Abstract: Energy-dispersive x-ray fluorescence is advantageous for trace analysis of soils present as thin films. A target thickness of about 2 mg cm-2 provides a compromise between optimal sensitivity and minimal absorption effect or optimal accuracy. Sample preparation involves only suspending the finely ground soil in water and drying this suspension on a thin mylar foil glued on a ring that fits into the x.r.f. spectrometer. The effective sample weight present in the exciting beam area is computed from the scatter peaks, a method that cancels out target heterogeneity problems. High accuracy is demonstrated for many elements in reference soil and rock materials; a precision around 5% and a detection limit around 10 ppm can be achieved. As an illustration, results for 16 trace elements and preliminary interpretation are given for a series of pedologically important soil samples from Brasil.

Abstract: The contamination of ground samples by a commercially available Lovibond McCrone Micronizing Mill is discussed. Tracer and weighing experiments showed that abrasion of corundum grinding elements was important, introducing 620 mg of abrasion products per minute of wet grinding. Agate grinding elements were abraded at ⩽6 mg min-1. The abrasion products and grinding elements were analyzed by x-ray fluorescence, spark-source mass spectrometry and neutron activation analysis. Contamination in trace element analysis of geological materials is likely to be negligible for agate grinding elements and, except for a few transition metals, also for corundum grinding elements. Contamination of typical biological samples is significant for a few elements even when agate elements are used, and is absolutely prohibitive for trace analysis when corundum elements are used.

Abstract: Analytical chemistry does play a key role in the chemical characterization of the environment and it appears that X-ray spectrometry, in its many forms, is one of the most relevant analytical techniques in preventive conservation, as it is in cultural heritage research in general. X-ray spectrometry has indeed been the method of choice for the characterization of the inorganic composition of atmospheric aerosols, for a long time. We have, over the last decade, intensively used various forms of X-ray spectrometry, viz., mostly energy-dispersive X-ray fluorescence, e.g. with polarized high-energy beam excitation, and automated electron probe X-ray microanalysis, together with other techniques, to identify particle types and their sources in indoor environments, including museums, while gaseous indoor pollutants were assessed using passive diffusion samplers. In each case, both bulk aerosols and individual aerosol particles were studied. For microanalysis of single particles, we have investigated a dozen techniques, but for wide, real-life applications, automated electron probe X-ray microanalysis is the most rewarding. We have first studied atmospheric aerosols in and around the Correr Museum in Venice, many other museums in Austria, Japan and England, and in the caves with prehistoric rock paintings in Altamira, Spain. Very recently, measurements were done in the Metropolitan Museum of Art in New York and theWawel Castle in Cracow, in Italian and Polish mountain churches, in a number of museums in Belgium and the Netherlands, and in cathedrals with medieval stained glass windows. In the Correr museum, it appeared that the particles most threatening for the Bellini paintings were released by the deteriorating plaster renderings, and this could be avoided by simply improving the rendering on the museum walls. In the Wawel Castle, outdoor pollution particles, like fine soot from diesel traffic, entering via leaks in the windows and doors, and also street-deicing salts and coal burning pollution particles, brought in by visitors, mostly in winter, were found to be most worrisome. Urgent questions that are not solved at this moment pertain to the deposition processes from the atmosphere to the cultural heritage items, the critical surface interactions that take place on these items, and the establishment of suitable particle concentration standards.

Abstract: Folding aerosol loaded filters in two with the loaded side inwards during the X-ray analysis not only reduces possible filter heterogeneity effects and improves sample protection, but also increases the sensitivity and renders filter paper absorption corrections simple and more accurate in many instances. It is shown that folding an aerosol loaded Whatman filter paper during Kα X-rays counting leads to an increased sensitivity for all elements up from calcium, scandium or titanium (depending on the sensitivity definition and on the aerosol load) and for all elements up from phosphorus, sulphur or chlorine in the case of the Nuclepore filter. Although the absorption by the filter, into which the aerosol penetrates to some extent, is always more important in the sandwich than in the usual geometry, the dependence of the absorption correction on the usually unknown average deposition depth is less pronounced. Assuming all the aerosol material to be collected at the very surface of the filter and hence being present in the centre of the sandwich to be analysed, leads to an extremely simple filter paper absorption correction which is less prone to uncertainties than more sophisticated corrections in the usual geometry requiring additional measurements. This is the case for all elements up from potassium on Whatman filters and up from phosphorus on Nuclepore filters.

Abstract: Proton Induced X-ray Emission, (PIXE), is capable of high precision analysis for trace element components of aerosol particle size fractions sampled by cascade impactor. A statistical evaluation of data quality has been carried out in order to distinguish between analytical uncertainties in the PIXE procedure, errors caused by cascade impactor performance and by other factors in the sampling procedure, and geophysical causes of differences in composition and particle size distributions of the elements in aerosols. Replicate analyses and simultaneous samplings taken in north Florida and St. Louis have been used for the data evaluation. In addition to the analytical error the sampling procedure contributes an error of ~ 10% to be added quadratically. The resulting precision is sufficient to evaluate the data in geophysical terms. This is illustrated by means of sample sets taken simultaneously in an urban, forest and coastal environment of the same region.

Abstract: The zirconium/hafnium ratios of zircons are determined using proton induced X-ray emission. Submilligram samples, imbedded in a starch layer and deposited on a 50 μg/cm2 polystyrene carrier, are irradiated for 1020 min with a 5 nA beam of 3.7 MeV protons, while the Hf-Lβ and Zr-Kα X-rays are counted with a Si(Li) detector. The standard deviation per analysis is in the 36 % range. Only few interferences are possible. To eliminate errors due to absorption effects the zircon layer thickness should be above 40 μm or reproducibly thin samples should be employed. Measuring the Hf-Lβ/Hf-Lα ratio for samples and standards might provide a practical check for the absence of absorption errors. The sensitivity is so favourable that, in practice, the minimal sample size is only limited by the minimal amount that can be handled properly.

Abstract: Aerosol samples have been collected over the southern bight of the North Sea from an aircraft. In this way, 96 samples were taken for single-particle analysis during 16 flights. Almost 45 000 individual particles were analyzed with electron probe X-ray microanalysis. More than 5000 of these were found to contain significant concentrations of one or more of the heavy metals Cr, Pb, and Zn. With the help of hierarchical, nonhierarchical, and fuzzy clustering techniques, various heavy metal-containing particle types could be identified. Significant differences in abundances were detected in the North Sea heavy metal aerosol, depending on the origin of the air masses. In samples with continental influence 50 times more Zn- and Pb-containing particles were found than in samples with a marine history. For Cr, on the other hand, we found abundances in the marine sector that were one-third of the values for continental sectors. This might point to a rather undefined marine source, which could be the recycling of previously deposited material by reinjection into the atmosphere by sea spray. The highest values for Cr-, Pb-, and Zn-containing particles were always detected under southeastern wind directions.