X‐ray fluorescence determination of Cs,Ba, La,Ce, Nd,and Ta concentrations in rocks of various composition

The technique has been developed for the quantification of small tantalum, cesium, barium, lanthanum, cerium, and neodymium concentration in rocks with X‐ray wavelength dispersive spectrometer S8 TIGER (Bruker AXS, Germany). The optimum conditions have been chosen for registration of the analyzed elements characteristic radiation and background positions. To determine the concentrations of analyzed elements accurately, the contribution of overlapping lines to the experimental intensities of the analytical lines has been taken into account. The sample of mass about 1.2 g has been pressed into pellet by the hydraulic press. Metrological studies showed that the accuracy in the determination of the concentration of analyzed elements for the developed technique meets the requirements for methods of III accuracy class. The Ta detection limits calculated for TaL_β1‐analytical and CsL_α1‐analytical lines were 2.6 and 3.4 ppm, respectively. The detection limit of Ba, La, Ce, and Nd was (in ppm), respectively, 4.3, 2.7, 5.8, and 4.7. The metrological characteristics of the previously developed and adapted techniques were compared. Ta concentration in granite pegmatite samples has been quantified. The samples of the highest tantalum content have been investigated additionally by powder diffraction and X‐ray microprobe analysis. The X‐ray diffraction method turned out to be insensitive to the detection of mineral phase of tantalum niobates, while micro‐XRF allowed detecting its presence in tourmaline grains. Copyright © 2017 John Wiley & Sons, Ltd.     

Sources and circulation of water and arsenic in the Giant Mine,Yellowknife, NWT,Canada

Recovery of gold from arsenopyrite-hosted ore in the Giant Mine camp, Yellowknife, NWT, Canada, has left a legacy of arsenic contamination that poses challenges for mine closure planning. Seepage from underground chambers storing some 237,000 tonnes of arsenic trioxide dust, has As concentrations exceeding 4000 ppm. Other potential sources and sinks of As also exist. Sources and movement of water and arsenic are traced using the isotopes of water and sulphate. Mine waters (16 ppm As; As^V/As^III ≈ 150) are a mixture of two principal water sources – locally recharged, low As groundwaters (0.5 ppm As) and Great Slave Lake (GSL; 0.004 ppm As) water, formerly used in ore processing and discharged to the northwest tailings impoundment (NWTP). Mass balance with δ¹⁸O shows that recirculation of NWTP water to the underground through faults and unsealed drillholes contributes about 60% of the mine water. ;[emsp]>Sulphate serves to trace direct infiltration to the As₂O₃ chambers. Sulphate in local, low As groundwaters (0.3–0.6 ppm As; δ³⁴S_SO4  ～ 4 ‰ and δ¹⁸O_SO4  ～ ? 10 ‰) originates from low-temperature aqueous oxidation of sulphide-rich waste rock. The high As waters gain a component of ¹⁸O-enriched sulphate derived from roaster gases (δ¹⁸O_SO4  = + 3.5 ‰), consistent with their arsenic source from the As₂O₃ chambers. High arsenic in NWTP water (～ 8 ppm As; δ¹⁸O_SO4  = ? 2 ‰) derived from mine water, is attenuated to close to 1 ppm during infiltration back to the underground, probably by oxidation and sorption by ferrihydrite.     

Quantitative Analysis of Added Ammonium and Nitrate in Silica Sand and Soil Using Diffuse Reflectance Infrared Spectroscopy

Diffuse reflectance infrared Fourier transform spectroscopy (DRIFTS) in both near infrared (NIR) and mid infrared (MIR) has been previously shown to be effective in quantifying soil nitrogen concentrations when calibrated using numerous field soil samples. However, such an approach incorporates samples that may contain substantial correlations between physical and chemical properties. To address these concerns, the performance of DRIFTS coupled with PLS regression in NIR regions, 5000–4000 cm^? 1 (2000–2500 nm) and 6500–5500 cm^? 1 (1540–1820 nm), and the MIR region, 3400–2400 cm^? 1 (2940–4170 nm), was assessed through analysis of the concentration of ammonium (NH₄ ⁺) (0–50 ppm) and nitrate (NO₃ ^?) (0–200 ppm) artificially incorporated into a series of silica sand samples with a consistent particle size. The influence of different particle sizes of sand was also analyzed quantitatively. The Pima clay loam soil was then evaluated with concentration ranges of 0–200 ppm NH₄ ⁺ and 180–1000 ppm NO₃ ^? added to the soil samples. With sand samples, accurate NH₄ ⁺ measurements could be performed using all three ranges. The MIR region was significantly more useful for NO₃ ^? measurement than those of NIR regions. The MIR region also performed reasonably well with soil samples but both NIR regions provided poor results. The detection limits for NH₄ ⁺ and NO₃ ^? measurements in sand were 9 ppm NH₄ ⁺ and 39 ppm NO₃ ^? with the correlation coefficients (R²) of roughly 97% and 96%, respectively, and in soil were 100 ppm NH₄ ⁺ and 330 ppm NO₃ ^? with the correlation coefficients (R²) of roughly 80% and 90%, respectively.     

Conference Report

Soil from Free-Air Carbon dioxide Enrichment (FACE) plots (FAL, Braunschweig) under ambient air (375 ppm; δ¹³C–CO₂?9.8‰) and elevated CO₂ (550 ppm; for six years; δ¹³C–CO₂?23‰), either under 100% nitrogen (N) (180 kg ha^?1) or 50% N (90 kg ha^?1) fertilisation treatments, was analysed by thermogravimetry. Soil samples were heated up to the respective temperatures and the remaining soil was analysed for δ¹³C and δ¹⁵N by Isotope Ratio Mass Spectrometry (IRMS). Based on differential weight losses, four temperature intervals were distinguished. Weight losses in the temperature range 20–200 °C were connected mostly with water volatilisation. The maximum weight losses and carbon (C) content were measured in the soil organic matter (SOM) pool decomposed at 200–360 °C. The largest amount of N was detected in SOM pools decomposed at 200–360 °C and 360–500 °C. In all temperature ranges, the δ¹³C values of SOM pools were significantly more negative under elevated CO₂ versus ambient CO₂. The incorporation of new C into SOM pools was not inversely proportional to its thermal stability. 50% N fertilisation treatment gained higher C exchange under elevated CO₂ in the thermally labile SOM pool (200–360 °C), whereas 100% N treatment induced higher C turnover in the thermally stable SOM pools (360–500 °C, 500–1000 °C). Mean Residence Time of SOM under 100% N and 50% N fertilisation showed no dependence between SOM pools isolated by increasing temperature of heating and the renovation of organic C in those SOM pools. Thus, the separation of SOM based on its thermal stability was not sufficient to reveal pools with contrasting turnover rates of C.     

Composition,Luminescence, and Color of a Natural Blue Calcium Carbonate from Madagascar

Concerning the transparent blue calcite crystals of blue marble from Madagascar, this work suggests that their cavities, accessorial quartz, and marble stress textures do not provide unambiguous characterization of the blue color compared to other white marbles. It is suggested that the presence of stronium (～850 ppm), barium (～18 ppm), vanadium (～10 ppm), and nickel (～2 ppm) might be considered influential chromophores for the blue color. Blue marble aliquots were characterized to determine their mineralogical, textural, and chemical composition to elucidate luminescence spectra and the causes of the blue color by use of different techniques.     

SrAl4O7:Tm3+/Yb3+ nanocrystalline blue phosphor: structural, thermal and optical properties

Strontium aluminate (SrAl₄O₇) nanophosphor codoped with Tm³⁺–Yb³⁺ has been synthesized through the combustion route using urea as the reducing agent. Structural, thermal and optical characterizations have been carried out. Heat treatment of the samples shows a change in the crystallite phases and the relative luminescence intensities for the different bands. The nanocrystalline particles in the as-synthesized sample seem to arrange in rod like shapes of submicrometer length on annealing. A broad (350–550 nm) emission in the UV–green region is observed when 266 nm radiation is used for excitation. Intense upconversion (UC) emissions in blue, red and infrared are seen with excitation by 976 nm radiation. An emission at 364 nm not observed earlier and attributed to ¹D₂→³H₆ transition in Tm³⁺ is also seen. The blue emission from SrAl₄O₇:Tm³⁺/Yb³⁺ codoped nanophosphor (annealed at 1200°C) exhibits high color purity (89%) and is comparable to phosphors used commercially. The energy transfer mechanisms, responsible for these UC emissions, are proposed and discussed.     

An experimental investigation on heat transfer enhancement in circular jet impingement on hot surfaces by using Al2O3/water nano-fluids and aqueous high-alcohol surfactant solution

The present article reports the heat transfer characteristics of a vertical stainless steel foil of 0.15 mm thickness (SS304) by circular impinging jets of various fluids such as pure water, nano-fluids (Al₂O₃-water, ф = 0.15%, 0.6%), and aqueous high-alcohol surfactant (HAS, i.e., 2-ethyl-hexanol, 100–400 ppm) studied using an infrared thermal imaging camera (A655sc, FLIR System). The enhancement in the heat transfer rates for Al₂O₃-water nano-fluids with ф = 0.15%, ф = 0.60%, and aqueous surfactant solution (150ppm) is found to be 140%, 207%, and 117% higher compared to pure water results, respectively. The surface characteristics of the foil after jet impingement by various fluids are also studied using scanning electron microscopy (SEM), energy dispersive spectrometer (EDS), and surface wettability.     

A Raman system for multi-gas-species analysis in power transformer

We have built a complete Raman detection system for multi-trace-gas diagnosis, which is suitable for analyzing the dissolved gases in electric power system. In the system, a high-sensitivity CCD device connected to a spectrometer is used as the detection unit of the Raman system. A near-confocal cavity is used for improving the detection sensitivity of the system. In the effective spectral range of about 570–710 nm, Raman spectra of eight typical gases are achieved by using this Raman system. The detection limits for different gases have been obtained: 126 ppm for CO₂, 21 ppm for CH₄, 63 ppm for C₂H₄, 42 ppm for C₂H₂, 96.6 ppm for H₂. The detectability of the system satisfies the requirements of gas diagnosis in power transformer.     

Matrix Isolation Infrared Spectroscopic and Density Functional Theory Study of the 1:1 Complex of Bromocyclohexane with NH3: Evidence for a Weak C–H–N Hydrogen Bond

ABSTRACT

The hydrogen-bonded bromocyclohexane–ammonia complex has been isolated and characterized for the first time in argon matrices at 16 K. Coordination of the proton adjacent to the Br substituent on the cyclohexane ring to the amino nitrogen was evidenced by distinct blue shifts of bending modes involving the H-C₁–Br unit. In particular, C–C₁–Br, H–C₁–Br, and C–C₁–H bending modes produced blue shifts ranging from 2.8 to 12.2 cm^?1. Density Functional Theory (DFT) calculations at the B3LYP/6–31 + G(d, p) level yield an essentially linear Br–C₁–H–NH₃ hydrogen bond with a C-H–N distance of 2.412 Å and a hydrogen bond energy of 2.95 kcal/mol.     

Pulse EPR, ENDOR, and ELDOR Study of Anionic Flavin Radicals in Na+-Translocating NADH:Quinone Oxidoreductase

The Na⁺-translocating nicotinamide adenine dinucleotide (NADH):quinine oxidoreductase (Na⁺–NQR) is a component of respiratory chain of various bacteria and it generates a redox-driven transmembrane electrochemical Na⁺ potential. It contains four different flavin prosthetic groups, including two flavin mononucleotide (FMN) residues covalently bound to the subunits NqrB and NqrC. Na⁺–NQR from Vibrio harveyi was poised at different redox potentials to prepare two samples, containing either both FMN_NqrB and FMN_NqrC or only FMN_NqrB in a paramagnetic state. These two samples were comparatively studied using pulse electron paramagnetic resonance (EPR), electron-nuclear double resonance (ENDOR), and electron-electron double resonance (ELDOR) spectroscopy. The echo-detected EPR spectra and electron spin relaxation properties were very similar for flavin radicals in both samples. The splitting of the outer peaks in the proton ENDOR spectra, assigned to the C(8α) methyl protons, allows to identify both radicals as anionic flavosemiquinones. The mean interspin distance of 20.7 Å between these radicals was determined by pulse ELDOR experiment, which allows to estimate the edge-to-edge distance (r _e) between these flavin centers as: 11.7 Å < r _e < 20.7 Å. The direct electron transfer between FMN_NqrB and FMN_NqrC during the physiological turnover of the Na⁺–NQR complex is suggested.     

Modification of the structural and optical properties of tin oxide nanoparticles by Co doping and thermal annealing

Enhancement of the UV photoluminescence emission of sol–gel synthesized tin oxide nanoparticles is achieved by a combination of thermal annealing and Co doping. The UV as well as the defect-related visible photoluminescence are correlated to the structural characteristics and surface Sn(OH)₂ content. The nanoparticle structure, size, crystallinity, and Sn(OH)₂ content are monitored by a combination of X-ray diffraction, transmission electron microscopy, and Raman spectroscopy. In the undoped powders, a suitable annealing leads to a significant UV luminescence at around 365 nm. After doping with Co and annealing, the UV emission is further enhanced. The improvement in the UV emission intensity following annealing and Co doping of SnO₂ is demonstrated to be due to a reduction in the hydroxyl content. The defect-related broad visible photoluminescence (～400–650 nm) can be deconvoluted into three bands at around 440 nm (blue), 510 nm (green), and 600 nm (orange). The green emission is related to Sn(OH)₂ determined by Raman spectroscopy. The blue and orange emissions are attributed to oxygen vacancies.     

Elastic moduli of nanocrystalline binary Al alloys with Fe,Co, Ti,Mg and Pb alloying elements

The paper studies the elastic moduli of nanocrystalline (NC) Al and NC binary Al–X alloys (X is Fe, Co, Ti, Mg or Pb) by using molecular dynamics simulations. X atoms in the alloys are either segregated to grain boundaries (GBs) or distributed randomly as in disordered solid solution. At 0 K, the rigidity of the alloys increases with decrease in atomic radii of the alloying elements. An addition of Fe, Co or Ti to the NC Al leads to increase in the Young’s E and shear μ moduli, while an alloying with Pb decreases them. The elastic moduli of the alloys depend on a distribution of the alloying elements. The alloys with the random distribution of Fe or Ti demonstrate larger E and μ than those for the corresponding alloys with GB segregations, while the rigidity of the Al–Co alloy is higher for the case of the GB segregations. The moduli E and μ for polycrystalline aggregates of Al and Al–X alloys with randomly distributed X atoms are estimated based on the elastic constants of corresponding single-crystals according to the Voigt-Reuss-Hill approximation, which neglects the contribution of GBs to the rigidity. The results show that GBs in NC materials noticeably reduce their rigidity. Furthermore, the temperature dependence of μ for the NC Al–X alloys is analyzed. Only the Al–Co alloy with GB segregations shows the decrease in μ to the lowest extent in the temperature range of 0–600 K in comparison with the NC pure Al.     

Finding confined water in the hexagonal phase of Bi0.05Eu0.05Y0.90PO4·xH2O and its impact for identifying the location of luminescence quencher

¹H MAS NMR spectra of Bi_0.05Eu_0.05Y_0.90PO₄·xH₂O show chemical shift from ?0.56 ppm at 300 K to ?3.8 ppm at 215 K and another one at 5–6 ppm, which are related to the confined or interstitial water in the hexagonal structure and water molecules on the surface of the particles, respectively. Negative value of the chemical shift indicates that H of H₂O is closer to metal ions (Y^3?+? or Eu^3?+?), which is a source of luminescence quencher. H coupling and decoupling ³¹P MAS NMR spectra at 300 and 250 K show the same chemical shift (?0.4 ppm) indicating that there is no direct bond between P and H. It is concluded that the confined water is not frozen even at 215 K because of the less number of H-bonding.     

Lightweight and thermally insulating aerogel glass materials

Glass represents an important and widely used building material, and crucial aspects to be addressed include thermal conductivity, visible light transmittance, and weight for windows with improved energy efficiency. In this work, by sintering monolithic silica aerogel precursors at elevated temperatures, aerogel glass materials were successfully prepared, which were characterized by low thermal conductivity [k ≈ 0.17–0.18 W/(mK)], high visible transparency (T _vis ≈ 91–96 % at 500 nm), low density (ρ ≈ 1.60–1.79 g/cm³), and enhanced mechanical strength (typical elastic modulus E _r ≈ 2.0–6.4 GPa). These improved properties were derived from a series of successive gelation and aging steps during the desiccation of silica aerogels. The involved sol → gel → glass transformation was investigated by means of thermo-gravimetric analysis, scanning electron microscopy, nanoindentation, and Fourier transform infrared spectroscopy. Strategies of improving further the mechanical strength of the obtained aerogel glass materials are also discussed.     

Green,blue, red,near-infrared up-conversion luminescence of Yb<Superscript>3+</Superscript>/Er<Superscript>3+</Superscript>/Tm<Superscript>3+</Superscript> co-doped YVO<Subscript>4</Subscript> nanoparticles

YVO₄:Yb³⁺,Er³⁺; YVO₄:Yb³⁺,Tm³⁺; and YVO₄:Yb³⁺,Er³⁺,Tm³⁺ were all synthesized via sol-gel method with a subsequent thermal treatment. Specifically, YVO₄:Yb³⁺,Er³⁺,Tm³⁺ phosphors were prepared with different annealing temperatures to study the influence of temperature. The transmission electron microscope (TEM), scanning electron microscope (SEM), X-ray diffractometer (XRD), and photoluminescent (PL) spectrofluorometer were used to investigate the morphology, crystal structure, and up-conversion luminescent properties of all samples. In summary, all samples were granular-like nanoparticles and well crystallized with the same tetragonal phase as YVO₄. Under the irradiation at 980 nm, YVO₄:Yb³⁺,Er³⁺ phosphors can generate green emission at 525 and 553 nm and red emission at 657 nm, while YVO₄:Yb³⁺,Tm³⁺ phosphors can generate blue emission at 476 nm, red emission at 648 nm, and near-infrared emission at 800 nm. Notably, YVO₄:Yb³⁺,Er³⁺,Tm³⁺ samples can exhibit green emission, blue emission, red emission, and near-infrared emission at the same time, which might endow the as-prepared samples with potential applications in many fields, such as luminous paint, infrared detection, and biological label.     

Electrical conduction and thermodynamic properties of K2NiP2O7

The pyrophosphate K₂NiP₂O₇ has been synthesized by the classic ceramic method and characterized by X-ray diffraction, solid-state ³¹P magic angle spinning (MAS) NMR, and IR and electrical impedance spectroscopy. The solid-state ³¹P MAS NMR, performed at 121.49 MHz, shows two isotropic resonances at ?17.66 and ?19.94 ppm, revealing the existence of two phosphorus environments in the structure. The electrical conductivity and dielectric properties have been investigated in the frequency and the temperature range of 200 Hz–1 MHz and 603–728 K, respectively. The frequency dependence of the conductivity is interpreted using the augmented Jonscher relation. The close values of activation energies obtained from the analysis of hopping frequency and dc conductivity imply that the transport is through ion hopping mechanism. The charge carrier concentration in the investigated sample has been evaluated using the Almond–West formalism and shown to be independent of temperature. Thermodynamic parameters such as the free energy of activation ΔF, the enthalpy ΔH, and the change in entropy ΔS have been calculated.     

Synthesis of magnetoresistive glass-ceramic composites in the SrO-MnO x -SiO2-La2O3 system

Magnetic glass-ceramic composites based on lanthanum-strontium manganite are obtained by thermal treatment of glass of the nominal composition La_0.7Sr_0.3MnO₃ + SrSiO₃ at 900–1200°C. At a magnetic field strength of 720 kA/m, the samples are characterized by a magnetization up to 18.6 A/(m 2 kg). The obtained composites possess magnetoresistive properties. At 77 K and magnetic field strength 160 kA/m, the magnitude of the negative magnetoresistance is 2–6.5%.     

NMR Studies of Crowded Diels–Alder Adducts of Phencyclone with N‐(2,6‐Dialkylphenyl)maleimides. Hindered Rotations and Magnetic Anisotropy

Abstract

Phencyclone, 1, reacted with N‐(2,6‐dimethylphenyl)maleimide, 2a; with N‐(2,6‐diethylphenyl)maleimide, 2b; and with N‐(2,6‐diisopropylphenyl)maleimide, 2c, respectively, to yield the corresponding Diels–Alder adducts, 3a–c. The adducts were extensively characterized by NMR (7 T) at ambient temperatures using one‐ and two‐dimensional (1D and 2D) proton and carbon‐13 techniques for assignments. Slow exchange limit (SEL) spectra were observed, demonstrating slow rotations on the NMR timescales, for the unsubstituted bridgehead phenyl groups [C(sp³)–C(aryl sp²) bond rotations] and for the 2,6‐dialkylphenyl groups [N(sp²)–C(aryl sp²) bond rotations]. Substantial magnetic anisotropic shifts were seen in the adducts. For example, in the N‐(2,6‐dialkylphenyl) moieties of the adducts, one of the alkyl groups is directed “into” the adduct cavity, toward the phenanthrenoid portion, and these “inner” alkyl proton NMR signals were shifted upfield. Thus, in CDCl₃, the “inner” methyl of adduct 3a exhibits a proton resonance at ?0.13 ppm, upfield of tetramethylsilane (TMS); the “inner” ethyl group signals from 3b appear at 0.026 ppm (CH₂, quartet), and ?0.21 ppm (CH₃, triplet); and the “inner” isopropyl group from 3c is seen at ?0.06 ppm (methine, approx. septet) and ?0.39 ppm (CH₃, doublet). Proton NMR of the crude N‐(2,6‐dialkylphenyl)maleamic acids (used as precursors of the maleimides, 2a–c) exhibited two sets of AB quartet signals, suggesting possible conformers from hindered rotation in the amide groups about the HN–C?O bonds.     

TDLAS–WMS based near-infrared methane sensor system using hollow-core photonic crystal fiber as gas-chamber

A near-infrared methane (CH₄) sensor system was implemented using a hollow-core photonic crystal fiber (HC-PCF) as gas-chamber. Coupling joints including ceramic ferrules and ceramic mating sleeve were used to realize butt coupling between hollow-core fiber and single-mode fiber. A near-infrared distribute feedback laser was used for CH₄ detection based on wavelength modulation spectroscopy technique. CH₄ measurements were conducted to derive the sensor-system performances. Using a 5.3 mW laser power and a 0.8 m-long HC-PCF, a minimum detection limit of ~8.7 ppm at 0.1 s averaging time was obtained and it can be further improved to 1.4 ppm at an averaging time of 10 s. A good linear calibration curve between the amplitude ratio (2f/1f) and the CH₄ concentration was obtained within the concentration range of 0–1000 ppm. This sensor system shows potential applications in distributed field measurements on CH₄ in industrial process control, environmental monitoring, etc.