<i>In Situ</i>Analysis of Copper Alloys by Femtosecond Laser Ablation Inductively Coupled Plasma Mass Spectrometry: Constrains on Matrix Effects

Direct analysis of copper-base alloys using laser ablation techniques is an increasingly common procedure in cultural heritage studies. However, main discussions remain focused on the possibility of using non-matrix matched external reference materials. To evaluate the occurrence of matrix effects during in situ microanalysis of copper-base materials, using near infrared femtosecond laser ablation techniques (NIR fs-LA-ICP-MS), two bronzes, i.e., (Sn-Zn)-ternary and (Sn)-binary copper-matrix reference materials, as well as a reference synthetic glass (NIST-SRM-610) have been analyzed. The results have been compared to data obtained on a sulfide-matrix reference material. Similar values in relative sensitivity averages of 63Cu, 118Sn and 66Zn, as well as in 118Sn/63Cu and 66Zn/63Cu ratios were obtained, for all analyzed matrix types, i.e., copper-base-, silicate-, and sulfide-reference materials. Consequently, it is possible to determinate major and minor element concentrations in copper alloys, i.e., Cu, Sn and Zn, using silicate and sulfide reference materials as external calibrators, without any matrix effect and over a wide range of concentrations (from wt.% to ppm). Equally, Cu, Sn and Zn concentrations can be precisely determined in sulfides using homogeneous alloys (reference) materials as an external calibrator. Thus, it is possible to determine Cu, Sn and Zn in copper-base materials and their ore minerals, mostly sulfides, in a single analytical session, without requiring specific external calibrators for each matrix type. In contrast, immiscible elements in copper matrix, such as Pb and Fe show notable differences in their relative sensitivity values and ratios for different matrix-materials analyzed, implying that matrix-matched external calibrations remain to be applied for their trace quantification.

Accumulation, transportation, and distribution of tetracycline and cadmium in rice

Co-exposure to heavy metal and antibiotic pollution might result in complexation and synergistic interactions,affecting rice growth and further exacerbating pollutant enrichment.Therefore,our study sought to clarify the influence of different Tetracycline (TC) and Cadmium(Cd) concentration ratios (both alone and combined) on rice growth,pollutant accumulation,and transportation during the tillering stage in hydroponic system.Surprisingly,our findings indicated that the interaction between TC and Cd could alleviate the toxic effects of TC/Cd on aerial rice structures and decrease pollutant burdens during root elongation.In contrast,TC and Cd synergistically promoted the accumulation of TC/Cd in rice roots.However,their interaction increased the accumulation of TC in roots while decreasing the accumulation of Cd when the toxicant doses increased.The strong affinity of rice to Cd promoted its upward transport from the roots,whereas the toxic effects of TC reduced TC transport.Therefore,the combined toxicity of the two pollutants inhibited their upward transport.Additionally,a low concentration of TC promoted the accumulation of Cd in rice mainly in the root tip.Furthermore,a certain dose of TC promoted the upward migration of Cd from the root tip.Laser ablation-inductively coupled plasma mass spectrometry demonstrated that Cd mainly accumulated in the epidermis and stele of the root,whereas Fe mainly accumulated in the epidermis,which inhibited the absorption and accumulation of Cd by the rice roots through the generation of a Fe plaque.Our findings thus provide insights into the effects of TC and Cd co-exposure on rice growth.

Direct Quantitative Determination of Rare Earth Elements in REE-rich Mineral Powders by LA-ICP-MS

For direct quantitative determination of rare earth elements（REE） in REE-rich minerals, a most acceptable reference material NIST 610 might be an alternative external calibration standard due to the lack of matrix-matched reference materials. Here, we aimed to develop an analytical method for direct quantitative determination of REE concentrations in REE-rich minerals via laser ablation-inductively coupled plasma-mass spectrometry（LA-ICP-MS）. The results show that the REE concentrations measured via LA-ICP-MS using NIST 610 as an extemal standard are in good agreement with reference values with relative percentage difference（Dr） mainly less than 15%. Overall, these results demonstrate that our proposed analytical method is robust and accurate for direct quantitative determination of REE concentrations in REE-rich minerals.