Controlling the chemical parameters of the anaerobic digestion (AD) process is essential for the bioconversion of organic matter to methane; among these parameters include the presence and concentration of volatile fatty acids (VFAs). It is thus necessary to use efficient analytical methods that are capable of identifying and quantifying VFAs in reactor effluents in order to obtain an immediate response to their conditions. In this study, the liquid-liquid extraction (LLE) method was optimized and validated - through an adaptation of the official method, using acetone and KHSO4, and gas chromatography with flame ionization detector (GC-FID) was used for the determination of acetic, propionic, isobutyric, butyric, isovaleric and valeric acids present in the effluents. The limit of detection (LOD) and limit of quantification (LOQ) obtained were 1.2-2.5 mg L-1 and 1.9-3.7 mg L-1, respectively, for all analytes. These low LODs and LOQs are essentially important because the presence of isobutyric and isovaleric acids above 5.0 mg can be considered indicative of imbalances in AD. The proposed method, which presented satisfactory results with good repeatability (4.2-20.7%) and recovery (90.9-104.0%) rates, was applied for the analysis of effluent samples from three continuous stirred-tank reactors (CSTR). AD (AD methane VFAs. . (VFAs) conditions study liquidliquid liquid LLE (LLE KHSO4 KHSO GCFID GC FID (GC-FID acetic propionic butyric LOD (LOD LOQ (LOQ 1.22.5 1225 1.2 2.5 1 2 5 1.2-2. L1 L L- 1.93.7 1937 1.9 3.7 9 3 7 1.9-3. L1, 1, respectively analytes 50 0 5. 4.220.7% 42207 4.2 20.7% 4 20 (4.2-20.7% 90.9104.0% 9091040 90.9 104.0% 90 104 (90.9-104.0% rates stirredtank stirred tank CSTR. CSTR (CSTR) (VFAs 22 1.22. 122 12 1. 25 2. 1.2-2 93 1.93. 193 19 37 3. 1.9-3 220 4.220.7 4220 42 4. 207 20.7 (4.2-20.7 9104 90.9104.0 909104 909 90. 1040 104.0 10 (90.9-104.0 (CSTR 1.22 1.2- 1.93 1.9- 4.220. 422 20. (4.2-20. 910 90.9104. 90910 104. (90.9-104. 4.220 (4.2-20 91 90.9104 9091 (90.9-104 4.22 (4.2-2 90.910 (90.9-10 (4.2- 90.91 (90.9-1 (4.2 (90.9- (4. (90.9 (4 (90. ( (90 (9

Food fraud, such as the adulteration of extra virgin olive oil (EVOO), is found to cause substantial negative impacts on both the economy and the health of consumers. This work was aimed at evaluating 19 EVOO samples commercialized in Foz do Iguaçu, a frontier city located around the triple border of Brazil, Argentina, and Paraguay. To detect the presence of adulteration in EVOO samples, the present study employed gas chromatography coupled to flame ionization detector (GC-FID) and headspace solid phase microextraction with gas chromatography coupled to mass spectrometry (HS-SPME-GC-MS) in order to evaluate fatty acids composition and volatile organic compounds (VOCs), respectively. The quantitative results obtained from the analysis of fatty acids composition showed that 32% of the EVOO samples were adulterated, presumably with soy oil, due to the high levels of linoleic, linolenic, and myristic acids present in them. Principal component analysis (PCA) conducted using the complete chromatographic aroma profiles obtained from the VOCs helped distinguish authentic EVOO samples from adulterated ones and the country of origin of the samples. The following aromatic compounds were first described, as possible adulterant markers: 3,3-dimethylheptanoic acid, propyl pentanoate, methyl cyclohexanecarboxylate, ethyl cyclohexanecarboxylate, 2-phenylethyl acetate, 6,10,14-trimethylpentadecan-2-one, and 1,2-dimethoxy-4-methylbenzene. fraud EVOO, , (EVOO) consumers 1 Iguaçu Brazil Argentina Paraguay GCFID GC FID (GC-FID HSSPMEGCMS HS SPME MS (HS-SPME-GC-MS VOCs, (VOCs) respectively 32 linoleic linolenic them PCA (PCA described markers 3,3dimethylheptanoic 33dimethylheptanoic dimethylheptanoic 3,3 3 acid pentanoate cyclohexanecarboxylate 2phenylethyl phenylethyl 2 acetate 6,10,14trimethylpentadecan2one, 61014trimethylpentadecan2one trimethylpentadecanone 6,10,14 trimethylpentadecan one, 6 10 14 one 6,10,14-trimethylpentadecan-2-one 1,2dimethoxy4methylbenzene. 12dimethoxy4methylbenzene dimethoxymethylbenzene 1,2 dimethoxy 4 methylbenzene. methylbenzene 1,2-dimethoxy-4-methylbenzene (EVOO (VOCs 3dimethylheptanoic 33 3, 14trimethylpentadecan2one 6,10,14trimethylpentadecan2one 61014 6,10,1 2dimethoxy4methylbenzene 1,2dimethoxy4methylbenzene 12 1, 6101 6,10, 610 6,10 61 6,1 6,

5-Hydroxymethylfurfural (HMF) can be obtained from the dehydration of monosaccharides present in biomass, which helps add value to the raw material. The present work sought to study the relationship between the parameters of biomass characterization, including the content of reducing sugars, total soluble solids and the mid-infrared (MIR) and near-infrared (NIR) spectra, and the formation of HMF after synthesis. A thorough analysis was conducted in order to evaluate the residual agricultural biomass samples from sugarcane bagasse, corn stover, cassava branch, banana pseudostem and mango fruits after the drying (45 °C maximum) and ball mill grinding pre-processing procedure. HMF synthesis was performed using 0.50 mol L-1 HCl and n-butanol as extracting solvent. The analytical quantification of HMF and furfural (co-product of synthesis) was performed using high-performance liquid chromatography coupled to diode-array detector (HPLC-DAD). The highest efficiency of the synthesis of HMF was observed for the mango fruits (55.0 kg ton-1) and sugarcane bagasse biomass (47.5 kg ton-1) samples. The application of data fusion and principal component analysis (PCA) allowed us to identify the samples with greater potential for HMF synthesis. 5Hydroxymethylfurfural Hydroxymethylfurfural 5 (HMF material characterization sugars midinfrared mid infrared MIR (MIR nearinfrared near NIR (NIR spectra stover branch 45 (4 C maximum preprocessing pre processing procedure 050 0 50 0.5 L1 L 1 L- nbutanol n butanol solvent coproduct co product highperformance high performance diodearray diode array HPLCDAD. HPLCDAD HPLC DAD . (HPLC-DAD) 55.0 550 55 (55. ton1 ton ton-1 47.5 475 47 (47. PCA (PCA 4 ( 05 0. (HPLC-DAD 55. (55 ton- 47. (47 (5

Abstract The inappropriate disposal of toxic compounds generated by industrial activity has considerably impacted the environment. Microbial communities inhabiting contaminated sites may represent ecological alternatives for the decontamination of environments. The present work aimed to search the potential of fungi isolated from wastewater treatment plant of a textile industry for bioremediation processes. Twenty-three fungi previously isolated from textile effluent were evaluated for their abilities to degrade pollutants using heavy metal and hydrocarbon tolerance assays. One isolate was subjected to pyrene degradation due its ability to tolerate hydrocarbon. The majority of isolates were resistant to at least two metals tested, i.e. chrome, copper, lead and aluminum. Isolates Penicillium sp. ITF 2, Penicillium rubens ITF 4, Penicillium sp. ITF 12 and ITF 20 (not identified) showed tolerance to tested heavy metals in all concentrations. ITF 12 and ITF 20 were able to tolerate benzene, toluene and hexane, separately. ITF 12 was able to degrade 24.9% of pyrene after 5 days of cultivation. The results encourage future studies to optimize the tolerance and degradation assay using the isolates that showed the best results, as well as studies on the treatment of environments contaminated with heavy metals and hydrocarbons, including industrial textile effluents.

RESUMEN El presente estudio tuvo como objetivo establecer los perfiles de ácidos grasos de una variedad de alimentos tradicionales que se consumen regularmente en Paraguay. Se evaluaron treinta y dos alimentos con alto contenido de lípidos mediante cromatografía de gases acoplada a detector de ionización de llama (GC-FID). Los productos cárnicos y lácteos presentaron un elevado nivel de ácidos grasos saturados, aumentando los índices de aterogenicidad y trombogenicidad. Entre los monoinsaturados, el ácido oleico (18: 1n-9c) se encuentró principalmente en aceitunas (71,7%) y chipa (62,7%), este último preparado industrialmente por adición de ácido oleico. En cuanto al contenido de ácidos grasos trans, los valores más altos se encontraron en los helados a base de leche (5,1%) y chipa guazú (3,8%). Los valores de la relación n-6 / n-3 fueron superiores a 37:1 en sopa paraguaya y empanada (frita) debido a la adición de aceite de soja y maíz utilizado en la preparación de alimentos. Los datos evaluados y presentados en este estudio pueden contribuir a la mejora de los hábitos alimentarios de la población paraguaya, así como ayudar a combatir los factores de riesgo comúnmente asociados con los malos hábitos alimentarios y los problemas crónicos de salud.

ABSTRACT The present study aims to establish the fatty acid profile of a variety of traditional foods consumed regularly in Paraguay. Thirty-two high-lipid content foods were evaluated by gas chromatography coupled with a flame ionization detector (GC-FID). Meat and dairy products were found to present high levels of saturated fatty acids, and this led to an increase in the atherogenicity and thrombogenicity indices of these products. Among the monounsaturated acids evaluated, oleic acid (18:1n-9c) was mainly found in olives (71.7%) and chipa (62.7%), which had been industrially prepared with the addition of oleic acid. Milk-based ice cream (5.1%) and chipa guazú (3.8%) presented the highest content of trans fatty acids. The n-6/n-3 fatty acids ratio obtained for the traditional sopa Paraguaya and empanada (fried pasty) was higher than 37:1; this can be attributed to the addition of soybean and corn oils in the preparation of these foods. The data evaluated and presented in this study can contribute toward the improvement of eating habits among the Paraguayan population, as well as help combat the risk factors commonly associated with bad eating habits and chronic health issues.

Beetroot leaves (Beta vulgaris L.) are commonly cut off and discarded before using its bulb due to lack of knowledge of how to use them. Aiming at using these leaves, in the present study, in natura and dehydrated beetroot leaves were chemically characterized in terms of fatty acid composition, proximate composition, minerals, total phenolic compounds (TPC), and antioxidant activity by DPPH• in different stages (60, 80, and 100 days) of development. The beetroot leaves showed significant levels of protein and lipids in all developmental stages, and all proximate composition nutrients decreased during these maturation stages; the highest content was observed at 60 days. The Fe content decreased during the developmental stages (from 342.75 to 246.30 mg.kg-1), while the content of K increased (from 13,367.64 to 20,784.90 mg.kg-1). With regard to to fatty acid composition, linolenic acid was present in the greatest quantity, and it increase up to 2.58 mg.g-1 (in natura) and 40.11 mg.g-1 (dehydrated) at 100 days of development. The n-6/n-3 ratios were low in all stages. The TPC and antioxidant activity by DPPH• changed during the developmental stages. The TPC was highest in the 100-day dehydrated leaves (15.27±0.12 mg GAE.g-1 FW), and the 50% inhibition of DPPH• (IC50 89.52 µg.mL-1) were better in the 60-day in natura leaves. This study shows that all developmental stages produced satisfactory results, and therefore, these leaves can be reused as food. The antioxidant activity and the chemical constituents, mainly the ω-3fatty acid, increased during the stages of development.

No Brasil, nas feiras livres, mercados e distribuidores de vegetais, são cortadas e descartadas as folhas e/ou ramas destes alimentos, incluindo as folhas de cenoura (Dacus carota L.). Visando diminuir este desperdício, realizou-se o presente trabalho, que teve como objetivo caracterizar quimicamente as folhas de cenoura de cultivo orgânico em três estádios de desenvolvimento e assim indicar a melhor época para a retirada e consumo na alimentação. As folhas foram desidratadas em estufa a 70 °C por 43 horas e, em seguida, fez-se as análises de composição centesimal, atividade antioxidante, clorofila total, composição em ácidos graxos e dos minerais cálcio (Ca), sódio (Na), potássio (K), magnésio (Mg), manganês (Mn), Ferro (Fe), zinco (Zn) e cobre (Cu). Baseado nas análises realizadas foi indicado o estádio de 100 dias de desenvolvimento como o ideal para a retirada e consumo das folhas de cenoura que apresentou bons resultados de atividade antioxidante, necessitando de apenas 63,78 ± 0,5 mg.L-1 de extrato metanólico da folha para inibir 50% da concentração do radical livre DPPH (2,2-difenil-1picrilidrazil), proteína total (18,23% ± 2,8) e de ácido graxo alfa linolênico (18:3n-3/AAL) 876,55 ± 20,62 mg.100 g-1 de matéria seca.

In Brazil, street markets and vegetable distributors discard vegetable leaves and stems, including those of carrot (Dacus carota L.). Seeking to reduce the waste of vegetable parts, this study characterized chemically the leaves of organically grown carrot in three stages of development to determine the best time for their removal and consumption as food. The leaves were dehydrated in an oven at 70 °C for 43 hours and analyzed for chemical composition, antioxidant activity, chlorophyll content, fatty acid composition, and also calcium (Ca), sodium (Na), potassium (K), magnesium (Mg), manganese (Mn), iron (Fe), zinc (Zn), and copper (Cu) contents. The analyses indicated 100 days of development as the ideal stage for the removal and consumption of carrot leaves with good antioxidant activity requiring only 63.78 ± 0.5 mg.L-1 methanol leaf extract to inhibit 50% of the concentration of the free radical DPPH (2,2-diphenyl-1picrilidrazil), and total protein and alpha-linolenic acid (18:3 n-3/LNA) contents of 18.23% ± 2.8 and 876.55 ± 20.62 mg.100 g-1 of dry matter, respectively.

Conduziu-se este estudo, com o objetivo de quantificar o ácido alfa-linolênico (LNA, 18:3n-3) em folhas de trigo secas e colhidas em diferentes estádios de desenvolvimento (20, 40 e 80 dias), determinar o potencial antioxidante e o conteúdo de fenólicos totais em folhas colhidas aos 80 dias, assim como realizar a analise de minerais (Na, K, Fe, Ca, Mg, P, Zn, Cu e Mn). Foi verificada uma predominância de ácidos graxos poli-insaturados (AGPI) comparado com os ácidos graxos saturados (AGS) na fração lipídica das folhas. As folhas colhidas em todos os períodos apresentaram razões de AGPI/AGS e de ácidos graxos ômega-6 e ômega-3 (n-6/n-3), dentro dos valores considerados adequados para a alimentação. O maior teor de LNA foi encontrado nas folhas colhidas aos 60 dias, correspondendo a 2.146,72 mg 100 g-1 de matéria seca. Entre 60 e 80 dias, observou-se uma queda de cerca de 30% na concentração de LNA. A fração acetato foi eficiente na inibição do radical DPPH, apresentando valor de IC50 de 154 µg mL-1, e o teor de compostos fenólicos foi de 615,4 ± 36,4 mg EAG L-1, ambas as análises para as folhas colhidas aos 80 dias. Nesse estádio de crescimento, as folhas apresentaram consideráveis teores dos minerais P, Zn, Cu e Mn. Tais resultados reforçam a importância do uso de folhas de trigo para alimentação humana, em função de seu potencial antioxidante e consideráveis teores de LNA.

The objective of this study was to quantify alpha-linolenic acid (LNA, 18:3n-3) of dried wheat leaves, harvested at different development stages (20, 40 and 80 days), to determine the antioxidant potential and the total phenolic compounds of leaves harvested at 80 days, as well as to perform mineral analysis (Na, K, Fe, Ca, Mg, P, Zn, Cu and Mn). It was observed a predominance of polyunsaturated fatty acids (PUFA) compared to saturated fatty acids (SFA) in the lipid fraction of leaves. Leaves collected in all periods presented ratios of PUFA/SFA, omega-6 and omega-3 fatty acids (n-6/n-3) considered suitable for food. The highest content of LNA was found in leaves harvested at 60 days, corresponding to 2.146,72 mg 100 g-1 dried matter. The range time between 60 and 80 days showed a decline of nearly 30% in the concentration of LNA. The acetate fraction was the most effective over DPPH radical assay, showing IC50 value of 154 µg mL-1, and the phenolic compounds content was 615.4 ± 36.4 mg EAG L-1, both analyses carried out in leaves harvested at 80 days. In this development stage, wheat leaves showed significant levels of the minerals P, Zn, Cu and Mn. These results reinforce the potential of using wheat leaves in foods, according to its antioxidant content and significant levels of LNA.

O objetivo deste estudo foi analisar a composição centesimal e de ácidos graxos de cinco marcas de steak empanado de frango (A, B, C, D e E). As análises de ácidos graxos foram realizadas por cromatografia gasosa e técnicas de quantificação absoluta. Os resultados experimentais foram comparados com valores constantes nos rótulos. Os valores encontrados para proteína de todas as marcas estavam em acordo com o estabelecido pela legislação brasileira, exceto o da amostra E, a qual apresentou o maior teor lipídico. Treze ácidos graxos foram identificados nas marcas avaliadas, sendo os majoritários os ácidos: oleico, linoleico e palmítico. As razões dos ácidos graxos poli-insaturados/ácidos graxos saturados encontraram-se dentro dos valores considerados adequados para a saúde humana, porém, as elevadas razões n-6/n-3 encontradas podem resultar em um desequilíbrio na ingestão destes ácidos graxos. Apenas amostras D e E podem ser consideradas livres de trans de acordo com a legislação vigente. A comparação entre os resultados das análises e os valores constantes nos rótulos apresentaram pequenas variações nos teores de proteína, entretanto, a maioria das marcas subestimou os teores de lipídios e valor energético. Os rótulos das marcas B e C declaravam-se livre de trans, entretanto os resultados obtidos apontam teores acima dos valores permitidos pela legislação para serem consideradas livre de trans.

The aim of this work was to analyze the fatty acid and proximate composition of five brands of breaded chicken steak (A, B, C, D, and E) by accurate chromatographic quantification and to compare the experimental results with food label nutrition facts. The protein values of all brands were in agreement with the Brazilian regulation values, except for that of sample E, which presented the highest lipid content. Thirteen fatty acids were identified in the studied brands and the major ones were oleic acid, linoleic acid, and palmitic acid. The polyunsaturated fatty acid/saturated fatty acid ratios were within the values considered appropriate for human health; however, the high n-6/n-3 ratios found can result in an unbalanced intake of these fat acids. Only samples D and E can be considered trans free according to the regulations. The comparison of the analyses' results and the food label nutrition facts showed little variation in protein values. Nevertheless, most brands underestimated their lipid and energy levels. Brand B and C labels declared "free of trans", but the obteined results showed levels excedding those especified by regulation to be considered trans free values.

O objetivo do presente trabalho foi avaliar os efeitos do óleo de linhaça sobre as concentrações dos teores de ácidos graxos poli-insaturados n-6 e n-3 (AGPI) em cabeças de tilápia do Nilo (Oreochromis niloticus), um resíduo do pescado normalmente descartado durante o processo de filetagem. A quantificação dos ácidos graxos poli-insaturados foi realizada utilizando-se cromatografia gasosa (CG), sendo a concentração dos ácidos graxos expressa em termos de massa absoluta através da utilização do éster metílico (23:0) como padrão interno e do TCFx (fator de correção teórica do FID). As tilápias receberam dietas com níveis crescentes de óleo de linhaça (0,00, 1,25, 2,50, 3,75 e 5,00%) em substituição ao óleo de girassol (controle) durante um período de cinco meses. A ingestão de LNA causa a dessaturação sequencial e alongamento das cadeias carbônicas de ácidos graxos presentes nas cabeças de peixes, levando a um aumento em todos os AGPIs n-3. Este experimento demonstrou claramente que a adição de óleo de linhaça na ração de tilápia do Nilo aumenta significativamente as concentrações (em 100 g-1 de cabeça) de LNA (100,8 para 973,6 mg), EPA (4,8 para 82,1 mg) e DHA (24,0 para 125,4 mg). Estas alterações contribuem acentuadamente para melhorar a razão AGPI n-6/n-3 e, desta forma, pode ser utilizada em suplementos alimentícios, transformando as cabeças de tilápia em valiosa alternativa como fonte de alimento para dieta humana.

The objective of this study was to examine the effects of linseed oil on n-6 and n-3 polyunsaturated (PUFA) fatty acid content in the heads of Nile tilapia (Oreochromis niloticus), these are normally discarded during the filleting process. The quantification of PUFA was carried out in absolute weights through the use of methyl ester (23:0), as an internal standard, and TCFx (theoretical FID correction factor) by GC gas chromatography. Tilapias were given diets with increasing levels (0.00, 1.25, 2.50, 3.75 and 5.00%) of linseed oil as a replacement for sunflower oil (control) for a period of five months. The ingestion of LNA causes sequential desaturation and elongation in fish heads, leading to an increase in all n-3 PUFAs. This experiment demonstrated clearly that adding linseed oil to the feed of Nile tilapia can markedly increase the amounts (per 100 g-1 of head) of LNA (100.8 to 973.6 mg), EPA (4.8 to 82.1 mg), and DHA (24.0 to 125.4 mg) in their heads, and thus, may be used to help balance n-6/n-3 PUFA ratios in dietary supplements, and creating a valuable alternative food source in the human diet.

O objetivo deste estudo foi quantificar o ácido alfa-linolênico [LNA, 18:3 (n-3)], avaliar a composição centesimal das folhas e caules de linho (Linum usitatissimum L.) submetidos à secagem e colhidos em diferentes estágios de desenvolvimento (40, 80 e 120 dias), e determinar o potencial antioxidante das folhas colhidas aos 80 dias através do teste com o radical DPPH. As folhas obtiveram maiores teores de cinzas, proteína e lipídios totais em relação aos caules. Tanto as folhas quanto os caules apresentaram razões de AGPI/AGS e n-6/n-3 dentro dos valores considerados adequados para a alimentação. Os caules colhidos nos diferentes tempos não apresentaram diferenças significativas (P<0,05), quanto ao teor de LNA. As folhas colhidas aos 80 dias apresentaram a maior concentração de LNA, correspondendo a 1,262,36 mg/100g de folhas desidratadas. Os diferentes extratos (metanólico, butanólico, acetato e aquoso) foram eficientes na inibição do radical DPPH, com destaque para as frações butanólica e acetato, sendo os valores de IC50 de aproximadamente 42ppm para as duas frações. Tais resultados evidenciaram a atividade antioxidante e potencial nutritivo das folhas e caules de linho para futuro uso na alimentação animal e humana.

The objective of this study was to quantify the alpha-linolenic acid [LNA, 18:3 (n-3)] and to evaluate the proximate composition of leaves and stems of flax (Linum usitatissimum L.) dried and harvested at different stages of development (40, 80 and 120 days), and to determine the antioxidant potential of the leaf harvested at 80 days using the test of DPPH radical. The leaves had higher levels of ash, protein and total lipids when compared to the stems. Both the leaves as the stems had ratios of PUFA/SFA and n-6/n-3 within the values considered suitable for food. Stems in the different stages showed no significant difference (P<0.05) of LNA content. Leaves harvested at 80 days showed the highest concentration of LNA, corresponding to 1,262.36 mg/100g dried leaf. The different extracts (methanol, butanol, acetate and water) were efficient in the inhibition of DPPH radical, with emphasis on the butanolic and acetate fractions and the values of IC50 were approximately 42 ppm. These results highlight the nutritional potential and antioxidant activity of leaves and stems of flaxseed for future use in the animal and human feeding.