The possibility of constructing the hydrogen scale of the absolute atomic masses of the elements

The paper presents a scheme for the experimental-empirical construction of the existing chemical, physical, and carbon scales of the relative nonintegral atomic masses of the elements. The quantitative interrelation between the nonintegral relative atomic masses, their minimized fractional positive and negative natural deviations from integral numbers, and their integral parts are reproduced mathematically. Nonisotopic fractional deviations are shown to be a consequence of methodological side effects of the scheme for theoretical processing of the data of thorough physical and chemical measurements performed by Stas and Aston in constructing scales of relative atomic masses. In conformity with the Prout hypothesis, the absolute atomic mass unit and the corresponding Avogadro’s number value are suggested for the construction of the hydrogen scale of absolute atomic masses of nonisotopic elements, individual isotopes, and isotope-containing elements.     

Determination of low atomic number elements at trace levels in uranium matrix using vacuum chamber total reflection X-ray fluorescence

Determinations of low atomic number elements Na, Mg and Al present at trace concentrations in uranium matrix were made by vacuum chamber total reflection X-ray fluorescence spectrometer for the first time. For this purpose, synthetic samples of uranium with known amounts of these low atomic number elements were prepared by mixing different volumes of their solutions with U solution of high purity. The concentrations of these elements in the samples were in the range of 100–300 μg/g with respect to uranium and 10–20 μg/mL in the solutions. Major matrix uranium was separated by solvent extraction with 30% solution of tri-n-butyl phosphate in dodecane. After the solvent extraction, aqueous phase containing trace elements was mixed with Sc internal standard and the samples were analyzed by vacuum chamber total reflection X-ray fluorescence spectrometer having a Cr Kα excitation source. The total reflection X-ray fluorescence results obtained, after blank corrections, indicated an average deviation of 14% from the calculated concentrations of these low atomic number elements on the basis of their preparation. However, the total reflection X-ray fluorescence determined concentration of Mg was exceptionally lower than the calculated concentration in two samples. These studies have shown that vacuum chamber total reflection X-ray fluorescence is a promising technique for the determination of low atomic number elements in uranium matrix after its separation.     

Target element dependence in the elastic and inelastic energy loss of fast heavy ions

The target atomic number dependence of elastic and inelastic stopping power has been investigated by using theoretical stopping power formulations from literature. The stopping powers for target elements with atomic numbers from 3 to 92 are calculated on the basis of the model of Montenegro et al. and the nuclear stopping power is calculated using the formulation of Wilson et al.. The target atomic number dependence of the electronic and nuclear stopping power is examined for some light and heavy projectiles by comparing the stopping powers for all considered targets. It is observed that there is a strong target atomic number oscillation for helium, nickel and silver ions in nuclear and electronic stopping as a result of varying densities of neighboring elements. We have also determined the target materials, which apply a maximum total stopping force for some incident ions.     

Determination of the elemental composition of tissues of the cardiovascular system by atomic spectrometry, mass spectrometry and X-ray spectrometry methods

The review discusses the published data on the concentrations of chemical elements in tissues of the cardiovascular system determined by atomic absorption and atomic emission spectrometry, mass spectrometry, and also X-ray fluorescence analysis, proton-induced X-ray emission, and X-ray microanalysis. The main parameters of X-ray spectrometry methods used for the examination of the cardiovascular system are compared, the new trends in the analysis of these samples and the main sample preparation approaches are considered.     

A new atomic database for X-ray spectroscopic calculations

The authors undertook to compile a database of recent values of the atomic parameters required for fundamental parameters (FP) calculation of X-ray fluorescence (XRF) spectra, calculation of X-ray absorption in crystals and other samples, and correction of X-ray absorption spectra for self-absorption effects. All values were obtained from published sources and include the elements hydrogen (atomic number 1) through californium (atomic number 98). The data were collected into a single unstructured ASCII text file.     

Determination of slopes of calibration lines in multi element XRF analysis of thin films using polychromatic excitation from Mo,Au, W,and Cr anodes and one standard

An algorithm is described for the theoretical calculation of the slopes of calibration lines for the elements of the K-series in multi element X-ray fluorescence analysis of thin films using polychromatic excitation with X-ray tubes producing widely differing primary radiation intensity profiles. The mathematical equations used to calculate slopes as a function of atomic number are based on the fundamental relationship between fluorescent intensity and atomic number, fluorescent yield, concentration and mass absorption coefficients of the analyte for primary radiation. A normalisation procedure based on a single known slope in the series ensured that the calculated slopes were correct for the particular measuring conditions.     

Site-sensitive X-ray photoelectron spectroscopy of Fe3O4 by photoelectron diffraction

Fe 2p core-level photoelectron spectra of magnetite were measured using soft X-ray and hard X-ray, and its emission angle dependence was investigated. The photoelectron diffraction pattern from different atomic sites differs because the atomic arrangement surrounding each site is different. By selecting the forward-focusing-peak (FFP) directions characteristic to each atomic site and measuring the kinetic energy dependence of the FFP intensities at the Fe 2p core-level range, we succeed in detecting the variation of the peak intensity of Fe 2p core-level spectra at different emission directions. This result, consistent with recent results, suggests that the lower-binding-energy peak of the Fe 2p core-level spectrum may be assigned as the B site component.     

Particle size determination by radioisotope x-ray absorptiometry with sedimentation method]

The possibility of radioisotope X-ray absorptiometry to determine the particle size of powder in conjunction with sedimentation was investigated. The experimental accuracy was primarily determined by Cow and X-ray intensity. where Co'=weight concentration of the particle in the suspension w'=(micron/rho)l/(mu/rho)s-rhol/rhos rho; density micron/rho; mass absorption coefficient, suffix l and s indicate dispersion and particle, respectively. The radiosiotopes, Fe-55, Pu-238 and Cd-109 have high w-values over the wide range of the atomic number. However, a source of high micron value such as Fe-55 is not suitable because the optimal X-ray transmission length, Lopt is decided by the expression, micronlLopt approximately 2/(1+C'ow') by using Cd-109 AgKX-ray source, the weight size distribution of particles from the heavy elements such as PbO2 to light elements such as Al2O3 or flyash was determined.     

Theory of the implementation of the fundamental parameter method for the X-ray fluorescence determination of low-atomic-number elements

The theory of X-ray fluorescence generation in elements with a low atomic number Z is extended to the case of host matrices with high Z. The total contribution of the selective excitation effects is estimated with regard to the cascade K-L transitions. The influence of the elemental composition of the matrix and the excitation conditions on the X-ray fluorescence intensity of the elements in study is assessed. The accuracy of the model of X-ray fluorescence generation in the low-atomic-number elements is confirmed by the agreement of the experimental and calculated intensities of carbon in various carbon-containing compounds.     

Dependence of analytical signal on the concentration of analyte in X-ray spectral analysis

The dependence of the intensity of analytical signals on the element concentrations expressed in weight percentages I(c) and atomic percentages I(a) in X-ray spectrochemical analysis is considered. It was shown that the change-over from the dependence I(a) to the dependence I(c), which took place in the 1950s, had no theoretical grounds, was based on an incorrect application of the concepts of density and Avogadro’s constant, and was accepted because of practical convenience. In the dependence I(c), the calibration characteristics becomes more complex; it requires corrections for matrix effects, even if these effects are absent. Analytical data published in weight percentages and obtained in the analysis of various samples by conventional X-ray fluorescence analysis (XRFA), X-ray radiometric analysis with an energy-dispersive spectrometer, absorption analysis, and electron probe microanalysis are recalculated into atomic percentages. These results and the data obtained by the author in the analysis of alloys and steels demonstrate a correlation between the intensity of characteristic lines and the atomic concentration of the components. If the calibration curve is based on I(a), a linear dependence over a wide range or the entire concentration range is observed in the majority of systems, the number of the necessary reference standard materials sharply decreases (to one), the sensitivity coefficient increases, and the corrections for matrix effects decrease or the necessity for them disappears.     

Analysis of ionic solids with SNMS

Summary The application of plasma-based SNMS to salt samples was examined to reveal the analytical features of this technique for the analysis of environmental material, which is frequently composed of ionic compounds. 10¹⁶ s^–1 cm^–2 argon ions of 300–500 eV energy were used to sputter halides, sulfates, nitrates and carbonates. The mass spectra are dominated by atomic signals of all elements of the salt and contain additional minor signals of binary homo- and heteroelemental clusters. The latter, such as salt monomers of alkali halides, are useful for compound identification. In sputter equilibrium the atomic mass signals can be used for elemental quantitation with a matrix dependence of about ±30% for the detection factors of most elements. As the average elemental detection factors are shown to be governed by atomic ionization probabilities the erosion flux from salts comprises mainly atoms. Results indicate that thermal release of atoms as well as emission of clusters are the main cause of the matrix dependence. The relative yield of the clusters was found to be strongly enhanced with increasing mass difference of the combined ions. The sputter yield of NaCl was determined to be 3.3 atoms/projectile at 490 eV argon ion energy which results in a depth propagation of 5 nm/s for the given sputter conditions.     

Analysis of organic compounds with SNMS

Summary Plasma-based Secondary Neutral Mass Spectrometry (SNMS) as a depth-resolving technique was examined for the first time as a method for the quantitative analysis of heterogeneously distributed organic compounds in environmental material. Using argon ion bombardment (340 eV, 2 mA/cm²) SNMS was applied to a variety of organic compounds. Aliphatic and aromatic hydrocarbons as well as organic compounds with heteroelements yielded mass spectra with predominant atomic signals of carbon and all other elements composing the organic compound. Except for molecularly bound chlorine and nitrogen these signals were found to be governed primarily by atomic ionization probabilities, a prerequisite for elemental quantitation with low matrix dependence. For oxygen as one of these elements matrix dependent variations of the relative detection factor of ±40% were obtained in agreement with average deviations reported for alloy samples. The organic character of the samples is manifested in the appearance of C_mH_n clusters with relative yields declining with increasing number of atoms. The CH signal turned out to be proportional to the hydrogen content regardless of the molecular structure of the compound. This is of analytical importance because low mass separation usually hampers reliable detection of atomic hydrogen with quadrupole mass filters. Other heteroelemental clusters were not detected in significant amounts.     

Volumetric intensity dependence on the formation of molecular and atomic ions within a high intensity laser focus

The mechanism of atomic and molecular ionization in intense, ultra-short laser fields is a subject which continues to receive considerable attention. An inherent difficulty with techniques involving the tight focus of a laser beam is the continuous distribution of intensities contained within the focus, which can vary over several orders of magnitude. The present study adopts time of flight mass spectrometry coupled with a high intensity (8 x 10(15) Wcm(-2)), ultra-short (20 fs) pulse laser in order to investigate the ionization and dissociation of the aromatic molecule benzene-d1 (C(6)H(5)D) as a function of intensity within a focused laser beam, by scanning the laser focus in the direction of propagation, while detecting ions produced only in a "thin" slice (400 and 800 microm) of the focus. The resultant TOF mass spectra varies significantly, highlighting the dependence on the range of specific intensities accessed and their volumetric weightings on the ionization/dissociation pathways accessed.     

Origin and impact of particle-to-particle variations in composition measurements with the nano-aerosol mass spectrometer

In the nano-aerosol mass spectrometer, individual particles in the 10–30 nm size range are trapped and irradiated with a high pulse energy laser beam. The laser pulse generates a plasma that disintegrates the particle into atomic ions, from which the elemental composition is determined. Particle-to-particle variations among the mass spectra are shown to arise from plasma energetics: Low ionization energy species are enhanced in some spectra while high ionization energy species are enhanced in others. These variations also limit the accuracy and precision of elemental analysis, with higher deviations generally observed when low ionization energy species are dominant in the mass spectrum. For standard datasets generated from nominally identical particles, it is shown that that the error associated with composition measurement is random and that averaging the spectra from a few tens of particles is sufficient for measuring the mole fractions of common elements to within about 10 % of the expected value. Averaging a greater number of particles offers limited improvement of the measurement precision but has the deleterious effect of degrading the measurement time-resolution, which is given by the time needed to obtain the required number of particle spectra for averaging. An internally mixed ambient particle dataset was found to give a similar result to the standard datasets, that is, the measured elemental composition converged to the average value after a few tens of particles were averaged.     

Mono-standard calibration approach to multi-element XRF analysis of thin films using polychromatic excitation

Summary A reliable method is described for the calculation of slopes of calibration lines for thin-film samples using polychromatic excitation. Theoretically calculated slopes for elements within one series, e.g. the K-series, are normalized using one or two known slopes for elements in the series. The mathematical equations used to interpolate slopes as a function of atomic number are based on the fundamental relationship between fluorescent intensity and atomic number, fluorescent yield, detector efficiency, concentration and mass absorption coefficients. Kramer's formula is used to approximate the shape of the primary radiation spectrum. The method was applied to the analysis of thin films.     

Kieselgelstandards für die Bestimmung von Spurenelementen in pulverförmigen Proben mit leichter Matrix durch Röntgenfluorescenzanalyse

The paper deals with homogeneous magnetic fields and added chemical substances both affecting the spectrochemical results obtained in arc excitation studies. The influence of a homogeneous magnetic field on the total intensity of lines of various analysis elements (Hg, Zn, Ga, Tl) in graphite has been examined. Furthermore, the axial and radial distributions of line intensities in arc plasma were determined. Parameters used were the magnetic field strength (0, 0.01, 0.02, 0.04 T) and the physical data of the analysis elements. It was found that the effect of the magnetic field varies with the ionization potential of the elements involved, their atomic mass and the strength of the magnetic field applied. A non-destructive method of measuring was introduced for studying the effects of a homogeneous magnetic field on the rates of evaporation. The results showed increased evaporation rates in presence of magnetic fields as a function of the evaporation heat of the elements involved. Effects of Ga₂O₃ additive on the line intensities of impurity elements are governed by the Ga₂O₃ concentration and the ionization potential of the elements examined.     

Investigation of thin surface films by microprobe analysis

The electron microprobe has been applied to study thin films on metallic substrates. The intensities of the characteristic X-rays emitted by thin films of various elements and thicknesses on sublayers of different materials were measured. Two different theoretical approaches (Bishop and Poole, as well as Yakowitz and Newbury) were applied to interpet the X-ray intensities and to determine the film thickness from the intensity measurements. The effect of backscattering from the substrate, resulting in an increase of the intensity of characteristic X-rays of the film, is being described on the basis of a theory given by Hutchins. The corresponding equation for the backscattering factor has been modified to take into account the transmission of the electrons through the film, depending on the mass thickness of the film and the electron energy. The results obtained from theory and experiment are in good agreement for the different experimental parameters applied, except for very thick layers of high atomic numbers measured at low energies where the absorption of electrons in the film plays a dominant role.     

Size-dependent extinction coefficients of PbS quantum dots

We report here on a detailed study on PbS colloidal quantum dots. A characterization via X-ray diffraction (XRD) and high-resolution transmission electron microscopy (HRTEM) allowed us to reliably determine the diameter and the shape of the nanocrystals. These data, together with second-derivative analysis of the absorption spectra, allowed us to determine the size dependence of seven transitions in the absorption spectrum; some of these transitions were identified on the basis of their normalized confinement energy. The size dependence of the first excitonic transition was best modeled by a four-band envelope approach which considers the anisotropy of the band edges (Andreev, A. D.; Lipovskii, A. A. Phys. Rev. B: Condens. Matter Mater. Phys. 1999, 59, 15402-15404). The extinction coefficients were calculated using concentrations obtained from inductively coupled plasma atomic emission spectrometry (ICP-AES), and their size dependence was found to follow a power law with exponent equal to approximately 2.5. In contrast with what was expected from the effective mass approximation, the per particle absorption cross section of the lowest transition was found to be strongly dependent on the particle size.     

The use of the ratios of intensities of spectral lines for X-ray fluorescence analysis of metal alloys and oxide materials

An X-ray fluorescence analysis technique is proposed, which is based on using ratios of intensities of spectral lines. The technique includes performing calculations for evaluation of calibration equations, which allows using few reference samples or carrying out standardless analysis, if necessary. That parameters of the calibration equations depend linearly on concentrations of disturbing elements allows one to simplify taking their influence into account. To apply the developed technique to analysis of samples containing a significant amount of undetectable light elements, a use of a dependence of intensity ratio of the characteristic radiation of the X-ray tube’s anode, coherently and incoherently scattered by a sample, on a total content of undetectable elements is proposed. The technique’s adequacy is demonstrated by analysis of standard steel samples, metal cuttings and iron-ore materials.     

电感耦合等离子体原子发射光谱法同时测定高强度玻璃纤维粉体中9种金属元素

建立电感耦合等离子体原子发射光谱法测定高强度玻璃纤维粉体中铝、镁、钙、铁、钛、锂、铈、钠、钾9种金属元素含量的方法。采用氢氟酸、高氯酸和盐酸分两段溶解样品,分别在选定的各元素分析谱线下,采用电感耦合等离子体原子发射光谱仪测定各元素含量。9种金属元素在各自的质量浓度范围内与光谱强度成良好的线性关系,相关系数均大于0.999,检出限为8.0~17.4 μg/g。测定结果的相对标准偏差小于1.8%(n=6),加标回收率为97.6%~103.7%。该方法准确,简便,快速,适用于高强度玻璃纤维中多金属元素的同时测定。