Investigation of different types of filters for atmospheric trace elements analysis by three analytical techniques

Different atmospheric aerosol samples were collected on three types of filters. Disks of both loaded and clean areas of each kind of filter were investigated by XRF, PIXE and Scanning Electron Microscope (SEM) methods. The blank concentration values of the elements Al, Si, P, S, Cl, K, Ca, Sc, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, As, Br and Pb in the three types of fiters are discussed. It is found that for trace elemental analysis, the Nuclepore membrane filters are the most suitable for sampling. These have much lower blank element concentration values than the glass fibres and ash free filters. It was found also that the PIXE method is a more reliable analytical technique for atmospheric aerosol particles than the other methods.     

XSQR: The technique of pixe-induced XRF

The XSQR technique uses nearly monoenergetic X-rays from the proton bombardment of a primary target to excite X-ray fluorescence for analytical purposes. With the proper choice of primary target, interferences from high concentration components in a matrix may be eliminated. An overview is given of the technique, the equipment it uses and its methodology. The application of the technique is described for the determination of Cr in steels using an Fe primary, Cu and Zn in gold objects using a Ge primary, multielemental analysis of geological and biological materials using primary targets such as Mo, Rh and Pd and Si in oils using a Ti primary target. The method serves as a useful complementary method to PIXE for the determination of the medium mass elements.     

Benchmarking the Fluxional Processes of Organometallic Piano-Stool Complexes

The correlation consistent Composite Approach for transition metals (ccCA-TM) and density functional theory (DFT) computations have been applied to investigate the fluxional mechanisms of cyclooctatetraene tricarbonyl chromium ((COT)Cr(CO)₃) and 1,3,5,7-tetramethylcyclooctatetraene tricarbonyl chromium, molybdenum, and tungsten ((TMCOT)M(CO)₃ (M = Cr, Mo, and W)) complexes. The geometries of (COT)Cr(CO)₃ were fully characterized with the PBEPBE, PBE0, B3LYP, and B97-1 functionals with various basis set/ECP combinations, while all investigated (TMCOT)M(CO)₃ complexes were fully characterized with the PBEPBE, PBE0, and B3LYP methods. The energetics of the fluxional dynamics of (COT)Cr(CO)₃ were examined using the correlation consistent Composite Approach for transition metals (ccCA-TM) to provide reliable energy benchmarks for corresponding DFT results. The PBE0/BS1 results are in semiquantitative agreement with the ccCA-TM results. Various transition states were identified for the fluxional processes of (COT)Cr(CO)₃. The PBEPBE/BS1 energetics indicate that the 1,2-shift is the lowest energy fluxional process, while the B3LYP/BS1 energetics (where BS1 = H, C, O: 6-31G(d′); M: mod-LANL2DZ(f)-ECP) indicate the 1,3-shift having a lower electronic energy of activation than the 1,2-shift by 2.9 kcal mol⁻¹. Notably, PBE0/BS1 describes the (CO)₃ rotation to be the lowest energy process, followed by the 1,3-shift. Six transition states have been identified in the fluxional processes of each of the (TMCOT)M(CO)₃ complexes (except for (TMCOT)W(CO)₃), two of which are 1,2-shift transition states. The lowest-energy fluxional process of each (TMCOT)M(CO)₃ complex (computed with the PBE0 functional) has a ΔG^‡ of 12.6, 12.8, and 13.2 kcal mol⁻¹ for Cr, Mo, and W complexes, respectively. Good agreement was observed between the experimental and computed ¹H-NMR and ¹³C-NMR chemical shifts for (TMCOT)Cr(CO)₃ and (TMCOT)Mo(CO)₃ at three different temperature regimes, with coalescence of chemically equivalent groups at higher temperatures.     

Teeth characterization using ion beam analysis

Summary A collaboration project between the School of Dentistry and the Institute of Physics of the University of S?o Paulo has been established to measure elemental concentrations in teeth by proton induced X-ray emission (PIXE) and heavy ion elastic recoil detection analysis (HI-ERDA) techniques. Data on trace elements in human, bovine and swine teeth, analyzed by PIXE with a 2.4 MeV proton beam, were compared and concentrations for several elements were obtained with tens of mg/g sensitivity. HI-ERDA measurements employing a 52 MeV Cl beam were done to evaluate changes in elementary concentration in dental enamel after bleaching treatment with different products in 25 bovine incisors teeth. This non-destructive technique allowed the measurements of Ca, P, O and C concentrations above the limit of 100 mg/g.     

Shape Controlled Preparation,Characterization and Gas Sensitivities of Shuttle-like Cr-doped α-Fe2O3 Nanoparticles

α-Fe2O3 nanoparticles doped with various mol% Cr3+ have been synthesized by a forced hydrolysis route, and were characterized by XRD, SEM, XPS and ICP techniques. The particles reserve shuttle-like shape in the presence of Cr3+ ions. The crystallite sizes of Fe2O3 become smaller with the increased Cr3+ concentration in solution. The responses of Cr doped α-Fe2O3 sensors were studied towards reducing gases such as ethanol, methanol, acetone, gasoline and n-hexane. Gas sensors based on these materials have higher sensitivities and rapid response/recovery time to alcohol than to hydrocarbon.     

Mg(OH)2•2MgSO4•2H2O晶体的水热生长过程

对MgSO4-NaOH-H2O四元交互体系在160 ℃水热条件下,相同物料配比,不同反应时间的晶体生长过程进行了研究,得到5Mg(OH)2•MgSO4•2H2O(简称MOS)晶须和Mg(OH)2•2MgSO4•2H2O棒状晶体两种硫氧镁化合物.通过化学分析、X-ray粉末衍射、FT-IR光谱和SEM对反应产物进行了表征.前者是该体系水热条件下介稳产物,而新的硫氧镁化合物Mg(OH)2•2MgSO4•2H2O是该体系的稳定相.     

Comparison of different types of filters for atmospheric trace element analysis by three analytical methods

Different atmospheric aerosol samples were collected on three types of filters. From both of the loaded and clean areas of each kind of filter, different disks were cut and investigated by XRF, PIXE and scanning electron microscopy (SEM). The blank concentration values of the elements Al, Si, P, S, Cl, K, Ca, Sc, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, As, Br and Pb in the three types of filter are discussed. It is found that for trace elemental analysis, the Nuclepore membrane filters are the most suitable for sampling. These filters have much lower blank element concentrations than the glass fiber and ash free filters. It was found also that PIXE is a more reliable analytical technique for atmospheric aerosol particles than the other methods used.     

Characterization of dust material emitted during harbour activities by k<Subscript>0</Subscript>-INAA and PIXE

The growing concern about air quality in harbours is a result of the high impact of the operations on human health and environment. Harbour activities such loading, unloading and transport of dusty materials are important emission sources of Atmospheric particulate matter (APM). The assessment of these fugitive emissions is a difficult task because they depend on the materials, the type of operation and the meteorological scenarios. The main objectives of this work were (1) to evaluate if the techniques k₀-based Instrumental neutron activation analysis (k₀-INAA) and Particle induced X-ray emission (PIXE) are suitable techniques to assess fugitive emissions in harbours and (2) to estimate the impact of harbour activities on APM levels and composition. Several experimental campaigns were carried out in a Portuguese harbour, during unloading operations of fertilizer and phosphorite provided from Syria and Morocco. PM_2.5 and PM_2.5–10 were collected, in polycarbonate filters, by Gent samplers. The techniques k₀-INAA and PIXE were applied as sensitive analytical tools to perform a complete chemical characterization of the collected samples. Results showed that manipulation of these materials during harbour operations resulted in high emissions of particles, principally from the coarse fraction. These emissions were very affected by the granulometry and nature of the handled materials. Fertilizer emissions were characterized by high concentration of Ca, P, K, Cr, Br and Zn, whereas phosphorite handling contributed principally for the increase of Ca, P and Cr levels.     

Sol–gel synthesis,crystal structure,surface morphology,and optical properties of Eu2O3-doped La2Mo3O12 ceramic

In this paper, we report the synthesis of the La–Mo–O tartrate gel precursors with the initial composition for La₂Mo₃O₁₂ ceramic prepared from different starting materials by an aqueous sol–gel synthesis route using tartaric acid as a complexing agent. Moreover, the La–Mo–O carbonate–tartrate and nitrate–tartrate gel precursors doped with x % of Eu₂O₃ (x = 0.5, 1.0, 2.0, 4.0, and 8.0) by aqueous sol–gel synthesis method were also prepared. The thermal decomposition of both the La–Mo–O carbonate–tartrate and nitrate–tartrate gels, which is the critical stage of this preparation technique, is investigated in detail. X-ray diffraction, scanning electron microscopy, and ultraviolet–visible spectroscopy were used for the determination of crystal structure, surface morphology, and optical properties of the La–Mo–O:xEu₂O₃ samples annealed at 400, 500, 600, 700, 800, 900, and 1,000 °C temperatures, respectively. The obtained results show that the thermal decomposition of the La–Mo–O tartrate gel precursors has occurred in a separate manner. The differences that came up during the thermal treatment of La–Mo–O tartrate gels have related only with the initial composition that determined the different crystallization ways of final compounds. Besides, the dopant concentration mainly influences the size of obtained particles and agglomeration of synthesized final materials. The initial composition of the La–Mo–O gel precursors has significant influence on the formation of final crystal phases at relatively lower temperatures than was expected according to the TG–DTA measurements. Finally, the optical properties of La–Mo–O tartrate gel precursors annealed at 500 °C depend on the nature of the initial compounds, which were used during the aqueous sol–gel process.     

XRF induced by PIXE: Comparison with PIXE

Two different modes of sample excitation have been used for elemental analysis of thin standard reference materials and of chemical standards with known composition. PIXE /2.5 MeV protons/ and XRF induced by PIXE, will be called XRF-PIXE /2.5 MeV protons on Mo primary target/. The same samples were alternatively exposed to protons and X-ray beams. The sensitivities under standard running conditions are determined for both an XRF-PIXE and a PIXE analysis system. It is shown that the sensitivity of the PIXE spectrometer depends strongly on the sample matrix, whereas the XRF-PIXE sensitivity is rather constant with respect to different kinds of samples. In addition, the advantages of one mode of excitation on the other are discussed. It is shown that XRF-PIXE can be a useful complement to PIXE analysis.     

H_6P_2Mo_(18)O_(62)/Zn(BDC)(Bipy)_(0.5)复合材料的合成、表征及对亚甲基蓝的吸附

在溶剂热条件下,以H6P2Mo18O62、对苯二甲酸(H2BDC)、4,4'-联吡啶(Bipy)和硝酸锌为原料构筑了1个三维金属有机骨架复合材料H_6P_2Mo_(18)O_(62)/Zn(BDC)(Bipy)_(0.5),并采用红外光谱(IR)、X射线衍射(XRD)、扫描电子显微镜(SEM)、热重分析(TG)、N2吸附-脱附等手段对产物进行了表征.同时,研究了产物对水溶液中亚甲基蓝(MB)的吸附性能,并探讨了MB初始p H值、初始浓度和温度对吸附量的影响.结果表明,产物的等温吸附模型符合Langmuir等温吸附模型,动力学符合拟二级动力学.H_6P_2Mo_(18)O_(62)/Zn(BDC)(Bipy)_(0.5)对亚甲基蓝的吸附是自发和放热的,此外,产物对甲基紫、罗丹明B、孔雀石绿等阳离子染料也具有良好的吸附性能.     

A convenient method for the preparation of barbituric and thiobarbituric acid transition metal complexes

A convenient method for the preparation of barbiturate transition metal complexes: (i) Cr(3+), Mn(2+), Fe(3+), Zn(2+) and Cd(2+) ions with barbituric acid (H(2)L) and (ii) Cr(3+) and Mo(5+) with 2-thiobarbituric acid (H(2)L') was reported and this has enabled seven complexes to be formulated as: [Cr(HL)(2)(OH)(H(2)O)].H(2)O, [Mn(HL)(2)(H(2)O)(2)], [Fe(2)(L)(OH)(3)(H(2)O)(4)].2H(2)O, [Zn(HL)(2)], [Cd(HL)(2)], [Cr(HL')(OH)(2)(H(2)O)].H(2)O and [Mo(HL')(2)]Cl. These new barbiturate complexes were synthesized and characterized by elemental analysis, molar conductivity, magnetic measurements, spectral methods (mid infrared, (1)H NMR, mass, X-ray powder diffraction and UV/vis spectra) and simultaneous thermal analysis (TG and DTG) techniques. The molar conductance measurements proved that, all complexes of barbituric and 2-thiobarbituric acids are non-electrolytes except for [Mo(HL')(2)]Cl. The electronic spectra and magnetic susceptibility measurements were used to infer the structures. The IR spectra of the ligands and their complexes are used to identify the mode of coordination. Kinetic and thermodynamic parameters such as: E, DeltaH, DeltaS and DeltaG are estimated according to the DTG curves. The two ligands and their complexes have been studied for their possible biological antifungal activity.     

Aqueous sol–gel synthesis and thermoanalytical study of the alkaline earth molybdate precursors

The preparation and characterization of the M′–Mo–O nitrate–tartrate (M′ = Mg, Ca, Sr, and Ba) gels, which were produced by the simple aqueous sol–gel method and calcined at 500, 600, 700, 800, 900, and 1,000 °C temperatures are reported. The crystalline alkaline earth metal molybdates (MgMoO₄, CaMoO₄, SrMoO₄, and BaMoO₄) and as-prepared M′–Mo–O nitrate–tartrate gels investigated by thermal analysis (TG/DSC), X-ray diffraction (XRD), and scanning electron microscopy (SEM). TG/DSC analysis showed the possible decomposition mechanism of synthesized gels. XRD studies allowed the identification of main types of crystalline structures in the MgMoO₄, CaMoO₄, SrMoO₄, and BaMoO₄ systems. Moreover, SEM analysis revealed the changes of surface morphology of the final compounds depending on annealing temperatures.     

Proton microprobe determination of fluorine depth distributions and surface multielement characterization in dental enamel

Particle induced X-ray emission analysis (PIXE) and nuclear reaction analysis have been applied to multielemental analysis of human dental enamel in a proton microprobe. The PIXE technique was excercised for the characterization of multielemental lateral distributions on and just below the sample surface. For the assessment of depth distributions of fluorine the resonant nuclear reaction¹⁹F(p,aλ)¹⁶O was used. The combination of two analytical techniques comprising both atomic and nuclear interactions in a microprobe was applied to enamel samples of different origins. One sample constituted a healthy enamel and the other one enamel from a restored tooth. The microprobe in the combined mode was demonstrated to permit the establishment of lateral, concentration gradients of elements heavier than phosphorus with a resolution of 15 μm in enamel and simultaneously of depth distributions of fluorine better than 0.7 μm. The detection limits approached, 10–25 ppm for most of the elements considered. Supported by the Swedish Natural Science Research Council     

PIXE Spectroscopy for Determination of Volatile Corrosion Inhibitor Concentration in Anticorrosion Polymer Films

Anti-corrosion polymer films used for 0 to 6 years were investigated to determine the type and content of volatile corrosion inhibitors (VCI) and how long the films emit it to protect the metal surface encased by the film. By FTIR and DSC low density polyethylene (LDPE) was identified as the polymer carrier. Particle induced X-ray emission (PIXE) spectroscopy of anti-corrosion polymer films revealed significant concentration of molybdenum implying that corrosion inhibitor was molybdate based. The films were divided into three groups according to different rate of the VCI concentration decrease with increasing age. The division of films into groups and diffusion of VCI was confirmed by significant decrease of Mo content determined by PIXE spectroscopy after accelerated ageing in vacuum at 50°C. It was concluded that films with initial concentration of Mo above 6000 ppm emit VCI for at least 6 years while the films with less than 4000 ppm of molybdenum do not emit the VCI in the ambient conditions.     

PIXE Spectroscopy for Determination of Volatile Corrosion Inhibitor Concentration in Anticorrosion Polymer Films

Summary. Anti-corrosion polymer films used for 0 to 6 years were investigated to determine the type and content of volatile corrosion inhibitors (VCI) and how long the films emit it to protect the metal surface encased by the film. By FTIR and DSC low density polyethylene (LDPE) was identified as the polymer carrier. Particle induced X-ray emission (PIXE) spectroscopy of anti-corrosion polymer films revealed significant concentration of molybdenum implying that corrosion inhibitor was molybdate based. The films were divided into three groups according to different rate of the VCI concentration decrease with increasing age. The division of films into groups and diffusion of VCI was confirmed by significant decrease of Mo content determined by PIXE spectroscopy after accelerated ageing in vacuum at 50°C. It was concluded that films with initial concentration of Mo above 6000 ppm emit VCI for at least 6 years while the films with less than 4000 ppm of molybdenum do not emit the VCI in the ambient conditions.     

Standardless PIXE analysis of thick biomineral structures

The particle-induced X-ray emission (PIXE) of thick biomineral targets provides pertinent surface analysis, but if good reference materials are missing then complementary approaches are required to handle the matrix effects. This is illustrated by our results from qualitative and semiquantitative analysis of biomaterials and calcified tissues in which PIXE usually detected up to 20 elements with Z > 14 per sample, many at trace levels. Relative concentrations allow the classification of dental composites according to the mean Z and by multivariate statistics. In femur bones from streptozotocin-induced diabetic rats, trace element changes showed high individual variability but correlated to each other, and multivariate statistics improved discrimination of abnormal pathology. Changes on the in vitro demineralization of dental enamel suggested that a dissolution of Ca compounds in the outermost layer results in the uncovering of deeper layers containing higher trace element levels. Thus, in spite of significant limitations, standardless PIXE analysis of thick biomineral samples together with proper additional procedures can provide relevant information in biomedical research.Abbreviations AAS Atomic absorption spectrometry - ERDA Elastic recoil detection analysis - ESR Electron spin resonance - FDA Factorial discriminant analysis - FTIR spectroscopy Fourier transform infra-red spectroscopy - HP Ge detector Hyperpure Ge detector - ICP-AES Inductively coupled plasma atomic emission spectrometry - NAA Neutron activation analysis - NRA Nuclear reaction analysis - PCA Principal component analysis - PIXE Particle-induced X-ray emission - PIGE Particle-induced -ray emission - RBS Rutherford backscattering spectroscopy - SRIXE Synchrotron radiation-induced X-ray emission     

Preparation of FeS/iron oxide composite and flax stem‐based porous carbon and its Cr(VI) removal ability

Using flax stem and ferrous sulfate, a composite porous carbon material was prepared by means of high‐temperature roasting and a one‐step process in a muffle furnace. The samples were characterized using X‐Ray diffraction (XRD) and Scanning electron microscopy (SEM), and the effects of ferrous sulfate concentration, carbonization temperature, and pH values of Cr(VI) aqueous solution on the removal performance of Cr(VI) were studied. XRD and SEM analysis showed that the prepared samples were amorphous porous carbon loaded with FeS/Fe₂O₃/Fe₃O₄. High FeSO₄ impregnation concentration, high carbonization temperature, and a low pH value of Cr(VI) aqueous solution were beneficial for Cr(VI) removal. When pH = 2, the amount of Cr(VI) removal was 99.93 mg/g by the sample obtained from 1 g flax powder impregnated in 4.5 mmol FeSO₄/40 mL H₂O solution and calcined for 2 hr at 800°C.     

Determination of chemical elements in airborne particulate matter collected at Lembang, Indonesia by particle induced X-ray emission

Monitoring the air quality in ambient air is an important step for assessing the air pollution level in one region and its impact to the human health. In this study, the determination of chemical elements concentrations in airborne particulate matter collected in suburban area of Lembang, Indonesia was carried out. Samples were collected using a Gent stacked filter unit sampler in two size fractions of <2.5 μm (fine) and 2.5–10 μm (coarse). Sampling was conducted twice a week for 24 h from January 2008 to June 2009 and 123 pairs of samples were collected. Black carbon was determined by reflectance and chemical elements analysis were performed using particle induced X-ray emission (PIXE). PIXE as one of ion beam analysis techniques is suitable for analyzing particulate matter for its multielemental analysis with good limits of detection. Results showed that none of daily concentrations of PM_2.5 and PM₁₀ exceeded the 24 h Indonesian NAAQS for PM_2.5 and PM₁₀. Chemical elements such as Mg, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, As, Hg and Pb were determined and the correlation between these elements was reported in order to understand the anthropogenic sources of particulate matter.     

Simultaneous determination of seven metal ions in water samples by solid-phase extraction on polyacrylonitrile activated carbon fibres

A new solid-phase extraction method utilising polyacrylonitrile activated carbon fibres (PAN-ACFs) as adsorbent was developed for the preconcentration of trace metal ions prior to their determination by inductively coupled plasma optical emission spectrometry (ICP-OES). The PAN-ACFs oxidised with nitric acid were characterised by FT-IR, XRD, SEM and BET analysis. Then the resulting PAN-ACFs were used as solid-phase adsorbent for simultaneously determination of trace Al(III), Be(II), Bi(III), Cr(III), Cu(II), Fe(III) and Pb(II) ions in aqueous solutions. The influences of the analytical parameters on the recoveries of the studied ions were investigated. The optimum experimental conditions of the proposed method were pH: 6.0; eluent concentration and volume: 3.0 mL of 1.5 mol L^?1 nitric acid; flow rates of sample and eluent solution: 1.5 mL min^?1. The preconcentration factors were found to be 67 for Al(III), Bi(III); 83 for Cr(III), Cu(II), Fe(III) and 50 for Be(II), Pb(II). The precision of this method was in range of 1.5%~3.5% and the detection limit of this metal ions was between 0.06~1.50 μg L^?1. The developed method was validated by the analysis of a certified reference sample and successfully applied to the determination of trace metal ions in water samples with satisfactory results.