Study of naphthenic acidity and corrosivity of brazilian crude oils by ESI(-) FT-ICR MS

CAPES - COORDENAÇÃO DE APERFEIÇOAMENTO DE PESSOAL DE NÍVEL SUPERIORCNPQ - CONSELHO NACIONAL DE DESENVOLVIMENTO CIENTÍFICO E TECNOLÓGICOFAPERJ - FUNDAÇÃO DE AMPARO A PESQUISA DO ESTADO DO RIO DE JANEIRONos últimos anos grande parte das reservas de petróleo descobertas no Brasil, com exceção das grandes reservas do pré-sal, bem como em todo o mundo, compreendem óleos de baixo grau API e de alto número de acidez total (Total Acid Number, TAN). Os ácidos n103625640CAPES - COORDENAÇÃO DE APERFEIÇOAMENTO DE PESSOAL DE NÍVEL SUPERIORCNPQ - CONSELHO NACIONAL DE DESENVOLVIMENTO CIENTÍFICO E TECNOLÓGICOFAPERJ - FUNDAÇÃO DE AMPARO A PESQUISA DO ESTADO DO RIO DE JANEIROCAPES - COORDENAÇÃO DE APERFEIÇOAMENTO DE PESSOAL DE NÍVEL SUPERIORCNPQ - CONSELHO NACIONAL DE DESENVOLVIMENTO CIENTÍFICO E TECNOLÓGICOFAPERJ - FUNDAÇÃO DE AMPARO A PESQUISA DO ESTADO DO RIO DE JANEIROsem informaçãosem informaçãosem informaçã

Petroleomics by ion mobility mass spectrometry: resolution and characterization of contaminants and additives in crude oils and petrofuels

Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES)Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq)Ion mobility-mass spectrometry (IM-MS), performed with exceptional resolution and sensitivity in a new uniform-field drift tube ion mobility quadrupole time-of-flight (IM-QTOF) instrument, is shown to provide a useful tool for resolving and characterizing crude oils and their contaminants, as well as petrofuels and their additives. Whereas direct analysis of a crude oil sample contaminated with demulsifiers by the classical ESI(+/-)-FTICR-MS petroleomic approach was unsatisfactory since it responds only with abundance and m/z, and ionization is impaired due to suppression of polar compounds of crude oil by additives likely used in petroleum industry, IM-MS enables mobility separation of ions, particularly of double bond equivalent (DBE) series for a giving CnX class providing separated spectra which are typical obtained either for the crude oil or the contaminants, even suffering of ion suppression or low ionization efficiency. The combination of improved IM resolution and high mass resolving power (40,000@400) of the QTOF instrument provides useful information on class (N, NO, NS, etc.), carbon number (C-n), and unsaturation (DBE) levels for crude oils, allowing one to infer geochemical properties from DBE trends that can be compared with IM-MS data. As demonstrated by results of gasoline samples with additives, the IM-MS system also allows efficient separation and characterization of additives and contaminants in petrofuels.Ion mobility-mass spectrometry (IM-MS), performed with exceptional resolution and sensitivity in a new uniform-field drift tube ion mobility quadrupole time-of-flight (IM-QTOF) instrument, is shown to provide a useful tool for resolving and characterizing71144504463FAPESP - FUNDAÇÃO DE AMPARO À PESQUISA DO ESTADO DE SÃO PAULOCAPES - COORDENAÇÃO DE APERFEIÇOAMENTO DE PESSOAL DE NÍVEL SUPERIORCNPQ - CONSELHO NACIONAL DE DESENVOLVIMENTO CIENTÍFICO E TECNOLÓGICOFundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES)Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq)FAPESP [2013/19161-4]2013/19161-4sem informaçãosem informaçãoWe would like to thank the Fundação de Amparo a Pesquisa do Estado de São Paulo (FAPESP) for the scholarship awarded to J.M.S. (process number 2013/19161-4), Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES) and Conselho Nacional de Des

Optimization of atmospheric pressure photoionization for the crude oil analysis using ultra-high resolution mass spectrometry

Design of experiments (DOE) applied to mass spectrometry (MS), mainly focusing on the optimization of ionization techniques, has been applied to optimize experiments in order to provide the highest amount of information with the lowest number of experiments. However. DOE has not been used in petroleomics. For the first time, we applied DOE to optimize the main parameters associated with the crude oil analysis in a petroleomics approach. For the ionization technique, atmospheric pressure photoionization (APPI) has been selected and data were acquired in a high resolution (400,000 at m/z 400) and high mass accuracy (< 1 ppm) Fourier transform ion cyclotron resonance (FT-ICR) MS. Full and fractional two-level factorial designs were applied for the APPI(+/-) FT-ICR MS data set from two different crude oil samples with distinct physical and chemical characteristics. The standard ionization parameters that affect the MS responses of the crude oil analysis were optimized for both APPI(+)-MS and APPI(-)-MS. Such ionization parameters were then successfully applied to a crude oil and its saturated, aromatics, resin and asphaltene fractions, all with superior features of merit. Thus, the optimized APPI(+/-)-MS parameters should serve as reference and can be used as a guide for new studies in petroleomics304819829FUNDAÇÃO DE AMPARO À PESQUISA DO ESTADO DE SÃO PAULO - FAPESP2013/19161-4Sao Paulo Research Foundation (FAPESP)Fundacao de Amparo a Pesquisa do Estado de Sao Paulo (FAPESP) [2013/19161-4]; Petrobra

Electrical activation of carbon in GaAs: Implantation temperature effects

Carbon was implanted into GaAs at the energy of 1 MeV with doses between 131013 and 2 31015 cm22 at temperatures of 80 K, nominal room temperature (RT), and 300 °C. A markedly higher electrical activation was obtained in the samples implanted at 80 K compared to those implanted at RT or 300 °C, attaining a maximum hole concentration of 231019 cm23. The redistribution of the C profile during rapid thermal annealing at temperatures from 700 to 950 °C for 10 s was found negligible, independently of the implantation temperature. Similar improvements in the electrical properties were also verified in samples implanted at 80 K with a lower energy of 60 keV. We consider that despite the light mass of C ions, the reduced dynamic annealing at 80 K allows the accumulation of an abundance of As vacancies, which assist the C activation as a p-type dopant

Ferromagnetic nanoclusters formed by Mn implantation in GaAs

Ferromagnetic clusters were incorporated into GaAs samples by Mn implantation and subsequent annealing. The composition and structural properties of the Mn-based nanoclusters formed at the surface and buried into the GaAs sample were analyzed by x-ray and microscopic techniques. Our measurements indicate the presence of buried MnAs nanoclusters with a structural phase transition around 40 °C, in accord with the first-order magneto-structural phase transition of bulk MnAs. We discuss the structural behavior of these nanoclusters during their formation and phase transition, which is an important point for technological applications. © 2005 American Institute of Physics

Ferromagnetic nanoclusters formed by Mn implantation in GaAs

Ferromagnetic clusters were incorporated into GaAs samples by Mn implantation and subsequent annealing. The composition and structural properties of the Mn-based nanoclusters formed at the surface and buried into the GaAs sample were analyzed by x-ray and microscopic techniques. Our measurements indicate the presence of buried MnAs nanoclusters with a structural phase transition around 40 °C, in accord with the first-order magneto-structural phase transition of bulk MnAs. We discuss the structural behavior of these nanoclusters during their formation and phase transition, which is an important point for technological applications

Petroleomics via orbitrap mass spectrometry with resolving power above 1 000 000 at m/z 200

sem informaçãoThe performance of the high-field MegaOrbitrap Fourier transform mass spectrometer (FT-MS) with electrospray ionization (ESI) was evaluated to perform petroleum sample characterization via classical petroleomics approaches. Pertinent parameters that under81161836191sem informaçãosem informaçãosem informaçã

Petroleomics by Traveling Wave Ion Mobility–Mass Spectrometry Using CO₂ as a Drift Gas

The technique of choice for petroleomics has been ultra-high-resolution and high-accuracy Fourier transform ion cyclotron resonance mass spectrometry (FT-ICR MS), but other techniques such as ion mobility have been shown to provide additional or alternative information about crude oil composition. Using the traveling wave ion mobility (TWIM) cell of a hybrid Q-TWIM-TOF first-generation Synapt instrument and electrospray ionization in both the positive and negative ion modes, different crude oil samples with different polar compound profiles and petro fuels (diesel and gasoline) with or without additives were analyzed using either CO₂ or N₂ as the drift gas. Parameters such as gas pressure, velocity, and wave height were optimized for each type of crude oil or fuel sample. The ability of TWIM–MS to separate crude oil components according to their classes was verified by comparison with FT-ICR data. Results showed separation of several classes of polar compounds (NO, O₂, and N), and their separation was improved using CO₂, which also enhanced the resolution between adjacent <i>m</i>/<i>z</i> species. Additives and contaminants presented in petro fuels could also be easily separated and characterized