Abstract: A comparison of four methods for the determination of barium, lanthanum, cerium and neodymium in lateritic materials from Brazil is presented. Three of the methods were based on x-ray fluorescence (XRF) spectroscopy: two by radioisotope excitation (Co-57 and Am-241) and one by secondary target XRF (a molybdenum target with a tungsten anode). The other method was based on neutron activation analysis employing both a Ge(Li) coaxial detector and a high-purity germanium detector. The results from these four methods were similar for lanthanum, cerium and neodymium, but for barium at low concentrations (<500 ppm) the neutron activation and the secondary target XRF methods were not suitable. Data on the precision and accuracy of these methods using a series of standard reference rocks are given. The advantages and limitations of each of these methods with respect to the analysis of lateritic materials are discussed.

Abstract: The electrochemical activation of C-X bonds requires very negative electrode potentials. Lowering the overpotentials and increasing the catalytic activity requires intensive electrocatalytic research. A profound understanding of the reaction mechanism and the influence of the electrocatalyst allows optimal tuning of the electrocatalyst. This can be achieved by combining electrochemical techniques with electron paramagnetic resonance (EPR) spectroscopy. Although this was introduced in the mid-twentieth century, the application of this combined approach in electrocatalytic research is underexploited. Several reasons can be listed, such as the limited availability of EPR instrumentation and electrochemical devices for such in situ experiments. In this work, a simple and inexpensive construction adapted for in situ EPR electrocatalytic research is proposed. The proof of concept is provided by studying a model reaction, namely the reductive cyclisation of allyl 2-bromobenzyl ether which has interesting industrial applications.

Abstract: In this paper, we used a multi-technique approach in order to identify the arsenic sulfide pigment used in the decorative panels of the Japanese tower in Laeken, Belgium. Our attention was drawn to this particular pigment because of its relatively good conservation state, despite its known tendency to fade over time when exposed to light. The pigment was used with different painting techniques, bound with oil and urushi in the lacquers and with an aqueous binder in the mat relief panels. In the latter case it is always applied as an underlayer mixed with ultramarine blue. This quite unusual pigment mixture also shows a good state of preservation. In this study, the orpiment used for the Japanese tower has been identified as an amorphous arsenic sulfide glass (AsxSx) with the aid of light microscopy, PLM, SEM-EDX and Raman microscopy. The pigment features different degrees of As4S4 monomer units in its structure, also known as realgar-like nano-phases. This most likely indicates different synthesis processes as the formation of these As4S4 monomers is dependent of the quenching temperature (Tq) to which the artificial pigment is exposed during the preparation phase.

Abstract: Cellulose filters with immobilized 2,2'-diaminodiethylamine (DEN) functional groups are studied for trace anion preconcentration from aqueous solution, with subsequent x-ray fluorescence measurements. For most oxoanions with a central metal atom, nearly quantitative collection can be achieved by 10-cm2 DEN filters under the following optimized conditions: pH 36, filtration rate up to 0.5 ml cm-2 min-1, and sample volume up to 100 ml cm-2. The collection yield is independent of the trace oxoanion concentration up to at least 1.5 μmol cm-2. Although the DEN filter exhibits some selectivity towards oxoanions with a central metal atom, ionic strength affects the results; the collection efficiency is strongly depressed with salt (e.g. NaCl) concentrations above 0.01 M. The applicability of the DEN filter in anion collection is therefore limited to dilute solutions.

Abstract: Trace amounts of heavy metals were preconcentrated on discs of polyurethane (PU) foam loaded with ammonium diethyldithiocarbamate (DDTC), to increase the sensitivity of XRF. Since the diameter of the cavities in the open-cell PU foams reaches 30300 μm, considerable heterogeneity effects might occur, which could reduce the accuracy of the method. The possible systematic error introduced by considering the sample to be homogeneous is calculated using the Berry et al. model. The calculations show that the underestimation of the absorption correction factor when considering the sample as being homogeneous is less than 2% for high-Z elements when the sample thickness is at least 2 mm. The detection limits are also around the minima for this thickness.