Radon exhalation and gamma radioactivity levels in soil and radiation hazard assessment in the surrounding area of National Thermal Power Corporation,Dadri (U.P.), India

In the present study soil samples were collected from the region around a National Thermal Power Corporation (NTPC) at Dadri (U.P.), India. Radon activity and radon exhalation rates were measured by using “sealed can technique” using LR 115-type II nuclear track detectors. Radon activities are found to vary from 177.5 ± 23.1 to 583.4 ± 4.9 Bq m⁻³ with an average value of 330.5 ± 30.4 Bq m⁻³. Surface exhalation rates in these samples vary from 63.9 ± 8.3 to 210.2 ± 15.1 mBq m⁻² h⁻¹ with an average value of 119.1 ± 11.1 mBq m⁻² h⁻¹, whereas mass exhalation rates vary from 2.5 ± 0.3 to 8.1 ± 0.6 mBq kg⁻¹ h⁻¹ with an average of 4.6 ± 0.4 mBq kg⁻¹ h⁻¹.Activity concentrations of naturally occurring radionuclides (²²⁶Ra, ²³²Th and ⁴⁰K) were also measured in these soil samples using high resolution γ–ray spectroscopic system. Activity concentrations of ²²⁶Ra, ²³²Th, and ⁴⁰K vary from 32.2 ± 6.0 to120.9 ± 4.5 Bq kg⁻¹, 19.3 ± 0.9 to 44.6 ± 1.5 Bq kg⁻¹ and 195.4 ± 2.8 to 505.4 ± 6.3 Bq kg⁻¹ with overall mean values of 70.0 ± 8.9 Bq kg⁻¹, 34.8 ± 1.2 Bq kg⁻¹ and 436.1 ± 5.6 Bq kg⁻¹ respectively. From the activity concentrations of ²²⁶Ra, ²³²Th and ⁴⁰K, radium equivalent activity (Ra_eq) and the external hazard index (H_ex) were calculated and found to vary from 73.4 to 214.7 Bq kg⁻¹ and from 0.2 to 0.6 respectively.     

EDXRF for elemental determination of nanoparticle-related agricultural samples

The number of studies dealing with nanoparticles (NPs) and plants has increased. They subsidize the advances of agriculture in the 21st century; however, so far, beneficial as well as detrimental results have been reported. In this context, analytical tools for monitoring macronutrients and micronutrients in plants exposed to NPs, with adequate performance and low cost, are required. This work assesses the use of energy-dispersive X-ray fluorescence (EDXRF) spectrometry for elemental content evaluation in NP-containing agricultural samples. For Phaseolus vulgaris (common bean) seedlings treated with ZnO NP, CuO NP, and Fe₃O₄ NP, the limits of detection (LODs) were 0.4 mg kg⁻¹ for Zn and Cu and 0.6 mg kg⁻¹ for Fe after dry-ashing digestion, thus being suitable for NP oxide monitoring in seed priming. For submicron suspension fertilizers, Mn, Cu, and Zn were quantified as thin films after sample dilution. The LODs for Mn, Cu, and Zn were 0.09, 0.1, and 0.08 mg L⁻¹, respectively. Finally, for P. vulgaris plants exposed to 300-nm ZnO NP, we monitored P, S, K, Ca, and Zn directly in powdered leaves, whose LODs ranged from 1.3 to 27 mg kg⁻¹. No critical spectral interference was observed, and notable repeatability and suitable trueness were found in the cases of studies. EDXRF revealed itself a simple, fast, and reliable alternative to evaluate the elemental content in suspensions or the uptake of NP by plants.     

Morphologically controlled preparation of CuO nanostructures under ultrasound irradiation and their evaluation as pseudocapacitor materials

Various morphologies of copper oxide (CuO) nanostructures have been synthesized by controlling the reaction parameters in a sonochemical assisted method without using any templates or surfactants. The effect of reaction parameters including molar ratio of the reactants, reaction temperature, ultrasound exposure time, and annealing temperature on the composition and morphology of the product(s) has been investigated. The prepared samples have been characterized by X-ray diffraction (XRD), field emission scanning electron microscopy (FESEM), energy dispersive X-ray (EDAX), and thermogravimetric analysis (TGA). It has been found that Cu₂(OH)₃NO₃ nanoplatelets are achieved in mild conditions which can be then converted to various morphologies of CuO nanostructures by either using high concentrations of OH⁻ (formation of nanorods), prolonging sonication irradiation (nanoparticles), or thermal treatment (nanospheres). Application of the prepared CuO nanostructures was evaluated as supercapacitive material in 1 M Na₂SO₄ solution using cyclic voltammetry (CV) in different potential scan rates ranging from 5 to 100 mV s⁻¹. The specific capacitance has been calculated using CV curves. It has been found that the pseudocapacitor performance of CuO can be tuned via employing morphologically controlled samples. Accordingly, the prolonged sonicated sample (nanoparticles) showed the high specific capacitance of 158 F.g⁻¹.     

Converting of the 2D graphene to its 3D by chicken red blood cells as sheets separator for construction supercapacitor electrode

Here, we report on a facile green and scalable method for the fabrication of porous 3D graphene as a well-known carbon-based material used in many energy storage devices. Chicken red blood cells were used as sheets spacer and heteroatom sources in the construction of 3D graphene. First, the red blood cells were separated from the blood and mixed with graphene oxide. Then, the mixture was freeze-dried and carbonized at 700 °C. The resulted 3D graphene containing heteroatoms was used as a supercapacitor electrode modifier on a glassy carbon electrode and tested with various electrochemical techniques. The supercapacitor electrode showed a specific capacitance of 330 F g⁻¹ at a current density of 1 A g⁻¹, maximum power density of 1958 W kg⁻¹, and maximum energy density of 85 Wh kg⁻¹. Furthermore, the supercapacitive performances were tested in a two-electrode symmetrical system which exhibited a specific capacitance of 238 F g⁻¹ for 1 A g⁻¹. It also showed a power density of 2200 W kg⁻¹ and an appreciable energy density of 160 Wh kg⁻¹. The excellent electrochemical behavior of 3D graphene indicates the promising abilities of the composite for other applications such as biosensors, batteries, electrocatalysts, etc.     

Synchrotron-based investigation of iron precipitation in multicrystalline silicon

We report on investigations of the precipitation of iron in block-cast multicrystalline silicon using the techniques of X-ray beam induced current, X-ray fluorescence microscopy and X-ray absorption microspectroscopy. The samples studied were intentionally contaminated with iron and annealed at temperatures between 850 and 1050 ^°C. Annealing at 950 ^°C was found to lead to well detectable iron precipitation inside the grains and at grain boundaries. Small only iron clusters were detected after the 850 ^°C anneal while no iron clusters were found after the 1050 ^°C treatment. X-ray absorption near edge structure analyses of the iron clusters revealed mostly iron silicide and in one case iron oxide. Under the given condition at the beamline, the detection sensitivity for iron was estimated to be 4×10⁷ atoms, corresponding to a spherical FeSi₂ particle of 40 nm radius.     

Direct determination of mineral nutrients in soybean leaves under vivo conditions by portable X-ray fluorescence spectroscopy

A portable energy dispersive X-ray fluorescence (XRF) spectrometer furnished with an Rh X-ray tube was evaluated for the determination of macronutrients and micronutrients in soybean leaves (Glycine max L.). XRF instrumental parameters were optimized in a univariate way, and emission intensities were measured for 60 s and under vacuum for macronutrients, and during 180 s, under air, and 305 μm Al/25.4 μm Ti filter, for micronutrients. Fresh and dried leaves were irradiated, and it was possible to identify P, K, Ca, S, Mn, Fe, Cu, and Zn Kα emission lines. For comparative purpose, the samples were also microwave assisted, digested and analyzed by inductively coupled plasma optical emission spectrometry. In general, linear correlations between K, Ca, Mn, Fe, Cu, and Zn concentrations in the tested samples and the corresponding portable XRF (pXRF) intensities were obtained. The linear correlation coefficients (R²) ranged from 0.42 to 0.86. In addition, the detection limits were suitable for plant nutrient diagnosis. It is demonstrated that pXRF is a simple and powerful tool for analysis of plant materials.     

Synthesis and performance of nickel hydroxide nanodiscs for redox supercapacitors

Herein, we report the facile synthesis of β-Ni(OH)₂ nanodiscs by chemical precipitation method and their use in supercapacitors. β-Ni(OH)₂ nanodiscs are characterized by FTIR, XRD, FESEM, XPS and TGA analysis. Morphological analysis revealed the uniform nanodisc morphology of β-Ni(OH)₂. The supercapacitor behavior is evaluated by cyclic voltammetry, galvanostatic charge–discharge, and electrochemical impedance spectroscopy measurements in 1-M aqueous KOH solution with 0- to 0.6-V potential window. The specific capacitance of β-Ni(OH)₂ nanodiscs is found to be 400 F g⁻¹. The energy and power densities of the β-Ni(OH)₂ nanodiscs are found to be 7.15 W h kg⁻¹ and 1716 W kg⁻¹, respectively, at the current density of 1 A g⁻¹. The cycle life test shows the good stability of the electrode with 83 % retention capacitance even after 1500 cycles.

     

Development of proton conducting biopolymer membrane based on agar–agar for fuel cell

A proton-conducting polymer electrolyte based on agar and ammonium nitrate (NH₄NO₃) has been prepared through solution casting technique. The prepared polymer electrolytes were characterized by impedance spectroscopy, X-ray diffraction, and Fourier transform infra-red spectroscopy. Impedance analysis shows that sample with 60 wt.% NH₄NO₃ has the highest ionic conductivity of 6.57 × 10⁻⁴ S cm⁻¹ at room temperature. As a function of temperature, the ionic conductivity exhibits an Arrhenius behaviour increasing from 6.57 × 10⁻⁴ S cm⁻¹ at room temperature to 1.09 × 10⁻³ S cm⁻¹ at 70 °C. Transport parameters of the samples were calculated using Wagner’s polarization method and thus shows that the increase in conductivity is due to the increase in the number of mobile ions. Fuel cell has been constructed with the highest proton conductivity polymer 40agar/60NH₄NO₃ and the open circuit voltage is found to be 558 mV.

     

Mechanical behavior and acoustic emission technique for detecting damage in sandwich structures

The present study investigates the mechanical behavior under static and dynamic loadings and assesses damage by the acoustic emission method of two types of sandwich composite materials. The sandwich structures under study are both made of cross-ply laminates as skins and PVC closed-cell as foam with different densities: 60 kg m⁻³ and 100 kg m⁻³. The mechanical behavior tests were conducted in static and cyclic fatigue loadings under 4-point bending. The sandwich structures considered in fatigue tests were damaged by a various number of shear damages in the foam. Static tests were performed to determine the failure parameters and characteristics used in fatigue tests. The damage density effect on the stiffness, hysteresis loops, dissipated energy and damping of sandwich structures, were studied for various numbers of cycles during cyclic fatigue tests. The acoustic emission method was used to identify and characterize the local damage in both types of sandwich materials under static 4-point bending tests.     

Magnetic properties and magnetic entropy changes of perovskite manganese oxide La0.8-xEuxSr0.2MnO3 (x = 0, 0.075)

Magnetocaloric effect and critical exponent analysis of La_0.8-xEu_xSr_0.2MnO_{3 (}x = 0, 0.075) manganites synthesized via a solid state reaction route have been explored. Rietveld analysis indicates that crystal structure of La_0.8-xEu_xSr_0.2MnO_{3 (}for x = 0.0) is in orthorhombic structure with pbnm space group. After the substitution of Eu, the structure changes from orthorhombic (for x = 0.0) to rhombohedral structure for (x = 0.075) with $\mathrm{R}\overline{3}c$ space group. The T_C is 287 K and 271 K for the samples with x = 0.000 and x = 0.075, respectively, and the magnetic entropy change is 2.76J K ^− 1•kg⁻¹ for x = 0.000 and 3.94J K ^− 1•kg⁻¹ for x = 0.075. The real cooling power (RCP) is 447.7 J•kg⁻¹ for the sample with x = 0.000 and 445 J•kg⁻¹ for the samples with x = 0.075. Both samples show a second order phase transition in the vicinity of T_C. The critical exponents were determined using modified Arrott plots and Kouvel-Fisher methods. The critical behavior of these two samples fit best with the mean field model.     

LFN and LSCFN perovskites — structure and transport properties

Structural, electronic and transport properties of LFN (LaFe_1−zNi_zO₃) and LSCFN (La_1−xSr_xCo_1−y −zFe_yNi_zO₃) perovskites synthesized by a modified citric acid method were studied. Structure of the samples was characterized by X-ray studies with Rietveld method analysis. Magnetic properties and valence states of iron ions were characterized by ⁵⁷Fe Moessbauer spectroscopy performed at RT, which were found to be greatly dependent on the chemical composition of the samples. Electrical conductivity was measured in the 20–800 °C temperature range and for some compositions relatively high values (exceeding 100 S cm^− 1) were observed in the 600–800 °C range. Chemical stability studies in relation to Ce_0.8Gd_0.2O_1.9 electrolyte, performed for selected perovskite samples, revealed decreasing stability with increasing Ni concentration and formation of solid solutions in CGO/perovskite composites. The coefficient of thermal expansion (CTE) of LFN perovskites was found to match that of CGO electrolyte (CTE in the 10–13 · 10^− 6 K^− 1 range).     

Critical view on TL/OSL properties of Li2B4O7 nanoparticles doped with Cu,Ag and co-doping Cu,Ag: Dose response study

Small size (25 nm) Li₂B₄O₇ nanoparticles doped with different concentrations of Cu, Ag and co-doped with Cu, Ag were prepared by solid state sintering at 700 °C. The crystalline phase and particle sizes analysis were carried out by XRD and TEM. FTIR study reveals the formation of vibrational bonds at 1600–1200 cm⁻¹, 1500–700 cm⁻¹, 950–870 cm⁻¹ and 870–415 cm⁻¹. The kinetic parameters of the TL glow curves were evaluated using CGCD procedure in R-software. The CW-OSL decay curves were fitted with third order exponential decay curves and photoionization cross sections of each component were evaluated. The lifetime of the main TL dosimetric peak were also calculated to check the stability of the signal. Dose responses of the synthesized Li₂B₄O₇ nanoparticles for both the TL and CW-OSL were studied in the range of 0.02 mGy to50 Gy and found to be linear upto this range. Fading of the CW-OSL decay curves were also studied. The MDD of the synthesized samples were also calculated and observed to be 15 μGy.     

Soil radioactivity levels and radiation hazard assessment in the highlands of northern Jordan

Determination of the natural radioactivity has been carried out, by means of gamma-ray spectrometry system, in surface soil samples collected from various geological formations in urban areas of the northern highlands of Jordan. These highlands, extending from Yarmouk River in the north to Wadi Wala in the south, form the agriculturally important regions of Jordan. Soils of the study region, at which about 70% of the total population of the country are living, mainly originated from limestones that are locally used in construction materials, making the evaluation of environmental radioactivity and estimating the current radiation hazards to the population an interesting issue. The total average concentrations of radionuclides ²²⁶Ra, ²³⁸U, ²³²Th, and ⁴⁰K were 42.5, 49.9, 26.7, and 291.1 Bq kg⁻¹, respectively. Correlations made among these radionuclides prove the existence of secular equilibrium in the investigated soils. The total average absorbed dose rate in the study areas is found to be 51.5 nGy h⁻¹, whereas the annual effective dose equivalent has an average value of 63.2 μSv y⁻¹. The external and internal hazard indices, the radium equivalent activity, and the annual gonadal dose equivalent associated with the investigated soils do not exceed the permissible limits except for soils originated from phosphate rocks. Moreover, the radio-elemental concentrations of uranium, thorium and potassium, evaluated for the various geological features in the study areas were calculated to indicate whether relative depletion/enrichment of radioisotopes had occurred. The results of the present study were discussed and compared with internationally recommended values.     

Performance of solid-state hybrid supercapacitor with LiFePO4/AC composite cathode and Li4Ti5O12 as anode

We report the studies on quasi-solid battery-supercapacitor (BatCap) systems fabricated using sol–gel-prepared LiFePO₄ and its composites (LACs) with activated charcoal (AC) as hybrid cathode and Li₄Ti₅O₁₂ powder as anode separator by flexible gel polymer electrolyte (GPE) film. The GPE film comprises 1.0 M lithium trifluoromethane sulfonate (LiTf) solution in ethylene carbonate (EC)–propylene carbonate (PC) mixture, immobilized poly(vinylidene fluoride-co-hexafluoro-propylene) (PVdF-HFP), which is of high ionic conductivity (∼3.8 × 10⁻³ S cm⁻¹ at 25 °C) and electrochemical stability window (∼3 V). The effect of the addition of AC in composite electrode LACs has been analyzed using various techniques such as X-ray diffraction, porosity analysis, and electrochemical methods. The interfaces of composite LACs and GPE film not only offer high rate performance but also show high specific energy (>27.8 Wh kg⁻¹) as compared to the symmetric supercapacitors and pristine lithium iron phosphate (LiFePO₄)-based lithium ion batteries. The full BatCap systems have been characterized by cyclic voltammetry and galvanostatic charge–discharge tests. The BatCap systems with composite electrodes (LACs) offer better cyclic performance as compared to that of pristine LiFePO₄-based BatCap or LIB LiFePO₄/Li₄Ti₅O₁₂.

     

Fe3O4/hydroxyapatite/graphene quantum dots as a novel nano-sorbent for preconcentration of copper residue in Thai food ingredients: Optimization of ultrasound-assisted magnetic solid phase extraction

Fe₃O₄/hydroxyapatite/graphene quantum dots (Fe₃O₄/HAP/GQDs) nanocomposite was synthesized and used as a novel magnetic adsorbent. This nanocomposite was characterized using scanning electron microscopy, transmission electron microscopy, Fourier transform infrared spectroscopy, X-ray diffraction, energy dispersive X-ray spectroscopy, and magnetization property. The Fe₃O₄/HAP/GQDs was applied to pre-concentrate copper residues in Thai food ingredients (so-called “Tom Yum Kung”) prior to determination by inductively coupled plasma-atomic emission spectrometry. Based on ultrasound-assisted extraction optimization, various parameters affecting the magnetic solid-phase extraction, such as solution pH, amount of magnetic nanoparticles, adsorption and desorption time, and type of elution solvent and its concentration were evaluated. Under optimal conditions, the linear range was 0.05–1500 ng mL⁻¹ (R² > 0.999), limit of detection was 0.58 ng mL⁻¹, and limit of quantification was 1.94 ng mL⁻¹. The precision, expressed as the relative standard deviation of the calibration curve slope (n = 5), for intra-day and inter-day analyses was 0.87% and 4.47%, respectively. The recovery study of Cu for real samples was ranged between 83.5% and 104.8%. This approach gave the enrichment factor of 39.2, which guarantees trace analysis of Cu residues. Therefore, Fe₃O₄/HAP/GQDs can be a potential and suitable candidate for the pre-concentration and separation of Cu from food samples. It can easily be reused after treatment with deionized water.     

Radium equivalent and annual effective dose from geological samples from Pedra – Pernambuco – Brazil

The natural radioactivity of an uranium-anomalous area utilized for agricultural activities in Pedra, Brazil, was monitored. For this, samples from the granite and calcium-silicate amphibole rocks underlying this area and also from samples of the soil derived from these rocks were collected and analyzed by high-resolution gamma spectrometry. The equivalent radium (Ra_eq) was used as a reference for estimating the rate of the effective equivalent dose. The average, minimum and maximum values for the samples were of 319.2 Bq kg^?1 (91.1–758.5 Bq kg^?1) for soil; 327.5 Bq kg^?1 (36.3–1624.0 Bq kg^?1) for granitic rocks and 70,124.5 Bq kg^?1 (16,979.6–147,159.0 Bq kg^?1) for the calcium-silicate amphibole rocks. An estimation of the external exposition was carried out based on the calculation of the parameters obtained.     

Ultrasonically assisted synthesis of barium stannate incorporated graphitic carbon nitride nanocomposite and its analytical performance in electrochemical sensing of 4-nitrophenol

We describe the ultrasonic assisted preparation of barium stannate-graphitic carbon nitride nanocomposite (BSO-gCN) by a simple method and its application in electrochemical detection of 4-nitrophenol via electro-oxidation. A bath type ultrasonic cleaner with ultrasonic power and ultrasonic frequency of 100 W and 50 Hz, respectively, was used for the synthesis of BSO-gCN nanocomposite material. The prepared BSO-gCN nanocomposite was characterized by employing several spectroscopic and microscopic techniques such as X-ray diffraction, X-ray photoelectron spectroscopy, fourier transform infra-red, field emission scanning electron microscopy, and high resolution transmission electron microscopy, to unravel the structural and electronic features of the prepared nanocomposite. The BSO-gCN was drop-casted on a pre-treated glassy carbon electrode (GCE), and their sensor electrode was utilized for electrochemical sensing of 4-nitrophenol (4-NP). The BSO-gCN modified GCE exhibited better electrochemical sensing behavior than the bare GCE and other investigated electrodes. The electroanalytical parameters such as charge transfer coefficient (α = 0.5), the rate constant for electron transfer (k_s = 1.16 s⁻¹) and number of electron transferred were calculated. Linear sweep voltammetry (LSV) exhibited increase in peak current linearly with 4-NP concentration in the range between 1.6 and 50 μM. The lowest detection limit (LoD) was calculated to be 1 μM and sensitivity of 0.81 μA μM⁻¹ cm⁻²_. A 100-fold excess of various ions, such as Ca²⁺, Na⁺, K⁺, Cl⁻, I⁻, CO₃²⁻, NO₃, NH₄⁺ and SO₄²⁻ did not able to interfere with the determination of 4-NP and high sensitivity for detecting 4-NP in real samples was achieved. This newly developed BSO-gCN could be a potential candidate for electrochemical sensor applications.     

On the structural stability and oxygen permeation behavior of inorganic SrCo0.8Fe0.2O3−δ membranes

The high oxygen permeability combined with reasonable structural stability of perovskite-type ABO_3−δ compounds is vital for their potential applications in gas separation, solid oxide fuel cells, sensors, etc. Hence, an attempt is made to develop SrCo_0.8Fe_0.2O_3−δ-based dense membranes with sol-gel-derived oxalates and study their phase stability and oxygen permeation. While X-ray diffraction confirms the presence of a perovskite-type cubic phase above 800 °C, X-ray photoelectron spectroscopy reveals the presence of cobalt and iron in 3+ and 4+ oxidation states with O₂ ²⁻, O₂ ⁻ and O⁻ species. The electrical conductivity increases up to a characteristic temperature and decreases slowly thereafter via pronounced carrier scattering. A 1.5-mm-thick membrane displays reasonable oxygen permeability of 1.05 × 10⁻⁶ mol cm⁻² s⁻¹ at 900 °C but has inadequate stability. Partial substitution of iron with zirconium is shown to improve permeability and stability significantly. Thus, SrCo_0.8Fe_0.15Zr_0.05O_3−δ membrane shows promise for oxygen permeation purposes.

     

Amorphous Cobalt Boride Alloy Synthesized by Liquid Phase Methods as Electrode Materials for Electrochemical Capacitors

An amorphous cobalt boride alloy with high electronic conductivity is fabricated through the liquid-phase reduction method. Benefiting from large specific surface area and hierarchical pore structure, the as-synthesized Co-B nanoflakes expose substantial electrochemical active sites, promote the transfer of electrons and ions, and accelerate the redox kinetic process. The as-obtained amorphous Co-B alloy sample displays a specific capacitance of 411 F g⁻¹ at 0.5 A g⁻¹, and with the current density increased to 10 A g⁻¹, it maintains 69% of the initial capacitance. The as-assembled asymmetric supercapacitor device reveals electrochemical properties comprising an excellent specific capacitance of 64.3 F g⁻¹ at 0.25 A g⁻¹, superior cyclical stability of 105% after 20,000 cycles at 3 A g⁻¹, and maximum energy density of 22.9 Wh kg⁻¹ at a power density of 200.3 W kg⁻¹. This study demonstrates great potential in developing high-conductivity materials for an asymmetric supercapacitor through utilizing an amorphous cobalt boride alloy as a promising electrode material.     

Oxygen nonstoichiometry,mixed valency and mixed conduction in (La,Sr)(Co,Fe)O3−δ

Defect chemistry for a mixed conductor, La_0.6Sr_0.4Co_0.2Fe_0.8O_3−δ was studied. Samples were treated under controlled oxygen partial pressure, P(O₂), conditions at 1273 K [10^− 11.1 ≤ P(O₂)/atm ≤ 1], and cooled to room temperature. Oxygen nonstoichiometry and valences of transition metal ions for the treated samples were evaluated by iodometry and X-ray absorption spectroscopy, respectively. With decreasing P(O₂), preferential reduction of Co³⁺ to Co²⁺ was observed, while iron preserved its higher valence above 3 under conditions studied. A dependency of its electrical conductivity on P(O₂) was discussed along with a change in concentration of oxygen vacancies and mixed valences.