Molecular dynamics (MD) modeling of the 10-Å phase, Mg3Si4O10(OH)2·xH2O, with x=2/3, 1.0 and 2.0 shows complex structural changes with pressure, temperature and water content and provides new insight into the structures and stabilization of these phases under subduction zone conditions. The structure(s) of this phase and its role as a reservoir of water in the mantle have been controversial, and these calculations provide specific predictions that can be tested by in situ diffraction studies. At ambient conditions, the computed structures of talc (x=0) and the 10-Å phases with x=2/3 and 1.0 are stable over the 350-ps period of the MD simulations. Under these conditions, the 10-Å phases show phlogopite-like layer stacking in good agreement with previously published structures based on powder X-ray diffraction data for samples quenched from high-pressure and high-temperature experiments. The calculations show that the 10-Å phase with x=2.0 is unstable at ambient conditions. The computed structures at P=5.5 GPa and T=750 K, well within the known stability field of the 10-Å phase, change significantly with water content, reflecting changing H-bonding configurations. For x=2/3, the layer stacking is talc-like, and for x=1.0, it is phlogopite-like. The calculations show that transformation between these two stackings occurs readily, and that the talc-like stacking for the x=2/3 composition is unlikely to be quenchable to ambient conditions. For x=2.0, the layer stacking at P=5.5 GPa and T=750 K is different than any previously proposed structure for a 10-Å phase. In this structure, the neighboring basal oxygens of adjacent magnesium silicate layers are displaced by b/3 (about 3 Å) resulting in the Si atoms of one siloxane sheet being located above the center of the six-member ring across the interlayer. The water molecules are located 1.2 Å above the center of all six-member rings and accept H-bonds from the OH groups located below the rings. The b/3-displaced structure does not readily transform to either the talc-like or phlogopite-like structure, because neither of these stackings can accommodate two water molecules per formula unit. There is likely to be a compositional discontinuity and phase transition between the b/3-displaced phase and the phase with phlogopite-like stacking. The simulations reported here are the first to use the recently developed CLAYFF force field to calculate mineral structures at elevated pressures and temperatures. 相似文献
We study the mineralogical changes suffered by specimens of natural miocene red and green continental sandstones (from Pozuelos Formation and Tiomayo Formation) cropping out in the Argentine Puna that increase their bulk magnetic susceptibility and change color when thermally treated. We hypothesize that on heating siderite, which is present in small quantities as cement in the studied sandstones, would oxidize and decompose into maghemite and/or magnetite. Subsequent heating to higher temperatures sometimes would bring about the conversion of maghemite and/or magnetite to hematite. Mössbauer spectroscopy proved to be a very valuable tool for the determination of the presence of siderite in small amounts in the studied samples. The present results show that further work is needed in order to fully understand the mineralogical changes suffered by continental sandstones during heating. The characterization of such changes occurred during laboratory routines is relevant, since they can help to better understand natural processes. 相似文献
Based on relevant experimental data of a petroleum cement paste under mechanical loading and chemical leaching, an elastic‐plastic model is first proposed by taking into account plastic shearing and pore collapse. The degradation of mechanical properties induced by the chemical leaching is characterized by a chemical damage variable which is defined as the increase of porosity. Both elastic and plastic properties of the cement paste are affected by the chemical damage. The proposed model is calibrated from and applied to describe mechanical responses in triaxial compression tests respectively on sound and fully leached samples. In the second part, a phenomenological chemical model is defined to establish the relationship between porosity change and calcium dissolution process. The dissolution kinetics is governed by a diffusion law taking into account the variation of diffusion coefficient with calcium concentration. The chemical model is coupled with the mechanical model, and both are applied to describe mechanical response of cement paste samples subjected to progressive chemical leaching and compressive stresses. Comparisons between experimental data and numerical results are presented. 相似文献
This article provides an analysis of the EU Emissions Trading Scheme (ETS) and the harmonized benchmark-based allocation procedures by comparing two energy-intensive sectors with activities in three Member States. These sectors include the cement industry (CEI) and the pulp and paper industry (PPI) in the UK, Sweden, and France. Our results show that the new procedures are better suited for the more homogeneous CEI, in which the outcome of stricter allocation of emissions allowances is consistent between Member States. For the more heterogeneous PPI – in terms of its product portfolios, technical infrastructures, and fuel mixes – the allocation procedures lead to diverse outcomes. It is the lack of product benchmark curves, and the alternative use of benchmark values that are biased towards a fossil fuel-mix and are based on specific energy use rather than emission intensity, which leads to allocations to the PPI that do not represent the average performance of the top 10% of GHG-efficient installations. Another matter is that grandfathering is still present via the historically based production volumes. How to deal with structural change and provisions regarding capacity reductions and partial cessation is an issue that is highly relevant for the PPI but less so for the CEI.
Policy relevance
After an unprecedented amount of consultation with industrial associations and other stakeholders, a harmonized benchmark-based allocation methodology was introduced in the third trading period of the EU ETS. Establishing a reliable and robust benchmark methodology for free allocation that shields against high direct carbon costs, is perceived as fair and politically acceptable, and still incentivizes firms to take action, is a significant challenge. This article contributes to a deeper understanding of the challenges in effectively applying harmonized rules in industrial sectors that are heterogeneous. This is essential for the debate on structural reformation of the EU ETS, and for sharing experiences with other emerging emissions trading systems in the world that also consider benchmark methodologies. 相似文献
Petroleum drill cuttings are usually treated by techniques suitable for particular contaminant groups. The significance of this study consists in the development of a treatment technology that can simultaneously handle the hydrocarbon and metal constituents of drill cuttings. Bioaugmentation is combined with stabilisation/solidification (S/S), within S/S monoliths and in granulated S/S monoliths. Portland cement was used for S/S treatment at 30% binder dosage. Bioaugmentation treatment involved two bacterial densities of a mixed culture bio-preparation. The effects of inclusion of compost, fertiliser and activated carbon were also evaluated. After 28 days, the combined S/S and bioaugmentation treatments recorded up to 15% higher total petroleum hydrocarbon (TPH) loss than control S/S treatment without bioaugmentation. Embedding fertiliser, activated carbon and higher bacterial density within S/S monoliths resulted in the highest (99%) TPH reduction but higher concentrations of metals. The addition of compost and lower bacterial density to granulated S/S monoliths led to similar (98%) TPH degradation and lower amounts of metals. The results suggest that with better mixture optimisation, combining S/S and bioaugmentation could engender more sustainable treatment of drill cuttings. 相似文献