A standardless method of energy dispersive X-ray fluorescence in conjunction with scanning electron microscopy was used to analyze selected areas of clay-size particles of talc, pyrophyllite, and kaolinite supported by a carbon planchet. Peak intensity ratios of fluorescing elements relative to silicon were converted directly to weight or mole ratios using conversion factors determined theoretically. The conversion factors depend upon particle thickness and mass adsorption coefficients of the sample for the elements analyzed. The effects of particle thickness become significant above ~0.1 μm. Without using particle thickness corrections, the mean molar ratios of metal to Si agreed to within 6.1,0.5, and 9.7% of the theoretical ratios for kaolinite, pyrophyllite, and talc, respectively.

Purification processes performed on natural clays to select specific clay minerals are complex and expensive and can lead to over-exploitation of some deposits. The present study aimed to examine physicochemical (mineralogy, morphology, size, surface charge, chemical composition, cation exchange capacity [CEC], and pH) and hydration (swelling, wettability, water sorption, and rheological behavior) properties of three native clays from Italian deposits for potential pharmaceutical and cosmetic uses due to the presence of phyllosilicate minerals. Particular emphasis was placed on energy dispersive X-ray (EDX) microanalysis coupled with the ‘cesium method’ to assay clay elemental composition and CEC. One bentonite of volcanic origin (BNT) and two kaolins, one of hydrothermal origin (K-H) and another of lacustrine-fluvial origin (K-L), were evaluated in comparison with a commercial, purified bentonite. The CEC assay revealed the complete substitution of exchangeable cations (Na+ and Ca2+) by Cs+ in BNT samples and CEC values consistent with those of typical smectites (100.64 ± 7.33 meq/100 g). For kaolins, partial substitution of Na+ cations occurred only in the K-L samples because of the interstratified mineral component which has small CEC values (11.13 ± 5.46 meq/100 g for the K-H sample and 14.75 ± 6.58 meq/100 g for the K-L sample). The degree of isomorphous substitution of Al3+ by Mg2+ affected the hydration properties of BNT in terms of swelling, water sorption, and rheology, whereas both of the poorly expandable kaolins exhibited significant water-adsorption properties. The EDX microanalysis has proved to be of considerable interest in terms of providing more information about clay properties in comparison with other commonly used methods and to identify the role played by both chemical and mineralogical composition of natural clays for their appropriate use in pharmaceutical and cosmetic fields.

This paper summarizes an oral presentation of the same title presented at the occasion of recognizing the “The 100th Anniversary of X-ray Spectroscopy” at DXC 2013. It gives an overview of the development in electronics with focus on (mainly) energy-dispersive X-ray detectors and related data processing. Naturally this has its origin in the early transistors and the first semiconductor junction detectors of the late 1940s. It was followed by refinement of semiconductor detector technology in general and particularly by the invention of Li-drifting and employment of low-noise field effect transistors until such devices matured sufficiently to be marketed by the late 1960s. Further improvement followed in resolution, speed, operability at room temperature, and development of junction arrays with imaging capabilities. An important aspect is the development of related software requiring affordable laboratory computers, programming languages, and databases of fundamental parameters. Today x-ray fluorescence analysis (and not only the energy-dispersive variant) is widely employed as an analytical tool for the traditional technical and industrial applications but notably also, at an expanding rate as well as variety, in other fields including environmental, medical, archaeological, space, arts, and many more.

A study was conducted to assess the effect of the supply of phosphorus and the major cations on the mineral nutrient composition of whole mature wheat grains and the electron-dense globoid crystals found in the aleurone cells. Ears of wheat plants, growing in the field, were detached after anthesis. The ears were cultured to maturity in a sterile control solution which contained all essential elements. Other ears were cultured in solutions which contained no phoshorus, no calcium, no magnesium, combinations of these (−P, −Ca; −P, −Mg) or a solution which contained additional potassium but no phosphorus, calcium or magnesium. Ears cultured in the control solution produced grains with higher concentrations of P, Mg, K and Ca than grains from ears which matured on plants in the field. All the −P treatments produced grains with lower concentrations of P and higher concentrations of Mg, K and Ca than the plants grown in the field. The appearance and elemental composition of the globoid crystals in the aleurone cells support the hypotheses that the size of globoid crystals is regulated, in part, by the amount of phosphorus deposited in the grain and also by the relative proportions of K, Mg and Ca in the tissue. The culture of individual ears of cereal plants is a useful technique by which to study the transfer to and deposition of mineral nutrients in cereal grains.