Abstract: An evaluation of the accuracy and suitability of the LachanceTraill algorithm using effective α-coefficients, and the De Jongh α approach for x-ray fluorescence analysis of borax glass beads prepared from geological material was performed. By using theoretical α-coefficients obtained from the same standard and calculated elemental intensities, the two algorithms were compared under identical conditions. When only the monitor standard is used, the LachanceTrail1 approach is found to be inferior to the De Jongh basic α method. If multi-standard calibration is performed for both approaches, the accuracies are almost identical and no significant difference is found in the results. The LachanceTraill algorithm has the advantage of being easier to implement on a minicomputer and, when used without standards, it is found to give results within a few percent of the true values, which is a useful indicator in the choice of appropriate standards for more accurate analytical work.

Abstract: Energy-dispersive X-ray fluorescence analysis was applied for the analysis of hair. The hair samples were digested in a mixture of nitric and perchloric acid and the heavy metals were precipitated with ammonium pyrrolidine dithiocarbamate. The accuracy, precision and recovery of the method for the elements Fe, Ni, Cu, Zn and Pb were evaluated through the analysis of a standard hair sample. The procedure was applied to the analysis of hair from an occupationally exposed group of Sudanese workers and a control group. The hair of the exposed group showed a range of 80550 ppm Fe, 612 ppm Cu, 57190 ppm Zn and 703700 ppm Pb, while that of the control group had a range of 60310 ppm Fe, 722 ppm Cu, 89170 ppm Zn and 317 ppm Pb.

Abstract: On aerosol and rain water samples, collected in the Southern Bight of the North Sea, single particle analyses were performed using both laser microprobe mass analysis and electron-probe X-ray microanalysis in combination with an automated image analysis system. In the aerosols collected from an air mass that had travelled from the Atlantic Ocean along the coast of North France, pure seasalt constituted the most abundant particle type, while aluminosilicates (mostly spherical fly-ash particles) amounted to about 20% and mixed seasalt/aluminosilicate, carbonaceous particles, CaSO4 and spherical iron oxides contributed each 510 %. In air masses that had a longer residence time over the continent, spherical iron oxides, carbonaceous particles and ammonium sulfates together made up 70 % of the total particle load. Seasalt particles were nearly all enriched in sulfate or nitrate, but they were seen to be washed out efficiently after a rain shower. In rain water, some 40 % of the particles appeared to be spherical or irregularly shaped aluminosilicates, from fly-ash and dust dispersal, but more than 50 % consisted of SiO2. The high relative abundance of these particles in rain water may be the result of Al leaching from fly-ash, or of more efficient scavenging by rain droplets.

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: Sixty-two samples of total sediments and the separated clay/silt size fractions were analysed by energy-dispersive X-ray fluorescence spectrometry to evaluate the pollution level and the trends in samples collected along the Belgian coast over a period of 6 yr and at four stations located in the Scheldt estuary where two of these were sampled periodically for 4 yr. Three correction methods for grain size effects were applied, either to the bulk sediment samples or to the clay/silt size fractions, and the results were compared. Local variations on the concentrations in some of the elements determined were used to establish whether they result from an anthropogenic or natural origin. The level of pollution was assessed as a function of the location, sampling date, and depth.

Abstract: Aerosols were sampled in the Amazon Basin, as part of the Global Tropospheric Experiment (GTE), during the Amazon Boundary Layer Experiment (ABLE 2A) in JulyAugust 1985. Fine- and coarse-particle fractions were analyzed for 22 elements by particle-induced X ray emission. Gravimetric mass, black carbon, sulfate, and nitrate concentrations were also determined. Morphological and trace element measurements of individual particles were carried out by automated electron probe X ray microanalysis. Various receptor models, including multivariate methods and a chemical mass balance model, were employed in the interpretation of the bulk trace element concentrations. Three factors explained over 85% of the variability of fine- and coarse-mode variables. On the basis of the elemental composition of the factors, two could be identified as plant related, and the third was a soil dust component. Of the coarse-mode aerosol mass concentration (of 7.6±1.6 μg/m3), 62% could be attributed to aerosols released by the vegetation and 11% to soil dust. In the fine mode, soil dust accounted for less than 10% of the measured mass concentration (of 6.8±3.9 μg/m3). The variables related to the plant component were K, P, S, Ca, Mg, Cl, Rb, and the gravimetric mass. The elemental profile of the plant component resembled the bulk plant composition. By single-particle analysis coupled with hierarchical cluster analysis, six to nine different biogenic-related particle groups could be identified in the fine- and coarse-aerosol modes. Almost all particle types consisted predominantly of carbonaceous material, with trace amounts of K, S, Ca, P, Cl, and Na. Only one group, comprising less than 11% of the total number of particles, consisted of soil dustrelated aerosol.

Abstract: The potential of laser microprobe mass analysis (LAMMA) as a sensitive microanalytical technique was explored in applications relevant to nephrology. Aluminum and associated elements, such as iron, were localized in fresh tissue biopsies obtained from uremic patients treatment by chronic hemodialysis. The LAMMA was applied to serum, liver, bone, and parathyroid glands of such patients. In addition, we used LAMMA to evaluate the specificity and sensitivity of routine histochemistry, in particular on human bone sections stained by the aluminon method. The high, multielemental sensitivity and molecular microprobe potential of LAMMA established important advantages over other microchemical methods forin situ analysis at the micron level in histological sections.

Abstract: Various bulk and surface analytical techniques were used to study the chemical deterioration of the 13th-to-15th century limestone cathedral in Mechelen, Belgium. The weathering crust on the walls was found to be rich in sulfate, regardless of the geographic orientation. Nitrate and chloride were only detected in minor amounts in the crust and run-off samples. Attack by gaseous sulfur compounds seems to play a dominant role in the stone deterioration mechanism. Electron microprobe analysis showed predominantly bar-shaped gypsum crystals in the crust, and laser microprobe mass spectrometry showed that carbon seems to be responsible for the blackness of most crust samples. Automated electron microprobe analysis also indicated significant differences in the analytical composition of suspensions in run-off water and in rain-water.

Abstract: Laser microprobe mass spectrometry is used to identify intrarenal microliths; they appear to consist of either oxalate, urate or phosphate. Crystalline and amorphous deposits in rat and human kidney are pin-pointed by the laser beam and their chemical composition determined by mass spectrometry. The method has the potential for wide application in the identification of single organic, inorganic or combination crystals in histological sections.

Abstract: Bed sediments were collected from the entire region of the Ganges basin and some parts of the Brahmaputra. In addition, selected stations were sampled for suspended sediments as well. The samples were analysed for a number of heavy metals (Fe, Mn, Ni, Cr, Cu, and Zn) by the thin-film energy dispersive X-ray fluorescence technique. There are pronounced temporal and spatial variations in the heavy metals distributions. Suspended sediments are 510 times richer than the bed sediments. None of the tributaries contribute significant heavy metal load, but around urban areas in Yamuna (tributary of Ganges), very high levels due to the distribution from the drainage network are observed. Compared to the Brahmaputra, the distribution and fractionation of heavy metals in the Ganges sediments are more erratic and highly variable. All the metals considered show high correlation among themselves. Given the high flux of suspended sediments from the Himalayan rivers (nearly 20% of the global flux), the worldwide budget for heavy metal transport may need to be suitably revised.

Abstract: A Monte Carlo simulation has been developed to describe the incoherent and coherent scatter processes for the complex geometry of a secondary target energy-dispersive x-ray fluorescence system. Photons are followed from the x-ray tube anode until the detection of scattered secondary target photons in the active Si layer of the detector. The program quantitatively shows the broadening of the incoherent scatter peak with increasing atomic number, and it models the incoherent peak shape adequately. The incoherent-to-coherent scatter intensity ratios obtained differ by 1030% from the theoretical values, while their dependence on the sample atomic number corresponds to that expected from theory.

Abstract: Sensitive multi-element analysis techniques together with major-element and isotopic analyses were applied to spring, mine and surface waters in the vicinity of an important known zinclead deposit in a carbonate environment, in the Les Malines area (Gard, France). Both the dissolved and suspended phases were investigated, and concretions and sediments were also considered in some cases. This methodological test shows that the ore body leaves various clear fingerprints, such as the Zn, As, Sb, Pb and U levels in the dissolved phase, the sulfate increment and the δ 34S. Some of the elements in solution are controlled by slightly soluble compounds, e.g. Zn by smithsonite and hydrozincite, Ba by barite, and Pb by hydrocerussite. Mapping the saturation indices for these elements appears useful for displaying the hydrogeochemical anomaly.

Abstract: A simple procedure is proposed for the calculation of the absorption correction factor in electron-probe x-ray microanalysis. It is based on the concept of an effective depth of x-ray production, assuming a rectangular depth distribution function for x-ray generation. This effective x-ray production depth is expressed as a fraction of the x-ray excitation depth given by Whelan's expression. Adequate values for this fraction are presented. Two versions are considered. In the first the effective x-ray production is a function of both the characteristic x-ray energy and the atomic numbers of the matrix elements, whereas in the second one, which is indicated for routine use, the energy dependence is neglected. Calculations pointed to satisfactory results, even for low x-ray energies and high overvoltages.