Mineralogy, geochemistry and classification of the new Smolenice iron meteorite from Slovakia

Abstract: A single 13.95 kg mass of a slightly weathered iron meteorite was found in the forest near Smolenice (48°31.2’N, 17°23.9’E; Trnava County, Slovakia). The bulk chemical composition (in wt. %) is: Fe 88.78, Ni 8.16, Co 0.38, P 0.05, S˂0.006 and (in μg/g): Ge˂0.18, Ir 1.67, Ga 1.80, Cr 87.3, Cu 135.1, As 4.52, Mo 5.82, Sn 1.53, W 0.56, Re 0.18, Ru 3.56, Rh 0.90, Pd 4.12, Pt 5.35, Au 1.19, Zn˂5, B˂0.68, Pb˂0.06. Bulk geochemistry, and Ni, Ga, Ge and Ir contents in particular suggest that the meteorite is an octahedrite belonging to the IVA group. The average thickness of kamacite lamellae is 0.22 mm, ranking it as fine octahedrite (Of). The mineral composition is simple, the most abundant minerals being iron (kamacite) (5.16–7.36 wt. % Ni) followed by taenite (16.73–33.93 wt. % Ni). Troilite nodules and daubréelite inclusions and thin veinlets are rare. The Widmanstätten pattern is uniform across the meteorite and plessite structure is developed locally. Analyses of cosmogenic radionuclides (14C and 26Al) indicate that the radius of the Smolenice meteorite could be 30±10 cm and its terrestrial age 11±2 kyr

Characterisation of CaCO3 phases during strain-specific ureolytic precipitation

Numerous microbial species can selectively precipitate mineral carbonates with enhanced mechanical properties, however, understanding exactly how they achieve this control represents a major challenge in the field of biomineralisation. We have studied microbial induced calcium carbonate (CaCO3) precipitation (MICP) in three ureolytic bacterial strains from the Sporosarcina family, including S. newyorkensis, a newly isolated microbe from the deep sea. We find that the interplay between structural water and strain-specific amino acid groups is fundamental to the stabilisation of vaterite and that, under the same conditions, different isolates yield distinctly different polymorphs. The latter is found to be associated with different urease activities and, consequently, precipitation kinetics, which change depending on pressure-temperature conditions. Further, CaCO3 polymorph selection also depends on the coupled effect of chemical treatment and initial bacterial concentrations. Our findings provide new insights into strain-specific CaCO3 polymorphic selection and stabilisation, and open up promising avenues for designing bio-reinforced geo-materials that capitalise on the different particle bond mechanical properties offered by different polymorphs

Deep carbon cycle constrained by carbonate solubility.

Earth's deep carbon cycle affects atmospheric CO2, climate, and habitability. Owing to the extreme solubility of CaCO3, aqueous fluids released from the subducting slab could extract all carbon from the slab. However, recycling efficiency is estimated at only around 40%. Data from carbonate inclusions, petrology, and Mg isotope systematics indicate Ca2+ in carbonates is replaced by Mg2+ and other cations during subduction. Here we determined the solubility of dolomite [CaMg(CO3)2] and rhodochrosite (MnCO3), and put an upper limit on that of magnesite (MgCO3) under subduction zone conditions. Solubility decreases at least two orders of magnitude as carbonates become Mg-rich. This decreased solubility, coupled with heterogeneity of carbon and water subduction, may explain discrepancies in carbon recycling estimates. Over a range of slab settings, we find aqueous dissolution responsible for mobilizing 10 to 92% of slab carbon. Globally, aqueous fluids mobilise [Formula: see text]% ([Formula: see text] Mt/yr) of subducted carbon from subducting slabs

Rich Polymorphism of a Metal–Organic Framework in Pressure–Temperature Space

International audienceWe present an in situ powder X-ray diffraction study on the phase stability and polymorphism of the metal–organic framework ZIF-4, Zn(imidazolate)2, at simultaneous high pressure and high temperature, up to 8 GPa and 600 °C. The resulting pressure–temperature phase diagram reveals four, previously unknown, high-pressure–high-temperature ZIF phases. The crystal structures of two new phases—ZIF-4-cp-II and ZIF-hPT-II—were solved by powder diffraction methods. The total energy of ZIF-4-cp-II was evaluated using density functional theory calculations and was found to lie in between that of ZIF-4 and the most thermodynamically stable polymorph, ZIF-zni. ZIF-hPT-II was found to possess a doubly interpenetrated diamondoid topology and is isostructural with previously reported Cd(Imidazolate)2 and Hg(Imidazolate)2 phases. This phase exhibited extreme resistance to both temperature and pressure. The other two new phases could be assigned with a unit cell and space group, although their structures remain unknown. The pressure–temperature phase diagram of ZIF-4 is strikingly complicated when compared with that of the previously investigated, closely related ZIF-62 and demonstrates the ability to traverse complex energy landscapes of metal–organic systems using the combined application of pressure and temperature

Carbonate assemblages in Cold Bokkeveld CM chondrite reveal complex parent body evolution

Funder: Royal Astronomical Society; Id: http://dx.doi.org/10.13039/501100000698Abstract: The paragenesis of carbonates in the Cold Bokkeveld CM chondrite is determined from a detailed petrographic, chemical, spectroscopic, and isotopic study of nine associations of carbonates (aragonite, calcite, and dolomite) with other secondary minerals that occur within the meteorite. Our study reveals the existence of carbonates displaying petrographic features that are distinct from those of type 1 and type 2 carbonates commonly observed in CM2 meteorites. These include carbonates interstitial to octahedral magnetite crystals, for which a new designation of “type 1c” is suggested. The O isotopic values of dolomite (δ18O ranging from +21.1 to +25.8‰ and Δ17O from −4.9 to −4.0‰) are similar to those measured in dolomites from other CM chondrites. The presence of complex carbonates with a CaCO3 core and Mg‐enriched rim implies several generations of fluids and/or their evolving composition on the CM parent body(ies). Petrographic characteristics indicate at least six stages of potentially overlapping carbonate and phyllosilicate formation events. We show that type 1 and type 2 calcite have distinct Raman spectral characteristics. Type 1 calcite is characterized by very broad peaks, whereas type 2 calcite displays narrow peaks similar to those of typical abiotic terrestrial calcite, suggesting high crystallinity. A carbonate Raman spectrum showing features characteristic of both aragonite and calcite likely documents an aragonite‐calcite phase transition. Raman spectroscopy also reveals the presence of organic matter in the majority of carbonates. This indicates that organic carbon was mobilized by aqueous fluids for extended periods

Rich Polymorphism of a Metal-Organic Framework in Pressure-Temperature Space.

We present an in situ powder X-ray diffraction study on the phase stability and polymorphism of the metal-organic framework ZIF-4, Zn(imidazolate)2, at simultaneous high pressure and high temperature, up to 8 GPa and 600 °C. The resulting pressure-temperature phase diagram reveals four, previously unknown, high-pressure-high-temperature ZIF phases. The crystal structures of two new phases-ZIF-4-cp-II and ZIF-hPT-II-were solved by powder diffraction methods. The total energy of ZIF-4-cp-II was evaluated using density functional theory calculations and was found to lie in between that of ZIF-4 and the most thermodynamically stable polymorph, ZIF- zni. ZIF-hPT-II was found to possess a doubly interpenetrated diamondoid topology and is isostructural with previously reported Cd(Imidazolate)2 and Hg(Imidazolate)2 phases. This phase exhibited extreme resistance to both temperature and pressure. The other two new phases could be assigned with a unit cell and space group, although their structures remain unknown. The pressure-temperature phase diagram of ZIF-4 is strikingly complicated when compared with that of the previously investigated, closely related ZIF-62 and demonstrates the ability to traverse complex energy landscapes of metal-organic systems using the combined application of pressure and temperature

Pressure promoted low-temperature melting of metal–organic frameworks

International audienceMetal–organic frameworks (MOFs) are microporous materials with huge potential for chemical processes. Structural collapse at high pressure, and transitions to liquid states at high temperature, have recently been observed in the zeolitic imidazolate framework (ZIF) family of MOFs. Here, we show that simultaneous high-pressure and high-temperature conditions result in complex behaviour in ZIF-62 and ZIF-4, with distinct high- and low-density amorphous phases occurring over different regions of the pressure–temperature phase diagram. In situ powder X-ray diffraction, Raman spectroscopy and optical microscopy reveal that the stability of the liquid MOF state expands substantially towards lower temperatures at intermediate, industrially achievable pressures and first-principles molecular dynamics show that softening of the framework coordination with pressure makes melting thermodynamically easier. Furthermore, the MOF glass formed by melt quenching the high-temperature liquid possesses permanent, accessible porosity. Our results thus imply a route to the synthesis of functional MOF glasses at low temperatures, avoiding decomposition on heating at ambient pressure

3 years of liraglutide versus placebo for type 2 diabetes risk reduction and weight management in individuals with prediabetes: a randomised, double-blind trial

Background: Liraglutide 3·0 mg was shown to reduce bodyweight and improve glucose metabolism after the 56-week period of this trial, one of four trials in the SCALE programme. In the 3-year assessment of the SCALE Obesity and Prediabetes trial we aimed to evaluate the proportion of individuals with prediabetes who were diagnosed with type 2 diabetes. Methods: In this randomised, double-blind, placebo-controlled trial, adults with prediabetes and a body-mass index of at least 30 kg/m2, or at least 27 kg/m2 with comorbidities, were randomised 2:1, using a telephone or web-based system, to once-daily subcutaneous liraglutide 3·0 mg or matched placebo, as an adjunct to a reduced-calorie diet and increased physical activity. Time to diabetes onset by 160 weeks was the primary outcome, evaluated in all randomised treated individuals with at least one post-baseline assessment. The trial was conducted at 191 clinical research sites in 27 countries and is registered with ClinicalTrials.gov, number NCT01272219. Findings: The study ran between June 1, 2011, and March 2, 2015. We randomly assigned 2254 patients to receive liraglutide (n=1505) or placebo (n=749). 1128 (50%) participants completed the study up to week 160, after withdrawal of 714 (47%) participants in the liraglutide group and 412 (55%) participants in the placebo group. By week 160, 26 (2%) of 1472 individuals in the liraglutide group versus 46 (6%) of 738 in the placebo group were diagnosed with diabetes while on treatment. The mean time from randomisation to diagnosis was 99 (SD 47) weeks for the 26 individuals in the liraglutide group versus 87 (47) weeks for the 46 individuals in the placebo group. Taking the different diagnosis frequencies between the treatment groups into account, the time to onset of diabetes over 160 weeks among all randomised individuals was 2·7 times longer with liraglutide than with placebo (95% CI 1·9 to 3·9, p<0·0001), corresponding with a hazard ratio of 0·21 (95% CI 0·13–0·34). Liraglutide induced greater weight loss than placebo at week 160 (–6·1 [SD 7·3] vs −1·9% [6·3]; estimated treatment difference −4·3%, 95% CI −4·9 to −3·7, p<0·0001). Serious adverse events were reported by 227 (15%) of 1501 randomised treated individuals in the liraglutide group versus 96 (13%) of 747 individuals in the placebo group. Interpretation: In this trial, we provide results for 3 years of treatment, with the limitation that withdrawn individuals were not followed up after discontinuation. Liraglutide 3·0 mg might provide health benefits in terms of reduced risk of diabetes in individuals with obesity and prediabetes. Funding: Novo Nordisk, Denmark

The origin and behaviour of carbonate minerals in diverse environments: from subduction zones to asteroids

Carbonate minerals are some of the most important carbon storage materials in both terrestrial and asteroidal settings. Understanding the origin and behaviour of carbonates as a function of pressure, temperature, and composition of coexisting phases is therefore crucial for modelling carbon fluxes. This work focuses on carbonate formation and behaviour in three distinct environments: subduction zones in Earth’s mantle, a clay- rich near-surface terrestrial environment, and the CM parent asteroid(s). Subduction zones play an important role in the deep carbon cycle that includes the transport of carbon-bearing phases in subducting slabs to deep Earth, their devolatilization, melting and dissolution in slab fluids, the transport of liberated carbon dioxide (CO2) in fluids and melts, followed by volcanic outgassing. Here, the anharmonicity and solubility of carbonates and associated metal speciation was assessed under subduction zone conditions by different in situ methods. In order to understand the anharmonicity of carbonates, the high-pressure and high-temperature vibrational properties of all naturally occurring aragonite- and calcite-group carbonates were measured by Raman spectroscopy experiments. The effects of fluid salinity, pressure, and temperature on the aqueous solubility of rhodochrosite (MnCO3) and smithsonite (ZnCO3) and Zn complexation were unravelled using the combination of synchrotron X-ray fluorescence spectroscopy and X-ray absorption spectroscopy in the diamond anvil cell (DAC). The aqueous solubility of dolomite [CaMg(CO3)2] and magnesite (MgCO3) was investigated using optical solubility experiments in the DAC. Following the experimental chapters, the role of clays in the formation of an iron oxide-bearing calcite phantom crystal is discussed and the potential of this natural composite as mineral mimetic material explored using the combination of Raman spectroscopy, scanning and transmission electron microscopy, and X-ray powder diffraction, and isotope analysis. Finally, the detailed paragenetic sequence of the CM parent asteroid(s), including multiple carbonate formation events was explored using the combination of Raman spectroscopy, electron probe microanalysis, and nanoscale secondary ion mass spectroscopy.Natural Environment Research Council Doctoral Training Partnerships Program (grant number NE/L002507/1