Abstract: Shelf sediments of the southern North Sea, were studied with a microanalytical [electron probe X-ray microanalysis (EPXMA)] and two bulk [X-ray diffraction (XRD) and X-ray fluorescence (XRF)] techniques. The investigation proved that the promptness of the microanalytical method is combined with a reasonable analytical reliability. XRD studies of such a type of sediments with monotonous mineral composition are not able to provide mineralogical information beyond the main well-crystalline minerals and the mineralogical quantitative characteristic of the sediment based on XRD estimations are incorrect. The EPXMA mineralogical interpretations are based on the statistical evaluation of a huge data set (thousands of mineral particles) and provide a rather correct quantitative determination of the main minerals. The comparative EPXMAXRF study revealed that the Al, Si, K, Ca, Fe and to some extent Ti contents estimated by EPXMA are fairly reliable. In this respect the accuracy of the EPXMA-based mineral identification of the pure silicates, pure aluminosilicates, and Al-, Ca-, Fe- and Ti-containing minerals with simple composition is very high. Mg-calcite, augite and apatite determinations are assessed to be correct. The supposed accuracy of the clay mineral determinations is slightly lower (7080%) than that of the other main minerals due to the complex and varying composition of the clays. The identification of XRD-invisible accessory minerals and quantification of their presence in the sediments is an essential advantage of the EPXMA, which makes it a useful approach in tracing the origin of the sediments, the pathways of their transport and the geochemical processes they have undergone. However, the EPXMA has several flaws, which need to be solved in the future sediment investigations: (1) calibration with natural standards is needed in order to provide a higher accuracy of the mineral determinations; (2) any EPXMA study of sediments needs to be secured with XRF examinations of selected samples since EPXMA gives only semi-quantitative information about the abundance of the elements; (3) ultra-thin window EPXMA of low-Z elements has to be used since some of them (O, C) are always present in the main sediment components: silicates, aluminosilicates, carbonates and metal oxyhydroxides; (4) the interpretations of the clay fraction have to be supported with detailed XRD investigations of selected samples, while the mineralogy of the silt and sand fractions needs to be backed up with optical microscopy studies. The information from different analytical techniques (EPXMA with XRFXRD-optical microscopy of selected samples) combined with the knowledge about the most possible minerals in a given environment, would give the most reliable results in studying mineralogical composition of shelf sediments.

Abstract: Vincent van Gogh's still lifes Irises and Roses were investigated to shed light onto the degree to which the paintings had changed, both individually and in relation to each other since they were painted, particularly in regard to the fading of the red lakes. Non-invasive techniques, including macroscopic X-ray fluorescence mapping, reflectance imaging spectroscopy, and X-radiography, were combined with microanalytical techniques in a select number of samples. The in-depth microchemical analysis was necessary to overcome the complications that arise when evaluating by non-invasive methods alone the compositions of passages with complex layering and mixing of paints. The results obtained by these two approaches were complemented by color measurements performed on paint cross-sections and on protected edges, and with historical information provided by the artist's own descriptions, early reviews and reproductions, and the data was used to carry out digital color simulations that provided, to a certain extent, a visualization of how the paintings may have originally appeared.

Abstract: We aimed to achieve improved instrumental sensitivity and detection limits for the analysis of several elements (Cu, Ni, Zn, Pb and Cd) in aqueous samples with energy dispersive X-ray fluorescence spectrometry (EDXRF). The metals were pre-concentrated from aqueous solutions using commercially available organic-based solid-phase extraction (SPE) disks functionalized with iminodiacetate groups. These thin-layer organic materials provide an ideal support for XRF analysis. The elements were collected on the SPE extraction disks using a simple filtration procedure (starting with 1 L of aqueous sample) that allows direct XRF measurements to be performed in the field (in situ). We evaluated the analytical possibilities and drawbacks of using this pre-concentration procedure in combination with the following XRF configurations: a handheld unit, a benchtop EDXRF system and a high-energy polarized-beam EDXRF instrument (HE-P-EDXRF). Using the HE-P-EDXRF system, the detection limits for all metals were more than one order of magnitude lower than those attained using handheld and benchtop EDXRF instrumentation. For the detection of metal concentrations higher than similar to 20 mu g/L, however, handheld or benchtop systems remain a very good option due to their extreme simplicity of operation and low-cost, compact design. We demonstrate the application of these methodologies, using the three equipment systems, to the analysis of trace concentrations of metals in different types of aqueous samples, including tap water and waste water. (C) 2011 Elsevier B.V. All rights reserved.

Abstract: Laser microprobe mass analysis (LAMMA) was applied to particulate matter from the Atlantic Ocean. Inferring information about the surface layer by LAMMA was not probe X-ray microanalysis (EPXMA). Geochemically relevant groups of particles had been identified by EPXMA and cluster analysis. For both locations, the most abundant ones appeared to be those rich in silicon and the alumino-silicates. Afterwards LAMMA was applied to obtain more information about the trace element composition and surface characteristics. The iron-rich phase appeared to contain significant amounts of heavy metals and of phosphate. Lead appeared to be associated in detectable amounts with alumino-silicates in the Scheldt but not with those in the Atlantic Ocean. Inferring information about the surface layer by LAMMA was not always unambiguous.

Abstract: In this article, it is shown that the efficiency of an electrochemical aptasensing device is influenced by the use of different nanoparticles (NPs) such as gold nanoparticles (Au), silver nanoparticles (Ag), hollow gold nanospheres (HGN), hollow silver nanospheres (HSN), silvergold core shell (Ag@Au), goldsilver core shell (Au@Ag), and silvergold alloy nanoparticles (Ag/Au). Among these nanomaterials, Ag@Au core shell NPs are advantageous for aptasensing applications because the core improves the physical properties and the shell provides chemical stability and biocompatibility for the immobilization of aptamers. Self-assembly of the NPs on a cysteamine film at the surface of a carbon paste electrode is followed by the immobilization of thiolated aptamers at these nanoframes. The nanostructured (Ag@Au) aptadevice for Escherichia coli as a target shows four times better performance in comparison to the response obtained at an aptamer modified planar gold electrode. A comparison with other (core shell) NPs is performed by cyclic voltammetry and differential pulse voltammetry. Also, the selectivity of the aptasensor is investigated using other kinds of bacteria. The synthesized NPs and the morphology of the modified electrode are characterized by UV-Vis absorption spectroscopy, scanning electron microscopy, energy dispersive X-ray analysis, and electrochemical impedance spectroscopy.

Abstract: For the isocratic ion chromatography (IC) separation of low-molecular-mass organic acids and inorganic anions three different anion-exchange columns were studied: IonPac AS14 (9 ìm particle size), Allsep A-2 (7 ìm particle size), and IC SI-50 4E (5 ìm particle size). A complete baseline separation for all analyzed anions (i.e., F−, acetate, formate, Cl−, NO2−, Br−, NO3−, HPO42− and SO42−) in one analytical cycle of shorter than 17 min was achieved on the IC SI-50 4E column, using an eluent mixture of 3.2 mM Na2CO3 and 1.0 mM NaHCO3 with a flow rate of 1.0 mL min−1. On the IonPac AS14 column, it was possible to separate acetate from inorganic anions in one run (i.e., less than 9 min), but not formate, under the following conditions: 3.5 mM Na2CO3 plus 1.0 mM NaHCO3 with a flow rate of 1.2 mL min−1. Therefore, it was necessary to adapt a second run with a 2.0 mM Na2B4O7 solution as an eluent under a flow rate of 0.8 mL min−1 for the separation of organic ions, which considerably enlarged the analysis time. For the Allsep A-2 column, using an eluent mixture of 1.2 mM Na2CO3 plus 1.5 mM NaHCO3 with a flow rate of 1.6 mL min−1, it was possible to separate almost all anions in one run within 25 min, except the fluoride-acetate critical pair. A Certified Multianion Standard Solution PRIMUS for IC was used for the validation of the analytical methods. The lowest RSDs (less than 1%) and the best LODs (0.02, 0.2, 0.16, 0.11, 0.06, 0.05, 0.04, 0.14 and 0.09 mg L−1 for F−, Ac−, For−, Cl−, NO2−, Br−, NO3−, HPO42− and SO42−, respectively) were achieved using the IC SI-50 4E column. This column was applied for the separation of concerned ions in environmental precipitation samples such as snow, hail and rainwater.

Abstract: A novel and versatile method, based on a membrane-free enzyme electrode in which both the enzyme and a mediator protein are entrapped in a gelatine hydrogel was developed for the fabrication of biosensors. As a proof of principle, we prepared a hydrogen peroxide biosensor by successfully entrapping both horse heart cytochrome c (HHC) and Saccharomyces cerevisae cytochrome c peroxidase (CCP) in a gelatin matrix which is immobilized on a gold electrode. This electrode was first pretreated with 6-mercaptohexanol. The biosensor displayed a rapid response and an expanded linear response range from 0 to 0.3 mM (R = 0.987) with a detection limit of 1 × 10− 5 M in a HEPES buffer solution (pH 7.0). This method of encapsulation is now further investigated for industrial biosensor applications.