Bio-oils from biomass pyrolysis have a highly promising potential as biofuels or sources of chemicals. The quantitative analysis of bio-oils is quite difficult and requires many standards. In this study, we developed a methodology using only 16 standards for determining the concentration of 49 compounds, representatives of the main chemical classes commons in bio-oils, using relative response factors (RRF) and analytical curves. Five Pinus sawdust bio-oils were analyzed using a GC-MS-DB-5 capillary column (60 m). SCAN mode (from 45 to 450 Daltons) and retention indices (LPTRI) were used for qualitative analysis. For quantitative analysis, SIM mode was preferred, and analytical curves were constructed from an initial solution at 400 mg g 1 of each of the 16 standards, with concentrations ranging from 1 to 150 mg g 1 added to the internal standard (methyl hexanoate) at 70 mg g 1. After the positive identification and quantification of 9 compounds (among the 16 standards used), the other compounds were quantified using the RRF obtained from a standard solution at 30 mg g 1, considering the similarities with those identified standards. 196 compounds were identified, while 49 compounds were quantified, highlighting the monoaromatic hydrocarbons, naphthalenes, benzofurans, alkyl phenols, and catechols.

The genus Bacillus is Gram-positive, anaerobic or aerobic facultative bacteria, often described to be associated with the mangrove rhizosphere. Secondary products of their metabolism, coming from places affected by pollution and environmental stresses, such as mangroves, have been attracting interest from the biotechnological point of view. In view of this scenario, this work analyzed the ethyl acetate extracts of the cultured Bacillus species, previously isolated from mangroves located in the state of Sergipe, Brazil. Chromatographic profiles of seven bacterial isolates collected from two different mangroves were analyzed using gas chromatography/mass spectrometry (GC-MS) and many important compounds of biotechnological interests, mainly those derived from azo-aromatic compounds such as pyrazines, pyrrolo-pyrazines, and piperazinediones, were detected. This study is one of the first, in our knowledge, prospecting volatile or semi volatile organic compounds from ethyl acetate extracts produced by bacteria isolated from the mangroves, and intents to increase the interest in this coastal ecosystem as a source of compounds with biotechnological applications.

Tea and yerba mate are traditional beverages prepared through the infusion of leaves of Camellia sinensis and Ilex paraguariensis, respectively. During this process, the leaching of pesticides onto the beverage, such as endosulfan, may occur. In this study, a bar adsorptive microextraction (BAµE) method prior to large gas chromatography mass spectrometry analysis was developed to analyze a- and b-endosulfan in teas and yerba mate infusions. Different sorbent coatings for BAµE were compared and the hydrophilic-lipophilic balanced polymer showed the best selectivity for endosulfan isomers. The method was validated providing good recoveries (varying from 80.4 ± 1.8 to 108 ± 4.9%) and linearities (r2 > 0.99), limits of detection from 8.0 to 4.0 µg kg-1 and limits of quantification from 40 to 20 µg kg-1 for a- and b-endosulfan, respectively. The application of the method in the analysis of real samples showed all free of endosulfan at the limit of detection of the analytical method.

Piper glabratum is a plant native from South America, which has been little studied, despite its use in folk medicine. In this study, chemical composition, antioxidant and antifungal activities of essential oils (EOs) from leaves of P. glabratum were investigated. The influence of seasonality on its chemical composition was also evaluated. The chemical characterization was performed by two-dimensional gas chromatography coupled with quadrupole mass spectrometry (GC×GC/qMS). Altogether, 199 compounds were identified in the EOs and their composition varied during the seasonal cycle. The main compounds found were sesquiterpenes and their oxygenated analogues. EOs showed antioxidant activity, measured by 2,2-diphenyl-1-picrylhydrazyl-DPPH (from 28.1 to 33.4 µg mL-1) and β-carotene assays (from 57.4 to 66.4%), and inhibitory action against C. albicans. The oils provided expressive properties; however, the yield of EO from winter was not enough for activities assays, remarking the influence of the seasonality on the biological activities of this plant.

Agro-industrial wastes are abundant and low-cost sources of energy and chemicals. Biomass account for 14% of the world’s energy production. Industrial residues of production of soluble coffee (spent coffee grounds - SCG) have great potential due to its large-scale production and can be transformed by pyrolysis, in liquid, solid and gaseous products with applications from energy to chemicals. This work has the objective of producing bio-oil from the pyrolysis of industrial SCG, characterize it by chromatography and indicate its possible applications. As SGC contains a large amount of glycerides, they were extracted from SGC before the pyrolysis, aiming to obtain a better bio-oil from the residue. The yield in vegetable oil was 5.2% and its analyses showed that 50% are saturated acids (mainly palmitic 27.6%) and other 50% are unsaturated ones (mainly linoleic acid 35.3%). This composition qualifies this oil for biodiesel purposes. The residue (SGC after extraction) was submitted to pyrolysis, yielding 30% in liquid products, being 6% bio-oil. The bio-oil was analyzed by gas chromatography being identified free fatty acids, hydrocarbons, phenols and N-compounds. The heteroatomic compounds limit the use as biofuel but can be interesting for the pharmaceutical, agrochemical and fine chemicals industries.

Morinda citrifolia (noni) is found in the Atlantic and Amazonian Forest in Brazil and with recognized uses in folk medicine. However, few studies exist in its chemical characterization. The present work aims to investigate the efficiency of the sonication for extracting bioactive compounds from fruits and leaves of noni, using an experimental design of 23, whose variables were time, temperature and mass of the plant. Parallel extractions were performed using two extraction solvents (hexane and ethanol) and the same experimental design. The compounds were identified by gas chromatography coupled to mass spectrometry. The independent variable was the mass yield and all the variables studied in the sonication process were significant (p < 0.05%) for the process. Ethanol was more effective than hexane and the leaves produced higher yield and diversity of compounds than fruits. Vitamin E (tocopherol), octanoic acid, hydroxymethylfurfural, phytol and squalene were the main compounds identified.

Bark of acuri and endocarp of baru are residues generated during the processing of these fruits. One alternative to consider is the pyrolysis of these materials to generate bio-oils, opening the perspective for the production of environment-friendly, added value products. Samples of acuri and baru were subjected to laboratorial scale pyrolysis. At the optimized pyrolysis conditions, the bio-oils yields (m/m) were 30% for bark of acuri and 29% for endocarp of baru. Next, the obtained bio-oil was submitted to proximate analysis and GC×GC-TOF/MS (two-dimensional gas chromatography with time-of-flight mass spectrometric detection). The bio-oil generated from the bark of acuri proved to be of the highest complexity with 113 identified compounds, while the bio-oil generated from the endocarp of baru sample led to 71 identified compounds. A total of 29 compounds were confirmed using standards in the acuri bark bio-oil, while 23 compounds were confirmed for endocarp of baru bio-oil. There was a predominance of phenols and ketones for the bio-oil generated from acuri bark, and hydrocarbons and phenols for the bio-oil from baru endocarp.

The aim of this study was to evaluate the antimicrobial activity of bio-oil (obtained by pyrolysis of biomass: soybean oil, eucalyptus sawdust and coffee grounds) added to the blend B10 (diesel and biodiesel). The bio-oil is compatible to diesel oil and it contains promising compounds that can exhibit antimicrobial activity during fuel storage. We evaluated the antimicrobial activity of bio-oil added to diesel oil B10 by determining the minimum inhibitory concentration at different concentrations (0-10%) using oil-deteriorating microorganisms for 10 days at 30 °C. Bio-oil was separated from the aqueous phase by solid phase extraction using ultrapure water and sodium hydroxide. The aqueous phase containing the solubilized compounds of bio-oil was characterized by comprehensive two-dimensional gas chromatography with time-of-flight mass spectrometric detection. Minimum inhibitory concentration in the range of 0.25% to 4% was observed for the tested inocula. The chromatographic analysis of both extracts allowed the identification of several oxygenated compounds, which the majority of the analytes consisted of phenolic compounds, followed by ketones.

<p>Solid phase microextraction, one-dimensional gas chromatography (1D-GC) and comprehensive two-dimensional gas chromatography (GC×GC) with mass spectrometric detector have been used to characterize the volatile profile of Moscatel sparkling wines. Predominant classes were esters, acids, alcohols and terpenes. The efficiency of GC×GC was apparent due to the higher number of compounds positively and/or tentatively identified through this technique (two and a half times higher than with 1D-GC), as well as by the separation of co-eluted compounds in 1D-GC. Principal components analysis showed that the volatile profile of the majority of sparkling wines is similar. Only two samples differed from others and the compounds responsible for this behavior were nerol, menthol, linalool acetate, limonene and geraniol. Furthermore, a clear separation among sparkling wines done with two Moscato grape varieties (Bianco and Giallo) was observed in cluster analysis due to the higher chromatographic area of terpenes and norisoprenoids verified in Giallo samples.</p>

Anise is frequently found among the ingredients described in the label of cosmetic products. However, the use of fennel instead of anise may occur due to the lower price of fennel. The main differences in volatile profile of anise and fennel fruits were, for the first time, evaluated using comprehensive two-dimensional gas chromatography with time-of-flight mass spectrometric detection (GC×GC/TOFMS) and chemometric analysis. Aproximately 950 peaks were found in chromatograms of each sample and Fisher ratio appointed 31 volatile analytes as the most discriminating between anise and fennel samples. These 31 compounds were used in principal component analysis and canonical discriminant analysis that designated seven compounds (estragole, methyl eugenol, 4,5-dehydro-isolongifolene, calamenene, linalool, β-ocimene and fenchol) as the most important to verify the use of fennel or anise in personal care products. Among these seven compounds, thrree coeluted with other compounds and were correctly identified only with the use of GC×GC/TOFMS.

O Brasil é um grande fabricante de celulose de eucalipto e experimentou progressos importantes na gestão ambiental nesta área nas últimas décadas. Entretanto, ainda há oportunidades para usos alternativos dos resíduos dessas fábricas, que podem resultar em produtos de maior valor agregado. As caracterizações qualitativa e semi-quantitativa da composição do bio-óleo de pirólise de três resíduos da indústria celulose (serragem de eucalipto, resíduo do digestor e lodo) foram realizadas utilizando-se cromatografia gasosa bidimensional abrangente com detector por espectrometria de massas por tempo de voo (GC×GC/TOF-MS). As melhores condições de pirólise para o resíduo do digestor foram aplicadas aos demais resíduos, obtendo-se bio-óleos complexos, sendo os bio-óleos do resíduo do digestor e da serragem qualitativamente semelhantes e o do lodo, um pirolisado de maior complexidade. As vantagens da técnica GC×GC/TOF-MS para esta aplicação específica são apresentadas, bem como o potencial dos componentes dos bio-óleos (fenóis e cetonas) para aplicações industriais importantes.

Brazil is a great manufacturer of Eucalyptus pulp and has experienced important improvements in the environmental management in the last decades. However, there are still opportunities for alternative uses of pulp mill residues, which may result in higher added value products. Qualitative and semi-quantitative characterizations of bio-oil composition of three pulp mill residues (Eucalyptus sawdust, digester residue and wastewater treatment sludge) were performed using comprehensive two-dimensional gas chromatography with time-of-flight mass spectrometric detection (GC×GC/TOF-MS). The best pyrolysis conditions achieved for the digester residue were applied to the other residues and similar bio-oils were obtained for sawdust and digester residue, while sludge rendered a more complex pyrolysate. The advantages of GC×GC/TOF-MS for this specific application are presented, as well as the potential of bio-oil components for important industrial applications.

O objetivo deste trabalho é comparar a eficiência de diferentes adsorventes na purificação de biodiesel produzido por transesterificação alcalina do óleo de soja (metanol/KOH). As metodologias propostas foram baseadas na utilização de Magnesol®, sílica, Amberlite BD10 DRY® e Purolite PD 206® como adsorventes e foram desenvolvidas por adsorção a 65 ºC. A eficiência de cada adsorvente foi medida através do teor residual de potássio, álcool, água e sabão, dissolvidos no biodiesel purificado. Como resultado, observamos que Magnesol® e sílica apresentaram melhores propriedades de adsorção que Amberlite BD10 DRY® e Purolite PD 206®, especialmente para remover sabão, glicerina livre e ligada e potássio. Em comparação com a lavagem ácida convencional, estas matrizes foram consideradas adequadas para a remoção de espécies contaminantes inorgânicas e orgânicas do biodiesel. Os principais resultados encontrados para estes dois adsorventes (Magnesol® 1% e sílica 2%) foram valores abaixo de 0,17 mg KOH g-1 de acidez, 1 mg kg-1 de potássio, 61 ppm de sabão, 500 mg kg-1 de água, 0,22% de metanol, 0,30% de glicerina livre e 0,03% de glicerina ligada

The purpose of this work is to compare the efficiency of different adsorbents in the purification of biodiesel produced by alkaline transesterification of soybean oil (Methanol/KOH). The proposed methodologies were based on the use of Magnesol®, silica, Amberlite BD10 DRY® and Purolite PD 206® as adsorbents and were developed by adsorption at 65 ºC. The response of each adsorbent was measured through the residual potassium, alcohol, water and soaps dissolved in the purified biodiesel. As a result, we observe that Magnesol® and silica showed better adsorption properties than Amberlite BD10 DRY® and Purolite PD 206®, especially for removing soap, free and bonded glycerol and potassium. In comparison to the conventional acid water washing, these matrices were found to be equally appropriate for the removal of inorganic and organic contaminant species from biodiesel. The main results found for these two adsorbents (Magnesol® 1% and silica 2%) were values below 0.17 mg KOH g-1 for acid number, 1 mg kg-1 of K, 61 ppm of soap, 500 mg kg-1 of water, 0.22% of methanol and 0.03% of free glycerol

The growth of biodiesel market and the implementation of regulations related to biodiesel production and biodiesel/diesel blending has encouraged the development of appropriate analytical methods to control the composition of this type of mixture. In this study, an evaluation of the potential of GC×GC for the characterization of samples of beef tallow biodiesel and the composition of blends of biodiesel/diesel is presented. The methodology was applied to beef tallow biodiesel and its mixtures with petrodiesel, ranging from B2 to B50. Results allowed not only the identification and quantification of the biodiesel esters, but also the biodiesel percentage in biodiesel/diesel blends.

Neste estudo, 14 agrotóxicos (captan, clorotalonil, deltametrina, dicloran, fention, folpete, iprodiona, linurom, malationa, prometrina, procloraz, procimidona, triclorfom e trifluralina) foram usados no desenvolvimento de um método multiresíduos (MRM), utilizando extração de cenouras com líquido pressurizado (PLE). A etapa de clean-up foi realizada por dispersão da matriz em fase sólida (MSPD), sendo testados como material dispersante o Florisil, XAD-4, XAD-7 e C18. Diclorometano, acetato de etila e acetona foram empregados como solventes para PLE, a 75 ºC e 1.500 psi. As recuperações dos analitos para cenouras liofilizadas ficaram na faixa de 70 a 133%. Entretanto, os percentuais de recuperação obtidos para as cenouras úmidas não foram satisfatórios (< 70%). Os coeficientes de determinação das curvas analíticas situaram-se na faixa de 0,9821 a 0,9997; os limites de detecção (LOD) e de quantificação (LOQ) para os vários compostos investigados ficaram entre 0,0024-0,1968 mg kg-1 e entre 0,0072-0,5963 mg kg-1, respectivamente.

In this study, 14 pesticides (captan, chlorothalonil, deltamethrin, dicloran, fenthion, folpet, iprodione, linuron, malathion, prometryn, prochloraz, procymidone, trichlorphon and trifluralin) were employed for developing a multiresidue method (MRM) using pressurized liquid extraction (PLE). In situ clean-up was achieved using matrix solid phase dispersion (MSPD), where Florisil, XAD-4, XAD-7 and C18 were tested as dispersing material for carrot samples. Dichloromethane, ethyl acetate and acetone were used as solvents in a PLE unit at 75 ºC and 1,500 psi. Recovery was in the range of 70 to 133 %. Results obtained with wet carrots were not satisfactory, since most of the recovery values were below 70%. Determination coefficients of the analytical curves presented values between 0.9821 and 0.9970. Limits of detection (LOD) and quantification (LOQ) for the various components varied from 0.0024 to 0.1968 mg kg-1, and 0.0072 to 0.5963 mg kg-1, respectively.

The xerogel p-anisidinepropylsilica was obtained. This solid presents some residual paraffin and also a small fraction of high organofunctionalized material that was leached in polar solvent. The xerogel purification could be achieved by exhaustively washing with hexane and dichloromethane solvents, or submitting the xerogel to thermal treatment up to 300 ºC, in vacuum. The resulting purified xerogel material present an appreciable thermal stability and resistance to leaching by solvents.