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In 2019, one of Brazil's most significant environmental disasters occurred, involving an oil spill that directly affected Pernambuco state. Contamination along the coast was evaluated by the quantification of polycyclic aromatic hydrocarbons (PAHs) in fifty seawater samples collected in the summer and winter of 2021. Analysis using fluorescence spectroscopy revealed that for all the samples, levels of dissolved/dispersed petroleum hydrocarbons (DDPHs) were higher than the regional baseline for tropical western shores of the Atlantic Ocean. GC-MS analyses quantified 17 PAHs in the samples, with highest total PAHs concentrations of 234 ng L-1 in summer and 33.3 ng L-1 in winter, which were consistent with the highest risks observed in ecotoxicity assays. The use of diagnostic ratios showed that the coast was impacted by a mixture of PAHs from petrogenic and pyrolytic sources. The results indicated the need for continuous monitoring of the regions affected by the 2019 spill.
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Monitoreo del Ambiente , Contaminación por Petróleo , Hidrocarburos Policíclicos Aromáticos , Agua de Mar , Contaminantes Químicos del Agua , Hidrocarburos Policíclicos Aromáticos/análisis , Brasil , Agua de Mar/química , Contaminantes Químicos del Agua/análisis , Petróleo/análisis , Océano Atlántico , Cromatografía de Gases y Espectrometría de MasasRESUMEN
The dating of documents is crucial in forensic chemistry, particularly for verifying their authenticity. This study aimed to develop a rapid and direct method for the dating of pen ink in documents, using a combination of Fourier transform infrared spectroscopy in attenuated reflectance mode (FTIR-ATR), desorption electrospray ionization mass spectrometry (DESI-MS) and multiple ensemble data modeling. Two sets of paper document samples containing writing in blue pen ink were investigated: (I) artificially aged documents and (II) real documents dating from 1960 to 2022. The FTIR-ATR spectra of both sets of samples showed a decrease in absorbance at â¼1584 cm-1, related to the chemical modification of the CîN bond in the molecular structure of Basic Violet 3 (BV3), one of the main dyes used in blue pen ink. DESI-MS confirmed the presence of BV3 and its degradation by-products in all the samples, indicating its widespread utilization in blue pen ink production. Moreover, DESI-MS detected combinations of dyes within the ink composition. The models were built using the DESI-MS and FTIR-ATR data separately, but the error and trend were significantly reduced when both sets of data were used. The combination of DESI-MS and FTIR-ATR spectral information resulted in a final predictive model with low error for pen inks from real documents in writing from the years 1960 to 2022. These analyses proved to be effective for the dating of pen inks and are suitable for use in routine forensic analysis, providing a direct and rapid method that allows for accurate prediction.
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The use of renewable sources for energy has increased due to the high demand of modern society and the environmental impacts caused by the use of fossil fuels. Environmentally friendly renewable energy production may involve thermal processes, including the application of biomass. We provide a comprehensive chemical characterization of sludges from domestic and industrial effluent treatment stations, as well as the bio-oils produced by fast pyrolysis. A comparative study of the sludges and the corresponding pyrolysis oils was performed, with characterization of the raw materials using thermogravimetric analysis, energy-dispersive X-ray spectroscopy, Fourier-transform infrared spectroscopy, elemental analysis, and inductively coupled plasma optical emission spectrometry. The bio-oils were characterized using comprehensive two-dimensional gas chromatography/mass spectrometry that identified compounds classified according to their chemical class, mainly related to nitrogenous (62.2%) and ester (18.9%) for domestic sludge bio-oil, and nitrogenous (61.0%) and ester (27.6%) for industrial sludge bio-oil. The Fourier transform ion cyclotron resonance mass spectrometry revealed a broad distribution of classes with oxygen and/or sulfur (N2O2S, O2, and S2 classes). Nitrogenous compounds (N, N2, N3, and NxOxclasses) were also found to be abundant in both bio-oils, due to the origins of the sludges (with the presence of proteins), making these bio-oils unsuitable for use as renewable fuels, since NOxgases could be released during combustion processes. The presence of functionalized alkyl chains indicated the potential of the bio-oils as sources of high added-value compounds that could be obtained by recovery processes and used for the manufacture of fertilizers, surfactants, and nitrogen solvents.
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Pirólisis , Aguas del Alcantarillado , Calor , Aceites/química , Aceites de Plantas/química , Nitrógeno/análisis , Oxígeno , Biocombustibles/análisisRESUMEN
After the wide oil spill reached the northeast of Brazil, the resurgence of oil was recorded and to evaluate this oil in detail, two samples collected in the state of Pernambuco in 2019 and 2021 were submitted to multiple analytical techniques. For both, we have found similar saturated biomarkers and triaromatic steroid ratios, implying that they are from the same spilled source. The n-alkanes, isoprenoids, and cycloalkanes were almost completely degraded due to evaporation, photooxidation, and/or biodegradation processes. The preferential loss of less alkylated PAHs than the more alkylated ones suggests that biodegradation was the most active process. This hypothesis is reinforced by the formation of mono and dicarboxylic acids assessed by GC × GC-TOFMS and ESI(-) FT-ICR MS high-resolution techniques. Furthermore, based on the ESI(-) FT-ICR MS results, three new ratios were proposed to evaluate the progress of the biodegradation process over time: Ox>2/O, SOx/SO, and SOx/N.
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Contaminación por Petróleo , Petróleo , Hidrocarburos Policíclicos Aromáticos , Contaminantes Químicos del Agua , Petróleo/análisis , Brasil , Hidrocarburos Policíclicos Aromáticos/análisis , Alcanos , Contaminación por Petróleo/análisis , Biomarcadores , Contaminantes Químicos del Agua/análisisRESUMEN
In 2019, much of the northeastern coast of Brazil was impacted by a mysterious oil spill that caused an environmental disaster affecting 1009 beaches. Four samples were collected in the beaches between Sergipe and Pernambuco for geochemical characterization of the spilled oil and to compare with those main produced in Sergipe-Alagoas basin. Our approach in this evaluation was the use of a highly selective technique of sequential mass spectrometry by multiple reaction monitoring, to obtain the diagnostic ratios of hopanes and steranes biomarkers. Using these biomarkers ratios associated with multivariate statistical analysis, we found direct correlation between the spilled oil collected along the northeastern coast and no relationship between Sergipe-Alagoas basin crude oils was found. Furthermore, reported data for oils from Orinoco belt in Venezuelan basins were used for qualitative evaluation considering the indicative aspects suggested by the literature. Presence of highly specific biomarker 18α(H)-oleanane, and five other important diagnostic ratios evidenced correlation between the spilled oil and Naricual formation crude oils. Besides, due to the oleanane index, Ayacucho's crude oil presented the strongest factor of correlation with the spilled oil found on the northeast coast of Brazil.
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Contaminación por Petróleo , Petróleo , Contaminantes Químicos del Agua , Biomarcadores , Brasil , Monitoreo del Ambiente , Aceites , Contaminación por Petróleo/análisis , Contaminantes Químicos del Agua/análisisRESUMEN
In this study, a comprehensively optimization of QuEChERS (quick, easy, cheap, effective, rugged and safe) method using design of experiments (DOE) was conducted to evaluate the best conditions to obtain the most effective extraction. Liquid chromatography coupled to tandem mass spectrometry (LC-MS/MS) analysis was performed to identify and quantify the antidepressants, with electrospray ionization acquired in positive mode. The method was validated for all analytes; the calibration curves were linear from 10-1000ng/mL, with R2>0.98, and with LOD and LOQ defined as 10ng/mL. Method imprecision and bias were less than 14.3% and 18.9%, respectively. Neither carryover nor interferences were observed. Overall, the optimized method was applied in postmortem real sample analysis to quantify the antidepressants. This study showed a viable method that can be applied for routine forensic analysis, with a quick and easy sample preparation and a rapid total run time of 8min for each analysis.
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Antidepresivos/sangre , Toxicología Forense/métodos , Cromatografía Liquida , Humanos , Límite de Detección , Extracción en Fase Sólida , Espectrometría de Masas en TándemRESUMEN
The contamination of terrestrial environments by oil spills creates biological risks to humans and affects the ecosystem's health. The studies that aim to evaluate the toxicity and changes in the environments are a field of potential interest to the scientific community. The objective of this study was to evaluate the changes in the chemical composition of crude oil fractions after the simulation of a spill in soil and sand, with emphasis on an immediate temporal investigation. Samples of intermediate (°API = 27.0) and heavy (°API = 20.9) oils from Sergipe-Alagoas basin were used. The evaporation process in the soil was highlighted; while the GC-FID chromatographic profiles demonstrated (1) the disappearance from n-C12 until n-C14 compounds, besides a decrease of more than 50% in n-C15 and n-C16 n-alkanes and (2) no changes in n-C17/Pr and n-C18/Ph ratios for both oils. Analysis of resins fraction performed by Orbitrap-MS has shown changes in the mass spectra profile and compound distribution during the soil and sand exposure process, with N1, O1, and O2 species showing changes in the relative abundance in ESI(+) mode, and O2, N1, and O1 for ESI(-). Changes in polar compounds of oil will depend on the extent of the time of interaction with soil and sand, taking into account intrinsic aspects, such as the nature of the soil and components in it as the organic matter.
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Contaminación por Petróleo , Petróleo , Contaminantes Químicos del Agua , Ecosistema , Humanos , Aceites , Contaminación por Petróleo/análisis , Contaminantes Químicos del Agua/análisisRESUMEN
The 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 underpin the main figures of merit, that is, signal to noise ratios, dynamic range, spectral error, scan speed, mass accuracy and mass resolving power = R p, and provide subsidies to develop these analyzers were tested. Comparisons are made with data obtained using the most common petroleomics instrument, which is a Fourier transform ion cyclotron resonance mass spectrometer (FT-ICR MS), that has been used in the last decade in our laboratory for crude oil analysis providing R p of 340 000 at m/z 400 with transients of 3 s duration, and has been extensively demonstrated to fulfill all major requirements for precise petroleomics investigations. The high-field compact MegaOrbitrap mass analyzer, when operated at an R p = 840 000 at m/z 400 (R p > 1 000 000 at m/z 200) with a detection time of 3 s, was found to be well suited for adequate characterization of crude oil. Accurate class classification and mass accuracy below 1 ppm was obtained leading to proper, comprehensive petroleomics characterization.
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In this study, we introduce a simple protocol to manufacture disposable, 3D-printed microfluidic systems for sample preparation of petroleum. This platform is produced with a consumer-grade 3D-printer, using fused deposition modeling. Successful incorporation of solid-phase extraction (SPE) to microchip was ensured by facile 3D element integration using proposed approach. This 3D-printed µSPE device was applied to challenging matrices in oil and gas industry, such as crude oil and oil-brine emulsions. Case studies investigated important limitations of nonsilicon and nonglass microchips, namely, resistance to nonpolar solvents and conservation of sample integrity. Microfluidic features remained fully functional even after prolonged exposure to nonpolar solvents (20 min). Also, 3D-printed µSPE devices enabled fast emulsion breaking and solvent deasphalting of petroleum, yielding high recovery values (98%) without compromising maltene integrity. Such finding was ascertained by high-resolution molecular analyses using comprehensive two-dimensional gas chromatography and gas chromatography/mass spectrometry by monitoring important biomarker classes, such as C10 demethylated terpanes, ααα-steranes, and monoaromatic steroids. 3D-Printed chips enabled faster and reliable preparation of maltenes by exhibiting a 10-fold reduction in sample processing time, compared to the reference method. Furthermore, polar (oxygen-, nitrogen-, and sulfur-containing) analytes found in low-concentrations were analyzed by Fourier transform ion cyclotron resonance mass spectrometry. Analysis results demonstrated that accurate characterization may be accomplished for most classes of polar compounds, except for asphaltenes, which exhibited lower recoveries (82%) due to irreversible adsorption to sorbent phase. Therefore, 3D-printing is a compelling alternative to existing microfabrication solutions, as robust devices were easy to prepare and operate.
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Recently, 3-nitrobenzonitrile (3-NBN) has been used to improve sensitivity of sonic-spray ionization mass spectrometry. Easy ambient sonic-spray ionization (EASI) is one of the simplest, gentlest and most used spray-based desorption/ionization ambient techniques, but limited sensitivity has been commonly taken as its major drawback. Herein we investigate the use of 3-NBN as a dopant in EASI-MS for improved sensitivity. Using a few typical EASI samples as test cases, the presence of 10 ppm (µg ml(-1) ) of 3-NBN in the spray solvent showed two to fourfold gains in EASI-MS sensitivity as measured both by total ion current and S/N ratios, accompanied with significant reductions in chemical noise. Sensitivity for DESI using 3-NBN as a dopant also improved and dopant DESI versus dopant EASI sensitivities were compared. The use of solvent dopants seems therefore to be a promising strategy to improve sensitivity for spray-based ambient MS techniques. Copyright © 2015 John Wiley & Sons, Ltd.
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Nitrilos/química , Nitrobencenos/química , Espectrometría de Masa por Ionización de Electrospray/métodos , Biocombustibles/análisis , Diseño de Equipo , Glicerofosfolípidos/análisis , Indicadores y Reactivos/química , Aceite de Oliva/análisis , Solventes/química , Solventes/clasificación , Espectrometría de Masa por Ionización de Electrospray/instrumentaciónRESUMEN
Ambient mass spectrometry has been demonstrated, via various proof-of-concept studies, to offer a powerful, rather universal, simple, fast, nondestructive, and robust tool in forensic chemistry, producing reliable evidence at the molecular level. Its nearly nondestructive nature also preserves the sample for further inquiries. This feature article demonstrates the applicability of ambient mass spectrometry in forensic chemistry and explains the challenges that need to be overcome for this technique to make the ultimate step from the academic world into forensic institutes worldwide. We anticipate that the many beneficial and matching figures of merit will bring forensic chemistry and ambient mass spectrometry to a long-term relationship, which is likely to get strongly consolidated over the years.
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Herein, we report the synthesis and mass spectrometry studies of several N-alkylbenzenesulfonamides structurally related to sulfanilic acid. The compounds were synthesized using a modified Schotten-Baumann reaction coupled with Meisenheimer arylation. Sequential mass spectrometry by negative mode electrospray ionization (ESI(-)-MS/MS) showed the formation of sulfoxylate anion (m/z 65) observed in the mass spectrum of p-chloro-N-alkylbenzenesulfonamides. Investigation of the unexpected loss of two water molecules, as observed by electron ionization mass spectrometry (EI-MS) analysis of p-(N-alkyl)lactam sulfonamides, led to the proposal of corresponding fragmentation pathways. These compounds showed loss of neutral iminosulfane dioxide molecule (M-79) with formation of ions observed at m/z 344 and 377. These ions were formed by rearrangement on ESI(+)-MS/MS analysis. Some of the molecules showed antagonistic activity against Kv3.1 voltage-gated potassium channels.
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Antibacterianos/química , Bloqueadores de los Canales de Potasio/química , Canales de Potasio Shaw/efectos de los fármacos , Ácidos Sulfanílicos/química , Sulfonamidas/química , Antibacterianos/síntesis química , Diseño de Fármacos , Espectrometría de Masa por Ionización de Electrospray , Sulfonamidas/síntesis química , Espectrometría de Masas en TándemRESUMEN
An integrative approach in mass spectrometry (MS) comprising gas chromatography coupled to MS (GC-MS), ultra-efficiency liquid chromatography coupled to MS (UPLC-MS) and easy ambient sonic-spray ionization MS (EASI-MS) is proposed for the comprehensive characterization of Amazonian oils. Coconut, andiroba and castor seed oils, which are vastly sold in markets of the Amazonian region of Brazil, were selected as a representative test set. These oils were found to contain several lipids such as triacylglycerides (TAGs), fatty acids (FAs), phytosterols and limonoids. In the analyzed samples 30 different TAGs, 11 FAs, 6 phytosterols and 7 limonoids were identified. The antioxidant capacity (AOC) of the oils, as measured by their oxygen radical absorbance capacity (ORAC), was also used to evaluate their potential biological properties as well as their possible consumption as food. Edible virgin coconut oil was the most active (0.720±0.001 Trolox eq./mmol), whereas considerable lower activity was observed for andiroba and castor seed oils. The antimicrobial activities of the oils were also recorded against a panel of pathogenic bacteria and fungi in which andiroba oil was the only one that was active, solely against Enterococcus aeruginosa.