Acute toxicities of six manufactured nanomaterial suspensions to Daphnia magna

The rapid growth of nanotechnology is stimulating research on the potential environmental impacts of manufactured nanomaterials (MNMs). This paper summarizes a comprehensive study on the 48-h acute toxicity of water suspensions of six MNMs (i.e., ZnO, TiO₂, Al₂O₃, C₆₀, SWCNTs, and MWCNTs) to Daphnia magna, using immobilization and mortality as toxicological endpoints. The results show that the acute toxicities of all MNMs tested are dose dependent. The EC₅₀ values for immobilization ranged from 0.622 mg/L (ZnO NPs) to 114.357 mg/L (Al₂O₃ NPs), while the LC₅₀ values for mortality ranged from 1.511 mg/L (ZnO NPs) to 162.392 mg/L (Al₂O₃ NPs). In these tests, TiO₂, Al₂O₃, and carbon-based nanomaterials were more toxic than their bulk counterparts. Moreover, D. magna were found to ingest nanomaterials from the test solutions through feeding behaviors, which indicates that the potential ecotoxicities and environmental health effects of these MNMs cannot be neglected.     

Degradation behavior and products of malathion and chlorpyrifos spiked in apple juice by ultrasonic treatment

Apple juice (13 °Brix) spiked with malathion and chlorpyrifos (2–3 mg l⁻¹ of each compound) was treated under different ultrasonic irradiations. Results showed that ultrasonic treatment was effective for the degradation of malathion and chlorpyrifos in apple juice, and the output power and treatment time significantly influenced the degradation of both pesticides (p < 0.05). The maximum degradations were achieved for malathion (41.7%) and chlorpyrifos (82.0%) after the ultrasonic treatment at 500 W for 120 min. The degradation kinetics of both pesticides were fitted to the first-order kinetics model well (R²  0.90). The kinetics parameters indicated that chlorpyrifos was much more labile to ultrasonic treatment than malathion. Furthermore, malaoxon and chlorpyrifos oxon were identified as the degradation products of malathion and chlorpyrifos by gas chromatography–mass spectrometry (GC–MS), respectively. The oxidation pathway through the hydroxyl radical attack on the PS bond of pesticide molecules was proposed.     

Eley–Rideal reaction dynamics between O atoms on β-cristobalite (1 0 0) surface: A new interpolated potential energy surface and classical trajectory study

We present a theoretical study of the collisions of atomic oxygen with O-precovered β-cristobalite (1 0 0) surface. We have constructed a multidimensional potential energy surface for the O₂/β-cristobalite (1 0 0) system based mainly on a dense grid of density functional theory points by using the interpolation corrugation-reducing procedure. Classical trajectories have been computed for quasithermal (100–1500 K) and state-specific (e.g., collision energies between 0.01 and 4 eV) conditions of reactants for different O incident angles (θ_v). Atomic sticking and O_2(adsorbed) formation are the main processes, although atomic reflection and Eley–Rideal (ER) reaction (i.e., O₂ gas) are also significant, depending their reaction probabilities on the O incident angle. ER reaction is enhanced by temperature increase, with an activation energy derived from the atomic recombination coefficient (γ_O(θ_v = 0°, T)) equal to 0.24 ± 0.02 eV within the 500–1500 K range, in close agreement with experimental data. Calculated γ_O(θ_v = 0°, T) values compare quite well with available experimental γ_O(T) although a more accurate calculation is proposed. Chemical energy accommodation coefficient β_O(T) is also discussed as a function of ER and other competitive contributions.     

Catalytic activation of hydrogen peroxide by Cr2AlC MAX phase under ultrasound waves for a treatment of water contaminated with organic pollutants

This study aims to investigate the sonocatalytic activation of hydrogen peroxide (H₂O₂) using Cr₂AlC MAX phase prepared by the reactive sintering process. The hexagonal structure of the crystalline MAX phase was confirmed by X-ray diffraction. Moreover, the compacted layered structure of the MAX phase was observed via scanning electron microscopy and high-resolution transmission electron microscopy. Under the desired operating conditions, Cr₂AlC MAX phase (0.75 g/L) showed suitable potential to activate H₂O₂ (1 mmol/L) under sonication, thereby allowing a considerable removal efficiency for various organic pollutants, including dimethyl phthalate (69.1%), rifampin (94.5%), hydroxychloroquine (100%), and acid blue 7 (91.5%) with initial concentration of 15 mg/L within 120 min of treatment. Kinetic analysis proved that the degradation reaction followed pseudo-first-order kinetics. Scavenging tests demonstrated that hydroxyl radicals and singlet oxygen were effective species during degradation. Furthermore, a probable mechanism for dimethyl phthalate degradation was suggested according to gas chromatography-mass spectroscopy and nuclear magnetic resonance analyses. The obtained results confirmed the capability of the triple Cr₂AlC/H₂O₂/US process as a promising method for treating contaminated water.     

Exploring the mechanism of NO–C2H4 reactions on the surface of stepped Pt(3 3 2)

Fourier transform infra red reflection–absorption spectroscopy (FTIR-RAS), thermal desorption spectroscopy (TDS), and auger electron spectroscopy (AES), were employed to explore the mechanism of NO reduction in the presence of C₂H₄ on the surface of stepped Pt(3 3 2). Both NO–Pt and C₂H₄–Pt interactions are enhanced when NO and C₂H₄ are co-adsorbed on Pt(3 3 2). As a result, C₂H₄ is dissociated at surface temperatures as low as 150 K, and the N–O stretch band is weakened. The presence of post-exposed C₂H₄ leads NO desorption from steps to decrease significantly, but the same effect on NO desorption from terraces becomes appreciable only at higher post-exposures of C₂H₄, e.g., 0.6 L and 1.2 L, and proceeds to a much slighter extent. Auger spectra indicate that as a result of the reaction with O from NO dissociation, the amount of surface C species is greatly reduced when NO is post-exposed to a C₂H₄ adlayer. It is concluded that reduction of NO in the presence of C₂H₄ proceeds very effectively on the surface of the Pt(3 3 2), through a mechanism of NO dissociation and subsequent O removal. Following this mechanism, the significant dissociation of adsorbed NO molecules on steps at surface temperatures below 400 K, and subsequent rapid reaction between the resultant O and C-related species, accounts for the considerable amount of N₂ desorption at temperatures below 400 K.     

Sonochemical advanced oxidation process for the degradation of furosemide in water: Effects of sonication’s conditions and scavengers

The intensive consumption of pharmaceuticals and drugs in the last decades has led to their increased concentrations in wastewaters from industrial sources. The present paper deals, for the first time, with the sonochemical degradation and mineralization of furosemide (FSM) in water. FSM is a potent loop diuretic used to treat fluid build-up due to heart failure, liver scarring, or kidney disease. The influence of several operating parameters such as acoustic intensity, ultrasonic frequency, initial FSM concentration, solution’s pH, nature of the dissolved gas (Ar, air and N₂) and radical scavengers (2-propanol and tert-butanol) on the oxidation of FSM was assessed. The obtained results showed that the degradation rate of the drug increased significantly with the increase of the acoustic intensity in the range of 0.83 to 4.3 W cm⁻² and decreased with the augmentation of the frequency in the range of 585–1140 kHz. It was also found that the initial rate of the sonolytic degradation of FSM increased with the increase of its initial concentration (2, 5, 10, 15 and 20 mg/L). The most significant degradation was achieved in acidic conditions at pH 2, while in terms of saturating gas, the rate of FSM degradation decreased in the order of Ar > air > N₂. The FSM degradation experiments with radical scavengers showed that the diuretic molecule degraded mainly at the interfacial region of the bubble by hydroxyl radical attack. Additionally, in terms of acoustic conditions, the sono-degradation of 30.24 µmol L^-1 of FSM solution demonstrate an optimal performance at 585 kHz and 4.3 W/cm², the results indicated that even if the ultrasonic action eliminated the total concentration of FSM within 60 min, a low degree of mineralization was obtained due to the by-products formed during the sono-oxidation process. The ultrasonic process transforms FSM into biodegradable and environmentally friendly organic by-products that could be treated in a subsequent biological treatment. Besides, the efficiency of the sonolytic degradation of FSM in real environmental matrices such as natural mineral water and seawater was demonstrated. Consequently, the sonochemical advanced oxidation process represent a very interesting technique for the treatment of water contaminated with FSM.     

Effect of In-content on the optical properties of a-Se films

The optical transmission spectra of amorphous (a-) Se_1−xIn_x films, with x = 0.0, 0.05, 0.18 and 0.35, that prepared by thermal evaporation from their corresponding bulk ingots, are recorded over the spectral region of 500–2500 nm. A simple straight forward procedure proposed by Swanepeol has been applied to determine the two components of the complex refractive index (). The dispersion of is examined in terms of the Wemple and DiDomenico model and is discussed in terms of In-content. An estimation of various optical parameters such as, the optical energy gap (E_g = 1.96–1.33 eV), single oscillator energy (E_o = 3.95–3.16 eV), oscillator dispersion energy (E_d = 22.6–31.6 eV), lattice oscillator strength (E_l = 0.38–0.61 eV) and wavelength at zero material dispersion (λ_c = 2.0569–2.0879 μm) have been given and discussed in relation to the coordination number, hydrostatic density and formed chemical bonds that are introduced in the network of a-Se with the introduction of up to 35 at.% In.     

Nano-sized polystyrene prepared using bifunctional vinyl urethane macromonomer in emulsion polymerization

The linear-type bifunctional vinyl urethane macromonomer (L-VUM: Mw; 40,453) was synthesized and applied to emulsion polymerization of styrene in DDI water. The structure of L-VUM was confirmed using ¹H NMR and FT-IR. The macromonomer served as a good nonionic surfactant resulted in stable polystyrene nanospheres. Polystyrene particles were prepared with various concentrations of macromonomoer (1–30 wt% refer to monomer), initiator (0.5–2 wt%) and different temperatures (60–80 °C). Monodisperse PS nanospheres with 30 wt% L-VUM have a number-average diameter (D_n) of 200 nm with good uniformity (1.011) and molecular weight (M_w) 231,180 g/mol. The particle morphology, molecular weight and distribution, uniformity and the stability of the nanospheres upon the reaction temperature and concentration of L-VUM will be thoroughly discussed.     

Ultrasonic and DFT study of intermolecular association through hydrogen bonding in aqueous solutions of glycerol

The experimental measurements of density, viscosity and ultrasonic velocity of aqueous glycerol solutions were carried out as functions of concentration (0.1 ≤ m [mol kg^− 1] ≤ 1.0) and temperature (303.15 ≤ T [K] ≤323.15). The isentropic compressibility (β_s), acoustic impedance (Z), hydration number (H_n), intermolecular free length (L_f), classical sound absorption (α/f²)_class and shear relaxation time (τ) were calculated by using the measured data. These parameters have been interpreted in terms of solute–solvent interactions. The quantum chemical calculations were performed to study the hydrogen bonding in interacting complex formed between glycerol and water molecules. Computations have been done by using Density Functional Theory (DFT) method at B3LYP/6–31 + g(d) level of theory to study the equilibrium structure of glycerol, glycerol–water interacting complex and vibrational frequencies. The solution phase study was carried out using Onsager's reaction field model in water solvent. The computed vibrational frequencies are in good agreement with the main features of the experimental spectrum when four water molecules are considered explicitly with glycerol. The interaction energy (E_total), hydrogen bond lengths and dipole moment (µ_m) of the interacting complex are also presented and discussed with in the light of solute–solvent interactions.     

Preparation of α-Fe2O3 nanoparticles by high-energy ball milling

α-Fe₂O₃ nanoparticles were prepared by high-energy ball milling using α-FeOOH as raw materials. The prepared samples were characterized by transmission electron microscopy (TEM), Mössbauer spectroscopy, X-ray diffraction (XRD) and differential thermal analysis–thermogravimetric analysis (DTA–TGA). The results showed that after 90 h milling α-Fe₂O₃ nanoparticles were obtained, and the particle size is about 20 nm. The mechanism of reaction during milling is supposed that the initial α-FeOOH powder turned smaller and smaller by the high-speed collision during ball milling, later these particles turned to be superparamagnetic, at last these superparamagnetic α-FeOOH particles were dehydrated and transformed into α-Fe₂O₃.     

Luminescence of Strontianite (SrCO3) from Strontian (Scotland, UK)

An historic Strontianite-type specimen from Strontian, Scotland, UK, was characterized to broaden our knowledge on luminescence properties of common carbonates. These fibrous aggregates are Strontianite (Sr_xCa_1−xCO₃) with circa 6% of CaO, interfacial water, hydrosilicate anions and substitutional divalent cations, e.g., Ca²⁺, Mn²⁺, Fe²⁺ in structural Sr²⁺ positions. The specimen was analyzed by X-ray Fluorescence Spectrometry (XRF), Environmental Scanning Electron Microscopy coupled with an Energy Dispersive X-ray Spectroscopy (ESEM-EDS) probe, Spatially-resolved Cathodoluminescence under the Scanning Electron Microscope (SEM-CL), Differential-Thermal Analyses (DTA), Thermogravimetry (TG), Thermoluminescence (TL), Radioluminescence (RL) and High Resolution Spectra Thermoluminescence (3DTL), to gain an overview of the spectral emissions, the defect linkages were modified by heating from room temperature (RT) up to 500 °C. Substitutional transition elements are probably responsible for the spectral emission bands from 500 nm to 800 nm and hydrous molecules from 300 nm to 400 nm. DTA–TG analyses performed on little chips, to preserve the fiber interfaces coherence, exhibit minor endothermic peaks attributed to outflow of water groups in fiber interfaces. Both, CL and RL curves show common spectral positions but UV–blue and red emission intensities are counterbalanced since electron irradiation reduces the UV–blue emissions while X-irradiation increases them. The TL curves show a top thermal limit at 300 °C for the 300–400 nm TL emissions which become irreversibly destroyed, whereas the longer wavelength region emits at higher temperature. The non-reversible changes observed in the 320 nm and 360 nm bands during the spectra 3DTL emission could be linked with non-bridging oxygen defects, protons and hydroxyl groups and the red emissions to the ⁴G (⁴T_1g)–⁶S Mn²⁺ ion transition. Following assignations and similar spectral CL patterns of Russian Strontianite samples, the emission-defect assignments: Dy³⁺ 480 nm; Tb³⁺ 540 nm; Dy³⁺ 580 nm and Sm³⁺ 640 nm cannot be disregarded.     

Consolidation of hydrogenation–disproportionation–desorption–recombination processed Nd–Fe–B magnets by spark plasma sintering

We have successfully consolidated hydrogenation–disproportionation–desorption–recombination (HDDR) processed Nd–Fe–Co–Zr–B–Ga powder by spark plasma sintering (SPS). The field compacted samples were sintered at different temperatures (T_S) from 550 to 600 °C with compressive pressure of 80 MPa for 20 min. Microstructural investigations by transmission electron microscopy indicated that the sintered specimen exhibits Nd₂Fe₁₄B grains of ~300 nm with Nd-rich grain boundary phase. The optimum magnetic properties of B_r: 1.22 T, H_c: 928 kA/m, _BH_c: 600 kA/m, (BH)_max: 210 kJ/m³ were obtained in the sample sintered at 550 °C. The strategy for further improving the coercivity and remanence is discussed based on the microstructure-property relationships.     

CW-Cavity Ring Down Spectroscopy of O3. Part 3: Analysis of the 6490–6900 cm region and overview comparison with the O3 main isotopologue

This paper is devoted to the third part of the analysis of the very weak absorption spectrum of the ¹⁸O₃ isotopologue of ozone recorded by CW-Cavity Ring Down Spectroscopy between 5930 and 6900 cm⁻¹. In the two first parts [A. Campargue, A. Liu, S. Kassi, D. Romanini, M.-R. De Backer-Barilly, A. Barbe, E. Starikova, S.A. Tashkun, Vl.G. Tyuterev, J. Mol. Spectrosc. (2009), doi: 10.1016/j.jms.2009.02.012 and E. Starikova, M.-R. De Backer-Barilly, A. Barbe, Vl.G. Tyuterev, A. Campargue, A.W.Liu, S. Kassi, J. Mol. Spectrosc. (2009) doi: 10.1016/j.jms.2009.03.013], the effective operators approach was used to model the spectrum in the 6200–6400 and 5930–6080 cm⁻¹ regions, respectively. The analysis of the whole investigated region is completed by the present investigation of the 6490–6900 cm⁻¹ upper range. Three sets of interacting states have been treated separately. The first one falls in the 6490–6700 cm⁻¹ region, where 1555 rovibrational transitions were assigned to three A-type bands: 3ν₂ + 5ν₃, 5ν₁ + ν₂ + ν₃ and 2ν₁ + 3ν₂ + 3ν₃ and one B-type band: ν₁ + 3ν₂ + 4ν₃. The corresponding line positions were reproduced with an rms deviation of 18.4 × 10⁻³ cm⁻¹ by using an effective Hamiltonian (EH) model involving eight vibrational states coupled by resonance interactions. In the highest spectral region – 6700–6900 cm⁻¹ – 389 and 183 transitions have been assigned to the ν₁ + 2ν₂ + 5ν₃ and 4ν₁ + 3ν₂ + ν₃ A-type bands, respectively. These very weak bands correspond to the most excited upper vibrational states observed so far in ozone. The line positions of the ν₁ + 2ν₂ + 5ν₃ band were reproduced with an rms deviation of 7.3 × 10⁻³ cm⁻¹ by using an EH involving the {(054), (026), (125)} interacting states. The coupling of the (431) upper state with the (502) dark state was needed to account for the observed line positions of the 4ν₁ + 3ν₂ + ν₃ band (rms = 5.7 × 10⁻³ cm⁻¹).The dipole transition moment parameters were determined for the different observed bands. The obtained set of parameters and the experimentally determined energy levels were used to generate a complete line list provided as Supplementary Materials.The results of the analyses of the whole 5930–6900 cm⁻¹ spectral region were gathered and used for a comparison of the band centres to their calculated values. The agreement achieved for both ¹⁸O₃ and ¹⁶O₃ (average difference on the order of 1 cm⁻¹) indicates that the used potential energy surface provides accurate predictions up to a vibrational excitation approaching 80% of the dissociation energy. The comparison of the ¹⁸O₃ and ¹⁶O₃ band intensities is also discussed, opening a field of questions concerning the variation of the dipole moments and resonance intensity borrowing by isotopic substitution.     

Sonochemical degradation of trimethoprim in water matrices: Effect of operating conditions,identification of transformation products and toxicity assessment

The sonochemical degradation of trimethoprim (TMP), a widely used antibiotic, in various water matrices was investigated. The effect of several parameters, such as initial TMP concentration (0.5–3 mg/L), actual power density (20–60 W/L), initial solution pH (3–10), inorganic ions, humic acid and water matrix on degradation kinetics was examined. The pseudo-first order degradation rate of TMP was found to increase with increasing power density and decreasing pH, water complexity (ultrapure water > bottled water > secondary wastewater) and initial TMP concentration.TMP degradation is accompanied by the formation of several transformation products (TPs) as evidenced by LC-QToF-MS analysis. Nine such TPs were successfully identified and their time-trend profiles during degradation were followed. An in silico toxicity evaluation was performed showing that several TPs could potentially be more toxic than the parent compound towards Daphnia magna, Pimephales promelas and Pseudokirchneriella subcapitata.     

Magnetic properties of FexCo1−x/CoyFe1−yFe2O4 composite under hydrothermal condition

The metal–ferrite composites Fe_xCo_1−x/Co_yFe_1−yFe₂O₄ are synthesized by using disproportion of Fe (II) and reduction of Co (II) by Fe⁰ under hydrothermal condition. The size of the particles of the composites decreases as the [KOH] decreasing. The composites are measured by TEM and it can be deduced that when [KOH] = 0.1, the size of the alloy body-centered cubic (BCC) in composites is 20 ± 7 nm, the size of the Cobalt ferrite (spinel) is 170 ± 50 nm. The maximal value of the saturation magnetization (Ms) of the composite is about 100.14 emu/g, which is synthesized under Co (II)/Fe (II) = 0.05, [KOH] = 1 N, T = 150 °C and t = 3 h. The value of Hc of the composite synthesized under Co (II)/Fe (II) = 0.5, t = 3 h, T = 150 °C and [KOH] = 10.2 mol/L is about 2878.19 Oe. The Fe–Co alloy is synthesized through a reduction reaction of the composites in a flowing gaseous mixture. There is a maximal value (302.9 emu/g) of the Ms for the alloys generated at 1000 °C, which is the Co_0.412Fe_0.588 alloy.     

Ion–ion interactions of LiPF6 and LiBF4 in propylene carbonate solutions

Self-diffusion coefficients of Li⁺ D_Li⁺, PF₆⁻ D_PF6⁻ and solvent propylene carbonate (PC) D_PC in LiPF₆−PC solutions were determined at 298 K by the pulse gradient spin echo (PGSE) NMR technique over the salt concentration range of 0.1–3.0 M (M = mol dm^– 3). The order of the diffusion coefficients was found to be D_Li⁺ < D_PF6⁻ < D_PC over the concentration range examined, and they were monotonically decreased with increasing the salt concentration. Haven ratio Λ/Λ_NMR, where Λ and Λ_NMR represent the ionic conductivity measured electrochemically and that estimated via the Nernst-Einstein equation using the diffusion coefficient, respectively, was evaluated as the measure of the ion–ion interaction in the LiPF₆–PC solutions. Though Λ/Λ_NMR values for LiPF₆-solutions decrease with increasing the salt concentration, they were greater than those for LiBF₄–PC solutions over the whole concentration range examined, which indicates that the ion pair formation ability of PF₆^– ion is weaker than that of the BF₄^– ion. The smaller value of the ionic conductivity for the highly concentrated LiPF₆–PC solution (above 2.0 M) than that of the LiBF₄-solutions can be attributed to the more rapidly increased viscosity relative to the LiBF₄-solution. Classic molecular dynamics (MD) simulations for the respective LiPF₆ and LiBF₄-solution of 0.5 and 1.0 M were also carried out based on the effective pair potentials. Diffusion coefficients, ionic conductivity and Haven ratio for these solutions were calculated from MD trajectories, and they qualitatively agree with those evaluated by experiments. Pair correlation functions g_LiO(r) (for Li⁺–O (PC) pair) and g_LiPF6(r) (for Li⁺–PF₆^– pair) or g_LiBF4(r) (for Li⁺–BF₄^– pair) revealed that the lithium ion weakly forms the contact ion pairs with PF₆^–, whilst strongly with BF₄^–, which supports the present experimental results. Moreover, the simulation results show that both anions in the contact ion pairs predominantly take the monodentate form, which is in contrast to the multidentate coordination predicted by ab initio calculation in gas phase.     

Tandem diazonium salt electroreduction and click chemistry as a novel, efficient route for grafting macromolecules to gold surface

Bis-alkynylated oligoethyleneglycol (OEG) and a monopropargyl-functionalized perfluorinated ethylene glycol (FEG) were clicked to azide-functionalized gold surface (Au–N₃) at room temperature via the well known 1,3 cycloaddition click chemical reaction. The Au–N₃ substrate was obtained by nucleophilic attack of NaN₃ on gold substrates modified by the electrochemical reduction of the , ⁺N₂–C₆H₄–CH₂Br diazonium salt. This electrochemical process yields aryl layer-modified gold of the type Au–C₆H₄–CH₂Br (hereafter Au–Br). The untreated and modified gold plates were examined by XPS, PMIRRAS and contact angle measurements. XPS brought evidence for electrografting aryl layers by the detection of Br3d; azide functionalization by the increase of the N/Br atomic ratio; and click reaction of OEG with Au–N₃ by the increase of O/N ratio. In addition, the perfluorinated plate (Au-FEG) exhibited F1s and characteristic C1s peaks from -(CF₂)₇- chain and terminal CF₃. Infra red spectroscopy (PMIRRAS) evidenced (i) grafting N₃ to Au–Br; (ii) characteristic stretching bands, from ethylene glycol units, C–O–C (1100–1300 cm⁻¹); CF₂ (1000–1100 cm⁻¹) and CF₃ (1100–1350 cm⁻¹) from FEG grafts; and (iii) suppression of alkynyl bands from OEG and FEG after surface click chemistry. More importantly, PMIRRAS results support an important bridging of the bispropargyl oligoethylene glycol at the gold surface. Water drop contact angles were found to be 48.7° and 83.0° for Au-OEG and Au-FEG, respectively, therefore highlighting the control over the hydrophilic/hydrophobic character of the clicked substrate.This work shows that clicking macromolecules to grafted, diazonium salt-derived aryl layers is a novel, simple and valuable approach for designing robust, functional surface organic coatings.     

Doppler-limited dye laser excitation spectroscopy of DCF

The dye laser excitation spectrum of the vibronic transition of DCF was observed between 17 200 and 17 400 cm⁻¹ with the Doppler-limited resolution. DCF was produced by the reaction of microwave-discharged CF₄ with CD₃F. The observed spectra, which were found to be nearly free of perturbations, were assigned to 858 transitions of the K′_a − K″_a = 4−5, 3−4, 2−3, 1−2, 0−1, 1−0, 2−1, 3−2, 3−3, 2−2, 1−1, 0−0, 2−0, and 0−2 subbands, and were analyzed to determine the rotational constants and centrifugal distortion constants for both the and à states. The rotational constants of DCF thus determined were combined with those of HCF to calculate the structural parameters for this molecule: r(C---H) = 1.138 Å, r(C---F) = 1.305 Å, and HCF = 104.1° for the ground state, and r(C---H) = 1.063 Å, r(C---F) = 1.308 Å, and HCF = 123.8° for the excited à state.     

Analysis of ultrasonic pre-treatment for the ozonation of humic acids

This paper presents an intensification study of an ozonation process through an ultrasonic pre-treatment for the elimination of humic substances in water and thus, improve the quality of water treatment systems for human consumption. Humic acids were used as representative of natural organic matter in real waters which present low biodegradability and a high potential for trihalomethane formation. Ultrasonic frequency (98 kHz, 300 kHz and 1 MHz), power (10–40 W) and sonicated volume (150–400 mL) was varied to assess the efficiency of the ultrasonic pre-treatment in the subsequent ozonation process. A direct link between hydroxyl radical (HO) formation and fluorescence reduction was observed during sonication pre-treatment, peaking at 300 kHz and maximum power density. Ultrasound, however, did not reduce total organic carbon (TOC). Injected ozone (O₃) dose and reaction time were also evaluated during the ozonation treatment. With 300 kHz and 40 W ultrasonic pre-treatment and the subsequent ozonation step (7.4 mg O₃/L_gas), TOC was reduced from 21 mg/L to 13.5 mg/L (36% reduction). HO attack seems to be the main degradation mechanism during ozonation. A strong reduction in colour (85%) and SUVA₂₅₄ (70%) was also measured. Moreover, changes in the chemical structure of the macromolecule were observed that led to the formation of oxidation by-products of lower molecular weight.     

Defect chemical and statistical thermodynamic studies on oxygen nonstoichiometric Nd2 − xSrxNiO4 + δ

In order to elucidate how oxygen content changes in Nd_2 − xSr_xNiO_4 + δ (x = 0, 0.2, 0.4), defect chemical and statistical thermodynamic analyses were carried out. The relationship among δ, P(O₂), and T were analyzed by a defect equilibrium model. Since Nd_2 − xSr_xNiO_4 + δ shows metal like band conduction at high temperatures, chemical potential of hole is expressed by the integration of the Fermi-Dirac distribution function and the density of state. The nonstoichiometric variation of oxygen content in Nd_2 − xSr_xNiO_4 + δ can be explained by the defect equilibrium model with a regular solution approximation. Partial molar entropy and partial molar enthalpy of oxygen are calculated from the nonstoichiometric data and Gibbs–Helmholtz equation. The relationship among defect structure, defect equilibrium, and thermodynamic quantities is elucidated by the statistical thermodynamic model. Thermodynamic quantities are calculated by the statistical thermodynamic model with the results of defect chemical analysis and compared with those obtained from experimental results. Thermodynamic quantities calculated by the statistical thermodynamic model can explain rough tendency of those obtained from the δ–T–P(O₂) relationship.