Raman study of the anharmonicity in YBa2_2Cu3_3Ox_x

A systematic Raman study in the visible carried out on the YBa2Cu316,18Ox (x=6-7) compounds, with isotopic substitution of 18O for 16O, has detected a doping dependent deviation from harmonic behavior for the frequency shift of the in-phase mode, a smaller amount of anharmonicity for the apex mode, and almost no effect for the out-of-phase B1g-symmetry phonon. It appears that the amount of anharmonicity depends strongly on the oxygen concentration; it diminishes close to the tetragonal to orthorhombic structural phase transition and close to optimal doping, while it reaches its maximum value for the ortho-II and a tetragonal phase. The almost zero anharmonicity at optimal doping persists even at 77K. The data in the overdoped oxygen concentration, where a softening of the in-phase phonon frequency occurs, indicate that the anharmonicity is not enhanced by the sudden increase in the CuO2 buckling. The results fully agree with recent studies of the ortho-II phase but they do not comply with a static double-well potential of the apical oxygen atom at optimal doping.Comment: Dedicated to Prof. K. A. M\"uller on the Occasion of his 90th Birthda

The incorporation of plutonium in lanthanum zirconate pyrochlore

The incorporation of plutonium (Pu) within lanthanum zirconate pyrochlore was investigated using air, argon, and N2–3.5%H2 sintering atmospheres together with Ca2+ and Sr2+ incorporation for charge compensation. The samples have been characterised in the first instance by X-ray diffraction (XRD), scanning electron microscopy (SEM) and diffuse reflectance spectroscopy (DRS). The results show Pu can be exchanged for La3+ on the A-site with and without charge compensation and for Zr4+ on the B-site. DRS measurements were made over the wavenumber range of 4000–19,000 cm−1 and the Pu in all air- and argon-sintered samples was found to be present as Pu4+ while that in samples sintered in N2–3.5%H2 was present as Pu3+. The Pu valence was confirmed for three of the samples using X-ray near-edge absorption spectroscopy (XANES). Pu valences >4+ were not observed in any of the samples. © 2013, Elsevier B.V

Characterization of cores from an in-situ recovery mined uranium deposit in Wyoming: Implications for post-mining restoration

In-situ recovery (ISR) of uranium (U) from sandstone-type roll-front deposits is a technology that involves the injection of solutions that consist of ground water fortified with oxygen and carbonate to promote the oxidative dissolution of U, which is pumped to recovery facilities located at the surface that capture the dissolved U and recycle the treated water. The ISR process alters the geochemical conditions in the subsurface creating conditions that are more favorable to the migration of uranium and other metals associated with the uranium deposit. There is a lack of clear understanding of the impact of ISR mining on the aquifer and host rocks of the post-mined site and the fate of residual U and other metals within the mined ore zone. We performed detailed petrographic, mineralogical, and geochemical analyses of several samples taken from about 7m of core of the formerly the ISR-mined Smith Ranch-Highland uranium deposit in Wyoming. We show that previously mined cores contain significant residual uranium (U) present as coatings on pyrite and carbonaceous fragments. Coffinite was identified in three samples. Core samples with higher organic (>1wt.%) and clay (>6-17wt.%) contents yielded higher 234U/238U activity ratios (1.0-1.48) than those with lower organic and clay fractions. The ISR mining was inefficient in mobilizing U from the carbonaceous materials, which retained considerable U concentrations (374-11,534ppm). This is in contrast with the deeper part of the ore zone, which was highly depleted in U and had very low 234U/238U activity ratios. This probably is due to greater contact with the lixiviant (leaching solution) during ISR mining. EXAFS analyses performed on grains with the highest U and Fe concentrations reveal that Fe is present in a reduced form as pyrite and U occurs mostly as U(IV) complexed by organic matter or as U(IV) phases of carbonate complexes. Moreover, U-O distances of ~. 2.05. Å were noted, indicating the potential formation of other poorly defined U(IV/VI) species. We also noted a small contribution from U. O at 1.79. Å, which indicates that U is partially oxidized. There is no apparent U-S or U-Fe interaction in any of the U spectra analyzed. However, SEM analysis of thin sections prepared from the same core material reveals surficial U associated with pyrite which is probably a minor fraction of the total U present as thin coatings on the surface of pyrite.Our data show the presence of different structurally variable uranium forms associated with the mined cores. U associated with carbonaceous materials is probably from the original U mobilization that accumulated in the organic matter-rich areas under reducing conditions during shallow burial diagenesis. U associated with pyrite represents a small fraction of the total U and was likely deposited as a result of chemical reduction by pyrite. Our data suggest that areas rich in carbonaceous materials had limited exposure to the lixiviant solution, continue to be reducing, and still hold significant U resources. Because of their limited access to fluid flow, these areas might not contribute significantly to post-mining U release or attenuation. Areas with pyrite that are accessible to fluids seem to be more reactive and could act as reductants and facilitate U reduction and accumulation, limiting its migration

Characterization of cores from an in-situ recovery mined uranium deposit in Wyoming: Implications for post-mining restoration

In-situ recovery (ISR) of uranium (U) from sandstone-type roll-front deposits is a technology that involves the injection of solutions that consist of ground water fortified with oxygen and carbonate to promote the oxidative dissolution of U, which is pumped to recovery facilities located at the surface that capture the dissolved U and recycle the treated water. The ISR process alters the geochemical conditions in the subsurface creating conditions that are more favorable to the migration of uranium and other metals associated with the uranium deposit. There is a lack of clear understanding of the impact of ISR mining on the aquifer and host rocks of the post-mined site and the fate of residual U and other metals within the mined ore zone. We performed detailed petrographic, mineralogical, and geochemical analyses of several samples taken from about 7m of core of the formerly the ISR-mined Smith Ranch-Highland uranium deposit in Wyoming. We show that previously mined cores contain significant residual uranium (U) present as coatings on pyrite and carbonaceous fragments. Coffinite was identified in three samples. Core samples with higher organic (>1wt.%) and clay (>6-17wt.%) contents yielded higher 234U/238U activity ratios (1.0-1.48) than those with lower organic and clay fractions. The ISR mining was inefficient in mobilizing U from the carbonaceous materials, which retained considerable U concentrations (374-11,534ppm). This is in contrast with the deeper part of the ore zone, which was highly depleted in U and had very low 234U/238U activity ratios. This probably is due to greater contact with the lixiviant (leaching solution) during ISR mining. EXAFS analyses performed on grains with the highest U and Fe concentrations reveal that Fe is present in a reduced form as pyrite and U occurs mostly as U(IV) complexed by organic matter or as U(IV) phases of carbonate complexes. Moreover, U-O distances of ~. 2.05. Å were noted, indicating the potential formation of other poorly defined U(IV/VI) species. We also noted a small contribution from U. O at 1.79. Å, which indicates that U is partially oxidized. There is no apparent U-S or U-Fe interaction in any of the U spectra analyzed. However, SEM analysis of thin sections prepared from the same core material reveals surficial U associated with pyrite which is probably a minor fraction of the total U present as thin coatings on the surface of pyrite.Our data show the presence of different structurally variable uranium forms associated with the mined cores. U associated with carbonaceous materials is probably from the original U mobilization that accumulated in the organic matter-rich areas under reducing conditions during shallow burial diagenesis. U associated with pyrite represents a small fraction of the total U and was likely deposited as a result of chemical reduction by pyrite. Our data suggest that areas rich in carbonaceous materials had limited exposure to the lixiviant solution, continue to be reducing, and still hold significant U resources. Because of their limited access to fluid flow, these areas might not contribute significantly to post-mining U release or attenuation. Areas with pyrite that are accessible to fluids seem to be more reactive and could act as reductants and facilitate U reduction and accumulation, limiting its migration

Human-landscape relations and the occupation of space: experiencing and expressing domestic gardens

A consideration of occupation and space is outlined to advance non-representational thinking about human-landscape relations. Empirical findings are presented from a research project based on data from the Mass Observation Archive relevant to gardens and gardening. The data is analysed to explore how 'ordinary' people (who have contributed to this archive) express and experience issues concerning their home gardens. Our analysis suggests for distinct modes of occupation relevant to the ways these lay writers describe their garden and gardening experiences and activities. The naturalistic mode is occupied with the garden as expressive of 'nature'; the nostalgic mode is occupied with memory and self-reflection; the pragmatic mode concerns tasks/activities that constitute the routine practices of gardening; and the mimetic mode is occupied with the interpersonal dynamics and processes of human social activity. The analysis is situated in the theoretical context of some recent developments in non-representational theory. We suggest that our approach and data are compatible with the process-orientation of non-representational thinkers, and that – contrary to certain objectivist tendencies within non-representational theorizing - this approach need not neglect the importance of issues of subjectivity and experience, and the relevance of textual data. We aim to lend empirical substance to recent theoretical and philosophical discussions on space, and speculations about why the home garden appears to be so important to many people

Photoemission from single crystals of EuBa2Cu3O7-x cleaved below 20 K: Temperature-dependent oxygen loss.

The first low-temperature photoemission spectra from well-oxygenated and characterized, cleaved single crystals of the 1:2:3-type superconductors, specifically EuBa2Cu3O7-x, are presented. In contrast with polycrystalline or higher-temperature single-crystalline studies, a distinct and very stable density of states is found at the Fermi edge below 20 K. As the crystal is warmed even to 80 K the emission is rapidly lost from both the upper and lower portions of the Cu-O hybrids. At room temperature there is a loss of intensity at the Fermi edge with an accompanying change in the Ba 4d core-level line shape and the presence of a charging effect indicative of an insulating surface. These results imply that upon warming from 20 K there is very rapid oxygen loss from the cleaved surface with a resulting loss of superconducting behavior. This suggests that future photoemission experiments, especially those investigating detailed band structure, should be performed at low temperatures. © 1988 The American Physical Society

Photoemission from single crystals of EuBa2Cu3O7-x cleaved below 20 K: Temperature-dependent oxygen loss.

The first low-temperature photoemission spectra from well-oxygenated and characterized, cleaved single crystals of the 1:2:3-type superconductors, specifically EuBa2Cu3O7-x, are presented. In contrast with polycrystalline or higher-temperature single-crystalline studies, a distinct and very stable density of states is found at the Fermi edge below 20 K. As the crystal is warmed even to 80 K the emission is rapidly lost from both the upper and lower portions of the Cu-O hybrids. At room temperature there is a loss of intensity at the Fermi edge with an accompanying change in the Ba 4d core-level line shape and the presence of a charging effect indicative of an insulating surface. These results imply that upon warming from 20 K there is very rapid oxygen loss from the cleaved surface with a resulting loss of superconducting behavior. This suggests that future photoemission experiments, especially those investigating detailed band structure, should be performed at low temperatures. © 1988 The American Physical Society