Solubility equilibria and geochemical modeling in the field of radioactive waste disposal

If a true thermodynamic equilibrium with a well-known solid is expected to establish, chemical equilibrium thermodynamics allows estimation of the maximum concentration of a given radionuclide in a specified pore fluid of an underground repository. However, in the course of the review process for the Nagra/PSI Chemical Thermodynamic Data Base 01/01, important cases of insufficient chemical knowledge were identified, leading to gaps in the database. First, experimental data for the ThO2-H2O and UO2-H2O systems cannot be interpreted by a unique set of thermodynamic constants. There, a pragmatic approach was chosen by including parameters in the database that are not thermodynamic constants in a strict sense, but that reproduced relevant experimental observations. Second, potentially important thermodynamic constants are missing because of insufficient experimental data. Estimations of these missing constants led to problem-specific database extensions. Especially constants for ternary mixed carbonato-hydroxo complexes of tetravalent actinides have been estimated by the "backdoor approach”, i.e., by adjusting thermodynamic constants to maximum feasible values that are still consistent with all available experimental solubility dat

VLT observations of the magnetar CXO J164710.2-455216 and the detection of a candidate infrared counterpart

We present deep observations of the field of the magnetar CXOJ164710.2-455216 in the star cluster Westerlund 1, obtained in the near-infrared with the adaptive optics camera NACO@VLT. We detected a possible candidate counterpart at the {\em Chandra} position of the magnetar, of magnitudes $\mathrm{J} = 23.5 \pm 0.2$, $\mathrm{H} = 21.0 \pm 0.1$, and $\mathrm{K}_\mathrm{S} = 20.4 \pm 0.1$. The K$_{\rm S}$-band measurements available for two epochs (2006 and 2013) do not show significant signs of variability but only a marginal indication that the flux varied (at the 2 $\sigma$ level), consistent with the fact that the observations were taken when CXOJ164710.2-455216 was in quiescence. At the same time, we also present colour--magnitude and colour--colour diagrams in the J, H, and K$_{\rm S}$ bands from the 2006 epoch only, the only one with observations in all three bands, showing that the candidate counterpart lies in the main bulk of objects describing a relatively well--defined sequence. Therefore, based on its colours and lack of variability, we cannot yet associate the candidate counterpart to CXOJ164710.2-455216. Future near-infrared observations of the field, following-up a source outburst, would be crucial to confirm the association from the detection of near-infrared variability and colour evolution.Comment: 5 pages, 3 figures, accepted for publication in MNRA

Novel applications of the “t-amino effect” in heterocyclic chemistry; synthesis of 1-alkylindoles

Thermal rearrangerment of 2-vinyl-1-(1-pyrrolidinyl)benzenes varies with the leaving group ability of substituents in the vinyl moiety; compound 3 having an OR group 9-(alkoxy-methyl)pyrrolo[1,2-a]indoles and compounds 6 (X = OAc, OTs or Cl) yield 1-alkylindoles

Synthesis of pyrrolizines by intramolecular capture of 1,4-dipolar intermediates in reactions of enamines with dimethyl acetylenedicarboxylate

Solvent polarity and reaction temperature strongly influence the reactions of dimethyl acetylenedicar-boxylate (DMAD) with 1-pyrrolidinyl enamines of acyclic and cyclic ketones. Whereas DMAD and 1-[1-phenyl-2-(phenylthio)ethenyl]pyrrolidine (3) give only a mixture of the isomeric 1,3-butadienes (5) in apolar solvents, in methanol the main product is the pyrrolizine 7, together with 5. Again in methanol, DMAD reacts at 0-5° with 8, 9 and 10 to give exclusively 1:1 adducts, the pyrrolizines 11,12 and 13, respectively, whereas at −50° 8 and 9 give 1:2 (enamine : DMAD) adducts, the pyrrolizines 14 and 15, respectively; a single crystal X-ray analysis of 14 gave the structure of the 1:2 adducts. In the same solvent methyl propiolate and 8 give only the linear Michael adduct 17. The enamine-ketone 18 reacts with DMAD in propylene carbonate at 0–5° to give, via (2 + 2)-cycloaddition and ring expansion, 19, and the linear Michael adduct 20. The mechanism of (2 + 2)-cycloaddition and pyrrolizine formation is discussed in terms of a common tied-ion pair intermediate formed in the first, rate-determining step, followed by a second solvent-dependent step

Estimating Be Star Disk Radii using H-alpha Emission Equivalent Widths

We present numerical models of the circumstellar disks of Be stars, and we describe the resulting synthetic H-alpha emission lines and maps of the wavelength-integrated emission flux projected onto the sky. We demonstrate that there are monotonic relationships between the emission line equivalent width and the ratio of the angular half-width at half maximum of the projected disk major axis to the radius of the star. These relationships depend mainly upon the temperatures of the disk and star, the inclination of the disk normal to the line of sight, and the adopted outer boundary for the disk radius. We show that the predicted H-alpha disk radii are consistent with those observed directly through long baseline interferometry of nearby Be stars (especially once allowance is made for disk truncation in binaries and for dilution of the observed H-alpha equivalent width by continuum disk flux in the V-band).Comment: 12 pages, 2 figures, ApJL in pres

A Search for Active Galactic Nuclei in Sc Galaxies with H II Spectra

(Abridged) We have searched for nuclear radio emission from a statistically complete sample of 40 Sc galaxies within 30 Mpc that are optically classified as star-forming objects, in order to determine whether weak AGNs might be present. Only three nuclear radio sources were detected, in NGC 864, NGC 4123, and NGC 4535. These galaxies have peak 6-cm radio powers of 10^{20} W/Hz at arcsecond resolution, while upper limits of the non-detected galaxies typically range from 10^{18.4} to 10^{20} W/Hz. The three nuclear radio sources all are resolved and appear to have diffuse morphologies, with linear sizes of ~300 pc. This strongly indicates that circumnuclear star formation has been detected in these three H II galaxies. Comparison with previous 20-cm VLA results for the detected galaxies shows that the extended nuclear radio emission has a flat spectrum in two objects, and almost certainly is generated by thermal emission from gas ionized by young stars in the centers of those galaxies. The 6-cm radio powers are comparable to predictions for thermal emission that are based on the nuclear H-alpha luminosities, and imply nuclear star formation rates of 0.08-0.8 solar masses/yr, while the low-resolution NRAO VLA Sky Survey implies galaxy-wide star formation rates of 0.3-1.0 solar masses/yr in stars above 5 solar masses. Although the presence of active nuclei powered by massive black holes cannot be definitively ruled out, the present results suggest that they are likely to be rare in these late-type galaxies with H II spectra.Comment: To appear in ApJ. 7 page