A computational study of order-disorder phenomena in Mg2TiO4 spinel (qandilite)

We have used a combination of classical and quantum-mechanical atomistic calculations, together with Monte Carlo simulations, to study order-disorder phenomena in the spinel mineral qandilite, Mg2TiO4. Using an interatomic potential model akin to those previously used for 2-3 spinels yielded a general increase in energy E as a function of inversion parameter x, and thus incorrectly predicted a normal-spinel ground state, whereas the E(x) behavior as modeled by density-functional theory exhibited a maximum at an intermediate degree of inversion and correctly predicted an inverse-spinel ground state. We therefore used the quantum-mechanical simulations to derive pair interaction parameters (for nearest-neighbor tetrahedral-tetrahedral, octahedral-octahedral, and tetrahedral-octahedral interactions) and chemical potential to use in Monte Carlo simulations of order-disorder in qandilite. The simulated cation distributions compared favorably with those obtained experimentally, although the long-range ordering transition to the tetragonal P4122 phase was not observed when using only nearest-neighbor interactions. However, this transition could be observed following the addition of two extra parameters to the model. The simulations were used to calculate the effect of short- and long-range cation order on the configurational entropy of qandilite as a function of temperature. The calculated entropy of the high-temperature cubic phase was in very good agreement with the experimental value recently determined, supporting the suggestion that there is considerable short-range order in qandilite

Low dimensional ordering and fluctuations in methanol-β\beta-hydroquinone-clathrate studied by X-ray and neutron diffraction

Methanol-$\beta$-hydroquinone-clathrate has been established as a model system for dielectric ordering and fluctuations and is conceptually close to magnetic spin systems. In X-ray and neutron diffraction experiments, we investigated the ordered structure, the one-dimensional (1D) and the three-dimensional (3D) critical scattering in the paraelectric phase, and the temperature dependence of the lattice constants. Our results can be explained by microscopic models of the methanol pseudospin in the hydroquinone cage network, in consistency with previous dielectric investigations

The Burmese Jade Mines belt : origins of jadeitites, serpentinites and ophiolitic peridotites and gabbros

MPS and NJG thank the Oxford-Burma Aung San Suu Kyi Trust and the Fell Fund for funding fieldwork in Myanmar.Ophiolitic peridotites in Burma (Myanmar) occur along three major tectonic zones, the Kaleymyo–Nagaland suture, Indo-Burman ranges, the Jade Mines belt, and the Tagaung–Mytkyina belt. These belts all show harzburgite–lherzolite–dunite peridotites, but the Hpakan-Taw Maw region (Jade Mines belt) hosts jadeitites including pure jadeite, mawsitsit (chromium-rich jadeite) kosmochlore (chromium-rich clinopyroxene), and albitite. High Na and Al contents of jadeitites require either very unusual Al-rich, Si-poor protoliths, or extensive fluid metasomatism, or both. The Hpakan jadeitites formed by Na-, Al-, (and Si) metasomatic alteration of pyroxenite–wehrlite intrusions into harzburgite–dunite, from widespread fluid alteration. Fluids could have been derived from a mid-Jurassic intermediate pressure subduction event during ophiolite formation and emplacement. In the Indawgyi Lake area, normal ophiolitic peridotites, including harzburgite and dunite with pyroxenite veins, have not been jadeitised. Gabbros related to the Jade Mines ophiolite gave a U-Pb zircon age of 169.71±1.3 Ma (MSWD 2.2), similar timing to the Myitkyina ophiolite (173 Ma) to the east, suggesting that the ophiolite belts were originally continuous. The jade ‘boulders’ in the Uru conglomerate beds at Hpakan have also resulted from normal in-situ serpentinisation weathering processes, followed by limited fluvial mass transport processes along the Uru river.Publisher PDFPeer reviewe

Quantifying geological uncertainty in metamorphic phase equilibria modelling; a Monte Carlo assessment and implications for tectonic interpretations

Pseudosection modelling is rapidly becoming an essential part of a petrologist’s toolkit and often forms the basis of interpreting the tectonothermal evolution of a rock sample, outcrop, or geological region. Of the several factors that can affect the accuracy and precision of such calculated phase diagrams, “geological” uncertainty related to natural petrographic variation at the hand sample- and/or thin section-scale is rarely considered. Such uncertainty influences the sample’s bulk composition, which is the primary control on its equilibrium phase relationships and thus the interpreted pressure–temperature (P–T) conditions of formation. Two case study examples—a garnet–cordierite granofels and a garnet–staurolite–kyanite schist—are used to compare the relative importance that geological uncertainty has on bulk compositions determined via (1) X-ray fluorescence (XRF) or (2) point counting techniques. We show that only minor mineralogical variation at the thin-section scale propagates through the phase equilibria modelling procedure and affects the absolute P–T conditions at which key assemblages are stable. Absolute displacements of equilibria can approach ±1 kbar for only a moderate degree of modal proportion uncertainty, thus being essentially similar to the magnitudes reported for analytical uncertainties in conventional thermobarometry. Bulk compositions determined from multiple thin sections of a heterogeneous garnet–staurolite–kyanite schist show a wide range in major-element oxides, owing to notable variation in mineral proportions. Pseudosections constructed for individual point count-derived bulks accurately reproduce this variability on a case-by-case basis, though averaged proportions do not correlate with those calculated at equivalent peak P–T conditions for a whole-rock XRF-derived bulk composition. The main discrepancies relate to varying proportions of matrix phases (primarily mica) relative to porphyroblasts (primarily staurolite and kyanite), indicating that point counting preserves small-scale petrographic features that are otherwise averaged out in XRF analysis of a larger sample. Careful consideration of the size of the equilibration volume, the constituents that comprise the effective bulk composition, and the best technique to employ for its determination based on rock type and petrographic character, offer the best chance to produce trustworthy data from pseudosection analysis.RMP acknowledges a NERC postgraduate grant (reference number NE/H524781/1) for funding analytical work performed at the University of Oxford, UK

Quantifying geological uncertainty in metamorphic phase equilibria modelling; a Monte Carlo assessment and implications for tectonic interpretations

Pseudosection modelling is rapidly becoming an essential part of a petrologist's toolkit and often forms the basis of interpreting the tectonothermal evolution of a rock sample, outcrop, or geological region. Of the several factors that can affect the accuracy and precision of such calculated phase diagrams, “geological” uncertainty related to natural petrographic variation at the hand sample- and/or thin section-scale is rarely considered. Such uncertainty influences the sample's bulk composition, which is the primary control on its equilibrium phase relationships and thus the interpreted pressure–temperature (P–T) conditions of formation. Two case study examples—a garnet–cordierite granofels and a garnet–staurolite–kyanite schist—are used to compare the relative importance that geological uncertainty has on bulk compositions determined via (1) X-ray fluorescence (XRF) or (2) point counting techniques. We show that only minor mineralogical variation at the thin-section scale propagates through the phase equilibria modelling procedure and affects the absolute P–T conditions at which key assemblages are stable. Absolute displacements of equilibria can approach ±1 kbar for only a moderate degree of modal proportion uncertainty, thus being essentially similar to the magnitudes reported for analytical uncertainties in conventional thermobarometry. Bulk compositions determined from multiple thin sections of a heterogeneous garnet–staurolite–kyanite schist show a wide range in major-element oxides, owing to notable variation in mineral proportions. Pseudosections constructed for individual point count-derived bulks accurately reproduce this variability on a case-by-case basis, though averaged proportions do not correlate with those calculated at equivalent peak P–T conditions for a whole-rock XRF-derived bulk composition. The main discrepancies relate to varying proportions of matrix phases (primarily mica) relative to porphyroblasts (primarily staurolite and kyanite), indicating that point counting preserves small-scale petrographic features that are otherwise averaged out in XRF analysis of a larger sample. Careful consideration of the size of the equilibration volume, the constituents that comprise the effective bulk composition, and the best technique to employ for its determination based on rock type and petrographic character, offer the best chance to produce trustworthy data from pseudosection analysis

Cretaceous age, composition, and microstructure of pseudotachylyte in the Otago Schist, New Zealand

At Tucker Hill, in Central Otago, New Zealand, a series of pseudotachylyte veins are hosted in quartzofeldspathic schist. Chilled margins, microlites, flow banding, and the crystallisation of mineral phases absent from the host rock provide unequivocal evidence for melting during pseudotachylyte formation. Whole rock analyses of pseudotachylyte reveal c. 3 enrichment of K2O, Ba, and Rb, and similar depletion of Na2O, CaO, Sr, and Eu, as compared to host schist. Formation age of pseudotachylyte is 95.9±1.8 Ma as measured by total fusion 40Ar/39Ar analyses. Stepwise heating of pseudotachylyte matrix yields an excellently defined 40Ar/39Ar plateau age of 96.0±0.3 Ma. These well-defined ages are attributed to the presence of potassium feldspar, low abundance of inherited lithic material from the host rock, and few fluid inclusions containing extraneous Ar. We propose that formation of these pseudotachylyte veins was related to Cretaceous extensional uplift and exhumation of the Otago Schist

Environmentally Sustainable Solvent-based Process Chemistry for Metals in Printed Circuit Boards

This chapter describes the development of several new processes relating to the fabrication, characterisation and recycling of printed circuit board (PCB) metal assemblies in alternative, sustainable solvent technologies based on an emergent class of liquids know as deep eutectic solvents (DES). It has been demonstrated that in many cases, the use of DES technologies can be disruptive to current process thinking and in principle can deliver benefits including increased efficiency,lower costs and better process control. These technologies offer the opportunity to incorporate new ideas into PCB fabrication and assembly that facilitate downstream, end-of-life recovery and separation consistent with a circular economy model. Current PCB manufacturing is carried out using many complex metal deposition processes involving aqueous solutions of toxic metal salts, strong inorganic acids, precious and expensive noble metals, and requires careful process control and monitoring. As a result, these processes are often costly to operate and inefficient. DES-based technologies can: (1) improve the economic and efficient use of essential metals; (2) reduce or eliminate use of precious and expensive metals; (3) reduce the use of complex and difficult to maintain process chemistry; (4) reduce reliance on toxic and noxious materials; and (5) improve recovery, recycling and reuse of PCB metals

Minimally invasive management of vital teeth requiring root canal therapy

The present study aimed to investigate the possible use of a non-instrumentation technique including blue light irradiation for root canal cleaning. Extracted human single rooted teeth were selected. Nine different groups included distilled water, NaOCl, intra-canal heated NaOCl, and NaOCl + EDTA irrigation after either instrumentation or non-instrumentation, and a laser application group following non-instrumentation technique. The chemical assessment of the root canal dentine was evaluated using EDS and FT-IR. Surface microstructural analyses were performed by using SEM. The antimicrobial efficacy of different preparation techniques was evaluated using microbial tests. Laser application didn’t change the Ca/P, carbonate/phosphate and amide I/phosphate ratios of the root canal dentin the root canal dentin preserved its original form after light application. The instrumentation decreased the carbonate/phosphate and amide I/phosphate ratios of the root canal dentin regardless of the irrigation solution or technique (p < 0.05). According to the microbiological tests, the light application could not provide antibacterial efficacy as much as NaOCl irrigation. The NaOCl irrigation both in the non-instrumentation and instrumentation groups significantly reduced the number of bacteria (p < 0,05). Minimally invasive root canal preparation techniques where the root canal is not instrumented and is disinfected by laser irradiation followed by obturation with a hydraulic cement sealer may be an attractive treatment option for management of vital teeth needing root canal therapy and does not have any detrimental effects on the chemical structure of dentin

Genome Biol.

With genome analysis expanding from the study of genes to the study of gene regulation, 'regulatory genomics' utilizes sequence information, evolution and functional genomics measurements to unravel how regulatory information is encoded in the genome