Loose‐powder technique for X‐ray fluorescence analysis of ancient pottery using a small (100 mg) powdered sample

A molded‐loose‐powder technique using a small powdered sample (100 mg) was developed for the X‐ray fluorescence analysis of 22 components (Na₂O, MgO, Al₂O₃, SiO₂, P₂O₅, K₂O, CaO, TiO₂, MnO, Fe₂O₃, V, Cr, Ni, Cu, Zn, Rb, Sr, Y, Zr, Nb, Ba, and Pb) in ancient pottery. This loose powder specimen was prepared by pressing the small powdered sample into a sample holder, formed from a stainless steel disk (48‐mm diameter × 0.8‐mm height) with a hole (11‐mm diameter), by hand. Calibration standards were prepared by homogenizing chemical reagents containing these 22 analytes using the concentration ranges of 166 ancient potteries and three clay materials from Japan. The calibration curves of these benchmark mixtures exhibited a good linearity (correlation coefficient, r = 0.990–1.000), accuracy, and reproducibility compared with those of other synthesized specimens and three reference standards. The lower limits of detection were less than tens of mg kg^?1 (e.g., 94 mg kg^?1 for Na₂O, 11 mg kg^?1 for P₂O₅, 1.1 mg kg^?1 for Rb, and 0.9 mg kg^?1 for Y). Using the present method, we determined 22 components in two prehistoric potteries from Japan. The advantage of this method is that only a small amount of sample is required, which can be prepared easily and rapidly and reused for other analyses. Copyright © 2012 John Wiley & Sons, Ltd.     

X‐ray fluorescence analysis of Co,Ni, Pd,Ag, and Au in the scrapped printed‐circuit‐board ash

A method for the quantitative analysis of Co, Ni, Pd, Ag, and Au in the scrapped printed‐circuit‐board ash by X‐ray fluorescence (XRF) spectrometry using loose powder was developed. The printed‐circuit‐board samples were converted to ash pyrolytically in porcelain crucibles by sequential heating using a gas burner and electric furnace, and then were ground with a ball mill. The calibrating standards were prepared by adding the appropriate amounts of NiO powder and aqueous standard solutions containing Co, Pd, Ag, and Au to the base mixtures of Al₂O₃ (5.0 mass%), SiO₂ (49 mass%), CaCO₃ (11 mass%), Fe₂O₃ (3.3 mass%), and CuO (30 mass%) as a matrix. Then, 10 g of the resulting mixtures were dried and homogenized for 90 min with a V‐type mixing machine. Specimens for XRF analysis were prepared from the so‐called loose‐powder method in which powder samples were compacted into a hole (12.0‐mm diameter and 5.0‐mm height) in an acrylic plate and covered with a 6‐µm thickness of polypropylene film. Matrix effects were corrected using the intensity value of Compton scattering for PdKα, AgKα, and AuLβ₂, and that of background scattering at 35.8° (2θ) for CoKα and NiKα. The detection limits corresponding to three times the standard deviation of the blank intensity were 2.5–45 µg g^?1. The proposed method was validated against the pressed‐powder‐pellet method by comparing the calibration curves. Moreover, the concentrations of Co, Ni, Pd, and Ag determined using the proposed XRF method were approximately the same as those resulting from an atomic‐absorption‐spectrometric analysis. Copyright © 2013 John Wiley & Sons, Ltd.     

Assessment of health hazard due to natural radioactivity in Kluang District,Johor, Malaysia

The radiation survey of the ambient environment was conducted using two gamma detectors, and the measurement results were used in the computation of the mean external radiation dose rate, mean-weighted dose rate and annual effective dose, which are 144 nGy h^?1, 0.891 mSv y^?1 and 178 μSv, respectively. A high-purity germanium detector was used to determine the activity concentrations of ²³²Th, ²²⁶Ra and ⁴⁰K in soil samples. The results of the gamma spectrometry of the soil samples show radioactivity concentration ranges from 19±1 to 405±13 Bq kg^?1 with a mean value of 137±5 Bq kg^?1 for ²³²Th, from 21±2 to 268±9 Bq kg^?1with a mean value of 78±3 Bq kg^?1 for ²²⁶Ra and from 23±9 to 1268±58 Bq kg^?1 with a mean value of 207±13 Bq kg^?1 for ⁴⁰K. Radium equivalent activity (Ra_eq) and external hazard index (H_ex) were 290 Bq kg^?1 and 0.784, respectively, which were safe for the population. The mean lifetime dose and lifetime cancer risk for each person living in the area with average lifetime (70 y) were 12.46 mSv and 7.25×10^?4 Sv year, respectively. The results were compared with values given in United Nations Scientific Committee on the Effects of Atomic Radiation 2000.     

Natural radionuclide concentrations in soils around Baoji coal-fired power plant,China

Radionuclides are released together with fly ash from the coal-fired power plant and thus add to the natural radiation. Fifty soil samples were collected around the Baoji coal-fired power plant from 25 locations and the natural radionuclide concentrations were determined by a gamma ray spectrometric system. The results show that the activity concentrations in soil samples range from 12.54 to 40.18 Bq kg^?1, 38.02 to 72.55 Bq kg^?1 and 498.02 to 1126.98 Bq kg^?1 for ²²⁶Ra, ²³²Th and ⁴⁰K with the mean values of 27.35, 52.66 and 764.72 Bq kg^?1, respectively. In order to evaluate the radiological hazard of the natural radioactivity, the radium equivalent activity (Ra_eq), the absorbed dose rate (D) and the annual effective dose rate have been calculated and compared with the internationally approved values. The radium equivalent activity in all the soil samples is lower than the safe limit set in the Organization for Economic Cooperation and Development report (370 Bq kg^?1). The average value of the calculated dose rates is higher than the global average value 55 nGy h^?1, and the calculated annual effective dose rate is significantly lower than the average annual external effective dose rate (460 μSv y^?1) of the normal background radiation.     

Soil depth profile of 137Cs, 210Pb and 40K in Algeria

ABSTRACT

Three soil depth profiles of ²¹⁰Pb, ¹³⁷Cs and ⁴⁰K at different areas of Algeria were studied. The soil sampling areas are near the location where the French nuclear tests took place at 1960–1966. The two depth soil profiles were collected at Ghardaia region and the third one at Reggane region. The vertical distributions of radionuclides at the two soil depth profiles from Ghardaia region are different, probably due to the different soil composition. The soil depth profile from sandy soil show uniformity in the distribution of radionuclides without a clear maximum (peak). The soil depth profile that characterised by silty sand show a clear peak at 20–50?cm depth for all studied radioactive nuclides, while the observed activities are two times higher than the corresponding values in sandy soil samples. More specifically in Ghardaia region the ²¹⁰Pb, ¹³⁷Cs, ⁴⁰K activity concentrations ranged between 27 and 50?Bq?kg^?1, 0.2 and 3?Bq?kg^?1 and 75 and 90?Bq?kg^?1 respectively in sandy soil type and between 37 and 75?Bq?kg^?1, 4 and 6?Bq?kg^?1 and 140 and 180?Bq?kg^?1 respectively in silty sand soil type. Finally, the third depth soil profile collected from Reggane site presents a completely different distribution of the studied radionuclides. The activity concentrations of ²¹⁰Pb, ¹³⁷Cs, ⁴⁰K ranged between 37 and 51?Bq?kg^?1, 0.16 and 0.39?Bq?kg^?1 and 120 and 309?Bq?kg^?1 respectively. Three peaks in the ¹³⁷Cs distribution revealed, were most probably, Chernobyl related ¹³⁷Cs accounts for the surface peak, while the deeper peaks are connected to the weapons fallout.     

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.     

Determination of gold and silver in dross using EDXRF technique

Gold and silver in dross were determined by energy‐dispersive X‐ray fluorescence technique. Sample was prepared by pressed pellet method using microcrystalline cellulose powder as binder, and a method of standard additions was used for quantification. L_β X‐ray of gold (11.4 keV) and K_β X‐ray of silver (24.9 keV) were used for analysis. The measured concentrations of gold and silver were 132 ± 8 and 1181 ± 84 mg kg^?1, respectively. The results were validated by instrumental neutron activation analysis technique. The t‐test indicated that there was no significant difference between results obtained by the two techniques. Energy‐dispersive X‐ray fluorescence is a simple, precise and accurate technique for the determination of gold and silver in dross. Copyright © 2014 John Wiley & Sons, Ltd.     

Natural radioactivity measurements in Pahang State,Malaysia

This study was aimed at providing the baseline data of terrestrial gamma dose rates and natural radioactivity to assess the corresponding health risk in the ambient environment of the Pahang State. Terrestrial gamma radiation (TGR) from 640 locations was measured with the mean value found to be 176?±?5 nGy h^?1. Ninety-eight soil samples were analysed using a high-purity germanium detector (HPGe), and the mean concentrations of the radionuclides ²²⁶Ra, ²³²Th and ⁴⁰K are 110?±?3, 151?±?5 and 542?±?51 Bq kg^?1, respectively.²²⁶Ra and ²³²Th concentrations were found to be three times the world average, while that of ⁴⁰K is quite higher than the world average value. The acid-intrusive geological formation has the highest mean concentrations for ²²⁶Ra (215?±?6 Bq kg^?1), ²³²Th (384?±?12 Bq kg^?1) and ⁴⁰K (1564?±?153 Bq kg^?1). The radium equivalent activities (Req) and the external hazard index (Hex) for the various soil types were also calculated. Some of the soil types were found to have values exceeding the internationally recommended levels of 370 Bq kg^?1 and the unity value, respectively.     

31P and1H powder ENDOR study of ozonide radicals in carbonated apatites,synthesized from aqueous solutions

An O ₃ ^? defect in Na⁺ CO ₃ ^2? containing apatite powder has been investigated with ENDOR after X-irradiation. The powder, synthesized by a hydrolysis of octo-calciumphosphate (OCP) and Na₂CO₃ was dried at 25°C until constant weight was reached. At low temperatures, both³¹P and¹H ENDOR spectra were recorded for different settings of the magnetic field (i.e., when the magnetic field is swept through the EPR O ₃ ^? spectrum). The ENDOR powder spectra were thoroughly analyzed using computer simulations based on the “orientation selection principle”. Interactions with two types of protons and two types of³¹P nuclei could be resolved. In this way, a detailed model could be established for the O ₃ ^? ion in the hydroxyapatite lattice. The defect is located between two successive vacant hydroxyl sites. The axis connecting the two outer oxygen atoms (g _y-axis) of the O ₃ ^? ion is found to be along the hexagonalc-axis of the lattice. The twofold axis of the defect ion (g _z-axis) is parallel to theb-axis of the lattice.     

Natural radioactivity and radiation hazards assessment of soil samples from the area of Tuzla and Lukavac,Bosnia and Herzegovina

The results of activity concentration measurements of natural occurring radioactive nuclides ²³⁸U, ²³⁵U, ²³²Th, ²²⁶Ra, and ⁴⁰K in surface soil samples collected in the area of cities Tuzla and Lukavac, northeast region of Bosnia and Herzegovina were presented. Soil sampling was conducted at the localities that are situated in the vicinity of industrial zones of these cities. The measured activity was in the range from (8?±?4) to (95?±?28) Bq kg^–1 for ²³⁸U, from (0.41?±?0.06) to (4.6?±?0.7) Bq kg^–1 for ²³⁵U, from (7?±?1) to (66?±?7) Bq kg^–1 for ²³²Th, from (6?±?1) to (55?±?6) Bq kg^–1 for ²²⁶Ra, and from (83?±?12) to (546?±?55) Bq kg^–1 for ⁴⁰K. In order to evaluate the radiological hazard of the natural radioactivity for people living near industrial zones, the absorbed dose rate, the annual effective dose and the radium equivalent activity have been calculated and compared with the internationally approved values.     

Molecular orbital interpretation of X-ray emission and esca spectral shifts in silicates

An approximate molecular orbital theory is presented, tested, and applied to silicon and aluminum oxyanions. The orbital structure of SiO₄^?4 is calculated and is used to assign the X-ray emission spectra. Calculations are performed at several internuclear distances and semiquantitative agreement is found with experimentally observed trends in A1Kα and SiKβ spectra. Calculations on Si₂O₇^?6 and AlSiO₇^?7 yield fair agreement with experimental trends relating to degree of SiO₄ polymerization and to Al/Si ratio. Charges for bridging and non-bridging oxygens in Si₂O₇^?6, combined with point charge potentials from metal ions in the orthopyroxene structure yield Ols binding energies in agreement with ESCA results.     

Vertical-slate-like MoS2 nanostructures on 3D-Ni-foam for binder-free,low-cost,and scalable solid-state symmetric supercapacitors

Here, we report binder-free vertical-slate-like MoS₂ nanostructures on 3D-Ni-Foam (VSL-MoS₂@3D-Ni foam) for low-cost high-performance solid-state symmetric supercapacitors (SSCs). The cost-effective, ecofriendly and scalable solvothermal method and its direct incorporation of VSL-MoS₂@3D-Ni-foam yield SSCs with excellent electrochemical properties with a wide potential window of 1.0?V. Furthermore, high specific capacitance of 34.1?F?g^?1 at a current density of 1.3?A?g^?1, an energy density of 4.7?W?h?kg^?1 at a high-power density of 650?W?kg^?1, and excellent stability with ～82.5% capacitance retention after 10,000 cycles were demonstrated even for SSCs with a binder free MoS₂ electrodes on 3D-Ni-foam. These excellent features of the SSCs with VSL-MoS₂@3D-Ni-foam substantiate their potential opportunity for future energy applications.     

Measurement of radionuclides and absorbed dose rates in soil samples of Peshawar,Pakistan, using gamma ray spectrometry

The analysis of gamma-emitting radionuclides in nature, i.e. ²²⁶Ra, ²³²Th, ⁴⁰K and ¹³⁷Cs, has been carried out in soil samples collected from Peshawar University Campus and surrounding areas using a high purity germanium detector coupled with a computer-based high-resolution multichannel analyser. The activity concentrations in soil ranged from 30.20±0.65 to 61.90±0.95, 50.10±0.54 to 102.80±1.04, 373.60±4.56 to 1082±11.38 and 9.50±0.11 to 46.60±0.42 Bq kg^?1 for ²²⁶Ra, ²³²Th, ⁴⁰K and ¹³⁷Cs, with a mean value of 45±7.70, 67±12.50, 878±180 and 19±9.20 Bq kg^?1, respectively. The radium equivalent activity, internal and external hazard indices have mean values of 203.40±29.40 Bq kg^?1, 0.56 and 0.68, respectively. The mean values of outdoor and indoor absorbed dose rates in air and the annual effective dose equivalents were found to be 106.50 and 128 nGy h^?1 and 0.19 and 0.54 mSv y^?1, respectively. In the present study, ⁴⁰K was the major radionuclide present in soil samples. The presence of ¹³⁷Cs indicates that this area also received some fallout from the nuclear accident of the Chernobyl power plant in 1986. The activity concentrations of radionuclides found in soil samples during the current investigation were nominal. Therefore, they are not associated with any potential source of health hazard to the public.     

Carbon isotopic signature reveals the geographical trend in methane consumption and production pathways in alpine ecosystems over the Qinghai–Tibetan Plateau

On the Qinghai–Tibetan Plateau, isotopic signatures in soil–atmosphere CH₄ fluxes were investigated in nine grasslands and three wetlands. In the grasslands, the fractionation factor for soil CH₄ uptake, α_soil, was much smaller than the usually reported value of 0.9975–1.0095. Stepwise multiple variation analysis indicates that α_soil is higher for higher soil water contents but is lower for higher C/N ratios of soil surface biomass. In the three wetlands, the soil-emitted δ¹³C–CH₄ was similar (?55.3?±?5.5?‰ and ?53.0?±?5.5?‰) in two bogs separated by >1000?km but was lower (?63.4?±?6.3?‰) in a marsh. Environmental factors related to intrasite variations in soil-emitted δ¹³C–CH₄ include the soil C/N ratio, oxidation–reduction potential, soil C concentration and soil water contents. Geographical isotopic surveys revealed environmental constraints on the CH₄ consumption pathways in grasslands and the biome type-specific consistency in CH₄ production pathways in wetlands.     

The temperature dependence of thermal expansion for p-type Ce0.9Fe3.5Co0.5Sb12 and n-type Co0.95Pd0.05Te0.05Sb3 skutterudite thermoelectric materials

During waste heat recovery applications, thermoelectric (TE) materials experience thermal gradients and thermal transients, which produce stresses that scale with the TE material's coefficient of thermal expansion (CTE). Thus, the temperature-dependent CTE is an important parameter for the design of mechanically robust TE generators. For three skutterudite thermoelectric compositions, n-type Co_0.95Pd_0.05Te_0.05Sb₃ (with and without 0.1 at. % cerium doping) and p-type Ce_0.9Fe_3.5Co_0.5Sb₁₂, the CTE was measured using two methods, i.e. X-ray diffraction on powder and bulk specimens and dilatometry on bulk specimens. Each bulk specimen was hot pressed using powders milled from cast ingots. Between 300?K and 600?K, the mean CTE values were 9.8–10.3?×?10^?6 K^?1 for the non-cerium-doped n-type, 11.6?×?10^?6 K^?1 for the 0.1 at. % cerium-doped n-type and from 12.7 to 13.3?×?10^?6 K^?1 for the p-type. In the literature, similar CTE values are reported for other Sb-based skutterudites. For temperatures >600?K, an unrecovered dilatational strain (perhaps due to bloating) was observed, which may impact applications. Also, the submicron particle sizes generated by wet milling were pyrophoric; thus, during both processing and characterization, exposure of the powders to oxygen should be limited.     

Statistical relationship between activity concentrations of radionuclides 226Ra, 232Th, 40K,and 137Cs and geological formations in surface soil of Jordan

An extensive study was conducted to determine the activity concentrations of natural and artificial radionuclides ²²⁶Ra, ²³²Th, ⁴⁰K, and ¹³⁷Cs in soil samples of each governate of Jordan. A total of 370 samples have been measured using a high-purity germanium detector. The activity concentration for ²²⁶Ra, ²³²Th, ⁴⁰K, and ¹³⁷Cs has mean values of 42?±?3, 23?±?3, 309?±?21, and 3.7?±?0.9 Bq kg^–1, respectively. The highest mean activity concentration for ²²⁶Ra was found to be 138?±?4 Bq kg^–1 in the Alkarak governate. In the Ajloun and Jarash governates, the highest mean activity concentration was 35?±?3 Bq kg^–1 for ²³²Th, and 14.2?±?1.9 Bq kg^–1 for ¹³⁷Cs, respectively. Geological influence on the activity concentrations was investigated using the one-way analysis of variance (ANOVA) and independent samples. The ANOVA results indicate that there are strong significant differences between the activity concentrations of ²³²Th, ⁴⁰K, and ¹³⁷Cs based on geological formations the radionuclides occur. The main contribution to gamma dose rate was due to ²²⁶Ra activity concentration. Radium equivalent and external hazard index are associated with a mean value of 98 Bq kg^–1, and 0.266, respectively.     

Two-electron,one-photon transitions in nickel

The two emission lines, Kα₁α₃^h and Kα₂α₃^h resulting from the two-electron transitions $\text{1s}{}^{\mathrm{?2}}\text{→ 2s}{}^{\mathrm{?1}}\text{2p}{}_{\mathrm{<mtext>3</mtext><mtext>2</mtext>}}{}^{\mathrm{?1}}$ and $\text{1s}{}^{\mathrm{?2}}\text{→ 2s}{}^{\mathrm{?1}}\text{2p}{}_{\mathrm{<mtext>1</mtext><mtext>2</mtext>}}{}^{\mathrm{?1}}$ were resolved for elemental nickel. Their measured energies agree well with calculations. Their relative intensity $\text{I(Kα}{}_1\text{α}{}_3{}^{\mathrm{h}}\text{)/I(Kα}{}_2\text{α}{}_3{}^{\mathrm{h}}\text{) ≈}\text{3}\text{4}$ and their intensity relative to that of the Kα diagram lines is about 10^?4. This is some 10⁴ times larger than both theoretical results and the results of ion-atom collision experiments.     

A qualitative test for detection of ferroelectricity in crystalline powder

By use of the pyroelectric temperature analysis (PTA) of the unsintered pressed powder samples in the temperature region of the phase transition it is possible to determine the value of the electric charge released during the transition. The comparison of results of the transition charges obtained from unpoled as well as from poled samples can differentiate a ferroelectric from nonferroelectric material. The proposed method is successfully validated with KH₂PO₄, (NH₄)₂SO₄ and NH₄H₂PO₄ pressed powder.     

2p3/2−13x−1–3x−13d3/2−1 x‐ray satellites in the Lα2 region

The energies and intensities of the various transitions corresponding to the transition scheme 2p_3/2^?13x^?1–3x^?13d_3/2^?1 (i.e. L₃M_x–M_xM₄) were used to compute theoretical Lα₂ satellite spectra in 13 elements in the atomic number range of 62 ≤ Z ≤ 90. The energies were calculated using available HFS data on K–LM and L–MM transition energies. The intensities of all the possible transitions were estimated by considering cross‐sections for the Auger transitions simultaneous to a hole creation and then distributing statistically the total cross‐sections for initial two‐hole states 2p_3/2^?13x^?1 (L₃M_x) amongst various allowed transitions from these initial states to 3x^?13d_3/2^?1 (M_xM₄) final states. Each transition was assumed to give rise to a Gaussian line and the overall spectrum was computed as the sum of these Gaussian curves. The calculated spectra were compared with the available measured Lα satellite spectra. The peaks in the theoretical satellite spectra were identified as the experimentally reported satellites Lα_s, La₁₃, La₁₄ and La₁₇, which lie on the high‐energy side of the Lα₂ dipole line. Copyright © 2005 John Wiley & Sons, Ltd.