Sensitivity improvement in ICP MS analysis of fuels and light petroleum matrices using a microflow nebulizer and heated spray chamber sample introduction

Reasons for signal suppression during the analysis of light petroleum matrices by inductively coupled plasma mass spectrometry (ICP MS) were examined. A decrease of the ionization efficiency of the plasma was found to be the principal factor responsible for this loss of sensitivity. Consequently, an interface based on a total consumption micronebulizer and a heated spray chamber was constructed to alleviate this problem. A method based on flow-injection ICP MS using this interface was developed for the direct multielement analysis of undiluted fuels (gasoline, kerosene) and gas condensates offering an increase in sensitivity by at least a factor of 3-4 in comparison with the existing setups.     

Surface analytical study of hydrothermally treated zirconia ceramics

Summary The hydrothermal instability of yttria-stabilized tetragonal zirconia polycrystals (Y-TZP) imposes serious problems on their range of applications as ceramic materials. It is well known that a generally uniform distribution of yttrium cations prevents the transformation of the metastable tetragonal into the monoclinic crystallographic modification. The induced crack propagation is widely considered to be a major source of mechanical failure in zirconia ceramics. The segregation was investigated of yttrium and other cations on the surface of hydrothermally treated ceramic samples with angle resolved XPS (X-ray photoelectron spectroscopy). The combination of this method with the high lateral resolution of SAM (scanning Auger microprobe) yields three dimensional distribution profiles of Y³⁺, Al³⁺ and Si⁴⁺. The relative content of the two crystallographic modifications of zirconia at the surface has been determined with XRD (X-ray diffraction). Additional Raman spectroscopic measurements partially confirm these results but suffer from quantification problems. A possible mechanism for the enrichment of yttrium in the surface layer and its promotive function for the phase transformation of zirconia is proposed. Preliminary results from experiments with temperature variable XPS measurements also indicate the formation of either yttrium- or zirconium hydroxide which are both suspected to contribute to crack propagation along the grain boundaries.     

Laser-induced particulate as carrier of analytical information in LA-ICPMS direct solid microanalysis

Laser ablation in combination with plasma spectrochemistry is an ideal technique for depth profiling analysis, based on signal profiles. However, signal profiles were found to be critically influenced by the characteristics of the ablated particles, especially their composition and size distribution, and consequently transport mechanism and plasma-assisted vaporization efficiency. Even for a refractory material like ceramic, relics of melting following laser irradiation were found, so that particles were non-stoichiometric as compared to the parent material. Estimates of transport efficiency showed that this is highly variable as a function of particle size. Large particles are likely to be lost in the sample chamber. Fine particles are prone to wall reaction, especially in Ar ambient. Variability in particle delivery to the ICP-MS was suspected to be the cause for an element-dependent analyte signal response. Fluctuation in particle vaporization degree as a consequence of plasma temperature instability was also responsible for element-dependent signal profile deviation. However, for a 10-fold higher mass load into the plasma, no direct fractionation effects were observed. Differential transport of chemically-differentiated analyte-carriers is suggested to be primary cause for element-dependent signal structure.     

One‐Step Microfluidic Fabrication of Polyelectrolyte Microcapsules in Aqueous Conditions for Protein Release

We report a microfluidic approach for one‐step fabrication of polyelectrolyte microcapsules in aqueous conditions. Using two immiscible aqueous polymer solutions, we generate transient water‐in‐water‐in‐water double emulsion droplets and use them as templates to fabricate polyelectrolyte microcapsules. The capsule shell is formed by the complexation of oppositely charged polyelectrolytes at the immiscible interface. We find that attractive electrostatic interactions can significantly prolong the release of charged molecules. Moreover, we demonstrate the application of these microcapsules in encapsulation and release of proteins without impairing their biological activities. Our platform should benefit a wide range of applications that require encapsulation and sustained release of molecules in aqueous environments.     

Thermal-induced change in surface termination of DyScO3(110)

Auger electron spectroscopy using excitation by grazing impact of protons and by impact of electrons was applied to determine the elemental composition of the topmost and near-surface layers of DyScO₃(110). The vicinal DyScO₃ crystals were annealed at 1320 K in O₂ and Ar atmospheres by varying annealing time. The prepared surfaces show regularly arranged, smooth terraces with single-atomic steps. The surfaces have DyO termination after annealing in oxygen flow for 30–60 min. Annealing for 600 min of DyScO₃ in oxidizing or inert atmospheres resulted in a ScO_x termination.     

Enhanced visualization of polysaccharides from aqueous suspensions

Aqueous suspensions of polysaccharides such as those prepared for domestic and industrial applications or present in natural waters, although difficult to visualize by conventional transmission electron microscopy (TEM) because of their poor electron density, can be characterized at the ultrastructural level by using milden bloc staining and contrast enhancement by energy-filtered TEM (EF-TEM). The advantages and drawbacks of the proposed method are discussed in relation to the different parameters controlling the quality of final images. It is shown, with synthetic polysaccharides, purified algal fibrils and lacustrine exocellular polymers as key examples, that optimizing specimen preparation and visualization parameters allows unbiased identification of organic substructures never revealed or strongly degraded by classical microscopic procedures.