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

FAPESP - FUNDAÇÃO DE AMPARO À PESQUISA DO ESTADO DE SÃO PAULODesign 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 experimen304819829FAPESP - FUNDAÇÃO DE AMPARO À PESQUISA DO ESTADO DE SÃO PAULOFAPESP - FUNDAÇÃO DE AMPARO À PESQUISA DO ESTADO DE SÃO PAULO2013/19161-

Fullerenes In Asphaltenes And Other Carbonaceous Materials: Natural Constituents Or Laser Artifacts.

The presence of fullerenes as natural constituents of carbonaceous materials or their formation as laser artifacts during laser desorption ionization (LDI) mass spectrometry (MS) analysis is reinvestigated and reviewed. The results using asphaltene samples with varying composition as well as standard polycyclic aromatic hydrocarbons (PAH) and fullerene samples as models have demonstrated that indeed Cn ring fullerenes are not natural constituents but they are formed as common and often as predominant artifacts upon laser radiation, and a series of incorrect assignments based on LDI-MS data of several carbonaceous materials seems unfortunately to have been made. When the present results are evaluated also in the light of the vast literature on LDI-MS of carbonaceous materials, the formation of fullerene artifacts seems particularly common for LDI-MS analysis of asphaltenes and other carbonaceous samples with considerably high levels of PAH and varies according to the type of laser used, and the intensity of the laser beam.14

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

Assessing Relative Electrospray Ionization, Atmospheric Pressure Photoionization, Atmospheric Pressure Chemical Ionization, And Atmospheric Pressure Photo- And Chemical Ionization Efficiencies In Mass Spectrometry Petroleomic Analysis Via Pools And Pairs Of Selected Polar Compound Standards

A total of 15 standard compounds with structures similar to those normally found in crude oils were analyzed using an ultrahigh-resolution and high-accuracy Fourier transform ion cyclotron resonance (7.2 T LTQ FT Ultra, Thermo Fisher, Bremen, Germany) mass spectrometer. Four different ionization techniques were used: electrospray ionization (ESI), atmospheric pressure chemical ionization (APCI), atmospheric pressure photoionization (APPI), and a novel technique that couples APCI and APPI, herein termed atmospheric pressure photo- and chemical ionization (APPCI). Relationships between chemical structures and ionization efficiencies were established for these techniques, which operate via different ionization mechanisms. The unsaturation level and position of the double bond were shown to be key factors on ionization efficiency for all ionization techniques. Comparisons between molecules with similar backbones but with different heteroatoms were also made. For the whole mixture, APPI showed the highest sensitivity for the positive ion mode and ESI showed the highest sensitivity for the negative ion mode. APPCI was found to be the most comprehensive ionization technique, whereas as expected, ESI preferentially ionized the most polar compounds. APPCI produced, however, more than one ionic species per molecule, a disadvantage in terms of data complexity. Such "splitting" was observed for APPI and APCI. Ions with the same molecular formula formed from different molecules were also detected by APPCI, producing composite abundances that would mislead chemical and geochemical conclusions based on petroleomic approaches. We suggest that, although less comprehensive, ESI is overall the most suitable ionization technique for petroleomic studies.30971257133Petroleo Brasileiro (Petrobras

Assessing Relative Electrospray Ionization, Atmospheric Pressure Photoionization, Atmospheric Pressure Chemical Ionization, and Atmospheric Pressure Photo- and Chemical Ionization Efficiencies in Mass Spectrometry Petroleomic Analysis via Pools and Pairs of Selected Polar Compound Standards

A total of 15 standard compounds with structures similar to those normally found in crude oils were analyzed using an ultrahigh-resolution and high-accuracy Fourier transform ion cyclotron resonance (7.2 T LTQ FT Ultra, Thermo Fisher, Bremen, Germany) mass spectrometer. Four different ionization techniques were used: electrospray ionization (ESI), atmospheric pressure chemical ionization (APCI), atmospheric pressure photoionization (APPI), and a novel technique that couples APCI and APPI, herein termed atmospheric pressure photo- and chemical ionization (APPCI). Relationships between chemical structures and ionization efficiencies were established for these techniques, which operate via different ionization mechanisms. The unsaturation level and position of the double bond were shown to be key factors on ionization efficiency for all ionization techniques. Comparisons between molecules with similar backbones but with different heteroatoms were also made. For the whole mixture, APPI showed the highest sensitivity for the positive ion mode and ESI showed the highest sensitivity for the negative ion mode. APPCI was found to be the most comprehensive ionization technique, whereas as expected, ESI preferentially ionized the most polar compounds. APPCI produced, however, more than one ionic species per molecule, a disadvantage in terms of data complexity. Such “splitting” was observed for APPI and APCI. Ions with the same molecular formula formed from different molecules were also detected by APPCI, producing composite abundances that would mislead chemical and geochemical conclusions based on petroleomic approaches. We suggest that, although less comprehensive, ESI is overall the most suitable ionization technique for petroleomic studies

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

Assessing biodegradation of brazilian crude oils via characteristic profiles of O1 and O2 compound classes: petroleomics by negative-ion mode electrospray ionization Fourier transform ion cyclotron resonance mass spectrometry

CAPES - COORDENAÇÃO DE APERFEIÇOAMENTO DE PESSOAL DE NÍVEL SUPERIORCNPQ - CONSELHO NACIONAL DE DESENVOLVIMENTO CIENTÍFICO E TECNOLÓGICOFAPERJ - FUNDAÇÃO CARLOS CHAGAS FILHO DE AMPARO À PESQUISA DO ESTADO DO RIO DE JANEIROProfiles for polar heteroatom compounds were obtained via Fourier transform ion cyclotron resonance mass spectrometry (FT-ICR MS) using electrospray ionization (ESI) in negative-ion mode for a set of 30 Brazilian oil samples from distinct sedimentary basi31766496657CAPES - COORDENAÇÃO DE APERFEIÇOAMENTO DE PESSOAL DE NÍVEL SUPERIORCNPQ - CONSELHO NACIONAL DE DESENVOLVIMENTO CIENTÍFICO E TECNOLÓGICOFAPERJ - FUNDAÇÃO CARLOS CHAGAS FILHO DE AMPARO À PESQUISA DO ESTADO DO RIO DE JANEIROCAPES - COORDENAÇÃO DE APERFEIÇOAMENTO DE PESSOAL DE NÍVEL SUPERIORCNPQ - CONSELHO NACIONAL DE DESENVOLVIMENTO CIENTÍFICO E TECNOLÓGICOFAPERJ - FUNDAÇÃO CARLOS CHAGAS FILHO DE AMPARO À PESQUISA DO ESTADO DO RIO DE JANEIROsem informaçãosem informaçãosem informaçãoThis work was supported by the Laboratory of Petroleum Engineering and Exploration of the North Fluminense State University (LENEP/UENF) and the Chemistry Institute, University of Campinas (UNICAMP). CENPES/Petrobras also provided the necessary infrastru

Assessing Biodegradation of Brazilian Crude Oils via Characteristic Profiles of O₁ and O₂ Compound Classes: Petroleomics by Negative-Ion Mode Electrospray Ionization Fourier Transform Ion Cyclotron Resonance Mass Spectrometry

Profiles for polar heteroatom compounds were obtained via Fourier transform ion cyclotron resonance mass spectrometry (FT-ICR MS) using electrospray ionization (ESI) in negative-ion mode for a set of 30 Brazilian oil samples from distinct sedimentary basins and used to estimate biodegradation extents. The samples were initially subjected to traditional geochemical biodegradation analysis to classify them in term of biodegradation levels as based on the Peters and Moldowan scale (PM scale). When the profiles were correlated with the PM scale, it was found that the O₁, N, NO₂, NO₃, and N₃O₂ classes decrease, whereas the O₂, O₃, and O₄ classes increase in relative abundance with biodegradation. The acyclic to cyclic acids (A/C) ratio of the O₂ class, mainly composed of naphthenic acids, provided a robust parameter to classify biodegradation levels of Brazilian oils. A modified saturated acid (SA) index was also used to classify biodegradation levels. For the O₁ class, two new monoaromatic (MA) indexes were proposed to predict the biodegradation extent. These MA parameters are based on the most readily degraded phenolic and/or benzylic O compounds by microorganisms and the persistence of O compounds with higher double bond equivalent (DBE) values in more degraded oils

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