C₆H₈O₇·H₂O as raw materials. The crystalline structure of the phosphors were characterized by X-ray diffraction, luminescent properties of phosphors were analyzed by fluorescence spectrophotometer. The effect of excitation wavelengths on the luminescent properties of Sr₃Al₂O₆:Eu²⁺, Dy³⁺ phosphors was discussed. The emission peak of Sr₃Al₂O₆:Eu²⁺, Dy³⁺ phosphor lays at 516 nm under the excitation of 360 nm, and at 612 nm under the excitation of 468 nm. The results reveal that the Sr₃Al₂O₆:Eu²⁺, Dy³⁺ phosphor will emit a yellow-green light upon UV illumination, and a bright red light upon visible light illumination. The emission mechanism was discussed according to the effect of nephelauxetic and crystal field on the 4f⁶5d¹ → 4f⁷ transition of the Eu²⁺ ions in Sr₃Al₂O₆. The afterglow time of (Sr_0.94Eu_0.03Dy_0.03)₃ Al₂O₆ phosphors lasts for over 600s after the excited source was cut off.     

White light generation in Al2O3:Ce:Tb:Mn films deposited by ultrasonic spray pyrolysis

Aluminium oxide (Al₂O₃) films doped with CeCl₃, TbCl₃ and MnCl₂ were deposited at 300 °C with the ultrasonic spray pyrolysis technique. The films were analysed using the X-ray diffraction technique and they exhibited a very broad band without any indication of crystallinity, typical of amorphous materials. Sensitization of Tb³⁺ and Mn²⁺ ions by Ce³⁺ ions gives rise to blue, green and red simultaneous emission when the film activated by such ions is excited with UV radiation. The overall efficiency of such energy transfer results to be about 85% upon excitation at 312 nm. Energy transfer from Ce³⁺ to Tb³⁺ ions through an electric dipole-quadrupole interaction mechanism appears to be more probable than the electric dipole-dipole one. A strong white light emission for the Al₂O₃:Ce³⁺(1.3 at.%):Tb³⁺(0.2 at.%):Mn²⁺(0.3 at.%) film under UV excitation is observed. The high efficiency of energy transfer from Ce³⁺ to Tb³⁺ and Mn²⁺ ions, resulting in cold white light emission (x = 0.30 and y = 0.32 chromaticity coordinates) makes the Ce³⁺, Tb³⁺ and Mn²⁺ triply doped Al₂O₃ film an interesting material for the design of efficient UV pumped phosphors for white light generation.     

The influence of the Pr 4f5d configuration on the S0 emission efficiency and lifetime in LaPO4

The photoluminescence and excitation spectra of Pr³⁺ activated LaPO₄ has been investigated in the 1.6-300 K temperature region. At room temperature, the luminescence of LaPO₄:Pr³⁺ is composed of the interconfigurational 4f¹5d¹ → 4f² emission transitions. However, in the 1.6-60 K temperature range, the emission spectrum also consists of the intraconfigurational emission transitions that emanate from the ¹S₀ state. A radiative lifetime of 145 ns is measured for the Pr³⁺¹S₀ → ¹I₆ emission transition in LaPO₄. This is one of the shortest radiative lifetime observed for this transition in a solid. The energy position of the Pr³⁺¹S₀ state in LaPO₄ is established by high-resolution emission spectrum at 46 375 ± 5 cm⁻¹. A detailed analysis of the thermal quenching of the ¹S₀ lifetime and emission intensity is presented. It is proposed that the lowest energy state of the relaxed 4f¹5d¹ configuration is situated energetically below that of the ¹S₀ state.     

Photoluminescence properties of Y2O3:Tb and YBO3:Tb green phosphors synthesized by hydrothermal method

In this work, two Tb³⁺ activated green phosphors: Y₂O₃:Tb³⁺ and YBO₃:Tb³⁺ were prepared by hydrothermal method. Photoluminescence properties of both phosphors were studied in details. Both phosphors exhibit similar luminescent characteristics symbolized by the dominant green emission at 545 nm. Concentration quenching occurs at the Tb³⁺ concentration of 1.60 atomic% and 2.57 atomic% for Y₂O₃:Tb³⁺ and YBO₃:Tb³⁺, respectively. Luminescence decay properties were characterized to better understand the mechanism of concentration quenching. Based on the calculation, the concentration quenching in both phosphors was caused by the dipole–dipole interaction between Tb³⁺ ions.     

Photoluminescence and radioluminescence of pure and Ce activated Na3Gd(PO4)2

The spectroscopic properties of Na₃Gd(PO₄)₂ and Na₃Gd(PO₄)₂:Ce³⁺ phosphors in the VUV-UV spectral range were investigated. Five excitation bands of Ce³⁺ ions at Gd³⁺ sites are observed at wavelengths of 205, 246, 260, 292, and 321 nm. Doublet Ce³⁺ 5d → 4f emission bands are observed at 341 and 365 nm with a decay constant τ_1/e around 26 ns. The X-ray excited luminescence of Na₃Gd_0.99Ce_0.01(PO₄)₂ at room temperature shows a photon yield of ∼17,000 photons/MeV of absorbed X-ray energy.     

High pressure luminescence and time resolved spectra of La2Be2O5:Pr

We present luminescence, luminescence excitation and luminescence time resolved spectra of La₂Be₂O₅:Pr³⁺ system. We used high pressure spectroscopy approaches, with high pressure applied in diamond anvil cell (DAC) and sapphire anvil cell (SAC), for detailed analysis of luminescence related to the 4f5d → 4f² and 4f² → 4f² transitions. We present effect of up-converted luminescence related to 4f5d → 4f² transition excited with 488 nm. We also discussed possibility of existence of praseodymium trapped exciton (PTE) states in La₂Be₂O₅:Pr³⁺ system. Lack of the PTE is attributed to high quantity of bulk modulus of this material.     

Synthesis and luminescent characteristic of Eu-doped (Gd,Lu)2O3 nanopowders

Eu³⁺ doped (Gd,Lu)₂O₃ nanopowders with particle sizes ranging from 20 to 70 nm were synthesized by the co-precipitant method using mixed precipitants, namely the mixture of ammonium hydroxide (NH₃⋅H₂O) and ammonium hydrogen carbonate (NH₄HCO₃). The precipitate precursor prepared by this method was believed to possess a basic carbonate composition and its thermal decomposition of the (Gd,Lu)₂O₃:Eu³⁺ powders were investigated by Thermogravimetric analysis and differential thermal analysis (TG-DTA). This preparation was followed by a calcination process at 800-1100 °C and corresponding phosphor structure were examined by X-ray diffraction (XRD) and transmission electron microscopy (TEM). Photoluminescence measurement of the (Gd,Lu)₂O₃:Eu³⁺ particles show typical red emission at the 612 nm corresponding to the ⁵D₀ → ⁷F₂ transition. We found that the optimal Eu³⁺ molar doping concentration, calcined temperature and reaction time were 7 mol%, 1000 °C, and 2 h, respectively, which is helpful to obtain the final transparent ceramics with excellent properties.     

Structure and magnetic property of CoFe2−xSmxO4 (x = 0–0.2) nanofibers prepared by sol–gel route

CoFe_2−xSm_xO₄ (x = 0–0.2) nanofibers with diameters about 100–300 nm have been prepared using the organic gel-thermal decomposition method. The composition, structure and magnetic properties of the CoFe_2−xSm_xO₄ nanofibers were investigated by X-ray diffraction, scanning electron microscopy, transmission electron microscopy, inductive coupling plasma mass analyzer and vibrating sample magnetometer. The CoFe_2−xSm_xO₄ (x = 0–0.2) nanofibers obtained at 500–700 °C are of a single spinel structure. But, at 800 °C with a relatively high Sm content of 0.15–0.2 the spinel CoFe_2−xSm_xO₄ ferrite is unstable and the second phase of perovskite SmFeO₃ occurs. The crystalline grain sizes of the CoFe_2−xSm_xO₄ nanofibers decrease with Sm contents, while increase with the calcination temperature. This grain reduction effect of the Sm³⁺ ions doping is largely owing to the lattice strain and stress induced by the substitution of Fe³⁺ ions with larger Sm³⁺ ions in the ferrite. The saturation magnetization and coercivity increase with the crystallite size in the range of 8.8–57.3 nm, while decrease with the Sm content from 0 to 0.2 owing to a smaller magnetic moment of Sm³⁺ ions. The perovskite SmFeO₃ in the composite nanofibers may contribute to a high coercivity due to the interface pinning, lattice distortion and stress in the ferrite grain boundary fixing and hindering the domain wall motion.     

Fabrication and capacitance of Ni-Fe LDHs/MnO2 layered nanocomposite via an exfoliation/reassembling process

Ni²⁺-Fe³⁺ layered double hydroxides (LDHs)/MnO₂ layered nanocomposite has been fabricated by using both layer-by-layer self-assembly method and flocculated technology, based on electrostatic interaction of positively charged Ni²⁺-Fe³⁺ LDHs nanosheets and negatively charged MnO₂ nanosheets. Ultraviolet-visible spectroscopy is used to probe the dynamic growth of the multilayer film, exhibiting progressive enhancement of optical absorption due to the assembly of Ni²⁺-Fe³⁺ LDHs nanosheets and MnO₂ nanosheets. The assembled Ni²⁺-Fe³⁺ LDHs/MnO₂ nanocomposite has been characterized by XRD, SEM and TEM. The electrochemical property of the synthesized Ni²⁺-Fe³⁺ LDHs/MnO₂ layered nanocomposite has been studied using cyclic voltammetry in a mild aqueous electrolyte. The Ni²⁺-Fe³⁺ LDHs/MnO₂ nanocomposite exhibits a relative good capacitive behavior in a neutral electrolyte system, and its initial capacitance value is 104 F g⁻¹.     

Low temperature luminescence of KMgF3:Eu crystal

Paper presents luminescence spectra and time resolved spectra of KMgF₃:Eu²⁺ system obtained at different temperatures and pressures, under excitation with 325 nm. At temperatures between 200 K and 292 K the spectra consist of sharp line peaked at 27,830 cm⁻¹ related to ⁶P_7/2 → ⁸S_7/2 transition in Eu²⁺ accompanied by the phonon sideband. Under pressure the red spectral shift with the rate equal to −0.6 cm⁻¹/kbar is observed. Luminescence decay is single-exponential with the lifetime equal to 5.2 ms independent of pressure and temperature. The emission spectra obtained at temperatures lower than 125 K consist of 5 sharp lines peaked at 27,590 cm⁻¹, and 27,670 cm⁻¹, 27,722 cm⁻¹, 27,766 cm⁻¹ and 27,809 cm⁻¹, that relative intensity depends on temperature. Pressure shift of these lines was found to be equal to −0.6 cm⁻¹/kbar; the same as ⁶P_7/2 → ⁸S_7/2 transition in Eu²⁺, whereas their lifetime is shorter and is equal to 0.7 ms at 100 K. These new lines disappear at temperature greater than 200 K. We tentatively related them to the luminescence of Eu²⁺-F center (fluorine vacancy with electron) complex.     

Synthesis and blue to near-infrared quantum cutting of Pr/Yb co-doped Li2TeO4 phosphors

Near-infrared (NIR) quantum cutting luminescent materials Li₂TeO₄ doped with Pr³⁺ and Yb³⁺ were synthesized by solid-state reaction method. The dependence of Yb³⁺ doping concentration on the visible- and NIR-emissions, decay lifetime, and quantum efficiencies of the phosphors are investigated. Quantum cutting down-conversion involving 647 nm red emission and 960-1050 nm broadband near-infrared emission for each 487 nm blue photon absorbed is realized successfully in the resulting phosphors, of which the process of near-infrared quantum cutting could be expressed as ³P₀(Pr³⁺) → ²F_5/2(Yb³⁺) + ²F_5/2(Yb³⁺). The maximum quantum cutting efficiency approaches up to 166.4% in Li₂TeO₄: 0.3 mol%Pr³⁺, 1.8 mol%Yb³⁺ sample corresponding to the 66.4% value of energy transfer efficiency.     

M2Si5N8:Eu-based (M = Ca, Sr) red-emitting phosphors fabricated by nitrate reduction process

M₂Si₅N₈:Eu²⁺-based (M = Ca, Sr) red-emitting phosphors were fabricated at relatively low temperature (1200 °C) and atmospheric pressure using a simple solid-state reaction process. Several processing parameters were systematically investigated to optimize the phosphors structural characterization and photoluminescence performance, including the amount of europium and the properties of the precursor and activated materials. The as-prepared M₂Si₅N₈:Eu²⁺-based (M = Ca, Sr) phosphors were orange in color and emitted intensively in the red region of 580-670 nm under 465 nm excitation. This simple fabrication technique can be readily used for the optimization of phosphor microstructures and high-performance red-emitting phosphors since it eliminates many air-sensitive precursors.