Neutron-rich Chromium Isotope Anomalies in Supernova Nanoparticles

Neutron-rich isotopes with masses near that of iron are produced in Type Ia and II supernovae (SNeIa and SNeII). Traces of such nucleosynthesis are found in primitive meteorites in the form of variations in the isotopic abundance of ^(54)Cr, the most neutron-rich stable isotope of chromium. The hosts of these isotopic anomalies must be presolar grains that condensed in the outflows of SNe, offering the opportunity to study the nucleosynthesis of iron-peak nuclei in ways that complement spectroscopic observations and can inform models of stellar evolution. However, despite almost two decades of extensive search, the carrier of ^(54)Cr anomalies is still unknown, presumably because it is fine grained and is chemically labile. Here, we identify in the primitive meteorite Orgueil the carrier of ^(54)Cr anomalies as nanoparticles (3.6 × solar). Such large enrichments in ^(54)Cr can only be produced in SNe. The mineralogy of the grains supports condensation in the O/Ne-O/C zones of an SNII, although a Type Ia origin cannot be excluded. We suggest that planetary materials incorporated different amounts of these nanoparticles, possibly due to late injection by a nearby SN that also delivered ^(26)Al and ^(60)Fe to the solar system. This idea explains why the relative abundance of ^(54)Cr and other neutron-rich isotopes vary between planets and meteorites. We anticipate that future isotopic studies of the grains identified here will shed new light on the birth of the solar system and the conditions in SNe

A general moment NRIXS approach to the determination of equilibrium Fe isotopic fractionation factors: application to goethite and jarosite

We measured the reduced partition function ratios for iron isotopes in goethite FeO(OH), potassium-jarosite KFe3(SO4)2(OH)6, and hydronium-jarosite (H3O)Fe3(SO4)2(OH)6, by Nuclear Resonant Inelastic X-Ray Scattering (NRIXS, also known as Nuclear Resonance Vibrational Spectroscopy -NRVS- or Nuclear Inelastic Scattering -NIS) at the Advanced Photon Source. These measurements were made on synthetic minerals enriched in 57Fe. A new method (i.e., the general moment approach) is presented to calculate {\beta}-factors from the moments of the NRIXS spectrum S(E). The first term in the moment expansion controls iron isotopic fractionation at high temperature and corresponds to the mean force constant of the iron bonds, a quantity that is readily measured and often reported in NRIXS studies.Comment: 38 pages, 2 tables, 8 figures. In press at Geochimica et Cosmochimica Acta. Appendix C contains new derivations relating the moments of the iron PDOS to the moments of the excitation probability function measured in Nuclear Resonant Inelastic X-ray Scatterin

Electronic environments of ferrous iron in rhyolitic and basaltic glasses at high pressure

The physical properties of silicate melts within Earth's mantle affect the chemical and thermal evolution of its interior. Chemistry and coordination environments affect such properties. We have measured the hyperfine parameters of iron-bearing rhyolitic and basaltic glasses up to ~120 GPa and ~100 GPa, respectively, in a neon pressure medium using time domain synchrotron Mössbauer spectroscopy. The spectra for rhyolitic and basaltic glasses are well explained by three high-spin Fe^(2+)-like sites with distinct quadrupole splittings. Absence of detectable ferric iron was confirmed with optical absorption spectroscopy. The sites with relatively high and intermediate quadrupole splittings are likely a result of fivefold and sixfold coordination environments of ferrous iron that transition to higher coordination with increasing pressure. The ferrous site with a relatively low quadrupole splitting and isomer shift at low pressures may be related to a fourfold or a second fivefold ferrous iron site, which transitions to higher coordination in basaltic glass, but likely remains in low coordination in rhyolitic glass. These results indicate that iron experiences changes in its coordination environment with increasing pressure without undergoing a high-spin to low-spin transition. We compare our results to the hyperfine parameters of silicate glasses of different compositions. With the assumption that coordination environments in silicate glasses may serve as a good indicator for those in a melt, this study suggests that ferrous iron in chemically complex silicate melts likely exists in a high-spin state throughout most of Earth's mantle

Solar Wind Abundances of C and O

Quantitative understanding of solar wind (SW) elemental fractionation is required to improve knowledge of the solar nebula abundances from Genesis samples, in particular abundances of volatile elements, depleted in CI chondrites. Ratios of elements with low and high first ionization potential (FIP) in the solar wind, e.g., Fe/He, are higher than photospheric abundances. C, O, and N have intermediate FIP and are thus critical as to whether this fractionation is stepwise or gradual as a function of FIP

A procedural development for the analysis of ^56/54Fe and ^57/54Fe isotope ratios with new generation IsoProbe MC-ICP-MS

We have developed a procedure for iron isotope analysis using a hexapole collision cell MC-ICP-MS which is capable of Fe isotope ratio analysis using two different extraction modes. Matrix effects were minimised and the signal-to-background ratio was maximised using high-concentration samples (~ 5μg Fe) and introducing 1.8 mL/min<sup>-1</sup> Ar and 2 mL/min H<sub>2</sub> into the collision cell to decrease polyatomic interferences. The use of large intensity on the faraday cups considerably decreases the internal error of the ratios and ultimately, improves the external precision of a run. Standard bracketing correction for mass bias was possible when using hard extraction. Mass bias in soft extraction mode seems to show temporal instability that makes the standard bracketing inappropriate. The hexapole rf amplitude was decreased to 50 % to further decrease polyatomic interferences and promote the transmission of iron range masses. We routinely measure Fe isotopes with a precision of ± 0.05 ‰ and ± 0.12 ‰ (2σ) for δ<sup>56</sup>Fe and δ<sup>57</sup>Fe respectively

Electronic environments of ferrous iron in rhyolitic and basaltic glasses at high pressure

The physical properties of silicate melts within Earth's mantle affect the chemical and thermal evolution of its interior. Chemistry and coordination environments affect such properties. We have measured the hyperfine parameters of iron-bearing rhyolitic and basaltic glasses up to ~120 GPa and ~100 GPa, respectively, in a neon pressure medium using time domain synchrotron Mössbauer spectroscopy. The spectra for rhyolitic and basaltic glasses are well explained by three high-spin Fe^(2+)-like sites with distinct quadrupole splittings. Absence of detectable ferric iron was confirmed with optical absorption spectroscopy. The sites with relatively high and intermediate quadrupole splittings are likely a result of fivefold and sixfold coordination environments of ferrous iron that transition to higher coordination with increasing pressure. The ferrous site with a relatively low quadrupole splitting and isomer shift at low pressures may be related to a fourfold or a second fivefold ferrous iron site, which transitions to higher coordination in basaltic glass, but likely remains in low coordination in rhyolitic glass. These results indicate that iron experiences changes in its coordination environment with increasing pressure without undergoing a high-spin to low-spin transition. We compare our results to the hyperfine parameters of silicate glasses of different compositions. With the assumption that coordination environments in silicate glasses may serve as a good indicator for those in a melt, this study suggests that ferrous iron in chemically complex silicate melts likely exists in a high-spin state throughout most of Earth's mantle

Coordinated Analyses of Presolar Grains in the Allan Hills 77307 and Queen Elizabeth Range 99177 Meteorites

We report the identification of presolar silicates (~177 ppm), presolar oxides (~11 ppm), and one presolar SiO2 grain in the Allan Hills (ALHA) 77307 chondrite. Three grains having Si isotopic compositions similar to SiC X and Z grains were also identified, though the mineral phases are unconfirmed. Similar abundances of presolar silicates (~152 ppm) and oxides (~8 ppm) were also uncovered in the primitive CR chondrite Queen Elizabeth Range (QUE) 99177, along with 13 presolar SiC grains and one presolar silicon nitride. The O isotopic compositions of the presolar silicates and oxides indicate that most of the grains condensed in low-mass red giant and asymptotic giant branch stars. Interestingly, unlike presolar oxides, few presolar silicate grains have isotopic compositions pointing to low-metallicity, low-mass stars (Group 3). The 18O-rich (Group 4) silicates, along with the few Group 3 silicates that were identified, likely have origins in supernova outflows. This is supported by their O and Si isotopic compositions. Elemental compositions for 74 presolar silicate grains were determined by scanning Auger spectroscopy. Most of the grains have non-stoichiometric elemental compositions inconsistent with pyroxene or olivine, the phases commonly used to fit astronomical spectra, and have comparable Mg and Fe contents. Non-equilibrium condensation and/or secondary alteration could produce the high Fe contents. Transmission electron microscopic analysis of three silicate grains also reveals non-stoichiometric compositions, attributable to non-equilibrium or multistep condensation, and very fine scale elemental heterogeneity, possibly due to subsequent annealing. The mineralogies of presolar silicates identified in meteorites thus far seem to differ from those in interplanetary dust particles.Comment: 23 pages, 16 figure

Sobre a (im)prescritibilidade da pretensão de ressarcimento de danos causados ao erário por ato de improbidade administrativa

TCC(graduação) - Universidade Federal de Santa Catarina. Centro de Ciências Jurídicas. Direito.O presente trabalho objetiva dirimir a dúvida existente acerca da sujeição da pretensão de ressarcimento de danos causados ao erário por ato de improbidade administrativa ao instituto da prescrição. Tal incerteza surge a partir da redação da ressalva contida no artigo 37, § 5º, da Constituição da República Federativa do Brasil, que possibilita variadas interpretações, algumas defendendo a imprescritibilidade de tal pretensão, outras advogando a tese da sujeição de tal pretensão a lapso prescricional. Com o fito de se concluir pelo entendimento mais condizente à ordem jurídico-normativa brasileira, divide-se o estudo em três capítulos principais. No primeiro, são delineados o conceito e a finalidade da prescrição, apresentando-se a garantia da segurança jurídica como sendo seu fundamento constitucional. Em seguida, são explanadas as noções de supremacia do interesse público e segurança jurídica, entendidas por boa parte dos estudiosos como os dois princípios a partir dos quais deve ser analisada a questão. Por fim, no terceiro e último capítulo, depois de serem descritas as principais interpretações que podem derivar da leitura do dispositivo, chega-se ao entendimento pela conformação da pretensão estudada ao manto prescricional. Esta acepção parece melhor se amoldar aos contornos pretendidos pelo ordenamento jurídico-constitucional contemporâneo para a construção de um Direito Administrativo efetivamente democrático, com a sobrevalorização dos direitos fundamentais, individuais e coletivos, e a realização da ideia de supremacia da Constituição. No plano legal e normativo, a compreensão pela prescritibilidade afigura-se coerente à própria construção histórica do comando constitucional, com a delimitação de dois regimes prescricionais distintos para as pretensões originadas com a prática de ato de improbidade. Da mesma forma, a identificação do ressarcimento como consequência, e não sanção, do ato ímprobo, bem como a evolução do tratamento dado à matéria pelo Supremo Tribunal Federal parecem caminhar no mesmo sentido interpretativo