Co2+ in trigonal fields of oxygen based structures: Electronic absorption spectra of buetschliite-type K2Co(SeO3)2, K2Co2(SeO3)3 and zemannite-type K2Co2(SeO3)3 · 2H2O

Polarized single crystal absorption spectra, in the spectral range 40 000–5 000 cm^-1, were obtained on Co²⁺ in trigonally distorted octahedral oxygen fields of buetschliite-type K₂Co(SeO₃)₂ (I), K₂Co₂(SeO₃)₃ (II) and zemannite-type K₂Co₂(SeO₃)₃ · 2H₂O (III). Site symmetries of Co²⁺ are m (D_3d) in I, 3m (C_3v) in II, and 3 (C₃) in III. The spectra can be interpreted on the basis of an electric dipole mechanism, wherein transitions of Co²⁺ in the centrosymmetric site in I gain intensity from dynamic removal of the inversion centre by vibronic coupling. In accordance with the elongation of the CoO₆ octahedra along the trigonal axis, the split component E_(g) of the ground state ⁴T_1g in octahedral fields is the ground state in all three compounds. Trigonal field parameters Dq_(trig), D, D and the Racah parameters B have been fitted to the energies of spin allowed transitions (293 K) as follows: I: 744, 94, -16, and 838 cm^-1, resp.; II: 647, 227, 42, and 798 cm^-1, resp.; III: 667, 181, 21, and 809 cm^-1, respectively. Racah parameters C were estimated from the energy of some observed spin-forbidden transitions to be 3770 (I), 3280 (II), and 3465 cm^-1 (III). Values of Dq and of the Racah parameters B and C indicate slight differences of Co²⁺-O bonding in I as compared to II and III, with somewhat higher covalency in compounds II and III which contain face-sharing CoO₆ octahedra with short Co-Co contacts. Also, in II and III the observed D values do not agree with theoretical D values, predicted from the magnitude of the mean octahedral distortions.     

Synthesis and stability of deerite,Fe 12 2+ Fe 6 3+ [Si12O40](OH)10, and Fe3+⇋Al3+ substitutions at 15–28 kb

Deerite, Fe ₁₂ ²⁺ Fe ₆ ³⁺ [Si₁₂O₄₀](OH)₁₀, thus far known from ten localities in glaucophane schist terranes, was synthesized at water pressures of 20–25 kb and temperatures of 550–600 °C under the of the Ni/NiO buffer. The X-ray powder diagram, lattice constants and infrared spectrum of the synthetic phase are closely similar to those of the natural mineral. A solid solution series extends from this ferri-deerite end member to some 20 mole % of a hypothetical alumino-deerite, Fe ₁₂ ²⁺ Al ₆ ³⁺ [Si₁₂O₄₀](OH)₁₀. The upper temperature breakdown of ferri-deerite to the assemblage ferrosilite +magnetite+quartz+water occurs at about 490 °C at 15 kb, and 610 °C at 25 kb fluid pressure for the of the Ni/NiO buffer. Extrapolation of these data to lower water pressures indicates that deerite can be a stable mineral only in very low-temperature, high-pressure environments.     

Biases on the cosmological parameters and thermal Sunyaev–Zel'dovich residuals

We examine the biases induced on cosmological parameters when the presence of secondary anisotropies is not taken into account in cosmic microwave background analyses. We first develop an exact analytical expression for computing the biases on parameters when any additive signal is neglected in the analysis. We then apply it in the context of the forthcoming Planck experiment. For illustration, we investigate the effect of the sole residual thermal Sunyaev–Zel'dovich signal that remains after cluster extraction. We find, in particular, that analyses neglecting the presence of this contribution introduce on the cosmological parameters n _s and τ biases, at least ∼6.5 and 2.9 times their 1σ confidence intervals. The Ω_b parameter is also biased to a lesser extent.     

Pressure-induced (Al,Si)[4]-ordering in dioctahedral micas?

Pure, synthetic 2M₁-muscovites (Ms) and 2M₁-paragonites (Pg) prepared at 7, 13.5, and 18 kbar have been subjected to careful X-ray powder diffractometry and IR powder spectrometry. The results of X-ray studies show that the lattice constants of these micas are independent of the pressure employed in synthesizing them. Similarly, the IR powder spectra of Ms and Pg remain unaffected by the synthesis pressure. Neither the Al^[4]-O-Al^[4] vibrations decrease in relative intensity nor do the Si-O-Al^[4] vibrations increase in intensity with increasing pressure of synthesis, as they should, if pressure-induced (Al, Si)^[4] ordering had been operative. Finally, the v _OH bands in Ms and Pg are also found to retain their fine structural details, regardless of the pressures employed in synthesizing these phases. In particular, the half widths of v _OH in these (Al,Si)^[4]-disordered micas remain constant at around 60 cm⁻¹, compared to ∼ 10 cm⁻¹ in (Al,Si)^[4]-ordered mica margarite. In the light of this study, shortening of the b lattice parameter and progressive (Al,Si)^[4] ordering with increasing pressure of synthesis of muscovites reported by Velde (1980) would appear to be anomalous. Consequently, any discussion of the effect of (Al,Si)^[4] ordering on the stability of muscovite is a moot point at present.     

Environmentalism and Natural Aggregate Mining

Sustaining a developed economy and expanding a developing one require the use of large volumes of natural aggregate. Almost all human activity (commercial, recreational, or leisure) is transacted in or on facilities constructed from natural aggregate. In our urban and suburban worlds, we are almost totally dependent on supplies of water collected behind dams and transported through aqueducts made from concrete. Natural aggregate is essential to the facilities that produce energy—hydroelectric dams and coal-fired powerplants. Ironically, the utility created for mankind by the use of natural aggregate is rarely compared favorably with the environmental impacts of mining it. Instead, the empty quarries and pits are seen as large negative environmental consequences. At the root of this disassociation is the philosophy of environmentalism, which flavors our perceptions of the excavation, processing, and distribution of natural aggregate. The two end-member ideas in this philosophy are ecocentrism and anthropocentrism. Ecocentrism takes the position that the natural world is a organism whose arteries are the rivers—their flow must not be altered. The soil is another vital organ and must not be covered with concrete and asphalt. The motto of the ecocentrist is man must live more lightly on the land. The anthropocentrist wants clean water and air and an uncluttered landscape for human use. Mining is allowed and even encouraged, but dust and noise from quarry and pit operations must be minimized. The large volume of truck traffic is viewed as a real menace to human life and should be regulated and isolated. The environmental problems that the producers of natural aggregate (crushed stone and sand and gravel) face today are mostly difficult social and political concerns associated with the large holes dug in the ground and the large volume of heavy truck traffic associated with quarry and pit operations. These concerns have increased in recent years as society's demand for living space has encroached on the sites of production; in other words, the act of production has engendered condemnation. Many other environmental problems that are associated with dust and noise and blasting from quarry and pit operations have been reduced through the efficient use of technology. Recycling concrete in buildings, bridges, and roads and asphaltic pavements will ultimately reduce the demand for virgin natural aggregate. The impact created by the large holes in the ground required for the mining of natural aggregate can be greatly reduced by planning their reclamation before mining begins.