Based on a computerized literature search through Chemical Abstracts for the period 1968–89 and on a manual search through Analytical Abstracts for 1988, trends in the literature are discussed for x‐ray emission spectrometry in general, and for x‐ray fluorescence analysis, proton‐induced x‐ray emission and synchrotron‐induced x‐ray fluorescence analysis. Relative contributions are derived for articles dealing with various excitation and detection modes, with different application fields and from different countries. Special attention is paid toenvironmental applications of x‐ray emission spectrometry.

In humans the toxic trace element lead (Pb) mainly accumulates in the skeletal tissue where it resides for a long period. Although Pb is known to play a role in bone and cartilage diseases, the distribution of Pb in these tissues is mostly unknown. Therefore synchrotron‐radiation‐induced micro x‐ray fluorescence analysis (SR µ‐XRF) in various geometries was used to determine the distributions of Pb, Ca, Zn and Sr at the cartilage‐bone interface in human femoral heads and patellae. SR µ‐XRF results were matched with backscattered electron (BE) images providing information on structural features of the tissue. Conventional SR µ‐XRF at HASYLAB beamline L showed that Pb mostly accumulates in a zone of some micrometers around the transition between non‐calcified and calcified cartilage. However, the relatively large sample thickness did not allow more precise conclusions. Exploiting the 3D capabilities of confocal SR µ‐XRF and SR microfluorescence tomography at ANKA Fluo‐Topo beamline and HASYLAB beamline L, the spatial resolution could be improved and a highly specific accumulation of Pb at the tidemark, the calcification front between non‐calcified and calcified cartilage, was detected. It was found that Pb and Zn accumulation coincide at the tidemark. Since the tidemark plays an important role in osteoarthritis, the results may strengthen other authors' conclusions that Pb is associated with this joint disease. Although offering less spatial resolution when compared to micro‐tomography, confocal SR µ‐XRF is best suited for such studies. It facilitates the comparison of element maps with other imaging techniques like BE imaging. Copyright © 2007 John Wiley & Sons, Ltd.

This paper reviews the major factors influencing the accuracy of the energy-dispersive X-ray fluorescence (EDXRF) analysis including physical and chemical matrix effects (resulting from particle size, surface irregularity, mineralogy, moisture, absorption and enhancement) as well as the correction procedures with emphasis on the analysis of unprepared samples. Quantification methods for thin samples, samples with intermediate thickness and thick samples are presented including fundamental parameter methods, influence coefficient algorithms, empirical coefficient algorithms and quantification methods based on scattered primary radiation. Quality control procedures are also reviewed.