XPS Investigations of Ruthenium Deposited onto Representative Inner Surfaces of Nuclear Reactor Containment Buildings

International audienceIn the case of a hypothetical severe accident in a nuclear power plant, interactions of gaseous RuO4 with reactor containment building surfaces (stainless steel and epoxy paint) could possibly lead to a black Ru-containing deposit on these surfaces. Some scenarios include the possibility of formation of highly radiotoxic RuO4(g) by the interactions of these deposits with the oxidising medium induced by air radiolysis, in the reactor containment building, and consequently dispersion of this species. Therefore, the accurate determination of the chemical nature of ruthenium in the deposits is of the high importance for safety studies. An experiment was designed to model the interactions of RuO4(g) with samples of stainless steel and of steel covered with epoxy paint. Then, these deposits have been carefully characterised by scanning electron microscopy (SEM/EDS), electron probe microanalysis (EPMA) and X-ray photoelectron spectroscopy (XPS). The analysis by XPS of Ru deposits formed by interaction of RuO4(g), revealed that the ruthenium is likely to be in the IV oxidation state, as the shapes of the Ru3d core levels are very similar with those observed on the RuO2,xH2O reference powder sample. The analysis of O1s peaks indicates a large component attributed to the hydroxyl functional groups. From these results, it was concluded that Ru was present on the surface of the deposits as an oxyhydroxide of Ru(IV). It has also to be pointed out that the presence of “pure” RuO2, or of a thin layer of RuO3 or Ru2O5, coming from the decomposition of RuO4 on the surface of samples of stainless steel and epoxy paint, could be ruled out. These findings will be used for further investigations of the possible revolatilisation phenomena induced by ozone

Validity and Reliability of a New Specific Parkour Test : Physiological and Performance Responses

Main aim of this study was examining validity and reliability of using a new specific Parkour repeated sprint ability test (SPRSA) for assessing repeated sprint ability while facing obstacles and establishing between-day reliability and sensitivity of SPRSA related to its physiological and performance responses. Thirteen high-level traceurs (three females) performed in random order and twice eight tests for assessing a total of 23 variables: SPRSA (a typical maximal-speed shuttle run interspersed with four Parkour competition-common fundamentals) and seven established fitness tests, core stability, hand-grip, vertical-jump, long-jump, pull-up, 300-m shuttle run (as a field test for anaerobic capacity), and Leger test. Except for muscular elasticity index of vertical jump test (intra-class Correlation Coefficient model 3,1 [ICC3,1] = 0.54 [fair]), fitness tests' ICC3,1s resulted excellent (ICC3,1: 0.93-1.00). SPRSA total time and time of its fastest sprint (SPRSA peak time) were significantly correlated with the majority of core stability (r: -0.79 to 0.59; P < 0.01-0.05), jumping (r: -0.78 to 0.67; P < 0.01-0.05), pull-up tests (r: -0.86; P < 0.01), 300-m shuttle run test total time (r: 0.77-0.82; P < 0.01), and Leger test-estimated VO2 max (r: -0.78; P < 0.01). Principal component analysis (PCA) of the 23 variables led to extraction of four significant components (each due to different variables' combinations), which explained 90.2% of 23 variables' total variance. SPRSA (i.e., total and peak time) showed high reliability (ICC3,1: 0.991-0.998 and standard-error-of-measurement %: 0.07-0.32). Finally, SPRSA showed high sensitivity (smallest-worthwhile-change %: 0.29-0.68). Considering its excellent logical and strong ecological validity, SPRSA may serve as a valid specific field test for Parkour sport. In addition, thanks to its high reliability and sensitivity, this test is suitable for monitoring, evaluating, and programming training processes for Parkour practitioners in repeated sprint ability involving crossing obstacles

Highly efficient separation of actinides from lanthanides by a phenanthroline-derived bis-triazine ligand

The synthesis, lanthanide complexation, and solvent ex- traction of actinide(III) and lanthanide(III) radiotracers from nitric acid solutions by a phenanthroline-derived quadridentate bis-triazine ligand are described. The ligand separates Am(III) and Cm(III) from the lanthanides with remarkably high efficiency, high selectivity, and fast extraction kinetics compared to its 2,2'-bipyridine counterpart. Structures of the 1:2 bis-complexes of the ligand with Eu(III) and Yb(III) were elucidated by X-ray crystallography and force field calculations, respec-tively. The Eu(III) bis-complex is the first 1:2 bis-complex of a quadridentate bis-triazine ligand to be characterized by crystallography. The faster rates of extraction were verified by kinetics measurements using the rotating membrane cell technique in several diluents. The improved kinetics of metal ion extraction are related to the higher surface activity of the ligand at the phase interface. The improvement in the ligand's properties on replacing the bipyridine unit with a phenanthroline unit far exceeds what was anticipated based on ligand design alone

Complexation of lanthanides, actinides and transition metal cations with a 6-(1,2,4-triazin-3-yl)-2,2’:6’,2’’-terpyridine ligand: implications for actinide(III) /lanthanide(III) partitioning

The quadridentate N-heterocyclic ligand 6-(5,5,8,8-tetramethyl-5,6,7,8-tetrahydro-1,2,4-benzotriazin-3-yl)-2,2’:6’,2’’-terpyridine (CyMe4-hemi-BTBP) has been synthesized and its interactions with Am(III), U(VI), Ln(III) and some transition metal cations have been evaluated by X-ray crystallographic analysis, Am(III)/Eu(III) solvent extraction experiments, UV absorption spectrophotometry, NMR studies and ESI-MS. Structures of the 1:1 complexes with Eu(III), Ce(III) and the linear uranyl (UO22+) ion were obtained by X-ray crystallographic analysis, and showed similar coordination behavior to related BTBP complexes. In methanol, the stability constants of the Ln(III) complexes are slightly lower than those of the analogous quadridentate bis-triazine BTBP ligands, while the stability constant for the Yb(III) complex is higher. 1H NMR titrations and ESI-MS with lanthanide nitrates showed that the ligand forms only 1:1 complexes with Eu(III), Ce(III) and Yb(III), while both 1:1 and 1:2 complexes were formed with La(III) and Y(III) in acetonitrile. A mixture of isomeric chiral 2:2 helical complexes was formed with Cu(I), with a slight preference (1.4:1) for a single directional isomer. In contrast, a 1:1 complex was observed with the larger Ag(I) ion. The ligand was unable to extract Am(III) or Eu(III) from nitric acid solutions into 1-octanol, except in the presence of a synergist at low acidity. The results show that the presence of two outer 1,2,4-triazine rings is required for the efficient extraction and separation of An(III) from Ln(III) by quadridentate N-donor ligand

Liquid Biopsy in Breast Cancer

fsffdgr

Interaction of 6,6′′-bis(5,5,8,8-tetramethyl-5,6,7,8-tetrahydro-1,2,4-benzotriazin-3-yl)-2,2′:6′,2′′-terpyridine (CyMe4-BTTP) with some trivalent ions such as lanthanide(iii) ions and americium(iii)

The new ligand 6,6 ''-bis(5,5,8,8-tetramethyl-5,6,7,8-tetrahydro-1,2,4-benzotriazin-3-yl)2,2':6 ',2 ''-terpyridine (CyMe4-BTTP) has been synthesized in 4 steps from 2,2':6',2 ''-terpyridine. Detailed NMR and mass spectrometry studies indicate that the ligand forms 1 : 2 complexes with lanthanide(III) perchlorates where the aliphatic rings are conformationally constrained whereas 1 : 1 complexes are formed with lanthanide(III) nitrates where the rings are conformationally mobile. An optimized structure of the 1 : 2 solution complex with Yb(III) was obtained from the relative magnitude of the induced paramagnetic shifts. X-Ray crystallographic structures of the ligand and of its 1 : 1 complex with Y(III) were also obtained. The NMR and mass spectra of [Pd(CyMe4-BTTP)](n)(2n+) are consistent with a dinuclear double helical structure (n = 2). In the absence of a phase-modifier, CyMe4-BTTP in n-octanol showed a maximum distribution coefficient of Am(III) of 0.039 (+/-20%) and a maximum separation factor of Am(III) over Eu(III) of 12.0 from nitric acid. The metal(III) cations are extracted as the 1 : 1 complex from nitric acid. The generally low distribution coefficients observed compared with the BTBPs arise because the 1 : 1 complex of CyMe4-BTTP is considerably less hydrophobic than the 1 : 2 complexes formed by the BTBPs. In M(BTTP)(3+) complexes, there is a competition between the nitrate ions and the ligand for the complexation of the metal