In 2019, large amounts of oil reached the northeast coast of Brazil, causing damage to the environment and the local economy, especially in the state of Pernambuco. In order to correlate with possible sources, investigation was made of the geochemical biomarkers of the oils using “gold standard” forensic protocols from the European Committee for Standardization (CEN). The biomarkers study was improved by using gas chromatography-tandem mass spectrometry (GC-MS/MS), rather than the standard protocol that suggests use of the selected ion monitoring (SIM) method. Analysis was made of thirteen oil samples from the Pernambuco coast, in order to identify their degrees of similarity and the possible presence of oils from unreported spills. The use of eighteen diagnostic ratios and multivariate analysis revealed a cluster formed by eleven samples with biomarker distributions typical of oil from the 2019 spill. However, two samples had anomalous fingerprints, especially due to the absence of the 18α(H)-oleanane and 18β(H)-oleanane isomers. Both the CEN protocol applied for the classical biomarkers and a comprehensive Fourier transform mass spectrometry (FT-MS) analysis of polar compounds confirmed the dissimilarities between the samples. The findings suggested that these two oils could have originated from an event unrelated to the mysterious 2019 spill.

Research to identify plant bioactive compounds led to the evolution of extraction methods. This study optimized ultrasound-assisted extraction (UAE) and microwave-assisted extraction (MAE) to extract the flavonoids of Croton grewioides Baill. species contributing to characterize the polar extract profile and understand the antioxidant potential of these plant constituents. The use of experimental design and statistical treatments enabled the determination of the ideal conditions for each technique. The extracts of five accessions of C. grewioides were obtained under the optimized extraction conditions and were analyzed using ultra high-resolution mass spectrometry (FT-Orbitrap MS) operating at negative ionization mode for flavonoids detection. The accurate experimental mass obtained to the main compounds was used to attribute the molecular formula. Chemical structures of the main compounds detected were proposed using structure data bases. Chemometric analysis were performed with two FT-Orbitrap MS spectra samples using the identified metabolites and, the antioxidant activity data, showing that for this species the MAE was most effective in extracting the antioxidant compounds. It was possible to propose the structures for forty compounds in the C. grewioides extracts, demonstrating the excellent performance of the FT-Orbitrap MS in providing information on the chemical profile of polar compounds in plant extracts. methods ultrasoundassisted ultrasound assisted UAE (UAE microwaveassisted microwave (MAE Baill constituents technique C highresolution high resolution FTOrbitrap FT Orbitrap detection formula bases

A method to pretreatment of biomasses using glycerol as a green solvent was developed. Optimization of organosolv pretreatment was performed using a 23 factorial design, investigating synergism among the variables particle size (from < 0.85 to > 2.0 mm), FeCl3 concentration (0.025-0.175 mol L-1), and temperature (160-220 °C). Although the effects of the variables differed according to the type of lignocellulose, it was nonetheless possible to find an optimal condition in common (< 0.85 mm; 0.025 mol L-1; 220 °C), which was economically and environmentally sustainable, employing a small amount of catalyst. The biomasses pretreated using this combination of factors exhibited enzymatic digestibility exceeding 93% after 48 h, reflecting efficient reduction of recalcitrance as a result of high removal of hemicellulose (ca. 90%), provided by the use of FeCl3, together with substantial delignification. There was low formation of inhibitors in the hydrolysate, indicating that it could be directly fermented. The lignin removed to liquors could be easily recovered by centrifugation. Tests carried out under the optimal condition revealed that after the pretreatment the biomass could be directly used in enzymatic hydrolysis, without washing and wet. Furthermore, after simple treatment, crude glycerol was as effective as commercial glycerol.

Abstract 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.

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 petroleomics.

Biodiesel is an alternative fuel obtained from different biomass sources and processes. Nowadays, this biofuel has gained importance due to environmental concerns and rising energy demand. In the biodiesel production chain, stability is a critical issue, as it is linked to the maintenance of its original properties. This work performed a study evaluating the influence of storage conditions on the quality aspects of biodiesel. Thus, different samples of biodiesel obtained from soybean and frying oils were produced and placed in containers made by plastic, glass and tin, and stored in presence or absence of an oxidative atmosphere, moisture and light. These samples were analyzed to evaluate the ester content, acidity, iodine value, kinematic viscosity and oxidative stability. The characterization with GC-MS and GC/FID were done aiming to determine the chemical composition. Blends with frying biodiesel into soybean biodiesel have also been produced in concentrations ranging from 1%, 5% and 10% (m/m) in order to evaluate the mixing effect. In the initial storage time, all tested parameters were in accordance to the legislation. Distinct behaviors were identified for each sample according to the container type, being the glass the most effective of them in maintenance of biodiesel characteristics.

The invasive aquatic plants Eichhornia crassipes (water hyacinth), Eichhornia azurea, and Nymphaea spp. were evaluated as sources of lignocellulosic biomass for the production of bio-oil. These plants have high growth rates that can lead to various environmental problems and the production of large amounts of waste biomass. The materials were characterized in terms of their contents of moisture, oil, and ash, and by analysis using thermogravimetry, infrared spectroscopy (IR), elemental analysis, and energy dispersive X-ray fluorescence spectrometry (EDX). The in natura biomasses had moisture contents of around 90%. Micropyrolysis studies were performed at 500 ºC using the dried biomasses (ca. 8% moisture). The liquid product of pyrolysis (bio-oil) was trapped in an adsorbent and then eluted with different solvents. The best recovery was achieved using tetrahydrofuran. The bio-oil solutions were derivatized with N-methyl-N-(trimethylsilyl) trifluoroacetamide (MSTFA) and analyzed by gas chromatography mass spectrometry (GC-MS). The main compounds found in the bio-oils were glycerol, o-benzenediol, p-benzenediol, arabinoic acid, levuglucosan, and hexadecanoic acid.

Bio-oil is classified as second-generation biofuel and it is produced mainly through the pyrolysis of a waste lignocellulosic biomass base. The application of this product is still very limited, due to some of its chemical characteristics. This paper presents a proposal for the reduction of the acidity of bio-oil obtained from waste fish oil, previously produced and characterized as described in the literature, applying the reactive distillation process. This process is primarily based on the conversion of carboxylic acids into their corresponding esters by adding a widely available alcohol and a simple and cheap catalyst in the process for the fractional distillation of crude bio-oil to obtain light and heavy bio-oil, that is, fractions which are equivalent to the fossil fuels gasoline and diesel, respectively. The alcohols tested were methanol and ethanol and the catalysts were H2SO4, H3PO4, NaOH and Na2CO3, in proportions of 10 and 0.5 wt.%, respectively. The light bio-oil was obtained within a temperature range of 42 to 198 ºC with yields of 27.0 to 43.1% and the heavy bio-oil was recovered at 93 to 230 ºC with yields of 42.6 to 49.2%. The greatest acidity reduction was observed employing methanol+H2SO4 (95% and 43% for light and heavy bio-oils, respectively). The fractions produced were characterized by gas cromatography/mass spectrometry (GC-MS) and gas chromatography with flame ionization detector (GC-FID), applying the compound classification process PIONA (Paraffins, Iso-paraffins, Olefins, Naphtenes and Aromatics), revealing a homologous series of 1-alkenes and n-alkanes along with some aromatic compounds. The 1H and 13C NMR analysis showed that the process had no significant influence in relation to the carbons and hydrogens associated with the methyl, methylene, methyne and olefinic groups.

The volatile components of the galls induced by the insect Baccharopelma dracunculifoliae (Hemiptera: Psyllidae) on leaves of Baccharis dracunculifolia (Asteraceae) were analyzed by gas chromatography-mass spectrometry (GC-MS) and gas chromatographyflame- ionisation detection (GC-FID), and then comparison with volatile oil samples from healthy leaves collected in the vicinity. The galls produced around 3.5% of the total organic volatiles whereas healthy leaves rendered an average yield of 0.6%. The observed higher proportions of germacrene D, bicyclogermacrene, limonene, and β-pinene in the galls suggest that all these compounds are important targets in the search for natural enemies of this Psyllid. Moreover, higher relative percentages of (E)-nerolidol and spathulenol were found in healthy leaves.

GC/MS/FID analyses of volatile compounds from cladodes and inflorescences from male and female specimens of Baccharis trimera (Less.) DC. collected in the states of Paraná and Santa Catarina, Brazil, showed that carquejyl acetate was the primary volatile component (38% to 73%), while carquejol and ledol were identified in lower concentrations. Data were subjected to hierarchical cluster analysis and principal component analysis, which confirmed that the chemical compositions of all samples were similar. The results presented here highlight the occurrence of the same chemotype of B. trimera in three southern states of Brazil.

Nos poucos estudos publicados comparando óleos essenciais de espécimes femininos e masculinos de espécies Baccharis, fortes diferenças entre as composições de ambas as amostras foram sempre encontradas. Os experimentos realizados nesta pesquisa utilizam estratégias para minimizar a interferência de fatores genéticos e ecológicos. Os óleos essenciais das folhas de espécimes femininos e masculinos de cinco espécies Baccharis foram pesquisados com uso de um cromatógrafo gasoso acoplado a um espectrômetro de massas e a um detector de ionização de chama (CG-EM-DIC): B. caprariaefolia e B. dracunculifolia, já pesquisadas anteriormente com objetivos similares; e B. coridifolia, B. semiserrata var. elaegnoides e B. pentaptera, as duas últimas ainda não mencionadas na literatura química. Os resultados foram acompanhados por análise hierárquica de grupos, verificando-se a formação de grupos indicativos da grande similaridade entre óleos essenciais dos espécimes masculinos e femininos de todas as cinco espécies. O estudo reafirma o valor das observações de campo na pesquisa de produtos naturais, e aponta fatores genéticos e ecológicos como principais responsáveis por diferenças no metabolismo secundário das plantas estudadas.

In the few studies published on essential oils from female and male specimens of Baccharis species, strong differences between the compositions of both samples were always found. The experiments conducted in this study make use of strategies to minimize the interference from genetic and environmental factors. Essential oils from leaves of female and male specimens of five Baccharis species were investigated by gas chromatography-mass spectrometry plus flame ionization detector (GC-MS-FID): B. caprariaefolia and B. dracunculifolia, which have been previously studied with similar aims; and B. coridifolia, B. semiserrata var. elaegnoides and B. pentaptera, the latter two not yet mentioned in the literature. The results were followed by hierarchical cluster analysis, verifying the formation of groups indicative of the great similarity of essential oils from male and female specimens of all five species. The study reinforces the value of field observation in natural product research and points genetic and ecological factors as main responsible for differences in the secondary metabolites of the studied plants.

The essential oil obtained by hydrodistillation from fresh leaves of Casearia lasiophylla Eichler, Salicaceae, was analyzed by gas capillary (GC/FID and GC/MS). The cytotoxicity of the leaves essential oil was tested in vitro againstU251 (glioma), UACC-62 (melanoma), MCF-7 (breast), NC1-ADR/RES (ovarian-resistant), NCI-H460 (lung), PC03 (prostate), OVCAR-3 (ovarian), HT-29 (colon) and K562 (leukemia) human cancer cells and against VERO (no cancer cell). The yield of oil was 0.02%. Fifty two compounds were identified, representing 87.1% of the total of the oil. The main components were identified as germacrene D (18.6%), β-caryophyllene (14.7%), δ-cadinene (6.2%), and α-cadinol (5.4%). The oil exhibited antiproliferative activity against all cell lines (TGI<100 µg/mL), with exception of NCI-H460 cell line (TGI 191.31 µg/mL). The highest activity was observed against UACC-62 (TGI 7.30 µg/mL), and K562 (TGI 7.56 µg/mL) cell lines. The observed activity could be related to high content of germacrene D and β-caryophyllene, compounds known as cytotoxic.

Neste trabalho, a espécie Piper hispidinervum (pimenta longa), endêmica do estado do Acre, foi cultivada na região do Vale do Itajaí - SC, e sua adaptação foi avaliada em relação à composição química do óleo essencial obtido pelos processos de hidrodestilação convencional e por micro-ondas. O safrol foi identificado como o constituinte majoritário do óleo essencial desta espécie, o qual foi empregado como parâmetro de avaliação da capacidade de adaptação desta planta à região sul do Brasil, já que a proposta abrange avaliar a utilização desta espécie como fonte alternativa de safrol, em substituição a Canela Sassafrás (Ocotea odorifera), espécie muito explorada até a década de 90 nesta região. As amostras da planta foram obtidas de diferentes regiões do Acre e foram cultivadas na estação experimental da EPAGRI - Itajaí-SC. O óleo essencial das folhas forneceu um teor médio de safrol entre 76,6% e 89,9%. A análise por CG-DIC e CG-EM do óleo com maior concentração de safrol, apresentou os seguintes constituintes: safrol (89,93%), α-terpineno (0,35%), (E)-β-ocimeno (0,54%), terpinoleno (3,10%), valenceno (0,21%), (Z)-β-bisaboleno (1,70%) e guaiol (0,29%).

In this work a Piper hispidinervum specie (long pepper), endemic from the Acre state, was grown in Itajaí Valley in Santa Catarina State, and its adaptation was evaluated in relation to chemical composition of essential oil obtained by traditional hydrodistillation and microwave hydrodistillation. The safrole was identified as the major constituent of the essential oil of this specie, which was used as a measure of evaluation of the adaptation capacity of this plant in the southern Brazil, as the proposal includes the evaluation of the usage of this specie as an alternative source of safrole, replacing Sassafras Cinnamon (Ocotea odorifera), widely explored specie in this region until the 90's decade. The plant samples were obtained from different regions of the Acre state and were cultivated at the experimental station of EPAGRI Itajaí - SC. The essential oil of the leaves provided an average content of safrole between 76.6% and 89.9%. The analysis by GC-FID and GC-MS of the oil with higher safrole content, presented the following relative constitution: safrole (89.93%), α-terpinene (0.35%), (E)-β-ocimene (0.54%), terpinolene (3.10%), valencene (0.21%), (Z)-β-bisabolene (1.70%) and guaiol (0.29%).

Óleo essencial de Hedyosmum brasiliense Miq., Chloranthaceae: composição e atividade antimicrobiana. Hedyosmum brasiliense Miq. Chloranthaceae, é uma espécie endêmica no Brasil, conhecida como "cidrão". Embora H. brasiliense seja utilizada como calmante na medicina popular, não foi ainda caracterizada quanto aos constituintes químicos. Este trabalho apresenta a composição do óleo essencial, obtido pela destilação de folhas frescas e de amostra de óleo essencial armazenada por três meses, analisadas por GC-FID e CG-MS. Os efeitos inibitórios do óleo essencial foram testados pelo método da diluição em agar, contra seis espécies de bactérias (Bacillus subtilis, Escherichia coli, Proteus mirabilis, Pseudomonas aeruginosa, Staphylococcus aureus e S. saprophyticus). Adicionalmente, seis espécies de fungos (Candida albicans, C. parapsilosis, Microsporum canis, M. gypseum, Trichophyton rubrum e T. mentagrophytes) foram incluídas. Dentre os principais constituintes, α-terpineol (10,2%), curzereno (8,9%), pinocarvona (8,4%) e β-tujeno (7,1%) foram os encontrados em maior quantidade. O σleo essencial apresentou baixa atividade contra microorganismos Gram-negativos. Entretanto, a atividade é extraordinária contra bactérias Gram-positivas e fungos, com valores de MIC entre 0,125 a 2,5% (v/v).

Hedyosmum brasiliense Miq., Chloranthaceae, is an endemic species of Brazil, locally known as "cidrão". Although H. brasiliense is popularly used as sedative, chemical constituents of this species remains uncharacterized. This work presents the essential oil composition, obtained by distillation of the fresh leaves and from a stored sample for three months, analysed by GC-FID and GC-MS. The inhibitory effects of essential oil were tested by the agar dilution method against six bacterial species (Bacillus subtilis, Escherichia coli, Proteus mirabilis, Pseudomonas aeruginosa, Staphylococcus aureus and S. saprophyticus). In addition, six fungal species (Candida albicans, C. parapsilosis, Microsporum canis, M. gypseum, Trichophyton rubrum and T. mentagrophytes) were included. Among the determined constituents, α-terpineol (10.2%), curzerene (8.9%), pinocarvone (8.4%) and β-thujene (7.1%) were found as the main components. The essential oil has only low activity against Gram-negative microorganisms. However, is remarkable active against Gram-positive bacteria and fungi with MIC values ranging from 0.125 to 2.5% (v/v).

Os óleos essenciais, isolados por hidrodestilação de folhas e flores de Myrcia obtecta (O. Berg) Kiaersk. var. obtecta, Myrtaceae, coletadas a cada dois meses em Curitiba, Paraná, durante o período de outubro/2005 a agosto/2006, foram analisados por CG e CG/EM. Os óleos das folhas foram caracterizados pelo elevado conteúdo de sesquiterpenos cíclicos (cerca de 70%) e quantidades variáveis de monoterpenos (5,6-16,7%), compostos alifáticos (0,4-5,5%) e salicilato de metila (0,1-1,5%). Foram identificados 55 componentes, sendo que trans-calameneno (17,029,3%) foi o componente majoritário em todas as amostras. Não houve mudanças significativas na composição, excepto em outubro (floração) quando α-terpineol e trans-calameneno atingiram os maiores níveis (11,2% e 29,3%, respectivamente). O óleo das flores contém salicilato de metila (89%) como constituinte majoritário.

The essential oils isolated by hydrodistillation from leaves and flowers of Myrcia obtecta (O. Berg) Kiaersk. var. obtecta, Myrtaceae, collected bimonthly in Curitiba, Paraná state, Brazil, from October/2005 to August/2006 were analyzed by capillary GC and GC/MS. Fifty-five components were identified in the leaf oils, which were characterized by predominance of cyclic sesquiterpenes (around 70%) and variable amounts of monoterpenes (5.616.7%), aliphatic compounds (0.4-5.5%) and methyl salicylate (0.1-1.5%). The major component in all samples was trans-calamenene (17.0-29.3%). The composition did not show significant seasonal variation, except in October (flowering) when α-terpineol and trans-calamenene peaked (11.2% and 29.3%, respectively). The flower oil was characterized by high content of methyl salicylate (89%).