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Variations in plasma properties among spectra and samples lead to significant signal uncertainty and matrix effects in laser-induced breakdown spectroscopy (LIBS). To address this issue, direct compensation for plasma property variations is considered highly desirable. However, reliably compensating for the total number density variation is challenging due to inaccurate spectroscopic parameters. For reliable compensation, a total number density compensation (TNDC) method was presented in our recent work, but its applicability is limited to simple samples because of its strict assumptions. In this study, we propose a new pre-processing method, namely extended TNDC (ETNDC), to reduce signal uncertainty and matrix effects in the more complex analytical task of uranium determination. ETNDC reflects the total number density variation with a weighted combination of spectral lines from all major elements and incorporates temperature and electron density compensation into the weighting coefficients. The method is evaluated on yellow cake samples and combined with regression models for uranium determination. Using the typical validation set and line combination, the mean relative standard deviation (RSD) of U II 417.159 nm in validation samples decreases from 4.92% to 2.27%, and the root mean square error of prediction (RMSEP) and the mean RSD of prediction results decrease from 4.81% to 1.93% and from 1.92% to 1.56%, respectively. Furthermore, the results of 10 validation sets and 216 line combinations show that ETNDC outperforms baseline methods in terms of average performance and robustness. For the first time, ETNDC explicitly addresses the temperature and electron density variations while compensating for the total number density variation, where the inaccurate spectroscopic parameters are avoided by fitting related quantities using concentration information. The method demonstrates effective and robust improvement in signal repeatability and analytical performance in uranium determination, facilitating accurate quantification of the LIBS technique. [Display omitted] • A novel data pre-processing method is proposed for laser-induced breakdown spectroscopy. • Temperature and electron density compensation is incorporated into total number density compensation. • Inaccurate spectroscopic parameters are avoided in compensation. • Effective and robust improvements in signal repeatability and analytical performance are achieved in uranium determination. [ABSTRACT FROM AUTHOR]

A non-denaturating isoelectric focusing (ND-IEF) gel electrophoresis protocol has been developed to study and identify uranium (U)-protein complexes with laser ablation-inductively coupled plasma mass spectrometry (LA-ICP MS) and electrospray ionization mass spectrometry (ESI-MS). The ND-IEF-LA-ICP MS methodology set-up was initiated using in vitro U-protein complex standards (i.e., U-bovine serum albumin and U-transferrin) allowing the assessment of U recovery to 64.4 ± 0.4 %. This methodology enabled the quantification of U-protein complexes at 9.03 ± 0.23, 15.27 ± 0.36, and 177.31 ± 25.51 nmol U L in digestive gland cytosols of the crayfish, Procambarus clarkii, exposed respectively to 0, 0.12, and 2.5 μmol of waterborne depleted U L during 10 days. ND-IEF-LA-ICP MS limit of detection was 19.3 pmol U L. Elemental ICP MS signals obtained both in ND-IEF electropherograms and in size exclusion chromatograms of in vivo U-protein complexes revealed interactions between U- and Fe- and Cu-proteins. Moreover, three proteins (hemocyanin, pseudohemocyanin-2, and arginine kinase) out of 42 were identified as potential uranium targets in waterborne-exposed crayfish cytosols by microbore reversed phase chromatography coupled to molecular mass spectrometry (µRPC-ESI-MS/MS) after ND-IEF separation. [Figure not available: see fulltext.] [ABSTRACT FROM AUTHOR]

Abstract: Laser-induced breakdown spectroscopy (LIBS) has been recognized as a promising technique for analyzing sensitive nuclear materials such as uranium, plutonium, and curium in a high-radiation environment, especially since the implementation of IAEA (International Atomic Energy Agency) safeguards. The uranium spectra of ore samples were quantitatively analyzed prior to analyzing sensitive materials in the nuclear industry. The purpose of this experiment is to extract quantitative information about the uranium in a uranium ore using a standard addition approach. The uranium ore samples containing different concentrations of U were prepared by mixing raw ore powder with natural uranium oxide powders. Calibration sets of 0.2, 0.4, 0.6, 0.8 and 1.0wt.% uranium concentrations within the uranium ore sample were achieved. A pulsed and Q-switched Nd:YAG laser at a wavelength of 532nm was used as a light source. An echelle spectrometer that covers a 190–420nm wavelength range is used to generate a calibration curve and determine the detection limit of uranium in the ore matrix. The neutral atomic-emission peak at a wavelength of 356.659nm indicated a detection limit of ~158ppm for uranium, and the uranium concentration was determined in a raw ore sample that has an unknown quantity of uranium. [Copyright &y& Elsevier]