Entwicklung von Kopplungsmethoden für die Analyse komplexer Mischungen

Erdöl als wichtigster Teil unserer Energieversorgung ist eine der wichtigsten Ressourcen für unsere technologisierte Gesellschaft. Obwohl enorme Anstrengungen unternommen werden, Energie aus erneuerbaren Quellen zu gewinnen, wird Erdöl auch über die nächsten Jahrzehnte als Grundstoff für Treibstoffe, als Rohstoff für die chemische Industrie und für etliche weitere Anwendungen benötigt werden. Die jeweiligen Produkte müssen gleichbleibend umweltfreundlich sowie auch ökonomisch produziert werden, obwohl die Rohstoffe sich kontinuierlich ändern. Die analytische Chemie ist hierbei von zentraler Bedeutung, da eine eingehende Analyse helfen kann, ungewollte Phänomene im Zuge der Produktion zu verstehen. Die genaue Analyse von Erdöl ist allerdings eine problematische Aufgabe. Im Laufe der letzten Jahre wurde gezeigt, dass es keine einzelne analytische Methode gibt, die eine vollständige Charakterisierung von Erdöl erlaubt. Allerdings hat sich die ultrahoch auflösende Fourier-Transformations-Massenspektrometrie (FTMS) zur Methode der Wahl entwickelt, um molekulare Informationen zu gewinnen. Ein Hauptproblem ist die Komplexität der Probe, die zu Unterdrückungseffekten bei der Ionisation und allgemein zu Empfindlichkeitsproblemen führt. Erdöl „sabotiert“ damit praktisch seine eigene Analyse. Ziel dieser Arbeit war die Entwicklung von Methoden zur Probenvereinfachung, um durch die Vermeidung von Diskriminierungseffekten die Detektion einzelner Analyten zu erleichtern. Dies wurde durch die Kopplung von FTMS mit Ionenmobilitätsspektrometrie (FAIMS) bzw. Ligandenaustauschchromatographie (LEC) erreicht. Ein neuer Quellenblock zur 1- und 2-Photonen Ionisation mit FAIMS-FTMS wurde für die Analyse unpolarer Analyten entwickelt. Details über die strukturelle Beschaffenheit einzelner Komponenten konnten gewonnen werden, indem Strukturmotive verschiedener isomerer Verbindungen untersucht wurden. Die Entwicklung einer LEC-Methode mit einer Pd-basierten stationären Phase erlaubte die gruppenselektive Analyse schwefelhaltiger Verbindungen. Die Methode löst eines der drängendsten Probleme der Erdölforschung: Die quantitative Analyse einzelner Verbindungen innerhalb einer komplexen Erdölprobe. Wegen unterschiedlicher Ansprechverhalten war dies bislang nicht möglich. Das Problem wurde mit ICP-MS/MS umgangen, die eine selektive Detektion mit einheitlichem Ansprechverhalten bietet. Die Kombination von gruppenselektiver Trennung mit einer qualitativen Analyse schwefelhaltiger Verbindungen durch LEC-FTMS und mit der Quantifizierung per LEC-ICP-MS/MS erlaubte zum ersten Mal die Quantifizierung verschiedener Typen von Schwefelverbindungen in Erdöl.Being the most important part in the energy supply chain, crude oil is one of the most important resources for our technology-driven society. Although strong efforts are undertaken to gain energy out of renewable resources, it is certain that crude oil will be needed at least for the next couple of decades as feedstock for transportation fuels, as raw material for the chemical industry and for a number of other different applications. The respective products need to be produced constantly in an environmentally friendly and economical way, even though feedstocks are continuously changing. Analytical chemistry is of particular importance here, as a detailed analysis can help understanding numerous adverse effects during production. The comprehensive analysis of crude oil, however, is a problematic task. Over the last years it has been shown that no single analytical technique exists that allows a complete description of a crude oil. However, ultra-high resolving Fourier transform mass spectrometry (FTMS) has developed into the method of choice to gain information on a molecular level. One major problem is the complexity of the sample which leads to suppression effects during ionization and overall sensitivity issues. Crude oil is thus “sabotaging” its own analysis. Aim of this work was the development of methods that allow a simplification of the sample and thus help analyte detection by reducing discrimination and suppression effects. This has been achieved by hyphenating FTMS to separation techniques such as ion mobility spectrometry (FAIMS) and ligand exchange chromatography (LEC). A new source block for 1- and 2-photon ionization with FAIMS FTMS was developed that allows also the studying of non-polar analytes. Details of the structural composition of individual components in very complex crude oil samples were investigated by detecting structural motifs in different isomeric compounds. A group-selective analysis of sulfur containing compounds was offered through the development of a LEC separation method on a Pd-based stationary phase. The application of this method solves one of the most glaring problems in petroleum research: The quantitative analysis of individual compounds within a complex crude oil sample. This had not been possible before due to unresolved response issues. This problem was addressed by selective detection with uniform response using ICP-MS/MS. The combination of class selective separation and qualitative analysis of sulfur containing compounds by LEC FTMS with quantitative analysis by LEC-ICP-MS/MS allowed the quantitative analysis of different sulfur containing compounds in crude oil for the first time

Comparing crude oils with different API gravities on a molecular level using mass spectrometric analysis. Part 2: resins and asphaltenes

FAPESP - FUNDAÇÃO DE AMPARO À PESQUISA DO ESTADO DE SÃO PAULOThe combination of fractionation methods for crude oils, such as saturate, aromatic, resin and asphaltene (SARA) fractionation, in combination with analysis by Fourier transform ion cyclotron resonance mass spectrometry (FT-ICR MS) has been used for reduc1110FAPESP - FUNDAÇÃO DE AMPARO À PESQUISA DO ESTADO DE SÃO PAULOFAPESP - FUNDAÇÃO DE AMPARO À PESQUISA DO ESTADO DE SÃO PAULO2013/19161-42015/05818-

Senso Comune as a Knowledge Base of Italian language: The Resource and its Development

International audienceSenso Comune is a linguistic knowledge base for the Italian Language, which accommodates the content of a legacy dictionary in a rich formal model. The model is implemented in a platform which allows a community of contributors to enrich the resource. We provide here an overview of the main project features, including the lexical-ontology model, the process of sense classification, and the annotation of meaning definitions (glosses) and lexicographic examples. Also, we will illustrate the latest work of alignment with MultiWordNet, to illustrate the methodologies that have been experimented with, to share some preliminary result, and to highlight some remarkable findings about the semantic coverage of the two resources

Effect of the Nano-Ca(OH)2 addition on the Portland clinker cooking efficiency

A new technology was tested to improve the cooking efficiency of the raw mixture for Portland clinker production by the use of nano-Ca(OH)2. A decrease in the free lime concentration after the firing of approximately 35% and 55% in the nano-added clinkers burned at 1350 °C and 1450 °C, respectively, with respect to the standard Portland clinkers was observed. Moreover, in the nano-added clinkers, a slight decrease in alite (C3S), of approximately 2-4 wt%, and increase in belite (C2S), of approximately 5-6 wt%, were observed. Despite these variations, the C2S and C3S abundance lies within the ranges for standard Portland clinkers. The results showed that the nano-addition leads to an increase of the raw mixtures' cooking efficiency. The relatively low energy required for the clinker firing could be used to increase the plant productivity and decrease the CO2 emissions during clinker burning. The decrease of the work index of the clinkers produced by the use of the nano-Ca(OH)2 also contributes to the energy saving during clinker grinding. Differences were also found in the pore size distribution among nano-added clinkers and the standard Portland clinker. The smallest porosities with the modal volume lying in the class of 3 × 10-6 mm3 were found to increase by the use of nano-Ca(OH)2. However, the pore volumes higher than 2.0 × 10-5 mm3 decreased in the nano-added clinkers. © 2019 by the authors

Influence of volatiles (H 2 O and CO 2 ) on shoshonite phase equilibria

t. Experiments were performed at 500 MPa, 1080 °C and water activities (aH2O) from 0.0 to 1.0, in fluid-present and fluid-absent conditions, with the aim of constraining the effect of volatiles on phase equilibrium assemblages of a shoshonite from Vulcanello (Aeolian Islands, Italy). Experiments were run both under reducing and oxidizing conditions and results show that proportions, shapes and size of crystals vary as a function of the volatile composition (XH2O and XCO2) and volatile content. Clinopyroxene (Cpx) is the main crystallising phase and is compositionally analogous to Cpx crystals found in the natural rock. Plagioclase (Pl) is stable only for water activity lower than 0.1, whereas Fe–Ti oxides are present in all experimental runs, except for those where log f O2 was lower than −9, (∆NNO −0.11) irrespective of the presence of CO2. The addition of CO2 (2.8 wt%) in nominally dry experimental charges substantially reduces the crystallinity by ca. 1/3 compared to volatile free experiments. This result has important consequences upon the physical properties of the magma because it influences its viscosity and, as a consequence, velocity during its travel to the Earth surface

Cooling history and emplacement of a pyroxenitic lava as proxy for understanding Martian lava flows

Terrestrial analogues are often investigated to get insights into the geological processes occurring on other planetary bodies. Due to its thickness and petrological similarities, the pyroxenitic layer of the 120m-thick magmatic pile Theo’s Flow (Archean Abitibi greenstone belt Ontario, Canada), has always been regarded as the terrestrial analogue for Martian nakhlites. However, its origin and cooling history and, as a consequence those of nakhlites, have always been a matter of vigorous debate. Did this lava flow originate from a single magmatic event similar to those supposed to occur on Mars or do the different units derive from multiple eruptions? We demonstrate, by a combination of geothermometric constraints on augite single crystals and numerical simulations, that Theo’s Flow has been formed by multiple magma emplacements that occurred at different times. This discovery supports the idea that the enormous lava flows with similar compositions observed on Mars could be the result of a process where low viscosity lavas are emplaced during multiple eruptions. This has profound implications for understanding the multiscale mechanisms of lava flow emplacement on Earth and other planetary bodies

Retrieving magma composition from TIR spectra: implications for terrestrial planets investigations

Emissivity and reflectance spectra have been investigated on two series of silicate glasses, having compositions belonging to alkaline and subalkaline series, covering the most common terrestrial igneous rocks. Glasses were synthesized starting from natural end-members outcropping at Vulcano Island (Aeolian Islands, Italy) and on Snake River Plain (USA). Results show that the shift of the spectra, by taking Christiansen feature (CF) as a reference point, is correlated with SiO2 content, the ScfM factor and/or the degree of polymerization state via the nBo/t and temperature. the more evolved is the composition, the more polymerized the structure, the shorter the wavelength at which CF is observable. CF shift is also dependent on temperature. The shape of the spectra discriminates alkaline character, and it is related to the evolution of Qn structural units. Vulcano alkaline series show larger amount of Q4 and Q3 species even for mafic samples compared to the subalkaline Snake River Plain series. Our results provide new and robust insights for the geochemical characterization of volcanic rocks by remote sensing, with the outlook to infer origin of magmas both on Earth as well as on terrestrial planets or rocky bodies, from emissivity and reflectance spectra

Measurement of ISR-FSR interference in the processes e+ e- --> mu+ mu- gamma and e+ e- --> pi+ pi- gamma

Charge asymmetry in processes e+ e- --> mu+ mu- gamma and e+ e- --> pi+ pi- gamma is measured using 232 fb-1 of data collected with the BABAR detector at center-of-mass energies near 10.58 GeV. An observable is introduced and shown to be very robust against detector asymmetries while keeping a large sensitivity to the physical charge asymmetry that results from the interference between initial and final state radiation. The asymmetry is determined as afunction of the invariant mass of the final-state tracks from production threshold to a few GeV/c2. It is compared to the expectation from QED for e+ e- --> mu+ mu- gamma and from theoretical models for e+ e- --> pi+ pi- gamma. A clear interference pattern is observed in e+ e- --> pi+ pi- gamma, particularly in the vicinity of the f_2(1270) resonance. The inferred rate of lowest order FSR production is consistent with the QED expectation for e+ e- --> mu+ mu- gamma, and is negligibly small for e+ e- --> pi+ pi- gamma.Comment: 32 pages,29 figures, to be submitted to Phys. Rev.

Optimasi Portofolio Resiko Menggunakan Model Markowitz MVO Dikaitkan dengan Keterbatasan Manusia dalam Memprediksi Masa Depan dalam Perspektif Al-Qur`an

Risk portfolio on modern finance has become increasingly technical, requiring the use of sophisticated mathematical tools in both research and practice. Since companies cannot insure themselves completely against risk, as human incompetence in predicting the future precisely that written in Al-Quran surah Luqman verse 34, they have to manage it to yield an optimal portfolio. The objective here is to minimize the variance among all portfolios, or alternatively, to maximize expected return among all portfolios that has at least a certain expected return. Furthermore, this study focuses on optimizing risk portfolio so called Markowitz MVO (Mean-Variance Optimization). Some theoretical frameworks for analysis are arithmetic mean, geometric mean, variance, covariance, linear programming, and quadratic programming. Moreover, finding a minimum variance portfolio produces a convex quadratic programming, that is minimizing the objective function ðð¥with constraintsð ð 𥠥 ðandð´ð¥ = ð. The outcome of this research is the solution of optimal risk portofolio in some investments that could be finished smoothly using MATLAB R2007b software together with its graphic analysis