Selective determination of airborne hexavalent chromium using inductively coupled plasma mass spectrometry

A new method for determining ultra-trace levels of hexavalent chromium in ambient air has been developed. The method involves a 24-h sampling of air into potassium hydroxide solution, followed by silica gel column separation of chromium (VI), then preconcentration by complexation and solvent extraction. The chromium (VI) complex was dissolved in nitric acid. The resultant chromium ions were determined by inductively coupled plasma mass spectrometry (ICP–MS) using a dynamic reaction cell (DRC) with ammonia as the reactive gas to reduce polyatomic interferences. The interconversion of chromium in potassium hydroxide solution and air sample matrix were investigated under ambient conditions. It was found that there was no conversion of chromium (VI) into chromium (III) species. However, it was observed that some chromium (III) species were converted into chromium (VI) species. For a KOH solution containing 100 μg l⁻¹ of chromium (III) species, the rate of conversion was found to be 3% after 24 h exposure, 8% after 48 h, 10% after 72 h and no further conversion was observed thereafter. However, in a solution containing air sample matrix, 9.3% of chromium (III) converted to chromium (VI) within 6 h, and during the course of a 11-day exposure period, 13% (range 8–17%) of chromium (III) converted to chromium (VI). The method detection limit (MDL) for chromium (VI) in potassium hydroxide solution (0.025 M) was found to be 2×10⁻² μg l⁻¹. This is equivalent to 0.2 ng m⁻³ (for 23 m³ air sampled into 200 ml of KOH solution over a 24-h period). The recovery of spiked chromium (VI) from solutions containing air sample matrix was 95±9% (n=8). Matrix related interferences were estimated to be less than 10% based on recovery studies. The concentration of airborne chromium (VI) in Sydney residential areas was found to be less than 0.2 ng m⁻³, however, in industrial areas the concentrations ranged from 0.2 to 1.3 ng m⁻³ using this analytical procedure.     

刚性弹丸侵彻钢筋混凝土的实验和简化分析模型

通过Φ57mm半穿甲弹对钢筋混凝土的垂直侵彻实验,得到了弹丸的撞靶速度、成坑深度、最大侵彻深度以及过载时程曲线等实验数据.对实验后钢筋的断裂特征进行分析,得到钢筋的典型破坏模式.将钢筋的破坏简化为弯曲+剪切断裂和弯曲+拉伸断裂这两种模式.根据混凝土侵彻模型和梁断裂失效理论,建立了刚性弹丸垂直侵彻钢筋混凝土的简化分析模型.将理论计算得到的侵彻深度、速度与过载时间历程分别与实验数据进行对比,结果表明两者吻合较好.研究表明,钢筋只对弹体侵彻过程产生局部影响,混凝土的抗侵彻阻力仍是钢筋混凝土抗侵彻阻力的主要组成部分.     

On the ellipsoidal statistical model for polyatomic gases

The aim of this article is to construct a BGK-type model for polyatomic gases which gives in the hydrodynamic limit the proper transport coefficient. Its construction relies upon a systematic procedure: minimizing Boltzmann entropy under suitable moments constraints (Levermore in J Stat Phys 83:1021–1065, 1996; Brull and Schneider in Cont Mech Thermodyn 20(2):63–74, 2008). The obtained model corresponds to the ellipsoidal statistical model introduced in Andries et al. (Eur J Mech B Fluids 19:813–830, 2000). We also study the return to equilibrium of its solutions in the homogeneous case.      

Evaluation of a Collision-Reaction Interface (CRI) for Carbon Effect Correction on Chromium Determination in Environmental Samples by ICP-MS

Spectral interferences in inductively coupled plasma quadrupole mass spectrometry (ICP-MS) may affect several trace element analyses. In this work, the performance of a collision-reaction interface (CRI) for correction of spectral interferences on chromium determination at m/z 52 affected by ⁴⁰Ar¹²C⁺ in a rich-carbon medium was evaluated. Hydrogen or He gases were introduced through sampler or skimmer cones of the CRI for promoting collisions and reactions. Background equivalent concentrations (BEC) and signal-background ratios (SBR) were the chosen parameters for evaluating CRI performance. It was observed that the introduction of both gases through the sampler cone was not effective considering the maximum gas flow rate evaluated at 140 mL min^?1. The best condition to reduce polyatomic interferences caused by carbon containing species was obtained while introducing 60 mL min^?1 of H₂ through the skimmer cone. The trueness of the developed procedure was checked by ⁵²Cr⁺ determination in certified reference materials. Sequential extractions in acetic acid and ammonium acetate (carbon sources) media, according to the Bureau Communautaire de Référence (BCR) of the Commission of the European Communities, was employed for BCR 701 (Lake Sediment) and microwave-assisted digestion was applied for Sewage Sludge from Industrial Origin (BCR 146 R). The feasibility of the CRI to overcome spectral interferences caused by molecular ions containing carbon on ⁵²Cr⁺ determined by ICP-MS was demonstrated.     

Mechanism of defect formation and polyanion transport in solid scandium tungstate type oxides

Abstract  The unique diffusion mechanism in the novel polyatomic anion conductor scandium tungstate is studied by molecular dynamics simulations of systems with artificially induced WO₄ ²⁻ defects and compared to our previous simulations of defect-free structure models. The diffusion activation energy obtained from structures with built-in defects is smaller than for the defect-free models and in the case of tungstate vacancies close to the experimental value, suggesting that extrinsic tungstate vacancies due to the volatility of WO₃ are important for the experimental conductivity. The validity of the force field used for the molecular dynamics simulations is further verified by investigating the orthorhombic to monoclinic phase transition of Sc₂(WO₄)₃ under compression. The lattice compressibility in both phases and the phase transition is qualitatively reproduced, though the simulated phase transition pressure occurred is about 0.55 GPa higher than the experimental one. Graphical abstract        

锥头弹丸撞击下固支金属厚靶的侵彻与穿透的理论研究(英文)

研究了在不同速度的刚性锥头弹丸撞击下固支金属厚靶的侵彻和穿透性能。假定靶板的变形是局部化的,且冲击能量仅通过侵彻过程吸收,同时假定弹体在侵彻过程中表面所受靶体的平均压力是由基于空穴膨胀理论的靶体材料弹塑性变形所引起的静态阻力以及速度效应引起的动阻力两部分组成,认为侵彻过程中靶体对弹体的静阻力要进行自由表面效应修正,而且动阻力是瞬时侵彻速度的函数。获得了锥头弹丸在侵彻和贯穿过程中的弹道极限速度和残余速度的公式。将理论预测与实验结果进行比较,发现两者符合得很好。     

Decay Analysis of Ge Isotopes Formed in Reactions Induced by Tightly and Loosely Bound Projectiles

The dynamical cluster-decay model (DCM) is employed to investigate the decay of ^68,70Ge^* compound nuclei formed respectively via tightly (⁴He) and loosely (⁶He) bound projectiles, using ⁶⁴Zn target. The study is carried out over a wide energy range (E_c.m.~5 MeV to 16 MeV) by including the quadrupole deformations (β2i) and optimum orientations (θ_i^opt) of the decaying fragments. The fusion cross-sections, obtained by adding various evaporation channels show nice agreement with the experimental data for ⁴He+⁶⁴Zn reaction. The contribution from competing compound inelastic scattering channel is also analyzed particularly for ⁶⁸Ge^* nucleus at above barrier energies. On the other hand, the decrement in the fusion cross-sections of ⁷⁰Ge^* nuclear system is addressed by presuming that ⁶⁵Zn ER is formed via two different modes:(i) the αn evaporation of ⁷⁰Ge^* nucleus, and (ii) 1n-evaporation of ⁶⁶Zn^* nuclear system, formed via breakup and 2n-transfer channels due to halo structure of the ⁶He projectile. Besides this, the suppression in 2np evaporation cross-sections suggests the contribution of another breakup and transfer process of ⁶He i.e. ⁴He+⁶⁴Zn. The contribution of breakup+transfer channels for ⁶He+⁶⁴Zn reaction is duly addressed by applying relevant energy corrections due to the breakup of " ⁶He" projectile into 2n and ⁴He. In addition to this, the barrier lowering, angular momentum and energy dependence effects are also explored in view of the dynamics of chosen reactions.     

Metal-assisted SIMS and cluster ion bombardment for ion yield enhancement

In addition to structural information, a detailed knowledge of the local chemical environment proves to be of ever greater importance, for example for the development of new types of materials as well as for specific modifications of surfaces and interfaces in multiple fields of materials science or various biomedical and chemical applications. But the ongoing miniaturization and therefore reduction of the amount of material available for analysis constitute a challenge to the detection limits of analytical methods. In the case of time-of-flight secondary ion mass spectrometry (TOF-SIMS), several methods of secondary ion yield enhancement have been proposed. This paper focuses on the investigation of the effects of two of these methods, metal-assisted SIMS and polyatomic primary ion bombardment. For this purpose, thicker layers of polystyrene (PS), both pristine and metallized with different amounts of gold, were analyzed using monoatomic (Ar⁺, Ga⁺, Xe⁺, Bi⁺) and polyatomic (SF₅⁺, Bi₃⁺, C₆₀⁺) primary ions. It was found that polyatomic ions generally induce a significant increase of the secondary ion yield. On the other hand, with gold deposition, a yield enhancement can only be detected for monoatomic ion bombardment.     

Molecular dynamics simulations of sputtering of organic overlayers by slow, large clusters

The ion-stimulated desorption of organic molecules by impact of large and slow clusters is examined using molecular dynamics (MDs) computer simulations. The investigated system, represented by a monolayer of benzene deposited on Ag{1 1 1}, is irradiated with projectiles composed of thousands of noble gas atoms having a kinetic energy of 0.1-20 eV/atom. The sputtering yield of molecular species and the kinetic energy distributions are analyzed and compared to the results obtain for PS4 overlayer. The simulations demonstrate quite clearly that the physics of ejection by large and slow clusters is distinct from the ejection events stimulated by the popular SIMS clusters, like C₆₀, Au₃ and SF₅ at tens of keV energies.