Electron Probe Microanalysis of Transition Metals using L lines: The Effect of Self-absorption.

Electron microprobe-based quantitative compositional measurement of first-row transition metals using their L$\alpha$ X-ray lines is hampered by, among other effects, self-absorption. This effect, which occurs when a broad X-ray line is located close to a broad absorption edge, is not accounted for by matrix corrections. To assess the error due to neglecting self-absorption, we calculate the L$\alpha$ X-ray intensity emitted from metallic Fe, Ni, Cu, and Zn targets, assuming a Lorentzian profile for the X-ray line and taking into account the energy dependence of the mass absorption coefficient near the absorption edge. We find that calculated X-ray intensities depart increasingly, for increasing electron beam energy, from those obtained assuming a narrow X-ray line and a single fixed absorption coefficient (conventional approach), with a maximum deviation of $\sim$15% for Ni and of $\sim$10% for Fe. In contrast, X-ray intensities calculated for metallic Zn and Cu do not differ significantly from those obtained using the conventional approach. The implications of these results for the analysis of transition-metal compounds by electron probe microanalysis as well as strategies to account for self-absorption effects are discussed.

Electron Probe Microanalysis of Ni Silicides Using Ni-L X-Ray Lines.

We report electron probe microanalysis measurements on nickel silicides, Ni5Si2, Ni2Si, Ni3Si2, and NiSi, which were done in order to investigate anomalies that affect the analysis of such materials by using the Ni L3-M4,5 line (Lα). Possible sources of systematic discrepancies between experimental data and theoretical predictions of Ni L3-M4,5 k-ratios are examined, and special attention is paid to dependence of the Ni L3-M4,5 k-ratios on mass-attenuation coefficients and partial fluorescence yields. Self-absorption X-ray spectra and empirical mass-attenuation coefficients were obtained for the considered materials from X-ray emission spectra and relative X-ray intensity measurements, respectively. It is shown that calculated k-ratios with empirical mass attenuation coefficients and modified partial fluorescence yields give better agreement with experimental data, except at very low accelerating voltages. Alternatively, satisfactory agreement is also achieved by using the Ni L3-M1 line (Lℓ) instead of the Ni L3-M4,5 line.

High-energy interference-free K-lines synchrotron X-ray fluorescence microscopy of rare earth elements in hyperaccumulator plants.

Synchrotron-based micro-X-ray fluorescence analysis (µXRF) is a nondestructive and highly sensitive technique. However, element mapping of rare earth elements (REEs) under standard conditions requires care, since energy-dispersive detectors are not able to differentiate accurately between REEs L-shell X-ray emission lines overlapping with K-shell X-ray emission lines of common transition elements of high concentrations. We aim to test REE element mapping with high-energy interference-free excitation of the REE K-lines on hyperaccumulator plant tissues and compare with measurements with REE L-shell excitation at the microprobe experiment of beamline P06 (PETRA III, DESY). A combination of compound refractive lens optics (CRLs) was used to obtain a micrometer-sized focused incident beam with an energy of 44 keV and an extra-thick silicon drift detector optimized for high-energy X-ray detection to detect the K-lines of yttrium (Y), lanthanum (La), cerium (Ce), praseodymium (Pr), and neodymium (Nd) without any interferences due to line overlaps. High-energy excitation from La to Nd in the hyperaccumulator organs was successful but compared to L-line excitation less efficient and therefore slow (∼10-fold slower than similar maps at lower incident energy) due to lower flux and detection efficiency. However, REE K-lines do not suffer significantly from self-absorption, which makes XRF tomography of millimeter-sized frozen-hydrated plant samples possible. The K-line excitation of REEs at the P06 CRL setup has scope for application in samples that are particularly prone to REE interfering elements, such as soil samples with high concomitant Ti, Cr, Fe, Mn, and Ni concentrations.

Cadmium accumulation characteristics of low-cadmium rice (Oryza sativa L.) line and F1 hybrids grown in cadmium-contaminated soils.

Cadmium (Cd) pollution has threatened severely to food safety and human health. A pot experiment and a field experiment were conducted to investigate the difference of Cd accumulation between rice (Oryza sativa L.) lines and F1 hybrids in Cd-contaminated soils. The adverse effect on biomass of rice lines was greater than that of F1 hybrids under Cd treatments in the pot experiment. The variations of Cd concentration among rice cultivars in different organs were smaller in stem and leaf, but larger in root and ear. Average proportion of Cd in root of F1 hybrids was 1.39, 1.39, and 1.16 times higher than those of rice lines at the treatment of 1, 2, and 4 mg Cd kg-1 soil, respectively. Cd concentrations in ear of F1 hybrids were significantly lower than rice lines with the reduction from 29.24 to 50.59%. Cd concentrations in brown rice of all F1 hybrids were less than 0.2 mg kg-1 at 1 mg Cd kg-1 soil, in which Lu98A/YaHui2816, 5406A/YaHui2816, and C268A/YaHui2816 could be screened out as cadmium-safe cultivars (CSCs) for being safe even at 2 mg Cd kg-1 soil. C268A/YaHui2816 showed the lowest Cd concentration in root among F1 hybrids, while Lu98A/YaHui2816 and 5406A/YaHui2816 showed lower capability of Cd translocation from root to shoot under Cd exposure, which eventually caused the lower Cd accumulation in brown rice. The lower level of Cd translocation contributed to reducing the accumulation of Cd in brown rice had been validated by the field experiment. Thus, Lu98A/YaHui2816, 5406A/YaHui2816, and C268A/YaHui2816 could be considered as potential CSCs to cultivate in Cd-contaminated soils (<2 mg Cd kg-1 soil).