X-ray absorption spectroscopy of transition-metal trichalcogenides

The sulfur K and metal L_III absorption spectra of transition-metal trichalcogenides (TMTC's) were measured. The matrix element effect plays an important role in these spectra. It was considered that the structures up to 5 eV above the absorption edge reflect the chalcogen antibonding band, the metal nonbonding d_z² band, and the metal d bands, and that the higher energy structures are derived from the metal s and p bands. The chalcogen antibonding band arises from chalcogen pairing and the metal d, s, and p bands are the mixture bands with chalcogen p orbitals. Evidence that shows that the lowest conduction band of the group IV TMTC's is the chalcogen antibonding band is presented. The overlap of the metal d and metal s bands is promoted by increasing the atomic number of chalcogen atoms.     

Total reflection X-ray fluorescence and energy-dispersive X-ray fluorescence analysis of runoff water and vegetation from abandoned mining of Pb–Zn ores

The present work reports on the heavy metal content: Cr, Mn, Fe, Co, Ni, Cu, Zn, As, Cd and Pb in running waters and vegetation around abandoned mining areas. Two species of mosses (Dicranum sp. and Pleurocarpus sp.) and three different species of wild grass (Bromus sp., Rumex sp. and Pseudoavena sp.) growing on the surrounding areas of old lead–zinc mines (Aran Valley, Pyrenees, NE Spain) have been analyzed. Both water and vegetation were collected in two different sampling places: (a) near the mine gallery water outlets and (b) on the landfill close to the abandoned mineral concentration factories. For the heavy metal content determination, two different techniques were used: total reflection X-ray fluorescence for water analysis and energy-dispersive X-ray fluorescence for vegetation study. Surface waters around mine outlets exhibit anomalous content of Co, Ni, Zn, Cd. Stream waters running on mining landfills exhibit higher Cu, Zn, Cd and Pb than those of the waters at the mine gallery outlets. The results allow us to assess the extent of the environmental impact of the mining activities on the water quality. The intake of these elements by vegetation was related with the sampling place, reflecting the metal water content and the substrate chemistry. Accumulation of metals in mosses is higher than those exhibited in wild grasses. Furthermore, different levels of accumulation were found in different wild grass. Rumex sp. presented the lowest metal concentrations, while Pseudoavena sp. reported the highest metal content.     

Total reflection X-ray fluorescence spectrometric determination of elements in water hyacinth from the Lerma River

The Lerma River is one of the most polluted body water in Mexico. For this reason, only the highly resistant organisms such as water hyacinth are able to reproduce in this river. The aim of this work was to evaluate the concentration of K, S, Fe, Ca, Mn, Ti, Zn, Sr, Rb, Cu, Cr, Ni, Pb and Br in roots of water hyacinth (Eichhornia crassipes) from the Lerma River. The samples were collected from five sites in the river and analyzed in triplicate using a TXRF Spectrometer ‘TX-2000 Ital Structures’ with a Si(Li) detector and a resolution of 140 eV (FWHM) at Mn Kα. A Mo tube (40 kV, 30 mA) with 17.4 KeV excitation energy was used for a counting time of 500 s. Results show that the average metal concentration in the water hyacinth roots decrease in the following order: K (9698.2 µg/g) > S (7593.3 µg/g) > Fe (4406.6 µg/g) > Ca (2601.8 µg/g) > Mn (604.2 µg/g) > Ti (230.7 µg/g) > Zn (51.65 µg/g) > Sr (43.55 µg/g) > Rb (18.61 µg/g) > Cu (12.78 µg/g) > Cr (6.45 µg/g) > Ni (4.68 µg/g) > Pb (4.32 µg/g) > Br (4.31 µg/g) and the bioconcentration factors in the water hyacinth decrease in the sequence: Ti > Fe > Mn > Cu > Ni > Zn > S > Pb > Rb > K > Cr > Sr > Br > Ca. The concentrations in roots of water hyacinth reflect the high pollution level of the river.     

Elemental content in deionized water by total-reflection X-ray fluorescence spectrometry

This study aimed to evaluate minor and trace elements in the water during different water purification steps of a deionized water production plant, located at CENA, by total-reflection X-ray fluorescence (TXRF) technique, using Ga as internal standard for elemental quantification. This approach was capable of determining Cr, Mn, Fe, Co, Ni, Cu, Zn, Ge, As, Se, Br, Rb at concentrations higher than 40–100 μg L⁻¹, and for K, Ca, Sc, Ti, V and Sr at concentrations higher than sub mg L⁻¹ in the water samples. TXRF spectrometer encompasses an X-ray tube with a Mo target with a Zr filter. The elemental characteristic X-rays were recorded by a Si(Li) semiconductor detector and the X-ray spectra deconvoluted by AXIL software.     

Core-electron spectroscopy of alkaline-earth and transition-metal ions in solution

Core-electron spectra of alkaline-earth and transition-metal ions in solution have been recorded. Solvation energies for the core-ionized species are derived using thermodynamic cycles which involve the free-ion to dissolved-ion binding energy shifts. The distinction between “soft” and “hard” ion behaviour is discussed in relation to the solvation energies and multi-line features in the transition-metal core spectra.     

Analysis of mineral water from Brazil using total reflection X-ray fluorescence by synchrotron radiation

The total reflection X-ray fluorescence using synchrotron radiation (SRTXRF) has become a competitive technique for the determination of trace elements in samples that the concentrations are lower than 100 ng ml⁻¹. In this work, thirty-seven mineral waters commonly available in supermarkets of Rio de Janeiro, Brazil, were analyzed by SRTXRF. The measurements were performed at the X-Ray Fluorescence Beamline at Brazilian National Synchrotron Light Laboratory (LNLS), in Campinas, São Paulo, using a polychromatic beam with maximum energy of 20 keV for the excitation. Standard solutions with gallium as internal standard were prepared for calibration of the system. Mineral water samples of 10 μl were added to Perspex sample carrier, dried under infrared lamp and analyzed for 200 s measuring time. It was possible to determine the concentrations of the following elements: Si, S, K, Ca, Ti, Cr, Mn, Ni, Cu, Zn, Ge, Rb, Sr, Ba and Pb. The elemental concentration values were compared with the limits established by the Brazilian legislation.     

Reactions of atomic transition-metal ions with long-chain alkanes

Understanding metal ion interactions with long-chain alkanes not only is of fundamental importance in the areas of organometallic chemistry, surface chemistry, and catalysis, but also has significant implication in mass spectrometry method development for the analysis of polyethylene. Polyethylene represents one of the most challenging classes of polymers to be analyzed by mass spectrometry. In this work, reactions of several transition-metal ions including Cr+, Mn+, Fe+, Co+, Ni+, Cu+, and Ag+ with long-chain alkanes, C28H58 and C36H74, are reported. A metal powder and the nonvolatile alkane are co-deposited onto a sample target of a laser desorption/ionization (LDI) time-of-flight mass spectrometer. The metal ions generated by LDI react with the vaporized alkane during desorption. It is found that all these metal ions can form adduct ions with the long-chain alkanes. Fe+, Co+, and Ni+ produce in-source fragment ions resulting from dehydrogenation and dealkylation of the adduct ions. The post-source decay (PSD) spectra of the metal-alkane adduct ions are recorded. It is shown that PSD of Ag+ alkane adduct ions produces bare metal ions only, suggesting weak binding between this metal ion and alkane. The PSD spectra of the Fe+, Co+, and Ni+ alkane adduct ions display extensive fragmentation. Fragment ions are also observed in the PSD spectra of Cr+, Mn+, and Cu+ alkane adduct ions. The high reactivity of Fe+, Co+, and Ni+ is consistent with that observed in small alkane systems. The unusually high reactivity of Cr+, Mn+, and Cu+ is rationalized by a reaction scheme where a long-chain alkane first forms a complex with a metal ion via ion/induced dipole interactions. If sufficient internal energy is gained during the complex formation, metal ions can be inserted into C-H and C-C bonds of the alkane, followed by fragmentation. The thermal energy of the neutral alkane is believed to be the main source of the internal energy acquired in the complex. Finally, the implication of this work on mass spectrometry method development for polyethylene analysis is discussed.     

An ion exchanger-epoxy resin pelletization method for sample preparation in X-ray fluorescence analysis. Microanalysis of metal ions in industrial waste water

Flame atomic emission and atomic absorption detection limits are compared on an absolute basis for the easily determined element, copper. Remarkably similar detection limits are obtained with a variety of atomization and sample introduction system combinations. Heated graphite atomizers offer significantly lower minimum detectable quantities.     

Total reflection X-ray fluorescence determination of rare earth elements in mineral water

A method is proposed for determination of lanthanum, cerium, praseodymium, neodymium, and samarium in mineral water by means of total-reflection X-ray fluorescence analysis. In this work, the combined technique of preconcentration of rare earth ions is used. This technique consists of coprecipitation of metal hydroxides on the collector (iron (III) hydroxide) and dispersive liquid–liquid microextraction of their complexes with 1-(2-pyridylazo)-2-naphthol by chloroform in the presence of ethanol. The use of the developed hybrid approach allows simultaneous determination of the mentioned metals in mineral water in the range n(10^–2–10¹) μg/L. The results of analysis of Arkhyz and Rychal-Su mineral waters by the proposed extraction–X-ray fluorescent method are confirmed by the literature data, obtained by inductively coupled plasma mass spectrometry.     

Determination of water content in silica nanopowder using wavelength-dispersive X-ray fluorescence spectrometer

A wavelength-dispersive X-ray fluorescence (WDXRF) technique that uses the scattered radiation of the X-ray tube lines and the fluorescence radiation of an element present in a powder sample is proposed as a non-destructive method for the determination of the water content in silica powder. Although direct X-ray fluorescence analysis of water using WDXRF is not adequate for the quantitative determination of water in powder, due to the very low fluorescence yield for hydrogen and oxygen, the fluorescence signal of silicon (Si) in silica powder is attenuated by water, and is shown to decrease in proportion to the water content in silica powder. In addition, it is demonstrated that the Compton- and Rayleigh-scattering of the X-ray tube lines is proportional to the water content. The coefficients of determination, R², of the linear regression equations obtained from the calibration curves for all individual scattered radiations and for the fluorescence radiation of Si were > 0.90. The sum of the peak intensities of the four scattering signals, i.e. the Rayleigh-scattered Rh K–L_2,3 and Rh K–M_2,3 lines, and Compton-scattered Rh K–L_2,3 and Rh K–M_2,3 lines, also showed fairly good linearity and sensitivity over a very wide range of water content from 0 wt.% to 61.5 wt.%. However, porosity had a significant effect on the X-ray signal at low water content, in the range from 0 wt.% to 7.5 wt.%, where the sensitivity for the silica nanopowder with well-defined mesopores (~ 3 nm in diameter) decreased to 0.40 kcps/wt.%, from 0.99 kcps/wt.% for the non-porous silica nanopowder. The use of the Si fluorescence signal along with the scattered radiation of the X-ray tube lines expands the applicability of conventional XRF spectrometers to the quantitative determination of water content in silica powder.     

Metal ions diffusion through polymeric matrices: A total reflection X-ray fluorescence study

This work proposes the use of X-ray fluorescence with total reflection geometry to explore the metal ions transport in aqueous hydrophilic polymer solutions. It is centered in the study of polymer concentration influence on ion diffusion. This subject is relevant to various and diverse applications, such as drug controlled release, microbiologic corrosion protection and enhanced oil recovery. It is anticipated that diffusion is influenced by various factors in these systems, including those specific to the diffusing species, such as charge, shape, molecular size, and those related to the structural complexity of the matrix as well as any specific interaction between the diffusing species and the matrix. The diffusion of nitrate salts of Ba and Mn (same charge, different hydrodynamic radii) through water-swollen polymeric solutions and gels in the 0.01% to 1% concentration ranges was investigated. The measurements of the metal concentration were performed by TXRF analysis using the scattered radiation by the sample as internal standard. Results are discussed according to different physical models for solute diffusion in polymeric solutions.     

X-ray fluorescence analysis of pottery from Northern Mongolia

Energy dispersive X-ray fluorescence (EDXRF) was used to determine the minor and trace element composition of ceramic wares and clays from the Egiin Gol valley in Northern Mongolia. Principal component analysis (PCA) and kernel density estimates (KDEs) suggest that there are five distinct sources of raw materials used to manufacture the pottery. These sources are verified with linear discriminant analysis (LDA). At this time it is uncertain whether these sources reflect the use of specific clay deposits, a widespread clay stratum, or a production workshop.     

New possibilities of energy-dispersive X-ray fluorescence technique in the analysis of potable water

The article considers specific features of schemes of X-ray fluorescence analysis of liquid samples in the geometry of thick layers and in thin layers using the X-ray optics scheme with total internal reflection. A scenario is proposed for the analysis of liquid samples in thin layers using a simple X-ray optics scheme lowering the detection limits 1000-fold in comparison with the traditional scheme in thick layers. The internal standard method is implemented to improve the reproducibility of the results. The proposed scenario was tested in the analysis of potable water.     

Study of peptide on-line complexation with transition-metal ions generated from sacrificial electrodes in thin-chip polymer microsprays

A miniaturized polymer electrospray-type interface is used to study metal-ion chelation with model peptides. Taking advantage of the intrinsic electrochemical behavior of electrospray, a sacrificial electrode is used to generate at the same time electrospray and transition-metal ions coming from the anodic dissolution of the electrode. The microspray interface provides enhanced mass transport due to its small dimensions, increasing the yield of possible reactions, in particular complex formation. Transition-metal electrodes, e.g. copper, zinc, nickel, iron and silver, are used to obtain on-line complexation with model peptides. It is demonstrated that the use of in-reservoir sacrificial electrodes is an efficient way to generate metal ions in order to form and study complexes with peptides, avoiding the addition of metallic salts.     

Enhanced capacity of chitosan for transition-metal ions in sulphate-sulphuric acid solutions

Batch measurements have shown that the collection yields of chitosan for chromium(III), iron(III), nickel, copper(II), zinc and mercury(II) from sulphuric acid solutions are higher when the solutions contain ammonium sulphate, or when chitosan conditioned in ammonium sulphate is used, particularly at pH 3.0 and 5.0. The contrary is verified for the oxy-anions vanadate, chromate and molybdate. Manganese is never collected. At pH 1.0 no collection occurs. A procedure for recycling chromatographic columns includes fixation of Cu or Ni from a sulphate solution at pH 3-5 on sulphate-conditioned chitosan, and elution with 0.1M sulphuric acid/0.1M ammonium sulphate at pH 1.0; the presence of sulphate in the eluent obviates the detrimental effect of sulphuric acid on the next cycle. Sulphate is the favoured counter-ion of the chelated cations and its action produces shorter chromatographic bands. The interaction of sulphate with chitosan is discussed in terms of crystallinity and steric distribution of the protonated amino-groups in the polymer. Data on the new diethylaminohydroxypropylcellulose are included.     

Complexes of the porphyrins of Karazhanbass petroleum with transition-metal ions

The possibility and prospects of the use of petroleum porphyrins isolated from Karazhanbass petroleum for the synthesis of complex compounds of the transition metals has been shown.Institute of the Petroleum and Natural Salts, Academy of Sciences of the Kazakh SSR, Bur'ev. Translated from Khimiya Prirodnykh Soedinenii, No. 5, pp. 621–624, September–October, 1990.     

X射线荧光光谱分析

本文评述了我国在2005年至2006年X射线荧光光谱,包括粒子激发的X射线光谱的发展和应用,内容包括仪器研制、激发源、探测器、软件、仪器改造、仪器维护和维修、样品制备技术、分析方法研究和应用.     

Separation of some transition-metal ions on silica-immobilized 2-pyridinecarboxaldehyde phenylhydrazone

A metal-ion extractant, prepared by chemical binding of 2-pyridinecarboxaldehyde phenylhydrazone on a silica support, is described and shown to be effective for use in separation and determination of trace amounts of iron, cobalt, nickel, and copper. Metal-ion sorption conforms to the Langmuir isotherm. The relative orders of the Langmuir constants K and the column retention-capacity factors k' for the four transition-metal ions are the same as the natural order of the stabilities predicted for their metal chelates: Fe(II) < Co(II) < Ni(II) < Cu(II).