Quantum-thermodynamic treatment of intrinsic anharmonicity; Wallace’s theorem revisited

Wallace (in Thermodynamics of crystals, 1972) developed a theorem, rooted in rigid lattice dynamics, which incorporates intrinsic anharmonic effects in solids. The practical application of this theorem in mineral physics is computationally involved and this is the main reason for the theorem not getting the attention it deserves. Because intrinsic anharmonicity is an important issue at the extreme conditions in planetary mantles, we derived a method which removes the computational obstacles in applying this theorem. We extended the theorem to incorporate details of the phonon spectrum and tested our algorithm on forsterite (Mg₂SiO₄). Using a least squares inversion technique applied to all available experimental data, we show that it results in an accurate representation of thermodynamic properties and sound wave velocities of Mg₂SiO₄ in its complete pressure–temperature stability range. We also show that the accuracy of our results is not significantly affected by the use of a different equation of state.     

Structural and tectonothermal evolution of the ultrahigh-temperature Bakhuis Granulite Belt,Guiana Shield,Surinam:Palaeoproterozoic to recent

We constrain the multistage tectonic evolution of the Palaeoproterozoic UHT metamorphic(P=0.9–1.0 GPa,T>1000℃,t=2088–2031 Ma)Bakhuis Granulite Belt(BGB)in Surinam on the Guiana Shield,using large-to small-scale structures,Al-in-hornblende thermobarometry and published fluid inclusion and zircon geochronological data.The BGB forms a narrow,NE–SW striking belt between two formerly connected,~E–W oriented granite-greenstone belts,formed between converging Amazonian and West African continental masses prior to collision and Transamazonian orogeny.Inherited detrital zircon in BGB metasediments conforms agewise to Birimian zircon of West Africa and suggests derivation from the subsequently subducted African passive margin.Ultrahigh-temperature metamorphism may have followed slab break-off and asthenospheric heat advection.Peak metamorphic structures result from layer-parallel shearing and folding,reflecting initial transtensional exhumation of the subducted African margin after slab break-off.A second HT event involves intrusion,at ca.0.49 GPa,of charnockites and metagabbros at 1993–1984 Ma and a layered anorthosite at 1980 Ma,after the BGB had already cooled to<400℃.The event is related to northward subduction under the greenstone belts,along a new active margin to their south.A pronounced syntaxial bend in the new margin points northward towards the BGB and is likely the result of indentation by an anticlinorial flexural bulge of the subducting plate.Tearing of the subducting oceanic plate along this bulge explains why the charnockites are restricted to the BGB.The BGB subsequently experienced doming under an extensional detachment exposed in its southwestern border zone.Exhumation was focused in the BGB as a result of the flexural bulge in the subducting plate and localised heating of the overriding plate by charnockite magmatism.The present,straight NE–SW long-side boundaries of the BGB are superimposed mylonite zones,overprinted by pseudotachylites,previously dated at ca.1200 Ma and 950 Ma,respectively.The 1200 Ma mylonites reflect transpressional popping-up of the BGB,caused by EW-directed intraplate principal compressive stresses from Grenvillian collision preserved under the eastern Andes.Further exhumation of the BGB involved the 950 Ma pseudotachylite decorated faulting,and Phanerozoic faulting along reactivated Meso-and Neoproterozoic lineaments.     

Enhanced bioremoval of refractory compounds from dyeing wastewater using optimized sequential anaerobic/aerobic process

The upflow anaerobic sludge blanket process followed by the biological aerated filter process was employed to improve the removal of color and recalcitrant compounds from real dyeing wastewater. The highest removal efficiency for color was observed in the anaerobic process, at 8-h hydraulic retention time, seeded with the sludge granule. In the subsequent aerobic process packed with the microbe-immobilized polyethylene glycol media, the removal efficiency for chemical oxygen demand increased significantly to 75 %, regardless of the empty bed contact time. The average influent non-biodegradable soluble chemical oxygen demand was 517 mg/L, and the average concentration in effluent from the anaerobic reactor was 363 mg/L, suggesting the removal of some recalcitrant matters together with the degradable ones. The average non-biodegradable soluble chemical oxygen demand in effluent from the aerobic reactor was 87, 93, and 118 mg/L, with the removal efficiency of 76, 74, and 67 %, at 24-, 12-, and 8-h empty bed contact time, respectively. The combined anaerobic sludge blanket and aerobic cell-entrapped process was effective to remove the refractory compounds from real dyeing wastewater as well as in reducing organic loading to meet the effluent discharge limits. This integrated process is considered an effective and economical treatment technology for dyeing wastewater.     

Natural manganese oxide: Combined analytical approach for solid characterization and arsenic retention

To understand the retention of As on a natural manganese sand, the structural, textural and chemical properties of the solid were first investigated by combining scanning electron microscopy (SEM), transmission electron microscopy (TEM), electron-energy-loss spectroscopy (EELS), X-ray diffraction (XRD), BET N₂ gas adsorption, diffuse reflectance Fourier transform infrared (FT-IR) spectroscopy and X-ray photoelectron spectroscopy (XPS) analysis. Manganese sand could be mainly described as a mixture of a phyllomanganate, lithiophorite [(Al,Li)MnO₂(OH)₂], and pyrolusite (MnO₂). Iron particle, kaolinite and gibbsite type-phases were also observed. Particles organization led to the presence of a mesoporosity with pore diameters ranging from 100 to 200 Å and a specific surface area of 23 m² g⁻¹. Contact with an As(V) solution (0.67 mmol L⁻¹) led to an average fractional surface coverage of 0.4. Both As (V) and (III) were present on the surface of the sand in a 1:1 ratio. As(V) was sorbed on lithiophorite-type particles through surface complexation type reaction. As(III) was thought to result from As(V) reduction mechanism on iron particles.     

Rigid Unit Modes in disordered nepheline: a study of a displacive incommensurate phase transition

 Calculations of the Rigid Unit Modes (RUMs) allowed in the nepheline structure are used to explain the diffuse scattering previously seen in electron diffraction experiments. The RUM calculations also show that the modulation wavelength for incommensurate nephelines is essentially determined by the framework topology. X-ray diffraction is used to measure the intensity of the diffuse scattering as a function of temperature. The diffuse intensity increases sharply at 308 K. This effect is interpreted as being due to the softening of a phonon mode, indicating a phase transition. Measurements of this phase transition below the transition temperature are made using hard mode infrared spectroscopy. Received: 17 February 1999 / Revised, accepted. 15 October 1999     

Effect of heat treatment on tourmaline from Brazil

The crystal-chemical behaviour of tourmaline from Araçuaí, Minas Gerais state, Brazil, when subjected to heating in air atmosphere has been studied by several techniques, including EMPA, UV–Vis, TGA, and Mössbauer spectroscopy. The tourmaline samples are typically intermediate members of the elbaite-schorl series. The origin of colour and of its change after treatment has been discussed in terms of local disorder, presence of metal transition elements, oxidation of ferrous iron at the octahedral site, and simultaneous trap of the excess electron. These findings may be used to enhance the colour in tourmaline crystals or generate wanted colour changes.