Oxygen ordering and superconductivity in La(Ba2−xLax)Cu3O7+δ
The observation of superconductivity above 90 K in the Y–Ba–Cu–O system1,2 has prompted a search for other structures that display high-temperature superconductivity. The discovery of superconductivity above 70 K in La3−xBa3+xCu6Ol4+y3 raises some questions concerning its relationship to the YBa2Cu3O7−δ structure and the origins of the high-temperature superconductivity. The original X-ray diffraction study of La3Ba3Cu6O14+y, indicated a tetragonal structure4,5, on the basis of which it has been proposed that La3−xBa3+xCu6O14+y is a new class of high-temperature superconductor which, in contrast to YBa2Cu3O7−δ, contains no Cu–O chains3. More recently, a neutron diffraction study of non-superconducting La3Ba3Cu6O14+y6has indicated that the correct structure of this compound is simply the tetragonal YBa2Cu3O7−δ structure with partial substitution of lanthanum on the barium site7–12. In the present neutron powder diffraction study of a series of La(Ba2−xLax)Cu3O7+δ compounds, we show that the superconducting phase is a similarly disordered isomorph of the orthorhom-bic YBa2Cu3O7−δ structure13–19. The region of solid solubility for this compound extends from x = 0.5 (La:Ba:Cu ratios of 3:3:6) to x≈ 0.25 and does not include the stoichiometric compound x = 0 (LaBa2Cu3O7−δ). The presence of Cu–O chains, and not just a formal copper charge state of ≥2, is vital for the occurrence of superconductivity.
Structure of Tetragonal YBa2Cu3O5.8
A single-phase YBa2Cu3O5.8 with a tetragonal symmetry shows a semiconductor-like resistivity down to 4.2 K. The crystal structure of this compound has been determined by the Rietveld profile analysis of neutron powder diffraction data measured at 10 K. The space group P4/mmm is confirmed, and lattice constants are a=3.8607(3) Å and c=11.774(1) Å. The oxygen site 2 g(0 0 0.1553) is fully occupied, but the occupation of the 4i site (1/2 0 0.3786) is 0.91 and that of the 2f site (1/2 0 0) is only 0.07.
O2 constraints from Paleoproterozoic detrital pyrite and uraninite
Redox-sensitive detrital grains such as pyrite and uraninite in sedimentary successions provide one of the most conspicuous geological clues to a different composition of the Archean and early Paleoproterozoic atmosphere. Today, these minerals are rapidly chemically weathered within short transport distances. Prior to the rise of oxygen, low O2 concentrations allowed their survival in siliciclastic deposits with grain erosion tied only to physical transport processes. After the rise of oxygen, redox-sensitive detrital grains effectively vanish from the sedimentary record. To get a better understanding of the timing of this transition, we examined sandstones recorded in a scientifi c drill core from the South African 2.415 Ga Koegas Subgroup, a mixed siliciclastic and iron formation–bearing unit deposited on the western deltaic margin of the Kaapvaal craton in early Paleoproterozoic time. We observed detrital pyrite and uraninite grains throughout all investigated sandstone beds in the section, indicating the rise of oxygen is younger than 2.415 Ga. To better understand how observations of detrital pyrite and uraninite in sedimentary rocks can quantitatively constrain Earth surface redox conditions, we constructed a model of grain erosion from chemical weathering and physical abrasion to place an upper limit on ancient environmental O2 concentrations. Even conservative model calculations for deltaic depositional systems with suffi cient transport distances (approximately hundreds of kilometers) show that redox-sensitive detrital grains are remarkably sensitive to environmental O2 concentrations, and they constrain the Archean and early Paleoproterozoic atmosphere to have <3.2 × 10 –5 atm of molecular O2. These levels are lower than previously hypothesized for redox-sensitive detrital grains, but they are consistent with estimates made from other redox proxy data, including the anomalous fractionation of sulfur isotopes. The binary loss of detrital pyrite and uraninite from the sedimentary record coincident with the rise of oxygen indicates that atmospheric O2 concentrations rose substantially at this time and were never again suffi ciently low (<0.01 atm) to enable survival and preservation of these grains in short transport systems.