Determination of Tourmaline Composition in Pegmatite From Buldan,Denizli (Western Anatolia,Turkey) Using XRD,XRF, and Confocal Raman Spectroscopy

ABSTRACT

Tourmaline minerals observed in different geologic environments show significant variations in terms of chemical compositions. Determination of tourmaline species gives useful petrogenetic information about both igneous and metamorphic environments. Microscopic, XRD, XRF, and confocal Raman spectroscopic features of tourmaline segregations that are 2–4 cm thick, dark-blue to black in color, and mostly fractured occurring in the Buldan pegmatite are reported. Under the microscope, tourmaline samples show indigo blue, light blue, and olive-brown pleochroism with a thin long columnar, bladed shape. They exhibit distinctive enrichments in Fe₂O₃ (7.83–10.16 wt%), V (245.0–591.0 ppm), Sn (70.1–147.3 ppm), W (1076.0–1887.0 ppm), U (1.2–18.2 ppm), and Th (9.6–28.0 ppm). In terms of geochemistry, the tourmaline samples are schorl with Fe/(Fe + Mg) ratios of 0.65–0.74 and Na/(Na + Ca) ratios of 0.88–0.93. Five characteristic bands of tourmaline samples are observed at 1050, 710, 370, 220–245, and 185 cm^?1. Tourmaline segregations in the Buldan pegmatite are schorl in composition and are probably generated from Li-poor granitoids and their associated pegmatites.     

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.     

Spectral,electron microscopic and chemical investigations of gamma-induced purple color zonings in amethyst crystals from the Dursunbey-Balıkesir region of Turkey

Amethyst crystals on matrix specimens from the Dursunbey-Bal?kesir region in Turkey have five representative purple color zonings: dark purple, light purple, lilac, orchid, and violet. The purple color zonings have been analyzed with optical absorption spectra in the visible wavelength region, chemical full trace element analyses (inductively coupled plasma-atomic emission spectroscopy and inductively coupled plasma-mass spectroscopy), and scanning electron microscopic images with high magnification. It can be proposed that the production of the purple color in amethyst crystals is due to three dominant absorption bands centered at 375, 530, and 675 nm, respectively. In addition, the purple color zonings are also due to four minor absorption bands centered at 435, 480, 620, and 760 nm. X-ray diffraction graphics of the investigated amethyst crystals indicate that these crystals are composed of a nearly pure alpha-quartz phase and do not include any moganite silica phase and/or other mineral implications. Trace element analyses of the amethyst crystals show five representative purple color zonings, suggesting that the absorption bands can be mainly attributed to extrinsic defects (chemical impurities). However, another important factor that influences all structural defects in amethyst is likely to be the gamma irradiation that exists during amethyst crystallization and its inclusion in host materials. This gamma irradiation originates from the large underlying intrusive granitoid body in the region of amethyst formation. Irradiation modifies the valence values of the impurity elements in the amethyst crystals. It is observed that the violet-colored amethyst crystals have the most stable and the least reversible coloration when exposed to strong light sources. This situation can be related to the higher impurity content of Fe (2.50 ppm), Co (3.1 ppm), Ni (38 ppm), Cu (17.9 ppm), Zn (10 ppm), Zr (3.9 ppm), and Mo (21.8 ppm).     

Photoluminescence Response from the Turkish Dentritic Agates

The three-dimensional photoluminescence emissions between 380 and 800 nm of the dentritic agate with white body color from the Dereyalak-?nönü-Eski?ehir (Turkey) region were obtained at the temperatures between 250 and 340 K under 366 nm excitation. The most advantage of three-dimensional photoluminescence graphic in a silica structure is to demonstrate clearly all vibronic structures through temperature increasing on the spectra. Hence, photoluminescence response from the gem-quality material was discussed in relation to chemical impurities of trivalent rare earth elements.

In the photoluminescence spectra, two strong and many weaker emission bands became clear at the lower temperature (250 K) conditions. First strong one is the purple band, and the highest emission peak is observed at 394 nm. Second strong one is the red band, and the highest emission peak is observed at 717 nm. The half-width of these main bands is approximately 17–19 nm, and such band's combination is typical for trivalent rare earth elements. Chemical analyses in this study show the abundances of many rare earth elements in the material. In order of abundance, they are yttrium (845 ppm), gadolinium (238 ppm), lutetium (196 ppm), dysprosium (45 ppm), neodymium (41 ppm), promethium (34 ppm), europium (18 ppm), and scandium (3 ppm). However, the two strong emission bands are, of course, due to yttrium and gadolinium ions, respectively.

As a result, the intensities of these bands gradually decreased forming a sequence until the temperature of 280 K. Hence, the photoluminescence of the Turkish dentritic agates does not exist at higher temperatures, mainly because of high iron (40.000 ppm) abundance.     

新疆哈密绿松石的矿物学和光谱学特征研究

最近在新疆哈密发现了可规模开采的宝石级绿松石矿床。采用X射线粉晶衍射仪、激光剥蚀电感耦合等离子体质谱仪、扫描电子显微镜、傅里叶变换红外光谱仪、拉曼光谱仪、紫外-可见光谱仪等测试方法,对该地绿松石的化学成分、矿物组成、表面微形貌、红外吸收光谱、拉曼散射光谱、紫外-可见吸收光谱等矿物学和光谱学特征进行了系统对比研究。新疆哈密绿松石的主要化学成分以富Cr (1 617 ppm),V (435 ppm),Ti (428 ppm),贫Ba (99.9 ppm)为特征,随着Fe₂O₃/CuO比值的递减,绿松石的色调由绿变蓝。由磷酸根、羟基和结晶水引起的特征峰出现在该地绿松石的拉曼光谱和红外吸收光谱,其中磷酸根的振动峰位于1 000~1 200和420~650 cm-1,羟基的振动峰出现在3 400~3 600 cm-1,而结晶水引起的振动峰位于3 000~3 300 cm-1。此外,该地绿松石的紫外-可见吸收光谱显示,在600~700和430 nm处分别有由Cu2+和Fe3+引起的吸收峰,这两处的峰强与绿松石的蓝绿色调之间的关系,和新疆哈密绿松石成分中Fe₂O₃/CuO的比值与颜色之间的关系对应一致。     

Cesium lead halide perovskite quantum dot-based warm white light-emitting diodes with high color rendering index

White light-emitting diodes (WLEDs) were fabricated by employing a combination of a commercial yellow emission Ce³⁺-doped Y₃Al₅O₁₂ (YAG:Ce)-based phosphor and all-inorganic perovskite quantum dots pumped with blue LED chip. Perovskite quantum dot solution was used as the color conversion layer with liquid-type structure. Red-emitting materials based on cesium lead halide (CsPb(X)₃) perovskite quantum dots were introduced to generate WLEDs with high efficacy and high color rendering index through compensating the red emission of the YAG:Ce phosphor-based commercialized WLEDs. The experimental results suggested that the luminous efficiency and color rendering index of the as-prepared WLED device could reach up to 84.7 lm/W and 89, respectively. The characteristics of those devices including correlated color temperature (CCT), color rendering index (CRI), and color coordinates were observed under different forward currents. The as-fabricated warm WLEDs showed excellent color stability against the increasing current, while the color coordinates shifted slightly from (0.3837, 0.3635) at 20 mA to (0.3772, 0.3592) at 120 mA and color temperature tuned from 3803 to 3953 K.     

The order of addition of corn starch/lithium perchlorate/glycerol affects the optical,mechanical, and electrical properties of a solid polymer electrolyte

Optical, mechanical, and electric properties of solid polymer electrolyte (SPE) were affected by the order of addition of corn starch (S), lithium perchlorate (Li), and glycerol (G) during the preparation process. Four formulations were made based on whether Li was added prior to S gelatinization (simultaneous formulations SGLi and SLi+G) or whether it was added after S was gelatinized (sequential formulations SG+Li and S+LiG). Simultaneous formulations produced films with smaller elongation-at-break response (60–75%) relative to their sequential counterparts (75–82%). The simultaneous formulations exhibited higher electrical conductivity (～0.7 mS cm^?1) and capacitance (～0.017 F cm^?2) and electrochemical stability than the sequential formulations (～0.9 mS cm^?1 and ～0.012 F cm^?2) at room temperature. Results from FTIR and DSC analyses indicated that starch re-crystallization in casting phase could lead to variations on electrical properties for the different SPE formulations. It was postulated that Li cations replace hydrogen ions inside starch molecules, retarding the re-crystallization of starch molecules.     

Detection of trace nitric oxide concentrations using 1-D laser-induced fluorescence imaging

Spectrally resolved laser-induced fluorescence (LIF) with one-dimensional spatial imaging was investigated as a technique for detection of trace concentrations of nitric oxide (NO) in high-pressure flames. Experiments were performed in the burnt gases of premixed methane/argon/oxygen flames with seeded NO (15 to 50 ppm), pressures of 10 to 60 bar, and an equivalence ratio of 0.9. LIF signals were dispersed with a spectrometer and recorded on a 2-D intensified CCD array yielding both spectral resolution and 1-D spatial resolution. This method allows isolation of NO-LIF from interference signals due to alternative species (mainly hot O₂ and CO₂) while providing spatial resolution along the line of the excitation laser. A fast data analysis strategy was developed to enable pulse-by-pulse NO concentration measurements from these images. Statistical analyses as a function of laser energy of these single-shot data were used to determine the detection limits for NO concentration as well as the measurement precision. Extrapolating these results to pulse energies of ～?16 mJ/pulse yielded a predicted detection limit of ～?10 ppm for pressures up to 60 bar. Quantitative 1-D LIF measurements were performed in CH₄/air flames to validate capability for detection of nascent NO in flames at 10–60 bar.     

Design and Performances of a Carbon Monoxide Sensor Using Mid-Infrared Absorption Spectroscopy Technique at 4.6 µm

Based on infrared absorption spectroscopy technique, a carbon monoxide sensor was developed using the fundamental absorption band of carbon monoxide molecule at the wavelength around 4.6 µm. The developed sensor consists of pulse-modulated wideband incandescence, open ellipsoid light-collector gas-cell, dual-channel detector, and control and signal-processing module. With the prepared standard carbon monoxide gas sample, sensing characteristics on carbon monoxide were investigated using the sensor. Experimental results reveal that the limit of detection is about 10 ppm, the relative error at the limit of detection point is less than 14%, and that is less than 7.8% within the low concentration range of 20～180 ppm. The maximum absolute errors of 50 min long-term measurement on the 0 and 14 ppm CO gas samples are about 3 and 3.17 ppm, respectively, and the standard deviations are as small as 0.18 and 1.25 ppm, respectively. Compared with the reported carbon monoxide detection systems utilizing quantum cascaded lasers and distributed feedback lasers, the proposed sensor shows potential applications in carbon monoxide detection under the circumstances of coal-mine and environmental protection, by virtue of high performance, low cost, simple optical structure, and so on.     

Radiometric analysis and radiological hazards of Chinese commercial marble

The activity concentrations of ²²⁶Ra, ²³²Th and ⁴⁰K in commercial marble materials have been determined using a NaI(Tl) γ-ray spectrometer with a matrix-inversion-based spectral stripping technique. Knowledge of radioactivity present in marble materials enables one to assess any possible radiological risks to human health. The concentrations of ²²⁶Ra, ²³²Th and ⁴⁰K in Chinese commercial marble range from 8.4 to 157.4, 5.6 to 165.5 and 44.1 to 1352.7 Bq kg^?1, respectively. The natural radionuclide concentration varied with color and production site of commercial marble. The activity concentrations of ²²⁶Ra, ²³²Th and ⁴⁰K in white, gray, black, green and yellow marble samples are comparatively smaller than those in brown and red marble samples. The radium equivalent activity (Ra_eq), the external hazard index (H _ex), the internal hazard index (H _in) and the annual gonadal dose equivalent were also calculated and compared with the internationally recommended values. One type of brown commercial marble (TSB) of China does not satisfy the universal standards.     

X-ray irradiation-induced changes in Bayfol DPF 5023 polycarbonate

Samples from sheets of the polymeric material Bayfol DPF 5023 have been exposed to X-ray radiation in the dose range 100–2300 Gy. The modifications induced in Bayfol samples due to X-ray irradiation have been studied through different characterization techniques such as X-ray diffraction (XRD), Fourier transform infrared (FTIR) spectroscopy, intrinsic viscosity, refractive index and color difference studies. The infrared spectroscopy indicated that crosslinking is the dominant mechanism at the dose range of 200–2300 Gy. The crosslinking reported by FTIR spectroscopy destroyed the degree of ordering in the Bayfol samples, as revealed by the XRD technique. Also, this crosslinking led to an increase in the value of intrinsic viscosity from 0.54 for the non-irradiated sample to 0.63 for the sample irradiated with 2300 Gy at 30 °C, indicating an increase in the average molecular mass. This was associated with an increase in the refractive index. Additionally, the non-irradiated Bayfol samples showed significant color sensitivity toward X-ray irradiation. This sensitivity appeared in the change of the blue color component of the non-irradiated Bayfol film to yellow after exposure to X-ray doses up to 2300 Gy. This is accompanied by a net increase in the darkness of the samples.     

Sugaring marble in the Monumental Cemetery in Bologna (Italy): characterization of naturally and artificially weathered samples and first results of consolidation by hydroxyapatite

The so-called sugaring of marble is a very common degradation phenomenon, affecting both historical monuments and modern buildings, which is originated by environmental temperature fluctuations. Thermal cycles are indeed responsible for micro-cracks formation at the boundaries between calcite grains, so that marble is subjected to granular disintegration and can be reduced to a sugar-like powder of isolated calcite grains by just the pressure of a finger. Since no effective, compatible and durable treatment for sugaring marble consolidation is currently available, in this paper a novel consolidating treatment recently proposed for limestone, based on the formation of hydroxyapatite inside the stone, was investigated for weathered marble. To test the new treatment on suitably decayed marble samples, some naturally sugaring marbles from the Monumental Cemetery in Bologna (Italy, nineteenth century) were firstly characterized by scanning electron microscope (SEM), mercury intrusion porosimetry (MIP) and ultrasonic pulse velocity (UPV) measurement. Then, artificially weathered samples were produced by heating fresh Carrara marble samples at 400 °C for 1 h. The effects of artificial weathering were characterized using the same techniques as above, and a very good agreement was found between microstructure and mechanical features of naturally and artificially weathered samples. Then, the hydroxyapatite-based treatment was tested on the so-obtained artificially weathered samples, and the treatment effects were characterized by UPV, MIP and SEM equipped with energy dispersive spectrometry and Fourier transform infrared spectroscopy. The hydroxyapatite-based treatment exhibited a remarkable ability of restoring marble cohesion and a good compatibility in terms of modifications in pore size distribution, which leads to regard this treatment as a very promising consolidant for weathered marble.     

Research on phosphor-conversion laser-based white light used as optical source of VLC and illumination

Visible light communication (VLC) based on light emitting diodes (LEDs) or laser diodes (LDs) has attracted considerable interest in recent years. Due to the advantages of laser diodes based on nitrides, such as small size, high brightness, visible light and high bandwidth, it can be applied to illumination and communication at the same time. In this paper, blue laser and yellow phosphors were employed to synthesize white light. And “efficiency droop” is not observed in the LIV characteristics of LD-based white light either. The bandwidth measurement system with high reliability was set up. The bandwidth of blue laser diode and phosphor-conversion laser-based white light was measured. The maximum of optical ?3 dB bandwidth of blue LD is around 1.8 GHz at 80 mA and maximum of optical ?3 dB bandwidth of white light is about 1.3 GHz at 60 mA. The color parameters of the synthetic white light were characterized through integrating sphere. Moreover the trends of test data with injection current were analyzed in detail. The problem of thermal degradation of yellow phosphors has been improved by a special design that can keep a certain distance between the blue laser diode and phosphors. The experiment results verified that laser diodes based on nitrides have promising applications in lighting and communications.     

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.     

Effect of fast neutron irradiation on the structural and optical properties of Makrofol DE 1-1 CC polycarbonate

Samples from sheets of the polymeric material Makrofol DE 1-1 CC have been exposed to neutrons of incident energy in the range of 0.8–19.2 MeV. The modifications induced in Makrofol samples due to neutron irradiation have been studied through different characterization techniques such as X-ray diffraction (XRD), Fourier transform infrared (FTIR) spectroscopy, intrinsic viscosity, refractive index and color difference studies. Infrared spectroscopy indicated that cross-linking is the dominant mechanism in the energy range of 2.3–19.2 MeV. The cross-linking reported by FTIR spectroscopy destroyed the degree of ordering in the Makrofol samples, as revealed by the XRD technique. Also, this cross-linking led to an increase in the values of intrinsic viscosity from 0.41 to 0.68 at 28 °C, indicating an increase in the average molecular mass, associated with an increase in the refractive index. Additionally, the non-irradiated Makrofol samples showed significant color sensitivity toward neutron irradiation. The sensitivity toward neutron irradiation can be seen by the change in the blue color component of the non-irradiated Makrofol film to yellow after the samples are exposed to neutrons up to 19.2 MeV. This is accompanied by a net increase in the darkness of the samples.     

TL,OA and ESR of spessartine garnet

Thermoluminescence (TL), optical absorption (OA), electron spin resonance (ESR) and their relation to point defects in spessartine have been investigated. The TL glow curve presented four peaks at 150, 220, 260 and 335 °C. The 150 and 335 °C TL peaks growth curves presented a linear growth with radiation dose up to about 400 Gy, supralinearity above this dose, and saturation around 800–1000 Gy. The OA spectrum presented allowed spin transition bands due to Fe³⁺ and Mn²⁺ in dodecahedral environment. Absorption bands due to ultraviolet charge transfer of Fe³⁺ in octahedral and tetrahedral positions were also observed. Two ESR, a strong one around g?～?2 due to Fe³⁺ in octahedral position, and another weaker one at g?～?4 due to Fe³⁺ in tetrahedral position, have been detected. The effect of high temperature annealing (600–900 °C) before irradiation was also investigated.     

High-pressure,high-temperature single-crystal study of Bi-IV

Bi-IV is the stable high-pressure, high-temperature phase of bismuth at ～4 GPa and ～500 K. It was first identified in 1958, but its structure has remained uncertain. An X-ray powder-diffraction study of Bi-IV reported the structure as monoclinic, but a subsequent reinterpretation of the same data concluded that the structure was C-centred orthorhombic (oC16), with the same atomic arrangement as in Cs-V and Si-VI. To resolve the uncertainty over the structure of Bi-IV, we investigated this phase at 3.2 GPa and 465 K by single-crystal synchrotron X-ray diffraction. All of the observed reflections could be indexed on the orthorhombic oC16 structure proposed by Degtyareva, with a=11.191(5) Å, b=6.622(1) Å and c=6.608(1) Å. The spacegroup was confirmed as Cmce. Refinement of the data resulted in an excellent fit (R=2.8% ), and gave atomic coordinates very similar to those of the oC16 structures in Cs-V and Si-VI.     

Effect of electron beam irradiation on the structural,thermal and optical properties of poly(vinyl alcohol) thin film

Poly(vinyl alcohol) (PVA) polymer was prepared using the casting technique. The obtained PVA thin films have been irradiated with electron beam doses ranging from 20 to 300 kGy. The resultant effect of electron beam irradiation on the structural properties of PVA has been investigated using X-ray diffraction (XRD) and Fourier transform infrared spectroscopy (FTIR), while the thermal properties have been investigated using thermo-gravimetric analysis and differential thermal analysis (DTA). The onset temperature of decomposition T ₀ and activation energy of thermal decomposition E _a were calculated, results indicate that the PVA thin film decomposes in one main weight loss stage. Also, the electron beam irradiation in dose range 95–210 kGy led to a more compact structure of the PVA polymer, which resulted in an improvement in its thermal stability with an increase in the activation energy of thermal decomposition. The variation of transition temperatures with electron beam dose has been determined using DTA. The PVA thermograms were characterized by the appearance of an endothermic peak due to melting. In addition, the transmission of the PVA samples and any color changes were studied. The color intensity Δ E was greatly increased with increasing electron beam dose, and was accompanied by a significant increase in the blue color component.     

Irradiation effects of 12 eV oxygen ions on polyimide and fluorinated ethylene propylene

Polyimide (PI) and Fluorinated Ethylene Propylene (FEP) samples (15 mm×15 mm×50 μm ) were exposed to atomic oxygen ions of average energy ～12 eV and flux ～5×10¹³ ions cm ^?2 s ^?1, produced in the Electron Cyclotron Resonance (ECR) plasma. The energy and the flux of the oxygen ions at different positions in the plasma were measured by a retarding field analyzer. The fluence of the oxygen ions was varied from sample to sample in the range of ～5×10¹⁶ to 2×10¹⁷ ions cm ^?2 by changing the irradiation period. The pre- and the post-irradiated samples were characterized by the weight loss, Scanning Electron Microscopy (SEM), X-ray Photoelectron Spectroscopy (XPS), and Fourier Transform Infrared (FTIR) techniques. The weight of the PI and FEP samples decreased with increasing the ion fluence. However, the erosion yield for the PI is found to be higher, by almost a factor five, when compared with that of FEP. On the surface region of irradiated samples, the concentrations of the carbon, fluorine, and oxygen and their corresponding chemical bonds have changed appreciably. Moreover, blisters and nanoglobules were also observed even at a fluence of ～10¹⁷ ions cm ^?2. This oxygen ion fluence is almost two orders of magnitude lower than that of the 5 eV atomic oxygen, which a satellite encounters in the space, at the low Earth orbit, during its mission period of about 7 years.     

Enhancement of performance for blue organic light emitting devices by utilizing an adjustable chromaticity layer

An adjustable chromaticity layer was successfully applied to a TBADN-based blue organic light-emitting device (BOLED) for improving chromaticity and luminance efficiency. The device was constructed by sandwiching an ultrathin [DPVBi: BCzVB] layer between hole-transport layer and primary emission layer. The optimized device gives the Commission Internationale de I’éclairage (CIE) color coordinates of (0.166, 0.201) at the current density of 20 mA/cm² and a maximum luminance efficiency of 8.43 cd/A at the driving voltage of 11 V.