Analysis of PCBs in soils and sediments by microwave-assisted extraction, headspace-SPME and high resolution gas chromatography with ion-trap tandem mass spectrometry

A procedure for the determination of seven indicator PCBs in soils and sediments using microwave-assisted extraction (MAE) and headspace solid-phase microextraction (HS-SPME) prior to GC-MS/MS is described. Optimization of the HS-SPME was carried out for the most important parameters such as extraction time, sample volume and temperature. The adopted methodology has reduced consumption of organic solvents and analysis runtime. Under the optimized conditions, the method detection limit ranged from 0.6 to 1 ng/g when 5 g of sample was extracted, the precision on real samples ranged from 4 to 21% and the recovery from 69 to 104%. The proposed method, which included the analysis of a certified reference material in its validation procedure, can be extended to several other PCBs and used in the monitoring of soil or sediments for the presence of PCBs.

Agar extraction from integrated multitrophic aquacultured Gracilaria vermiculophylla: Evaluation of a microwave-assisted process using response surface methodology

Microwave-assisted extraction (MAE) of agar from Gracilaria vermiculophylla, produced in an integrated multitrophic aquaculture (IMTA) system, from Ria de Aveiro (northwestern Portugal), was tested and optimized using response surface methodology. The influence of the MAE operational parameters (extraction time, temperature, solvent volume and stirring speed) on the physical and chemical properties of agar (yield, gel strength, gelling and melting temperatures, as well as, sulphate and 3,6-anhydro-Lgalactose contents) was evaluated in a 2^4 orthogonal composite design. The quality of the extracted agar compared favorably with the attained using traditional extraction (2 h at 85ºC) while reducing drastically extraction time, solvent consumption and waste disposal requirements. Agar MAE optimum results were: an yield of 14.4 ± 0.4%, a gel strength of 1331 ± 51 g/cm2, 40.7 ± 0.2 _C gelling temperature, 93.1 ± 0.5ºC melting temperature, 1.73 ± 0.13% sulfate content and 39.4 ± 0.3% 3,6-anhydro-L-galactose content. Furthermore, this study suggests the feasibility of the exploitation of G. vermiculophylla grew in IMTA systems for agar production.

Determination of ochratoxin A in bread: evaluation of microwave-assisted extraction using an orthogonal composite design coupled with response surface methodology

An analytical method using microwave-assisted extraction (MAE) and liquid chromatography (LC) with fluorescence detection (FD) for the determination of ochratoxin A (OTA) in bread samples is described. A 24 orthogonal composite design coupled with response surface methodology was used to study the influence of MAE parameters (extraction time, temperature, solvent volume, and stirring speed) in order to maximize OTA recovery. The optimized MAE conditions were the following: 25 mL of acetonitrile, 10 min of extraction, at 80 °C, and maximum stirring speed. Validation of the overall methodology was performed by spiking assays at five levels (0.1–3.00 ng/g). The quantification limit was 0.005 ng/g. The established method was then applied to 64 bread samples (wheat, maize, and wheat/maize bread) collected in Oporto region (Northern Portugal). OTAwas detected in 84 % of the samples with a maximum value of 2.87 ng/g below the European maximum limit established for OTA in cereal products of 3 ng/g.

Extraction of volatile oil from aromatic plants with supercritical carbon dioxide: experiments and modeling

An overview of the studies carried out in our laboratories on supercritical fluid extraction (SFE) of volatile oils from seven aromatic plants: pennyroyal (Mentha pulegium L.), fennel seeds (Foeniculum vulgare Mill.), coriander (Coriandrum sativum L.), savory (Satureja fruticosa Beguinot), winter savory (Satureja montana L.), cotton lavender (Santolina chamaecyparisus) and thyme (Thymus vulgaris), is presented. A flow apparatus with a 1 L extractor and two 0.27 L separators was built to perform studies at temperatures ranging from 298 to 353 K and pressures up to 30.0 MPa. The best compromise between yield and composition compared with hydrodistillation (HD) was achieved selecting the optimum experimental conditions of extraction and fractionation. The major differences between HD and SFE oils is the presence of a small percentage of cuticular waxes and the relative amount of thymoquinone, an oxygenated monoterpene with important biological properties, which is present in the oils from thyme and winter savory. On the other hand, the modeling of our data on supercritical extraction of volatile oil from pennyroyal is discussed using Sovova's models. These models have been applied successfully to the other volatile oil extractions. Furthermore, other experimental studies involving supercritical CO2 carried out in our laboratories are also mentioned.

Comparison of Disposable Pipette Extraction and Dispersive Solid-Phase Extraction in the QuEChERS Method for Analysis of Pesticides in Strawberries

In this study, we sought to assess the applicability of GC–MS/MS for the identification and quantification of 36 pesticides in strawberry from integrated pest management (IPM) and organic farming (OF). Citrate versions of QuEChERS (quick, easy, cheap, effective, rugged and safe) using dispersive solid-phase extraction (d-SPE) and disposable pipette extraction (DPX) for cleanup were compared for pesticide extraction. For cleanup, a combination of MgSO4, primary secondary amine and C18 was used for both the versions. Significant differences were observed in recovery results between the two sample preparation versions (DPX and d-SPE). Overall, 86% of the pesticides achieved recoveries (three spiking levels 10, 50 and 200 µg/kg) in the range of 70–120%, with <13% RSD. The matrix effects were also evaluated in both the versions and in strawberries from different crop types. Although not evidencing significant differences between the two methodologies were observed, however, the DPX cleanup proved to be a faster technique and easy to execute. The results indicate that QuEChERS with d-SPE and DPX and GC–MS/MS analysis achieved reliable quantification and identification of 36 pesticide residues in strawberries from OF and IPM.

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.

Uso Sustentável de Vapor

Em 2006, a IEA (Agência Internacional de Energia), publicou alguns estudos de consumos mundiais de energia. Naquela altura, apontava na fabricação de produtos, um consumo mundial de energia elétrica, de origem fóssil de cerca 86,16 EJ/ano (86,16×018 J) e um consumo de energia nos sistemas de vapor de 32,75 EJ/ano. Evidenciou também nesses estudos que o potencial de poupança de energia nos sistemas de vapor era de 3,27 EJ/ano. Ou seja, quase tanto como a energia consumida nos sistemas de vapor da U.E. Não se encontraram números relativamente a Portugal, mas comparativamente com outros Países publicitados com alguma similaridade, o consumo de energia em vapor rondará 0,2 EJ/ano e por conseguinte um potencial de poupança de cerca 0,02 EJ/ano, ou 5,6 × 106 MWh/ano ou uma potência de 646 MW, mais do que a potência de cinco barragens Crestuma/Lever! Trata-se efetivamente de muita energia; interessa por isso perceber o onde e o porquê deste desperdício. De um modo muito modesto, pretende-se com este trabalho dar algum contributo neste sentido. Procurou-se evidenciar as possibilidades reais de os utilizadores de vapor de água na indústria reduzirem os consumos de energia associados à sua produção. Não estão em causa as diferentes formas de energia para a geração de vapor, sejam de origem fóssil ou renovável; interessou neste trabalho estudar o modo de como é manuseado o vapor na sua função de transporte de energia térmica, e de como este poderá ser melhorado na sua eficiência de cedência de calor, idealmente com menor consumo de energia. Com efeito, de que servirá se se optou por substituir o tipo de queima para uma mais sustentável se a jusante se continuarem a verificarem desperdícios, descarga exagerada nas purgas das caldeiras com perda de calor associada, emissões permanentes de vapor para a atmosfera em tanques de condensado, perdas por válvulas nos vedantes, purgadores avariados abertos, pressão de vapor exageradamente alta atendendo às temperaturas necessárias, “layouts” do sistema de distribuição mal desenhados, inexistência de registos de produção e consumos de vapor, etc. A base de organização deste estudo foi o ciclo de vapor: produção, distribuição, consumo e recuperação de condensado. Pareceu importante incluir também o tratamento de água, atendendo às implicações na transferência de calor das superfícies com incrustações. Na produção de vapor, verifica-se que os maiores problemas de perda de energia têm a ver com a falta de controlo, no excesso de ar e purgas das caldeiras em exagero. Na distribuição de vapor aborda-se o dimensionamento das tubagens, necessidade de purgas a v montante das válvulas de controlo, a redução de pressão com válvulas redutoras tradicionais; será de destacar a experiência americana no uso de micro turbinas para a redução de pressão com produção simultânea de eletricidade. Em Portugal não se conhecem instalações com esta opção. Fabricantes da República Checa e Áustria, têm tido sucesso em algumas dezenas de instalações de redução de pressão em diversos países europeus (UK, Alemanha, R. Checa, França, etc.). Para determinação de consumos de vapor, para projeto ou mesmo para estimativa em máquinas existentes, disponibiliza-se uma série de equações para os casos mais comuns. Dá-se especial relevo ao problema que se verifica numa grande percentagem de permutadores de calor, que é a estagnação de condensado - “stalled conditions”. Tenta-se também evidenciar as vantagens da recuperação de vapor de flash (infelizmente de pouca tradição em Portugal), e a aplicação de termocompressores. Finalmente aborda-se o benchmarking e monitorização, quer dos custos de vapor quer dos consumos específicos dos produtos. Esta abordagem é algo ligeira, por manifesta falta de estudos publicados. Como trabalhos práticos, foram efetuados levantamentos a instalações de vapor em diversos sectores de atividades; 1. ISEP - Laboratório de Química. Porto, 2. Prio Energy - Fábrica de Biocombustíveis. Porto de Aveiro. 3. Inapal Plásticos. Componentes de Automóvel. Leça do Balio, 4. Malhas Sonix. Tinturaria Têxtil. Barcelos, 5. Uma instalação de cartão canelado e uma instalação de alimentos derivados de soja. Também se inclui um estudo comparativo de custos de vapor usado nos hospitais: quando produzido por geradores de vapor com queima de combustível e quando é produzido por pequenos geradores elétricos. Os resultados estão resumidos em tabelas e conclui-se que se o potencial de poupança se aproxima do referido no início deste trabalho.

User Profiling and Knowledge Extraction For Tourism

O sector do turismo é uma área francamente em crescimento em Portugal e que tem desenvolvido a sua divulgação e estratégia de marketing. Contudo, apenas se prende com indicadores de desempenho e de oferta instalada (número de quartos, hotéis, voos, estadias), deixando os indicadores estatísticos em segundo plano. De acordo com o “ Travel & tourism Competitiveness Report 2013”, do World Economic Forum, classifica Portugal em 72º lugar no que respeita à qualidade e cobertura da informação estatística, disponível para o sector do Turismo. Refira-se que Espanha ocupa o 3º lugar. Uma estratégia de mercado, sem base analítica, que sustente um quadro de orientações específico e objetivo, com relevante conhecimento dos mercados alvo, dificilmente é compreensível ou até mesmo materializável. A implementação de uma estrutura de Business Intelligence que permita a realização de um levantamento e tratamento de dados que possibilite relacionar e sustentar os resultados obtidos no sector do turismo revela-se fundamental e crucial, para que sejam criadas estratégias de mercado. Essas estratégias são realizadas a partir da informação dos turistas que nos visitam, e dos potenciais turistas, para que possam ser cativados no futuro. A análise das características e dos padrões comportamentais dos turistas permite definir perfis distintos e assim detetar as tendências de mercado, de forma a promover a oferta dos produtos e serviços mais adequados. O conhecimento obtido permite, por um lado criar e disponibilizar os produtos mais atrativos para oferecer aos turistas e por outro informá-los, de uma forma direcionada, da existência desses produtos. Assim, a associação de uma recomendação personalizada que, com base no conhecimento de perfis do turista proceda ao aconselhamento dos melhores produtos, revela-se como uma ferramenta essencial na captação e expansão de mercado.

In situ evaluation of single-cell lysis by cytosol extraction observation through fluorescence decay and dielectrophoretic trapping time

We present a new method for lysis of single cells in continuous flow, where cells are sequentially trapped, lysed and released in an automatic process. Using optimized frequencies, dielectrophoretic trapping allows exposing cells in a reproducible way to high electrical fields for long durations, thereby giving good control on the lysis parameters. In situ evaluation of cytosol extraction on single cells has been studied for Chinese hamster ovary (CHO) cells through out-diffusion of fluorescent molecules for different voltage amplitudes. A diffusion model is proposed to correlate this out-diffusion to the total area of the created pores, which is dependent on the potential drop across the cell membrane and enables evaluation of the total pore area in the membrane. The dielectrophoretic trapping is no longer effective after lysis because of the reduced conductivity inside the cells, leading to cell release. The trapping time is linked to the time required for cytosol extraction and can thus provide additional validation of the effective cytosol extraction for non-fluorescent cells. Furthermore, the application of one single voltage for both trapping and lysis provides a fully automatic process including cell trapping, lysis, and release, allowing operating the device in continuous flow without human intervention.

Characterization of volatile organic gunshot residues in fired handgun cartridges by headspace sorptive extraction

In forensic investigation of firearm-related cases, determination of the residual amount of volatile compounds remaining inside a cartridge could be useful in estimating the time since its discharge. Published approaches are based on following the decrease of selected target compounds as a function of time by using solid phase micro-extraction (SPME). Naphthalene, as well as an unidentified decomposition product of nitrocellulose (referred to as "TEA2"), are usually employed for this purpose. However, reliability can be brought into question given their high volatility and the low reproducibility of their extracted quantities. In order to identify alternatives and therefore develop improved dating methods, an extensive study on the composition and variability of volatile residues in nine different types of cartridges was carried out. Analysis was performed using headspace sorptive extraction (HSSE), which is a more exhaustive technique compared to SPME. 166 compounds were identified (several of which for the first time), and it was observed that the final compositional characteristics of each residue were strongly dependent on its source. Variability of single identified compounds within and between different types of cartridge, as well as their evolution over time, was also studied. Many explosion products containing up to 4 aromatic rings were found to be globally present in high proportions amongst residues. 27 of them (excluding naphthalene) also presented detectable decreases during the first 24 h. Therefore, they could be used as complementary target analytes in future dating methods.