Comparison of allocation approaches in soybean biodiesel life cycle assessment

This work shows the influence of using different allocation approaches when modelling the inventory analysis in a soybean biodiesel life cycle assessment (LCA). Results obtained using mass, energy and economic based allocations are compared, focusing on the following aspects: normalised potential environmental impact (PEI) categories, total PEI and relative contributions to the total PEI from each life cycle stage and environmental impact category. Similar results are obtained either using economic and energy based allocations. However, different results are obtained when mass based allocation is used when compared with the other two. This study also illustrates that using different allocation approaches in biodiesel LCA may influence the final conclusions, especially in comparative assertions, emphasising the need to perform a sensitivity analysis in the LCA interpretation step.

Optimization of QuEChERS procedure coupled to GC-ECD for organochlorine pesticide determination in carrot samples

An optimised version of the Quick, Easy, Cheap, Effective, Rugged and Safe (QuEChERS) method for simultaneous determination of 14 organochlorine pesticides in carrots was developed using gas chromatography coupled with electron-capture detector (GC-ECD) and confirmation by gas chromatography tandem mass spectrometry (GC-MS/MS). A citrate-buffered version of QuEChERS was applied for the extraction of the organochlorine pesticides, and for the extract clean-up, primary secondary amine, octadecyl-bonded silica (C18), magnesium sulphate (MgSO4) and graphitized carbon black were used as sorbents. The GC-ECD determination of the target compounds was achieved in less than 20 min. The limits of detection were below the EUmaximum residue limits (MRLs) for carrots, 10–50 μg kg−1, while the limit of quantification did exceed 10 μg kg−1 for hexachlorobenzene (HCB). The introduction of a sonication step was shown to improve the recoveries. The overall average recoveries in carrots, at the four tested levels (60, 80, 100 and 140 μg kg−1), ranged from 66 to 111% with relative standard deviations in the range of 2– 15 % (n03) for all analytes, with the exception of HCB. The method has been applied to the analysis of 21 carrot samples from different Portuguese regions, and β-HCH was the pesticide most frequently found, with concentrations oscillating between less than the limit of quantification to 14.6 μg kg−1. Only one sample had a pesticide residue (β-HCH) above the MRL, 14.6 μg kg−1. This methodology combines the advantages of both QuEChERS and GC-ECD, producing a very rapid, sensitive and reliable procedure which can be applied in routine analytical laboratories.

Ligand-Induced structural changes in TEM‑1 probed by molecular dynamics and relative binding free energy calculations

The TEM family of enzymes has had a crucial impact on the pharmaceutical industry due to their important role in antibiotic resistance. Even with the latest technologies in structural biology and genomics, no 3D structure of a TEM- 1/antibiotic complex is known previous to acylation. Therefore, the comprehension of their capability in acylate antibiotics is based on the protein macromolecular structure uncomplexed. In this work, molecular docking, molecular dynamic simulations, and relative free energy calculations were applied in order to get a comprehensive and thorough analysis of TEM-1/ampicillin and TEM-1/amoxicillin complexes. We described the complexes and analyzed the effect of ligand binding on the overall structure. We clearly demonstrate that the key residues involved in the stability of the ligand (hot-spots) vary with the nature of the ligand. Structural effects such as (i) the distances between interfacial residues (Ser70−Oγ and Lys73−Nζ, Lys73−Nζ and Ser130−Oγ, and Ser70−Oγ−Ser130−Oγ), (ii) side chain rotamer variation (Tyr105 and Glu240), and (iii) the presence of conserved waters can be also influenced by ligand binding. This study supports the hypothesis that TEM-1 suffers structural modifications upon ligand binding.

Enantiomeric fraction evaluation of pharmaceuticals in environmentalmatrices by liquid chromatography-tandem mass spectrometry

The interest for environmental fate assessment of chiral pharmaceuticals is increasing and enantioselective analytical methods are mandatory. This study presents an enantioselective analytical method for the quantification of seven pairs of enantiomers of pharmaceuticals and a pair of a metabolite. The selected chiral pharmaceuticals belong to three different therapeutic classes, namely selective serotonin reuptake inhibitors (venlafaxine, fluoxetine and its metabolite norfluoxetine), beta-blockers (alprenolol, bisoprolol, metoprolol, propranolol) and a beta2-adrenergic agonist (salbutamol). The analytical method was based on solid phase extraction followed by liquid chromatography tandem mass spectrometry with a triple quadrupole analyser. Briefly, Oasis® MCX cartridges were used to preconcentrate 250 mL of water samples and the reconstituted extracts were analysed with a Chirobiotic™ V under reversed mode. The effluent of a laboratory-scale aerobic granular sludge sequencing batch reactor (AGS-SBR) was used to validate the method. Linearity (r2 > 0.99), selectivity and sensitivity were achieved in the range of 20–400 ng L−1 for all enantiomers, except for norfluoxetine enantiomers which range covered 30–400 ng L−1. The method detection limits were between 0.65 and 11.5 ng L−1 and the method quantification limits were between 1.98 and 19.7 ng L−1. The identity of all enantiomers was confirmed using two MS/MS transitions and its ion ratios, according to European Commission Decision 2002/657/EC. This method was successfully applied to evaluate effluents of wastewater treatment plants (WWTP) in Portugal. Venlafaxine and fluoxetine were quantified as non-racemic mixtures (enantiomeric fraction ≠ 0.5). The enantioselective validated method was able to monitor chiral pharmaceuticals in WWTP effluents and has potential to assess the enantioselective biodegradation in bioreactors. Further application in environmental matrices as surface and estuarine waters can be exploited.

Milk intake is inversely related to body mass index and body fat in girls

Dairy foods comprise a range of products with varying nutritional content. The intake of dairy products (DPs) has been shown to have beneficial effects on body weight and body fat. This study aimed to examine the independent association between DP intake, body mass index (BMI), and percentage body fat (%BF) in adolescents. A cross-sectional, school-based study was conducted with 1,001 adolescents (418 boys), ages 15–18 years, from the Azorean Archipelago, Portugal. Anthropometric measurements were recorded (weight and height), and %BF was assessed using bioelectric impedance analysis. Adolescent food intake was measured using a self-administered, semiquantitative food frequency questionnaire. Data were analyzed separately for girls and boys, and separate multiple linear regression analysis was used to estimate the association between total DP, milk, yogurt, and cheese intake, BMI, and %BF, adjusting for potential confounders. For boys and girls, respectively, total DP consumption was 2.6 ± 1.9 and 2.9 ± 2.5 servings/day (P = 0.004), while milk consumption was 1.7 ± 1.4 and 2.0 ± 1.7 servings/day (P = 0.001), yogurt consumption was 0.5 ± 0.6 and 0.4 ± 0.7 servings/day (P = 0.247), and cheese consumption was 0.4 ± 0.6 and 0.5 ± 0.8 servings/day (P = 0.081). After adjusting for age, birth weight, energy intake, protein, total fat, sugar, dietary fiber, total calcium intake, low-energy reporters, parental education, pubertal stage, and physical activity, only milk intake was negatively associated with BMI and %BF in girls (respectively, girls: β = −0.167, P = 0.013; boys: β = −0.019, P = 0.824 and girls: β = −0.143, P = 0.030; boys: β = −0.051, P = 0.548). Conclusion: We found an inverse association between milk intake and both BMI and %BF only in girls.

Modelação de um Sistema de AVAC, em Software LabVIEW

Na União Europeia, a energia utilizada nos edifícios é responsável por uma grande parte do consumo total, cerca de 40%, de toda a energia produzida, contribuindo em grande escala para as emissões de gases de efeito de estufa, como o CO2. [ADENE, 2014]. A minimização deste consumo, durante o período de ciclo de vida de um edifício, é um grande desafio associado ao ambiente e à economia. Na atualidade assistimos, cada vez mais, ao emergir de novas tecnologias. Faz parte dessa realidade, o crescimento e o desenvolvimento das UTA’s, que surgem como resposta do ser humano pela busca de otimização da sua zona de conforto, da qualidade de ar interior e da eficiência energética. Assim, para que não se sacrifique o conforto térmico, há que conciliar a qualidade de ar interior com a energia dispensada para climatizar os espaços. Para ajudar à minimização de CO2 em conjunto com uma eficiência energética e conforto térmico, traduzindo-se numa melhor qualidade de ar no interior de espaços climatizados, surge o objetivo de implementar uma aplicação através do software LabVIEW para prever uma experiência real. Como solução, recorreu-se a modelos matemáticos que traduzissem os vários balanços térmicos, balanços de massa e de CO2. As principais conclusões deste trabalho foram: validação do comportamento do modelo matemático da temperatura; validação do comportamento do modelo matemático de CO2; humidade relativa com 25% de registos válidos.

Exposure of Lycopersicon Esculentum to Microcystin-LR: Effects in the Leaf Proteome and Toxin Translocation from Water to Leaves and Fruits

Natural toxins such as those produced by freshwater cyanobacteria have been regarded as an emergent environmental threat. However, the impact of these water contaminants in agriculture is not yet fully understood. The aim of this work was to investigate microcystin-LR (MC-LR) toxicity in Lycopersicon esculentum and the toxin accumulation in this horticultural crop. Adult plants (2 month-old) grown in a greenhouse environment were exposed for 2 weeks to either pure MC-LR (100 μg/L) or Microcystis aeruginosa crude extracts containing 100 μg/L MC-LR. Chlorophyll fluorescence was measured, leaf proteome investigated with two-dimensional gel electrophoresis and Matrix Assisted Laser Desorption Ionization Time-of-Flight (MALDI-TOF)/TOF, and toxin bioaccumulation assessed by liquid chromatography-mass spectrometry (LC-MS)/MS. Variations in several protein markers (ATP synthase subunits, Cytochrome b6-f complex iron-sulfur, oxygen-evolving enhancer proteins) highlight the decrease of the capacity of plants to synthesize ATP and to perform photosynthesis, whereas variations in other proteins (ribulose-1,5-bisphosphate carboxylase/oxygenase large subunit and ribose-5-phosphate isomerase) suggest an increase of carbon fixation and decrease of carbohydrate metabolism reactions in plants exposed to pure MC-LR and cyanobacterial extracts, respectively. MC-LR was found in roots (1635.21 μg/kg fw), green tomatoes (5.15–5.41 μg/kg fw), mature tomatoes (10.52–10.83 μg/kg fw), and leaves (12,298.18 μg/kg fw). The results raise concerns relative to food safety and point to the necessity of monitoring the bioaccumulation of water toxins in agricultural systems affected by cyanotoxin contamination.

QuEChERS: a sample preparation for extraction of carbaryl from rat feces

Carbamate compounds are an important group of cholinesterase inhibitors. There is a need for creating awareness regarding the risks of the inadequate carbamate use in the residential areas due to potential adverse human effects. Carbaryl is a commonly used pesticide worldwide. A simple, fast, and high throughput method was developed employing liquid chromatography with fluorescence detector to determine carbaryl residues in rat feces. The extraction was performed by using a rapid, easy, cheap, effective, reliable, and safe (QuEChERS) method, using acetonitrile as the extracting solvent. The parameters for the performance of the extraction method were optimized, such as ratio of mass of sample per volume of extraction solvent, QuEChERS content, and cleanup columns. Linear response was obtained for all calibration curves (solven and matrix-matched) over the established concentration range (5 500 mg/L) with a correlation coefficients higher than 0.999. The achieved recovery was 97.9% with relative standard deviation values of 1.1% (n D 4) at 167 mg/kg fortified concentration level and the limits of detection and quantification were 27.7 and 92.3 mg/kg respectively.

Eruca sativa: Benefits as antioxidants source versus risks of already banned pesticides

Eruca sativa (rocket salad) has been intensely consumed all over the world, insomuch as, this work was undertaken to evaluate the antioxidant status and the environmental contamination (positive and negative nutritional contribution) of leaves and stems from this vegetable. Antioxidant capacity of rocket salad was assessed by mean of optical methods, such as the total phenolic content (TPC), reducing power assay and DPPH radical scavenging activity. The extent of the environmental contamination was reached through the quantification of thirteen organochlorine pesticides (OCP) by using gas chromatography coupled with electron-capture detector (GC-ECD) and compound confirmations employing gas chromatography tandem mass-spectrometry (GC-MS/MS). The OCP residues were extracted by using Quick, Easy, Cheap, Effective, Rugged and Safe (QuEChERS) methodology.The extent of the environmental contamination was reached through the quantification of thirteen OCP by using gas chromatography coupled with electron-capture detector (GC-ECD) and compound confirmations employing GC-MS/MS. The OCP residues were extracted by using Quick, Easy, Cheap, Effective, Rugged and Safe (QuEChERS) methodology. This demonstrated that leaves presented more antioxidant activity than stems, emphasizing that leaves contained six times more polyphenolic compounds than stems. In what concerns the OCP occurrence, the average recoveries obtained at the three levels tested (40, 60 and 80 µg kg−1) ranged from 55% to 149% with a relative standard deviation of 11%, (except hexachrorobenzene). Three vegetables samples were collected from supermarkets and analysed following this study. According to data, only one sample achieved 16.21 of β-hexachlorocyclohexane, confirmed by GC-MS/MS. About OCP quantification, the data indicated that only one sample achieved 16.21 µg kg−1 of β-hexachlorocyclohexane, confirmed by GC-MS/MS, being the QuEChERS a good choice for the of OCPs extraction. Furthermore, the leaves consumption guaranty higher levels of antioxidants than stems.

Produção de Biodiesel em reator de ultrassons

A contínua subida dos preços dos combustíveis fósseis tradicionais aliada à crescente pressão por parte de várias instituições mundiais para uma política “verde” no que diz respeito aos combustíveis, levam a um aumento da procura dos biocombustíveis e é neste contexto que surge o biodiesel como um dos principais intervenientes. O biodiesel pode ser definido como um derivado éster monoalquílico de ácidos gordos de cadeia longa proveniente de fontes renováveis como óleos vegetais ou gorduras animais e que apresenta características semelhantes ao diesel de petróleo, podendo ser utilizado sem qualquer problema em motores de ignição por compressão. Este trabalho apresenta como principal objetivo o estudo da aplicação da tecnologia de ultrassons na produção de biodiesel. Foi utilizado neste trabalho como matéria-prima um óleo doméstico usado. Este óleo foi previamente filtrado sendo depois analisado o seu índice de acidez para avaliar o seu teor em ácidos gordos livres. O valor obtido para o índice de acidez do óleo foi de 1,91 mg KOH/g, um valor relativamente baixo permitindo a sua utilização sem ser necessário um tratamento inicial via esterificação para diminuir a acidez do mesmo. Foram realizados três ensaios de reação independentes, o primeiro recorrendo ao método tradicional de produção de biodiesel através de transesterificação e recorrendo a agitação mecânica e aquecimento, o segundo utilizando uma sonda de ultrassons com a potência de 500 W e um terceiro ensaio de reação utilizando uma sonda de ultrassons de 2000 W. Em todas as reações foi utilizada uma proporção de 1:5 de óleo usado e metanol e 0,5 % (em relação á massa de óleo utilizada) de catalisador metilato de sódio. Todas as alíquotas recolhidas durante os ensaios foram analisadas através de cromatografia gasosa de modo a determinar o conteúdo em ésteres presente em cada uma delas. A reação convencional teve uma duração total de 150 minutos e decorreu a uma temperatura de 65ºC e a agitação constante de 500 rpm. Ao longo da reação foram retiradas alíquotas de cerca de 25 ml, que foram tratadas de imediato e posteriormente analisadas de modo a estudar-se o comportamento da reação ao longo do tempo. A percentagem de ésteres metílicos no biodiesel obtida ao fim de 90 minutos foi de 81,3%. Em seguida realizou-se uma reação utilizando uma sonda de ultrassons de 500 W de potência mergulhada num recipiente reacional devidamente isolado com uma rolha de cortiça de modo a minimizar as perdas de metanol por evaporação. O tempo total de reação foi de 90 minutos e foram-se retirando alíquotas de cerca de 25 ml para acompanhar o desenrolar da reação, tendo-se obtido uma percentagem de ésteres metílicos de 85,9% ao fim dos 90 minutos. Foi realizada por fim um terceiro ensaio de reação utilizando uma sonda de 2000 W com uma duração total de 90 minutos, tendo-se obtido resultados pouco satisfatórios (77,7%), provavelmente devido a algum problema operacional relacionado com a sonda de ultrassons utilizada ou devido a uma geometria do reator pouco eficiente. Os produtos resultantes da reação convencional e da reação utilizando a sonda de ultrassons de 500 W, assim como o óleo utilizado como matéria-prima foram caracterizados em termos de índice de acidez, densidade a 15ºC e viscosidade a 40ºC.

Análise do ciclo de vida da produção do butanol

Este trabalho teve como objetivo avaliar e comparar os impactes ambientais da produção do butanol considerando três processos produtivos: um que usa fontes fósseis e dois que usam fontes renováveis, nomeadamente palha de trigo e milho. Para o primeiro caso considerouse o processo oxo e os restantes usaram o processo de produção ABE (acetona, butanol e etanol). Na primeira etapa estudaram-se e descreveram-se os diferentes processos referidos. A análise do ciclo de vida foi depois aplicada efetuando as quatro fases nomeadamente definição do âmbito e objetivo, inventário, avaliação de impactes e interpretação dos resultados obtidos. O inventário foi efetuado tendo em conta a bibliografia existente sobre estes processos e com o auxílio da base de dados Ecoinvent Versão3 Database™. Na avaliação de impactes utilizou-se o método Impact 2002 + (Endpoint). Concluiu-se que a produção do butanol pelo processo ABE utilizando o milho é a que apresenta maior impacte ambiental e a que produção do butanol pelo processo ABE usando a palha de trigo é a que apresenta um menor impacte ambiental, quando o processo de alocação foi efetuado tendo em conta as massas de todos os produtos produzidos em cada processo. Foi efetuada uma análise de sensibilidade para a produção de butanol usando palha de trigo e milho relativa aos dados de menor qualidade. No processo da palha de trigo fez-se variar a quantidade de material enviado para a digestão anaeróbia e a quantidade de efluente produzida. No processo relativo ao milho apenas se fez variar a quantidade de efluente produzida. As variações tiveram um efeito pouco significativo (<1,3%) no impacte global. Por fim, efetuou-se o cálculo dos impactes considerando uma alocação económica que foi executada tendo em conta os preços de venda para o ano 2013 na Europa, para os produtos produzidos pelos diferentes processos. Considerando o valor económico verificou-se um aumento do peso relativo ao butanol, o que fez aumentar significativamente o impacte ambiental. Isto deve-se em grande parte ao baixo valor económico dos gases formados nos processos de fermentação. Se na alocação por massa for retirada a massa destes gases os resultados obtidos são similares nos dois tipos de alocação.