A wind environment and Lorentz factors of tens explain gamma-ray bursts X-ray plateau

Gamma-ray bursts (GRBs) are known to have the most relativistic jets, with initial Lorentz factors in the order of a few hundreds. Many GRBs display an early X-ray light-curve plateau, which was not theoretically expected and therefore puzzled the community for many years. Here, we show that this observed signal is naturally obtained within the classical GRB "fireball" model, provided that the initial Lorentz factor is rather a few tens, and the expansion occurs into a medium-low density "wind". The range of Lorentz factors in GRB jets is thus much wider than previously thought and bridges an observational gap between mildly relativistic jets inferred in active galactic nuclei, to highly relativistic jets deduced in few extreme GRBs. Furthermore, long GRB progenitors are either not Wolf-Rayet stars, or the wind properties during the final stellar evolution phase are different than at earlier times. We discuss several testable predictions of this model.Comment: 61 pages, 24 figures, 9 tables. A final edited version will appear in Nature Communication

Extraction, Storage and Eruption of Multiple Isolated Magma Batches in the Paired Mamaku and Ohakuri Eruption, Taupo Volcanic Zone, New Zealand

The Taupo Volcanic Zone (TVZ) is well known for its extraordinary rate of rhyolitic magma generation and caldera-forming eruptions. Less is known about how large volumes of rhyolitic magma are extracted and stored prior to eruption, and the role tectonics might play in the process of melt extraction and control of caldera eruption(s). Here we present a new model for the extraction, storage and simultaneous eruption of the >245 km3 paired Mamaku and Ohakuri magmas sourced from calderas centred ∼30 km apart (the Rotorua and Ohakuri calderas, respectively) in the central TVZ. The Mamaku and Ohakuri ignimbrites share a similar bulk pumice composition and the same phenocryst assemblage; however, bulk-rock compositions suggest several poorly mixed magma types in each erupted volume, which are randomly distributed throughout the eruptive deposits. To refine models of the pre-eruptive geometry of the magmatic system and discuss a possible origin for triggering of each eruption, we present an expanded database of matrix glass and quartz-hosted melt inclusion compositions along with the existing bulk-rock and mineral compositions. Major and trace element compositions show that the region produced five different magma batches, extracted from the same source region, and a continuous intermediate mush zone beneath the Mamaku-Ohakuri region is suggested here. These magma batches were most probably juxtaposed but isolated from each other in the upper crust, and evolved separately until eruption. The observed geochemical differences between the batches are likely to be generated by different extraction conditions of the rhyolitic melt from a slightly heterogeneous mush. The lack of evidence for more mafic recharge prior to eruption (for example, there are no bright cathodoluminescence rims on quartz crystals) suggests that a magmatic input is unlikely to be an eruption trigger. However, tectonic activity could be an efficient way to trigger the eruption of isolated magma batches, with the evacuation of one magma batch causing a disturbance to the local stress field and activating regionally linked faults, which then lead to the eruption of additional magma batches and associated caldera subsidence. In addition, the extensional tectonic regime coupled with a high heat flux could be the controlling factor in the emplacement of some of the shallowest and most SiO2-rich magmas on Eart

Carbenic nitrile imines: Properties and reactivity

Structures and properties of nitrile imines were investigated computationally at B3LYP and CCSD(T) levels. Whereas NBO analysis at the B3LYP DFT level invariably predicts a propargylic electronic structure, CCSD(T) calculations permit a clear distinction between propargylic, allenic, and carbenic structures. Nitrile imines with strong IR absorptions above ca. 2150 cm-1 have propargylic structures with a CN triple bond (RCNNSiMe 3 and R2BCNNBR2), and those with IR absorptions below ca. 2150 cm-1 are allenic (HCNNH, PhCNNH, and HCNNPh). Nitrile imines lacking significant cumulenic IR absorptions at 1900-2200 cm -1 are carbenic (R-(C:)-N=N-R′). Electronegative but lone pair-donating groups NR2, OR, and F stabilize the carbenic form of nitrile imines in the same way they stabilize "normal" singlet carbenes, including N-heterocyclic carbenes. NBO analyses at the CCSD(T) level confirm the classification into propargylic, allenic, and carbenic reactivity types. Carbenic nitrile imines are predicted to form azoketenes 21 with CO, to form [2+2] and [2+4] cycloadducts and borane adducts, and to cyclize to 1H-diazirenes of the type 24 in mildly exothermic reactions with activation energies in the range 29-38 kcal/mol. Such reactions will be readily accessible photochemically and thermally, e.g., under the conditions of matrix photolysis and flash vacuum thermolysis

Standardization of Marine Meteorological Data from FINO Offshore Platforms

KlimawandelDer Ausbau der Offshore-Windenergie gehört zu den erklärten Zielen der Bundesregierung. Um bessere Ken ntnisse der Bedingungen auf See zu erlangen, wurden drei Forschungsplattformen in der Nordsee (FINO 1 und 3) und Ostsee (FINO 2) errichtet. An diesen werden meteorologische und ozeanographische Größen in unterschiedlichen Höhen gemessen, um unter anderem Aussagen zu Vertikalprofilen der Windgeschwindigkeit treffen zu können. Da sich die Plattformen und Masten im Design unterscheiden und sich insbesondere bei den Windmessungen deutlich ein richtungsabhängiger Einfluss auf die Messungen zeigt, ist für die Vergleichbarkeit der Standorte eine standardisierte Auswertung der Messergebnisse erforderlich. Ziel des Projektes FINO-Wind ist es, die Vergleichbarkeit der Daten der drei Standorte zu verbessern und den Datennutzern nach standardisierten Methoden qualitätsgeprüfte Daten zur Verfügung zu stellen. Es sollen deshalb Standardisierungsverfahren zur Auswertung der Winddaten entwickelt werden. Insbesondere die verschiedenen Masteffekte werden eingehend untersucht und durch Windkanalmessungen, Vergleich mit LiDAR-Daten, CFD (Computational Fluid Dynamics)-Modellierungen und Anwendung der UAM (Uniform ambient flow mast correction)-Methode abgeschätzt. Daraus werden Korrekturfaktoren für Windmessungen abgeleitet, die später angewendet werden sollen. Die Messdaten, die als 10-Minuten-Werte vorliegen, werden des Weiteren einer umfassenden und automatisierten Qualitätsprüfung unterzogen. Dabei durchlaufen die Daten in aufeinanderfolgenden Schritten formale, klimatologische, zeitliche, Wiederholungs- und Konsistenzprüfungen und werden nach erfolgreichem Abschluss jeder Sequenz mit spezifischen Qualitätsflags gekennzeichnet. Aus der Analyse und dem Vergleich der Instrumentierung in unterschiedlichen Höhen, der Installation und Ausrichtung sowie die Mastkonstruktionen sollen Empfehlungen herausgearbeitet werden, wie zukünftige Anwendungen im Bereich der Offshore-Windmessungen verbessert werden können

Metasomatic Vein Formation By Stationary Fluids In Carbonate Xenoliths At The Eastern Margin Of The Bergell Intrusion, Val Sissone, Italy

Fluid flow is an important mechanism associated with heat and mass transport within the Earth’s crust. The study of veins, which represent channelling of fluids, can thus be key in understanding these fluid movements, unravelling fluid composition and origin, paleo stress regimes, and the history of the host-rock. New stable isotope data on carbonates and silicates have been combined with phase petrology, mass balance, and field observations to evaluate the formation mechanism of metasomatic reaction veins in dolomitic xenoliths in the Bergell tonalites (Val Sissone, Italy). Multiple generations of extensional veins can be followed from the contact zone between the dolomites and the intrusion to a few meters within either the tonalites (with the epidote-quartz veins), or within the dolomites, where they terminate. Each type of vein contains a central zone, which is formed by open fracture crystallization. This central fracture is framed by relatively symmetric replacement zones, where the original dolomite reacted to form either forsterite, diopside, tremolite or talc, all accompanied by calcite in either a succession of reaction zones or in simpler bi-mineral (silicate + calcite) veins. The δ18O and δ13C values across the veins allow temperatures to be estimated from different mineral pairs (silicate + calcite), and which confirm vein formation along a retrograde cooling path of the intrusion. At least four different fluid infiltration events are required, the first one around 555 °C to form the forsterite-calcite veins, followed by the epidote-quartz veins at temperatures around 430 °C, then the tremolite-calcite veins at around 390 °C, and finally the talc-calcite veins at around 140 °C. The shape of the δ18O and δ13C profiles, which are flat across the central part and the replacement zones of the veins (buffered by the intrusion), change substantially over short distances. Both of these isotope profiles overlap with the equally sharp mineralogical front between the veins and the unreacted dolomites. These profiles are interpreted to be the result of an isotopic exchange mechanism driven by dissolution and re-precipitation reactions. All veins are oriented perpendicular to the contact with the intrusive body, except for the late talc veins. Elevated fluid pressures, above the confining pressures caused by the regional and intrusion emplacement stress field, are suggested to be responsible for the initial fracturing of the carbonates and intrusive rocks. The contact zones between the tonalites and carbonates likely served as fluid conduits, where fluids accumulated and the pressure built up until hydrofracturing occurred. We propose that the veins formed through episodic pulses of highly reactive fluids that remained stationary during reaction, rather than a system where fluids flushed through the veins. Based on the XCO2-constrained mass balance, the formation of the veins would only require a relatively small amount of fluid, which could potentially originate from the intrusive rocks in vicinity of the xenoliths. Veining is not ubiquitous around the Bergell intrusion, suggesting that it only may have been a localized event and thus there is no need to involve a larger convective hydrothermal system for their formation

Linear and nonlinear optical properties of a series of Ni-dithiolene derivatives

Some linear and nonlinear optical (NLO) properties of Ni(SCH)4 and several of its derivatives have been computed by employing a series of basis sets and a hierarchy of methods (e.g., HF, DFT, coupled cluster, and multiconfigurational techniques). The electronic structure of Ni(SCH)4 has been also analyzed by using CASSCF/CASPT2, ab initio valence bond, and DFT methods. In particular we discuss how the diradicaloid character (DC) of Ni(SCH)4 significantly affects its NLO properties. The quasidegeneracy of the two lowest-energy singlet states 1 mathg and 1 math1u, the clear DC nature of the former, and the very large number of low-lying states enhance the NLO properties values. These particular features are used to interpret the NLO properties of Ni(SCH)4. The DC of the considered derivatives has been estimated and correlated with the NLO properties. CASVB computations have shown that the structures with Ni(II) are the dominant ones, while those with Ni(0) and Ni(IV) have negligible weight. The weights of the four diradical structures were discussed in connection with the weight of the structures, where all the electrons are paired. Comparative discussion of the properties of Ni(SCH)4 with those of tetrathia fulvalene demonstrates the very large effect of Ni on the properties of the Ni-dithiolene derivatives. A similar remarkable effect on the NLO properties is produced by one or two methyl or C3S groups. The considered Ni-dithiolene derivatives have exceptionally large NLO properties. This feature in connection with their other physical properties makes them ideal candidates for photonic [email protected]

VESIcal Part I: An Open-Source Thermodynamic Model Engine for Mixed Volatile (H<inf>2</inf>O-CO<inf>2</inf>) Solubility in Silicate Melts

Abstract: Thermodynamics has been fundamental to the interpretation of geologic data and modeling of geologic systems for decades. However, more recent advancements in computational capabilities and a marked increase in researchers' accessibility to computing tools has outpaced the functionality and extensibility of currently available modeling tools. Here, we present VESIcal (Volatile Equilibria and Saturation Identification calculator): the first comprehensive modeling tool for H 2 O, C O 2 , and mixed ( H 2 O‐ C O 2 ) solubility in silicate melts that: (a) allows users access to seven of the most popular models, plus easy inter‐comparison between models; (b) provides universal functionality for all models (e.g., functions for calculating saturation pressures, degassing paths, etc.); (c) can process large datasets (1,000s of samples) automatically; (d) can output computed data into an Excel spreadsheet or CSV file for simple post‐modeling analysis; (e) integrates plotting capabilities directly within the tool; and (f) provides all of these within the framework of a python library, making the tool extensible by the user and allowing any of the model functions to be incorporated into any other code capable of calling python. The tool is presented within this manuscript, which may be read as a static PDF but is better experienced via the Jupyter Notebook version of this manuscript. Here, we present worked examples accessible to python users with a range of skill levels. The basic functions of VESIcal can also be accessed via a web app (https://vesical.anvil.app). The VESIcal python library is open‐source and available for download at https://github.com/kaylai/VESIcal, or it can be installed using pip. It is recommended to read and interact with this manuscript as an executable Jupyter Notebook, available at https://mybinder.org/v2/gh/kaylai/vesical-binder/HEAD?filepath=Manuscript.ipynb

Concentration dependent refractive index of a binary mixture at high pressure

In the present work binary mixtures of varying concentrations of two miscible hydrocarbons, 1,2,3,4-tetrahydronaphtalene (THN) and n-dodecane (C12), are subjected to increasing pressure up to 50 MPa in order to investigate the dependence of the so-called concentration contrast factor (CF), i.e., (∂n/∂c)p, T, on pressure level. The refractive index is measured by means of a Mach-Zehnder interferometer. The setup and experimental procedure are validated with different pure fluids in the same pressure range. The refractive index of the THN-C12 mixture is found to vary both over pressure and concentration, and the concentration CF is found to exponentially decrease as the pressure is increased. The measured values of the refractive index and the concentration CFs are compared with values obtained by two different theoretical predictions, the well-known Lorentz-Lorenz formula and an alternative one proposed by Looyenga. While the measured refractive indices agree very well with predictions given by Looyenga, the measured concentration CFs show deviations from the latter of the order of 6% and more than the double from the Lorentz-Lorenz prediction

Liquid mixtures involving hydrogenated and fluorinated alcohols: thermodynamics, spectroscopy, and simulation

This article reports a combined thermodynamic, spectroscopic, and Computational study on the interactions and structure of binary mixtures of hydrogenated and fluorinated substances that simultaneously interact through strong hydrogen bonding. Four binary mixtures of hydrogenated and fluorinated alcohols have been studied, namely, (ethanol + 2,2,2-trifluoroethanol (TFE)), (ethanol + 2,2,3,3,4,4,4-heptafluoro-1-butanol), (1-butanol (BuOH) + TFE), and (BuOH + 2,23,4,4,4-heptafluoto-1-butanol). Excess molar volumes and vibrational spectra of all four binary mixtures have been measured as a function of composition at 298 K, and molecular dynamics simulations have been performed. The systems display a complex behavior when compared with mixtures of hydrogenated alcohols and mixtures of alkanes and perfluoroalkanes. The combined analysis of the results from different approaches indicates that this results from a balance between preferential hydrogen bonding between the hydrogenated and fluorinated alcohols and the unfavorable dispersion forces between the hydrogenated and fluorinated chains. As the chain length increases, the contribution of dispersion increases and overcomes the contribution of H-bonds. In terms of the liquid structure, the simulations suggest the possibility of segregation between the hydrogenated and fluorinated segments, a hypothesis corroborated by the spectroscopic results. Furthermore, a quantitative analysis of the infrared spectra reveals that the presence of fluorinated groups induces conformational changes in the hydrogenated chains from the usually preferred all-trans to more globular arrangements involving gauche conformations. Conformational rearrangements at the CCOH dihedral angle upon mixing are also disclosed by the spectra

Avaliação do impacto das amostras de treinamento na acurácia da classificação random forest dos sistemas integrados de produção agropecuária.

Ao conduzir uma classificação supervisionada com algoritmos de aprendizado de máquina, como o Random Forest, a estratégia de balanceamento das amostras é fundamental, pois impacta diretamente nos resultados. Estes classificadores são sensíveis às proporções das amostras de treinamento das diferentes classes. Compreender como estes fatores influenciam na classificação de áreas de produção agropecuária, sobretudo de sistemas minoritários e complexos como o iLP (Integração Lavoura-Pecuária) são de extrema importância para contribuir com metodologias de monitoramento. Para avaliar o impacto do balanceamento, foram testados três grupos de dados de aprendizagem do Random Forest: (i) Bset01: dados balanceados entre três classes prioritárias no estado do Mato Grosso; (ii) Bset02: dados desbalanceados com as proporções refletindo a realidade de campo e (iii) Bset03: superestimando a classe rara iLP. Os melhores valores de fscore da classe iLP foram para Bset01 (0,81) e Bset02 (0,83), com um erro de comissão mais alto para Bset01, sugerindo uma melhor performance do Bset02